JP2897789B2 - Alkoxyiminoacetic acid amide compounds and their use as agricultural fungicides - Google Patents

Description

The present invention relates to a novel alkoxyiminoacetamide compound and its use as an agricultural fungicide.

BACKGROUND OF THE INVENTION Certain alkoxyiminoacetic acid amide compounds are known, some of which are known for use as fungicides or herbicides (e.g. JP 63-30463).
JP-A-63-23852, JP-A-56-29560, JP-A-55
-5006, JP-A-56-55368 and the like. However, the relationship between chemical structure and biological activity has not yet been sufficiently elucidated, and it is difficult to predict the biological activity of a novel compound. The present inventors have found that a certain kind of alkoxyiminoacetic acid amide compound, which is a novel substance, has a broad antibacterial spectrum against plant pathogenic bacteria and has a strong antibacterial activity, and based on this finding, completed the present invention. I came to.

[Constitution of the Invention] The present invention has a general formula Wherein R ¹ and R ² are each hydrogen or lower alkyl; R ³ is lower alkyl; A is lower alkyl, lower alkenyl, lower alkynyl, lower alkyloxy, lower alkenyloxy, lower alkynyloxy, halo-lower alkyl, cyano 10 ring-constituting atoms which may have at least one substituent selected from lower alkyl, halo-lower alkyloxy, halo-lower alkylthio, cyano-lower alkyloxy, oxo, halogen and phenyl and divalent lower alkylene. monocyclic or bicyclic aromatic carbocyclic or heterocyclic group does not exceed; B is a bond or -CH ₂
Represents-. And an agricultural fungicide containing the compound as an active ingredient.

In the definitions of the symbols of the above general formula, the term "lower" is generally used to represent a group having 8 or less carbon atoms, preferably 6 or less, more preferably 4 or less, unless otherwise specified. For example, "lower alkyl" preferably refers to alkyl having 6 or less carbon atoms, particularly 4 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tertiary butyl. The “lower alkenyl” generally has 2 to 8 carbon atoms, preferably 3 to 6 carbon atoms.
Alkenyl groups, such as allyl, propenyl,
Includes isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, hexadienyl and the like. "Lower alkoxy" refers to alkoxy having preferably 6 or less carbon atoms, particularly 4 or less carbon atoms, and includes, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and the like. "Halogen" includes fluorine, chlorine, bromine and iodine. “Halo lower alkyl” is
Lower alkyl substituted with at least one, preferably three or less halogens, and specific examples thereof include chloromethyl, fluoromethyl, trifluoromethyl, dichloroethyl and the like. Similarly, both “halo lower alkyloxy” and “halo lower alkylthio” represent lower alkyloxy or lower alkylthio substituted with at least one, and preferably three or fewer, halogens.

Specific examples of the monocyclic or bicyclic aromatic carbocyclic or heterocyclic group having not more than 10 ring atoms represented by A include phenyl, naphthyl, pyridyl, benzothiazolyl, benzoxazolyl, benzopyranyl And the like, which may have an appropriate number, preferably 3 or less substituents. When the substituent is a divalent lower alkylene, the divalent lower alkylene is bonded to two positions of the carbon ring or the heterocyclic group to form a saturated condensed ring.

The main object of the present invention is to provide novel alkoxyiminoacetic amide compounds having the general formula (I) which are useful as agricultural fungicides.

The alcoholic iminoacetic acid amide compounds of the general formula (I) include, in particular, compounds of the formula: Wherein A ′ is lower alkyl, lower alkyloxy, lower alkynyloxy, halo-lower alkyl, halo-lower alkylthio, oxo, halogen and phenyl;
Phenyl, naphthyl, pyridyl, benzothiazolyl, benzoxazolyl or benzoranyl, which may have at least one substituent selected from valence lower alkylene, and A ″ is a substituent selected from lower alkenyloxy and cyano lower alkyloxy Wherein R ² and R ³ have the same meaning as described above.] The alkoxyiminoacetic amide compound (I) can be produced by various methods, and typical examples thereof are as follows. The method is the corresponding expression: [Wherein, R ³ is the same as defined above for B. And carrying out the amidation of the carboxyl group and the etherification of the hydroxyl group directly or adjacent to the benzene ring in any order. This can be represented by the following equation: In the first method, a carboxylic acid (II) or a reactive derivative at a carboxyl group thereof has the formula: HNR ¹ R ² (a) wherein R ¹ and R ² are as defined above. And reacting the resulting carboxylic acid amide (III) with a compound represented by the formula: AX (b) wherein X is a reactive group, particularly a halogen atom (for example, chlorine or bromine) or a sulfonyloxy group. (For example, methanesulfonyloxy, ethanesulfonyloxy, toluenesulfonyloxy), and A is as defined above. Wherein the desired alkoxyiminoacetic imide compound (I) is obtained by reacting an etherifying agent represented by the following formula:
In the second method, a carboxylic acid (II) is reacted with an etherifying agent (b), and the obtained ether (IV) is reacted with an amine (a) to obtain a desired alkoxyiminoacetic imide compound (I). Things.

The starting carboxylic acid (II) may be used as such or in the form of a reactive derivative for its carboxyl group. Examples of reactive derivatives include esters, acid anhydrides, acid halides, and the like.

The amidation and the etherification are each known per se and can be carried out by means well known to those skilled in the art. In general, these reactions are carried out in a solvent, preferably under conditions which facilitate or accelerate the reaction, from room temperature to the reflux temperature of the reaction mixture, for example from 10 to 200 ° C.

Conditions that facilitate or facilitate the reaction can be determined as appropriate, taking into account the type of reactants or the types of by-products to be removed from the reaction product. For example, the first
The amidation in the method described in the above is carried out by carboxylic acid or ester (eg, methyl ester, ethyl ester, cyanomethyl ester, p-nitrophenyl ester), acid anhydride (eg, mixed acid anhydride with trichloroacetic acid), acid halide (eg, acid The reaction is carried out between a reactive derivative at a carboxyl group such as chloride and acid bromide) and an amine (a). In order to remove these by-products, a condensing agent (for example, 1,3-dicyclohexylcarbodiimide (DCC), N-cyclohexyl-N'-morpholinoethylcarbodiimide, 1,3-diisopropylcarbodiimide, methyl chloroformate, ethyl chloroformate), dehydration Agents (eg, thionyl chloride, sulfuryl chloride, phosphorus oxychloride, phosphorus tribromide, phosphorus pentachloride, polyphosphoric acid), acid removers (eg, pyridine, triethylamine, sodium methoxide, sodium hydroxide, sodium formate), etc. can do. Further, the etherification of the amide (III) with the etherifying agent (b) is usually carried out in the presence of the above-mentioned acid removing agent in order to remove an acid which may be a by-product. The etherification and amidation in the second method may be carried out under the same conditions as described above.

The amination and etherification reactions are performed using dioxane, methylene chloride, chloroform, ether, tetrahydrofuran (THF), acetone, dimethylformamide (DM
F), in dimethyl sulfoxide (DMSO), pyridine, acetonitrile, benzene, toluene, xylene and the like in an inert solvent appropriately selected.

The alkoxyiminoacetic acid amide compound (I) has E and Z isomers as isomers, and can be isolated by applying appropriate separation and purification means. Therefore, the compound of the present invention includes E-form, Z-form and a mixture of E-form and Z-form.

The alkoxyiminoacetic acid amide compound (I) of the present invention
Is a variety of cultivated plants, for example, rice, wheat, barley, rye, corn, millet, millet, buckwheat, soybean, red bean, peanut, cucumber, eggplant, tomato, pumpkin, kidney bean, orange, grape, apple, pear, peach Pathogens, especially rice blast fungus (Pyricularia or
yzae), rice sheath blight (Rhizoctonia solani), wheat powdery mildew (Erysiphe graminis), cucumber powdery mildew (Sphaerotheca fuliginea), tobacco powdery mildew (Erysiphe cichoracearum), potato blight (Phyt)
ophthora infestans), Pseudopero
nospora cubensis, soybean downy mildew (Peronospora mans)
hurica), grape downy mildew (Plasmopara viticola),
Botrytis cinerea, such as vegetables and grapes,
Sclerotinia scleroti (Pythium aphanidermatum), buckwheat, soybeans, rape seeds, etc.
orum), soybeans, red beans, potatoes, peanuts, and other fungi such as Corticium rolfsii. Therefore, the alkoxyiminoacetic acid amide compound (I) of the present invention is useful as an agricultural fungicide.

The alkoxyiminoacetic acid amide compound (I) of the present invention is applied to plants by a method such as spraying, spraying, and applying. Further, the present invention may be applied to plant seeds, soil around animals, soil where seeds are sown, paddy fields, water for hydroponics, and the like.
The application can be made before or after the plant is infected with the pathogen.

The alkoxyiminoacetic acid amide compound (I) can be used in the form of a usual preparation, for example, a liquid, wettable powder, emulsifier, suspension, liquid concentrate, tablet, granule, aerosol, powder, paste, smoke and the like. It can be used as a drug suitable for such agricultural germicides. Such embodiments comprise at least one alkoxyiminoacetic amide compound (I) and suitable solid or liquid carriers and, if desired, suitable auxiliaries for dispersing the active substance or improving other properties (e.g. (Surfactants, spreading agents, dispersants, stabilizers).

Examples of solid carriers or diluents include botanicals (eg, cereal flour, tobacco stalk flour, soy flour, walnut hull flour, vegetable flour, canna flour, bran, bark flour, fibrous flour, vegetable mid-autumn residue), Fibrous substances (eg, paper, corrugated cardboard, rags), artificial plastic powders, viscosities (eg, kaolin, bentonite, clay), talc and inorganic substances (eg, pyrophyllite, sericite, pumice, sulfur powder, activated carbon), chemical Fertilizers (eg, ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride) and the like.

Examples of the liquid carrier and diluent include water, alcohols (eg, methanol, ethanol), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, diethyl ether, dioxane, cellosolve, tetrahydrofuran), aromatic hydrocarbons (eg, benzene, Toluene, xylene, methylnaphthalene), aliphatic hydrocarbons (eg, gasoline, kerosene, kerosene), esters, nitriles, acid amides (eg, dimethylformamide, dimethylacetamide), halogenated hydrocarbons (eg, dichloroethane, carbon tetrachloride) and so on.

Examples of surfactants include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, polyethylene glycol ethers, polyhydric alcohol esters, and the like. Examples of spreading or dispersing agents include casein, gelatin, starch powder, carboxymethyl cellulose, acacia, alginic acid, lignin, bentonite, molasses, polyvinyl alcohol, pine oil, agar and the like. Examples of the stabilizer include PAP (isopropyl phosphate mixture), tricresyl phosphate (TCP), true oil, epoxy oil, surfactants, fatty acids and esters thereof, and the like.

In addition to the above components, the formulations of the present invention can be used in admixture with other fungicides, insecticides, herbicides, fertilizers, and the like.

These preparations usually contain at least one alkoxyiminoacetic acid amide compound (I) in an amount of 1 to 95% by weight, preferably
It is contained at a ratio of 2.0 to 80% by weight. These preparations can be used alone or in a diluted form. The alkoxyiminoacetic acid amide compound (I) is usually used at a ratio of about 1.0 g / 5 g / ha, preferably about 2 to 100 g / ha, usually about 1 g / ha. It is applied at a concentration of 50,00050,000 ppm, preferably about 100-5,000 ppm.

[Example] Next, a specific method for producing the alkoxyiminoacetic acid amide compound (I) will be described with reference to examples.

Example 1 (first method) (A) Production of N-methyl-2- (2-hydroxymethylphenyl) -2-methoxyiminoacetamide: -methyl 2-[(2-hydroxymethylphenyl)-
A methanol solution of methylamine (5.5 ml) was added to 2-methoxyiminoacetate (1.5 g), and the mixture was stirred at room temperature for 15 hours. The solvent was removed and the residue was purified by silica gel chromatography to give the title compound (1.05 g).

(B) N-methyl-2- [2- (3-chloro-5-trifluoromethylpyridin-2-yloxymethyl) phenyl] -2-methoxyiminoacetamide (Compound No. 4
Preparation of 4):-N-methyl-2-[(2-hydroxymethylphenyl) -2-methoxyiminoacetamide (200 mg)
% Sodium hydride (43 mg) in tetrahydrofuran (3 ml) was added, and the mixture was stirred at room temperature for 2 hours. And a few more
Dichloro-5-trifluoromethylpyridine (234mg)
Was added and stirred for 1 hour. After neutralization with diluted hydrochloric acid, the mixture was extracted with ethyl acetate. The extract was dried, the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 330 mg of the title compound.

Example 2 (first method) (A) Production of N-methyl-2- [2- (3-hydroxyphenoxy) phenyl] -2-methoxyiminoacetamide: -methyl 2- [2- (3- [Hydroxyphenoxy) phenyl] -2-methoxyiminoacetate (3.3 g) in methanol solution (20 ml) of methylamine was added.
Stirred for hours. The solvent was distilled off, and the residue was recrystallized from diethyl ether to obtain 2.4 g of the title compound.

(B) Production of N-methyl-2- [2- (3-allyloxyphenoxy) phenyl] -2-methoxyiminoacetamide (Compound No. 58): -N-methyl-2- [2- (3- Hydroxyphenoxy) phenyl] -2-methoxyiminoacetamide (200m
g) was added to a suspension of potassium carbonate (138 mg) in dimethylformamide (2 ml), allyl bromide (120 mg) was further added, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was neutralized with dilute hydrochloric acid and extracted with ethyl acetate. The extract was dried, the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 216 mg of the title compound.

Example 3 (second method) (A) Preparation of methyl 2- [2- (2,3-dimethylphenoxymethyl) phenyl] -2-methoxyiminoacetate: -methyl 2- (2-bromomethylphenyl) -2-methoxyiminoacetate (400 mg), 2,3-xylenol (342 mg) and potassium carbonate (580 mg) were suspended in dimethylformamide (2 ml), and the mixture was stirred at room temperature for 12 hours.
Methyl 2- [2- (2,3-dimethylphenoxymethyl) phenyl] -2-methoxyiminoacetate was produced.

(B) Production of N-methyl-2- [2- (2,3-dimethylphenoxymethyl) phenyl] -2-methoxyiminoacetamide (Compound No. 14): -Methyl 2- [2- (2,3 -Dimethylphenoxymethyl) phenyl] -2-methoxyiminoacetate in a methanol solution of methylamine (540 m
g) was added and stirred for 1 hour. The reaction mixture was neutralized with dilute hydrochloric acid and extracted with ethyl acetate. The extract was dried, the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 366 mg of the title compound as an oil. This was crystallized from diethyl ether.

Hereinafter, specific examples of the alkoxyiminoacetic acid amide compound (I) produced according to the above Examples are shown in Table 1. Compound Nos. 1 to 13, 15 to 43 and 51 to 57 were prepared in Example 3.
Compound Nos. 45 to 50 were prepared according to Example 1, and Compound No. 59 was prepared according to Example 2.

[Production Examples] The following shows formulation examples of agricultural fungicides that can be formulated from the compounds of the present invention.

Formulation Example 1 A mixture of compound No. 3 (2 parts by weight) and talc (98 parts by weight) is pulverized and formulated into a powder.

Formulation Example 2 Compound No. 3 (40 parts by weight), sodium ligninsulfonate (10 parts by weight) and water (50 parts by weight) are mixed to prepare a suspension.

Formulation Example 3 Compound No. 3 (10 parts by weight), Twin 20 (trademark) (1 part by weight) and isopropanol (89 parts by weight) are mixed to prepare a liquid preparation.

Formulation Example 4 Compound No. 4 (50 parts by weight), sodium alkylbenzenesulfonate (6 parts by weight), sodium ligninsulfonate (4 parts by weight) and clay (40 parts by weight) are mixed and ground to prepare a wettable powder.

Formulation Example 5 Compound No. 3 (5 parts by weight), an equivalent mixture of bentonite and talc (90 parts by weight) and sodium alkylbenzenesulfonate (5 parts by weight) are mixed and pulverized, and formed into granules.

Formulation Example 6 Compound No. 1 (25 parts by weight), polyoxyethylene alkylphenyl ether (8 parts by weight), sodium alkylbenzenesulfonate (2 parts by weight) and xylene (65 parts by weight)
Parts by weight) to obtain an emulsion.

[Test Example] Next, the effect of the agricultural fungicide of the present invention will be described by test examples (tests for controlling various plant diseases by foliage application (pot test)).

Test method The test liquid was sprayed on the test plant, and the pathogen was inoculated 24 hours later. The test liquid was prepared by dissolving the test compound in a small amount of N, N-dimethylformamide and diluting it to a predetermined concentration with distilled water containing a spreading agent.

The control value was determined by the following equation.

Test Example 1 (Rice blast control effect test) Rice (cultivar, Aichi Asahi) seedlings 2 weeks after sowing were transplanted into a plastic cup having a diameter of 9 cm, and after raising the seedlings for 2 weeks, a solution or suspension of the test compound was subjected to foliage. Was sprayed. The pathogen is inoculated by spraying a conidia suspension of rice blast (Pyricularia oryzae) cultured in oatmeal medium, and after inoculation, in a humid chamber (28 ° C, 100% R.
H.) for 24 hours, and further raised in a greenhouse for 5 days. Six days after inoculation, the number of lesions appearing on the inoculated leaves was measured, and the control value was determined.

Test Example 2 (Test for controlling rice sheath blight) Rice (cultivar, Aichi Asahi) seedlings 2 weeks after sowing were transplanted into a plastic cup having a diameter of 9 cm, and after 2 weeks of seedling raising, a solution or suspension of the test compound was added. The foliage was sprayed.
The pathogen is inoculated by placing the hypha of Rhizoctonia solani, which has been previously cultured in a rice grain culture medium, together with the rice grain culture medium in the region of the rice seedling. After inoculation, the seedlings were raised for 5 days in a wet room (28 ° C., 100% RH). The investigation was carried out by measuring the height of hyphae extending to the rice leaf sheath, and the control value was determined.

Test Example 3 (Cucumber Powdery Mildew Control Effect Test) Seed in a plastic cup having a diameter of 9 cm, and put a solution of the test compound or a solution of the test compound on the first true leaf surface salt of cucumber (cultivar, Tsukuba Shirabo) seedling after raising for 2 to 3 weeks. The suspension was sprayed. The pathogen was inoculated by spraying a conidia suspension of cucumber powdery mildew (Sphaerotheca fuliginea) cultured on cucumber leaves. After inoculation in a greenhouse at 20 ° C
After keeping for 10 days, the area occupied by the signs that appeared on the inoculated leaves was investigated to determine the control value.

Test Example 4 (Cucumber gray mold control effect test) Seed in a plastic cup with a diameter of 9 cm, and compound solution or suspension on the first true leaf surface of cucumber (cultivar, Tsukuba white bowl) after raising seedling for 2 to 3 weeks The solution was sprayed. The inoculation of the pathogen was performed using a hyphal disk (φ4m) of Botrytis cinerea grown on potato decoction agar medium with sucrose.
m) was placed on the cucumber leaf surface. After inoculation, the lesions were kept in a humidity chamber at 20 ° C. for 2 days, and the lesion diameter was measured to determine the control value.

Test Example 5 (Cucumber downy mildew controlling effect test) A solution or suspension of a test compound on the surface of the first true leaf of a cucumber (cultivar, Tsukuba Shirobo) seedling seeded in a plastic cup having a diameter of 9 cm and raised for 2 to 3 weeks The solution was sprayed. The pathogen was inoculated by dropping a zoosporangium suspension of cucumber downy mildew (Pseudoperonospora cubensis) cultured on cucumber leaves onto the back of the cucumber leaf (the drug-untreated surface). After the inoculation, the cells were kept in a moist chamber at 20 ° C for 10 days, and then the extent of lesion development around the inoculated area was investigated to determine the control value.

 Table 2 shows the results of Test Examples 1 to 5.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C07C 251 / 48,255 / 13,323 / 20 C07D 213 / 64,311 / 16 C07D 277 / 68,263 / 58 A01N 37 / 50,48 / 18,43 / 40 A01N 43 / 16,43 / 76,47 / 02 CA (STN) REGISTRY (STN)

Claims (10)

(57) [Claims] An agricultural fungicide containing an alkoxyiminoacetic acid amide compound selected from the following group as an active ingredient: N-methyl-2- [2- (2,3-dimethylphenoxymethyl) phenyl] -2- Methoxyiminoacetamide; N-methyl-2- [2- (2,4-dimethylphenoxymethyl) phenyl] -2-methoxyiminoacetamide; N-methyl-2- [2- (2,5-dimethyl Phenoxymethyl) phenyl] -2-methoxyiminoacetamide; N-methyl-2- [2- (2-methyl-4-chlorophenoxymethyl) phenyl] -2-methoxyiminoacetamide; N-methyl-2 -[2- (2,3,5-trimethylphenoxymethyl) phenyl] -2-methoxyiminoacetamide; N-methyl-2- [2- (3-chloro-5-trifluoromethylpyridine-2-i Oxymethyl) phenyl]
-2-methoxyiminoacetamide; N-methyl-2- [2- (3,5-dichloropyridine-2)
-Yloxymethyl) phenyl] -2-methoxyiminoacetamide; N-methyl-2- [2- (3-trifluoromethyl-6
-Chloropyridin-2-yloxymethyl) phenyl]
-2-methoxyiminoacetamide; N-methyl-2- [2- (5-trifluoromethyl-6
-Chloropyridin-2-yloxymethyl) phenyl]
-2-methoxyiminoacetamide. 2. The method according to claim 1, wherein the active ingredient is N-methyl-2- [2- (2,3
-Dimethylphenoxymethyl) phenyl] -2-methoxyiminoacetamide. 3. The method according to claim 1, wherein the active ingredient is N-methyl-2- [2- (2,4
-Dimethylphenoxymethyl) phenyl] -2-methoxyiminoacetamide. 4. An active ingredient comprising N-methyl-2- [2- (2,5
-Dimethylphenoxymethyl) phenyl] -2-methoxyiminoacetamide. 5. The method according to claim 1, wherein the active ingredient is N-methyl-2- [2- (2-
Methyl-4-chlorophenoxymethyl) phenyl] -2
The fungicide according to claim 1, which is -methoxyiminoacetamide. 6. An active ingredient comprising N-methyl-2- [2- (2,3,
The fungicide according to claim 1, which is 5-trimethylphenoxymethyl) phenyl] -2-methoxyiminoacetamide. 7. An active ingredient comprising N-methyl-2- [2- (3-
The fungicide according to claim 1, which is chloro-5-trifluoromethylpyridin-2-yloxymethyl) phenyl] -2-methoxyiminoacetamide. 8. The method according to claim 8, wherein the active ingredient is N-methyl-2- [2- (3,5
-Dichloropyridin-2-yloxymethyl) phenyl] -2-methoxyiminoacetamide.
The disinfectant according to the above. 9. An active ingredient comprising N-methyl-2- [2- (3-
The fungicide according to claim 1, which is trifluoromethyl-6-chloropyridin-2-yloxymethyl) phenyl] -2-methoxyiminoacetamide. 10. An active ingredient comprising N-methyl-2- [2- (5
-Trifluoromethyl-6-chloropyridin-2-yloxymethyl) phenyl] -2-methoxyiminoacetamide.