JP2692266B2 - Cyanoacetic acid amide derivative and its use - Google Patents

Description

TECHNICAL FIELD The present invention relates to a plant disease control agent containing a cyanoacetic acid amide derivative as an active ingredient.

<Prior Art> Until now, various plant disease controlling agents have been developed, but they cannot be said to be sufficiently satisfactory in terms of 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, X represents a hydrogen atom, a fluorine atom, a chlorine atom or a lower alkoxy group, and Y represents a chlorine atom, a bromine atom, a trifluoromethyl group or a lower fluoroalkoxy group. However, when X represents a hydrogen atom,
Y is not a chlorine atom or a bromine atom. ] It was found that the cyanoacetic acid amide derivative represented by the following (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, leading to the present invention. .

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 (Cochliobolus miyabeanus) of rice and scab (Ventu) of apple.
ria inaequalis), Pear scab (Venturia nashicol)
a), anthracnose of oyster (Gloeosporium kaki), anthracnose of cucumber (Colletotrichum lagenarium), anthracnose of kidney bean (Colletotrichum lindemuthianum), black spot of peanut (Mycosphaerella personatum), brown spot (Cerco)
spora arachidicola), tobacco anthracnose (Colletotrich
um tabacum), brown leaf spot of sugar beet (Cercospora beticol)
a), etc.

 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 [In the formula, X and Y have the same meanings as described above. ] The α-methylbenzylamine derivative represented by and α-cyano-tert-butylacetic acid or a reactive derivative thereof,
It can be obtained by reacting in the presence of a reaction aid, if necessary.

In the above reaction, α-cyano-tert-butylacetic acid or its reactive derivative used may be a corresponding carboxylic acid, acid anhydride, acid chloride, acid bromide, carboxylic acid methyl ester or carboxylic acid ethyl ester. Carboxylic acid esters and the like can be mentioned, and as the reaction aid, for example, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl), depending on α-cyano-tert-butylacetic acid or its reactive derivative. )
Carbodiimide hydrochloride, 1,1'-carbonyldiimidazole, phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, thionyl chloride, phosgene, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, triethylamine, pyridine, Examples thereof include quinoline, N, N-dimethylaniline, N, N-diethylaniline and N-methylmorpholine.

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 to be used in the reaction is α-cyano-tert-butylacetic acid or its reactive derivative (α) represented by the general formula [II]. The methylbenzylamine derivative 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, triene, 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 α-methylbenzylamine derivative represented by the general formula [II], which is one of the starting compounds for producing the compound of the present invention, can be prepared, for example, by Organic Reaction
s, Vol.5, 301-330 (1949), Leuckart reaction, etc. [In the formula, X and Y have the same meanings as described above. ] It can synthesize from the compound etc. which are shown.

Further, the other raw material compound α-cyano-tert-butylacetic acid or a reactive derivative thereof is, for example, J. Am.
m.Soc. 72, 4791 (1950) or Justus Liebigs Ann.Che
m. 718, 101 (1968) and the usual derivatization method, ie hydrolysis of the carboxylic acid ester to give the carboxylic acid (Arkiv Kemi, 2 , 321 (1950)). It can be synthesized by the method of converting a carboxylic acid into an acid halide to obtain a carboxylic acid halide (Tetrahedron, 35 , 1965 (1979)) and the like.

The compound of the present invention has four stereoisomers (optical isomers) derived from the asymmetric carbon atom.
It also includes these isomers and mixtures thereof.

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 formulation auxiliary agents. Mixed with emulsions, wettable powders, suspensions,
It is formulated into granules and powders for use.

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, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob flour, walnut flour, urea, ammonium sulfate, fine powder or granules of synthetic hydrous silicon oxide, etc. The liquid carrier includes
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
When the emulsion, wettable powder, suspending agent and the like are diluted with water and applied, the application concentration is 0.00005 to 0.5%, preferably 0.0001 to 0.2%. Apply as is without 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. Note that the present invention is not limited to these examples.

 First, a production example will be described.

Production Example 1 (Compound (3)) 0.28 g (2 mmol) of α-cyano-t-butylacetic acid was added to anhydrous TH
Dissolve in F and add 1,1'-carbonyldiimidazole 0.
36 g (2.2 mmol) was added slowly. After stirring at room temperature for 1 hour, 0.41 g (2 mmol) of 1- (4-trifluoromethoxyphenyl) ethylamine was added. After stirring at room temperature for 4 hours, ether was added and 5% hydrochloric acid water, saturated sodium bicarbonate water,
Washed sequentially with saturated saline. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain 0.70 g of a viscous liquid. This was purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 5: 1) to give 0.56 g of compound (3), ie, N- [1- (4-trifluorotomexiphenyl) ethyl] -2-. Cyano-3,3-dimethylbutanamide was obtained.

mp 91-94 ℃ ¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 1.06 and 1.11 (each s, total 9H), 1.42 and 1.44 (each d, J = 7Hz, total 3H), 3.25 and 3.27 (each s, 1H in total), 4.65 to 5.25 (m, 1H), 6.75 to 7.35 (m, 5H) Production Example 2 (Compound (7)) 0.42 g (3 mmol) of α-cyano-t-butylacetic acid To a solution dissolved in 5 ml of anhydrous tetrahydrofuran, 0.58 g (3.6 mmol) of 1,1′-carbonyldiimidazole was added little by little,
Stirred at room temperature for 1 hour. 1- (4-chloro-
0.56 g (3 mmol) of 2-methoxyphenyl) ethylamine was added dropwise, and the mixture was stirred at room temperature for 2 hours. After the reaction, the solvent is distilled off,
Purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 2: 1), 0.83 g of N-
[1- (4-chloro-2-methoxyphenyl) ethyl]
2-Cyano-3,3-dimethyl-butanamide was obtained.

mp 144-147 ℃ ¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 1.08 and 1.16 (each s, total 9H), 1.45 (d, J = 7Hz, 3H), 3.05 and 3.09 (each s, 1H), 3.85 (s, 3H), 4.85 to 5.4 (m, 1H), 6.7 to 7.4 (m, 4H) Mass spectrum (m / e, 70eV) 308 (M ⁺ ), 293,251,184,169,108 The compounds of the present invention that can be produced by

Next, a production example of the α-methylpentylamine derivative represented by the general formula [II] will be shown.

Reference Production Example 1 A mixture of 9.44 g (40 mmol) of p- (1,1,2,2-tetrafluoroethoxy) acetophenone, formamide (160 mmol), and 1 ml of 90% formic acid was heated at 180 to 190 ° C. for 5 hours, Cooled. The generated crystals were collected and washed successively with cold water and cold hexane. The crystals obtained (10.7 g) were added to ethanol 2
The suspension was suspended in 0 ml, 20 ml of 6N-hydrochloric acid was added, and the mixture was heated at 50 ° C for 1 hour. After ice cooling, water was added, and the mixture was extracted twice with methylene chloride. The aqueous layer was made alkaline with 15 ml of 40% caustic soda aqueous solution while cooling with ice, and then extracted twice with ether.

After drying over anhydrous magnesium sulfate, by concentrating,
¹ on H-NMR nearly pure 1- [4- (1,1,2,2-tetrafluoroethoxy) phenyl] ethylamine 5.97 g (63%)
I got

Reference Production Example 2 7.43 g of 4-chloro-2-methoxyacetophenone (40.
3 mmol), formamide 7.48 g (161.2 mmol), and 90
A mixture of 1% by weight formic acid was heated at 180-190 ° C for 6 hours and cooled. After adding water, the mixture was extracted with chloroform and concentrated. 4 ml of concentrated hydrochloric acid was added to the obtained oily residue (9.37 g),
Heated at 100 ° C. for 1 hour. After cooling with ice, water was added, and the mixture was extracted twice with chloroform. The water layer was made alkaline with an aqueous solution of sodium hydroxide while cooling with water, and then extracted twice with ether. After drying over anhydrous magnesium sulfate and concentration, 5.24 g (70%) of 1- (4-chloro-2-methoxyphenyl) ethylamine, which was almost pure by ¹ H-NMR, was obtained.

The α represented by the general formula (II) can be produced in this manner.
Some of the -methylbenzylamine derivatives are shown below.

Compound represented by Next, formulation examples are shown. 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 each of the compounds (1) to (11) of the present invention, 3 parts of calcium lignin sulfonate, 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 (11) 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 (11) 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 of the compounds of the present invention.

Formulation Example 4 20 parts each of the compounds (1) to (11) 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 present compounds (1) to (11), 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 thereto. 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 rice seedling was diluted with water as a test agent prepared as an emulsion according to Formulation Example 4, and a predetermined amount thereof was irrigated into the soil. After the irrigation, the plants were grown in a greenhouse for 7 days, and a spore suspension of blast fungus was sprayed and inoculated. 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.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yoshitaka Takano 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd. (56) Reference JP-A-63-72663 (JP, A)

Claims (2)

(57) [Claims] (1) Expression Cyanoacetic acid amide derivative represented by. 2. A rice blast control agent comprising the cyanoacetamide derivative according to claim 1 as an active ingredient.