JP2692277B2 - Amide derivative and plant disease controlling agent containing the same as an active ingredient - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel amide derivative, a method for producing the same, and a plant disease controlling agent containing the same as an active ingredient.

<Prior Art> Various plant disease control agents have been developed so far, but it is hard to say that they are not completely satisfactory in terms of their efficacy and the like.

<Problems to be Solved by the Invention> An object of the present invention is to develop a compound having an excellent controlling effect on plant diseases.

<Means for Solving the Problems> In order to achieve the above object, the present inventors have conducted intensive studies and found that the general formula [In the formula, R ¹ represents a lower alkyl group or a lower alkenyl group, X represents a cyano group or a bromo atom, R ² represents a furyl group optionally having a halogen atom or a lower alkyl group as a substituent, thienyl. Represents a group, a thiazolyl group, a pyrazolyl group, a benzofuranyl group, a benzothienyl group, a naphthyl group, or a pyridyl group. However, when X represents a bromo atom, R ² is not a naphthyl group. The present invention has been found out that the amide derivative represented by the formula (hereinafter, referred to as the compound of the present invention) has excellent foliar preventive disease control efficacy and systemic transitional disease control efficacy particularly against rice blast disease.

The compound of the present invention is particularly useful for rice blast (Pyricularia oryz).
ae) has an excellent control effect, but other plant diseases that can be controlled are sesame leaf blight (Cochli) of rice.
obolus miyabeanus), apple scab (Venturia inae)
qualis), pear scab (Venturia nashicola), oyster anthracnose (Gloeosporium kaki), cucumber anthracnose (Col)
letotrichum lagenarium), anthracnose of kidney bean (Collet
otrichum lindemuthianum), peanut black sickness (Myc
osphaerella personatum), brown spot (Cercospora arach)
idicola), tobacco anthracnose (Colletotrichum tabacu
m), sugar beet brown spot (Cercospora beticola) and the like.

 Next, the production method of the compound of the present invention will be described in detail.

The compound of the present invention has the general formula [Wherein, R ² has the same meaning as described above. ] The amine derivative represented by [In the formula, R ¹ and X have the same meanings as described above. ] It can be obtained by reacting a carboxylic acid represented by or a reactive derivative thereof in the presence of a reaction aid, if necessary.

In the above reaction, examples of the carboxylic acid represented by the general formula [III] or its reactive derivative include corresponding carboxylic acid, acid anhydride, acid chloride, acid bromide, carboxylic acid methyl ester and carboxylic acid ethyl ester. Examples thereof include carboxylic acid esters, and examples of the reaction aid include dicyclohexylcarbodiimide, 1-ethyl-3-, depending on the carboxylic acid or its reactive derivative.
(3-dimethylaminopropyl) carbodiimide hydrochloride, 1,1′-carbonyldiimidazole, phosphorus pentachloride,
Phosphorus trichloride, phosphorus oxychloride, thionyl chloride, phosgene, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, triethylamine,
Pyridine, quinoline, N, N-dimethylaniline, N, N-diethylaniline, N-methylmorpholine and the like can be mentioned.

In the above reaction, the reaction temperature is typically from 0 to 200.
The reaction time is 0.1 to 24 hours, and the amount of the reagent used in the reaction is represented by the general formula [II] with respect to 1 mol of the carboxylic acid represented by the general formula [III] or its reactive derivative. The amine derivative used is 1 to 1.2 mol, and the reaction aid is 1 mmol to 5 mol.

In the above reaction, a reaction solvent is not necessarily required, but generally the reaction is carried out in the presence of a solvent.

As the solvent that can be used, hexane, heptane, aliphatic hydrocarbons such as ligroin, benzene, toluene, aromatic hydrocarbons such as xylene, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, ethers such as diethylene glycol dimethyl ether, Dichloromethane, chloroform, carbon tetrachloride, 1,
Solvents containing halogen atoms such as 2-dichloroethane and chlorobenzene, solvents such as dimethylformamide, dimethylsulfoxide, acetonitrile, and water, and mixtures thereof.

After completion of the reaction, usual post-treatments such as filtration, extraction and concentration are performed, and if necessary, operations such as column chromatography and recrystallization are carried out to obtain the desired compound of the present invention. The amine derivative represented by the general formula [II], which is one of the starting compounds for producing the compound of the present invention, is, for example, Organic Reactions, Vol.
According to the Leuckart reaction described in (1949), the general formula [Wherein, R ² has the same meaning as described above. And the like.

The other raw material compound, a carboxylic acid represented by the general formula [III] or a reactive derivative thereof is, for example, JA
m.Chem.Soc. 72 , 4791 (1950), J.Am, Chem.Soc. 66 , 886 (1
944), J. Organomet. Chem., 285 , 395 (1985) or J. Am.
Chem. Soc. 55 , 4209 (1933) and a conventional derivatization method, that is, a carboxylic acid ester is hydrolyzed to obtain a carboxylic acid, and the obtained carboxylic acid is converted into an acid halide to form a carboxylic acid. It can be synthesized by a method of obtaining a halide or the like.

When the compound of the present invention is used as an active ingredient of a plant disease controlling agent, it may be used as it is without adding any other components, but it is usually a solid carrier, a liquid carrier, a surfactant, and other auxiliary substances for pharmaceutical preparations. And used in the form of emulsions, wettable powders, suspensions, granules, powders and the like.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 99%, preferably 0.2 to 95%.

As the solid carrier, kaolin clay, ttattalgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, synthetic hydrated silicon oxide or the like fine powder or Granular materials are mentioned, and liquid carriers include
Aromatic hydrocarbons such as xylene and methylnaphthalene; 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. Can be

Surfactants used for emulsification, dispersion, wet spreading, etc. include alkyl sulfates, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphates, and naphthalene sulfones. Examples include anionic surfactants such as acid formalin condensate, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester.

Pharmaceutical adjuvants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC
(Carboxymethylcellulose), PAP (acidic isopropyl phosphate) and the like.

These preparations may be used as they are, or diluted with water and sprayed on foliage, or powdered and dispersed in soil, mixed or applied to soil. In addition, by mixing with other plant disease controlling agents to be used, it can be expected to enhance the controlling effect. Further, it can be used in combination with an insecticide, an acaricide, a nematicide, a herbicide, a plant growth regulator, a fertilizer, a soil conditioner and the like.

When the compound of the present invention is used as an active ingredient of a plant disease controlling agent, the treatment amount varies depending on weather conditions, formulation form, treatment time, method, place, target disease, target crop, etc., but is usually 0.05 to 1 per are. 200 g, preferably 0.1
~ 100g, when the emulsion, wettable powder, suspension, etc. are diluted with water and applied, the application concentration is preferably 0.005 to 0.5%.
0.01 to 0.2%, and granules, powders, etc. are applied as they are without any dilution.

<Effects of the Invention> Since the compound of the present invention has an excellent effect on plant diseases caused by various plant pathogenic fungi including rice blast, it can be used for various purposes as an active ingredient of a plant disease controlling agent.

<Example> Hereinafter, the present invention will be described in more detail with reference to Production Examples, Formulation Examples, and Test Examples. The present invention is not limited to these examples.

 First, a production example will be described.

Production Example (Compound (2)) Anhydrous 0.42 g (3 mmol) of α-cyano-tert-butylacetic acid
Dissolve in THF and add 1.1'-carbonyldiimidazole to it.
0.53 g (3.3 mmol) was added slowly. After stirring at room temperature for 1 hour, 0.62 g (3 mmol) of 1- [2- (5-bromothienyl)] ethylamine was added. After stirring at room temperature for 4 hours, ether was added, and the mixture was washed successively with 5% aqueous hydrochloric acid, saturated sodium bicarbonate solution and saturated saline. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain 0.98 g of a viscous liquid. This was purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 3: 1) to give 0.81 g of compound (2), that is, N- [1- {2- (5-bromothienyl)} ethyl]-. 2-Cyano-3,3-dimethylbutanamide was obtained.

mp 117-120 ℃ ₁ H-NMR (DMSO-d ₆ / TMS, δ (ppm)) 1.04 and 1.07 (each s, total 9H), 1.38 and 1.40 (each d, J = 7Hz, total 3H), 3.27 (s, 1H), 4.75 to 5.35 (m, 1H), 6.6 to 7.1 (m, 2H), 8.45 to 8.85 (br d, 1H) Some of the compounds that can be produced by such a production method are shown in Table 1. Shown in.

The compound of the present invention has a total of two asymmetric points (one or more depending on the compound) on each of the acid side and the amine side, and a total of four stereoisomers (or more depending on the compound). Although present, the present invention also includes those isomers and mixtures thereof.

Next, formulation examples are shown. The compounds of the present invention are shown by the compound numbers in Table 1. Parts represent parts by weight.

Formulation Example 1 50 parts each of the compounds (1) to (36) 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, and a wettable powder for each of the compounds of the present invention is prepared. To get

Formulation Example 2 25 parts each of the compounds (1) to (36) of the present invention, 3 parts polyoxyethylene sorbitan monooleate, 3 parts CMC and water.
69 parts are mixed and wet-pulverized until the particle size of the active ingredient is 5 μm or less to obtain a suspension of each compound of the present invention.

Formulation Example 3 2 parts of each of the compounds (1) to (36) of the present invention, 88 parts of kaolin clay and 10 parts of talc are well pulverized and mixed to obtain a powder of each compound of the present invention.

Formulation Example 4 20 parts each of the compounds (1) to (36) of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzene sulfonate, and 60 parts of xylene were mixed well to form an emulsion of each of the compounds of the present invention. obtain.

Formulation Example 5 2 parts of each of the compounds (1) to (36) 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 are well pulverized and mixed, and water may be added. After kneading, the mixture is granulated and dried to obtain granules of the compounds of the present invention.

Next, Test Examples show that the compounds of the present invention are useful as plant disease controlling agents. 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.

In addition, the control efficacy was evaluated by visually observing the disease state of the test plant at the time of the survey, ie, the flora of leaves and stems, and the degree of the lesion. "4" when recognized, "3" when recognized about 30%, "2" when recognized about 50%, "1" when recognized about 70%, and the disease state when the compound is not used for more than that If no difference is found, the evaluation is made as “0” and evaluated on a six-point scale, and indicated by 5, 4, 3, 2, 1, and 0, respectively.

Test Example 1 Rice Blast Control Test (Preventive Effect) A plastic pot was filled with sandy loam, and rice (Kinki 33
No. 2) and bred in a greenhouse for 20 days. A test solution prepared as a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the rice seedling was sprayed with foliage so as to sufficiently adhere to the leaves. After spraying, the plants were sprayed and inoculated with a spore suspension of air-dried blast fungus. After inoculation, the plants were grown for 4 days at 28 ° C. in a dark and humid environment, and their control efficacy was examined. Table 3 shows the results.

Test Example 2 Rice blast control test (penetration and transfer effect) A plastic pot was filled with sandy loam, and rice (Kinki 33
No.) and cultivated in a greenhouse for 14 days. A reagent prepared as an emulsion according to Formulation Example 4 was diluted with water in a rice seedling, and a predetermined amount thereof was irrigated into soil. After irrigation, they were grown in a greenhouse for 7 days, and sprayed and inoculated with a spore suspension of the blast fungus. After the inoculation, the plants were placed at 28 ° C. in the dark and in a humid environment for 4 days, and the control effect was examined. Table 4 shows the results.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area A01N 43/40 101 A01N 43/40 101C 43/56 43/56 C 43/78 43/78 B C07C 231/02 9547-4H C07C 231/02 233/09 9547-4H 233/09 Z 255/27 9357-4H 255/27 C07D 213/40 C07D 213/40 213/61 213/61 231/14 231/14 231 / 16 231/16 277/28 277/28 307/52 307/52 307/81 307/81 333/20 333/20 333/28 333/28 333/66 333/66

Claims (4)

(57) [Claims] (1) General formula [In the formula, R ¹ represents a lower alkyl group or a lower alkenyl group, X represents a cyano group or a bromo atom, R ² represents a furyl group optionally having a halogen atom or a lower alkyl group as a substituent, thienyl. Represents a group, a thiazolyl group, a pyrazolyl group, a benzofuranyl group, a benzothienyl group, a naphthyl group or a pyridyl group. However, when X represents a bromo atom, R ² is not a naphthyl group. ] The amide derivative shown by these. 2. The amide derivative according to claim 1, wherein X is a cyano group. 3. A plant disease controlling agent comprising the amide derivative according to claim 1 as an active ingredient. 4. A rice blast control agent, which comprises the amide derivative according to claim 1 as an active ingredient.