JP2518353B2 - Cyanoacetic acid amide derivative and its production intermediate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel cyanoacetic acid amide derivative and an intermediate for producing the same.

<Prior Art> Various plant disease control agents have been developed so far, but it cannot be said that they are always sufficiently satisfactory.

<Problems to be Solved by the Invention> The present invention aims to develop a compound having an excellent controlling effect against plant diseases.

<Means for Solving the Problems> The inventors of the present invention have conducted extensive studies in order to achieve the above object, and as a result, the general formula [Wherein R ¹ and R ² are the same or different and each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or
R ¹ and R ² combine to represent an alkylene group having 3 to 6 carbon atoms. X and Y are the same or different and each represents a hydrogen atom or a chlorine atom, and Z represents a chlorine atom, a bromine atom or a trifluoromethyl group. ] 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 osmotic transition disease control efficacy, leading to the present invention.

Plant diseases that can be controlled by the compound of the present invention include:
Rice blast (Pyricularia oryzae), sesame leaf blight (Cochliobolus miyabeanus), apple scab (Ventu)
ria inaequalis), Pear scab (Venturia nashicol)
a), oyster carbon disease (Gloeosporium kaki), cucumber anthracnose (Colletotrichum lagenarium), green bean anthracnose (Colletotrichum lindemuthianum), peanut black spot (Mycosphaerella personatum), and brown spot (Cerco).
spora arachidicola), tobacco anthracnose (Colletotrich
um tabacum), brown leaf spot of sugar beet (Cercospora beticol)
a) and the like.

 Next, the method for producing 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 are the same or different and each represents a hydrogen atom or a chlorine atom, and Z represents a chlorine atom, a bromine atom or a trifluoromethyl group. ] A cyanoacetic acid amide compound represented by Wherein, R ¹ and R ² are the same or different, or R ¹ represents 1-4 alkyl hydrogen atom or a carbon atoms
And R ² combine to represent an alkylene group having 8 to 6 carbon atoms. ] It can be obtained by subjecting a carbonyl compound represented by the following to a dehydration condensation reaction in the presence of a reaction aid, if necessary.

In the above reaction, examples of the reaction aid include acetic acid, ammonium acetate, p-aminophenol, piperidine, β-alanine and the like, and mixtures thereof, depending on the carbonyl compound used in the reaction.

In the above reaction, the reaction temperature is typically from 0 to 200.
C., the reaction time is 0.1 to 24 hours, and the amount of the reagent to be used in the reaction is 1 mol of the cyanoacetic acid amide compound represented by the general formula [II], and Is 1 to 3 mol, and the reaction aid is 1 mmol to 5 mol.

In the above reaction, a reaction solvent is not always necessary, but it is generally carried out in the presence of a solvent.

As the solvent that can be used, benzene, toluene, aromatic hydrocarbons such as xylene, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane,
Ethers such as diethylene glycol methyl ether,
Examples thereof include halogen atom-containing solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, solvents such as acetic acid 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 cyanoacetic acid amide compound represented by the general formula [II], which is one of the starting compounds for producing the compound of the present invention, has the general formula [In the formula, X, Y and Z have the same meanings as described above. ] It can be obtained by reacting the α-methylbenzylamine derivative represented by the above with cyanoacetic acid or its reactive derivative in the presence of a reaction aid, if necessary.

In addition, a commercially available carbonyl compound represented by the general formula [III], which is the other starting compound for producing the compound of the present invention, can be used.

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 component, but it is usually a solid carrier, a liquid carrier, a surfactant or other auxiliary agent for formulation. Mixed with emulsions, wettable powders, suspensions,
It is used by formulating it into granules, powders, etc.

These formulations 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 powder, walnut shell powder, urea, ammonium sulfate, fine powder of synthetic hydrous silicon oxide or the like. Granules can be mentioned, and the liquid carrier is
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. To 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
(Carboxymethyl cellulose), PAP (isopropyl acid phosphate) and the like.

These preparations are used as they are, or diluted with water and sprayed on foliage, powdered or dispersed in soil and 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. Furthermore, it can be used by mixing with insecticides, acaricides, nematicides, herbicides, plant growth regulators, fertilizers, soil conditioners and the like.

When the compound of the present invention is used as an active ingredient of a plant disease control agent, the amount to be treated varies depending on weather conditions, formulation form, treatment time, method, location, target disease, target crop, etc., but is usually 0.05 to 1 are. 200 g, preferably 0.1
When the emulsion, wettable powder, suspension or the like is diluted with water and applied, the application concentration is 0.00005 to 0.5%, preferably 0.0001 to 0.2%, and the granules, powders, etc. Apply as is without diluting.

<Effects of the Invention> Since the compound of the present invention has an excellent effect on plant diseases caused by various plant disease fungi, it can be used for various uses 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, Production Examples, and Test Examples. The present invention is not limited to these examples.

 First, a production example is shown.

Production Example 1 (Compound (2)) N- [1- (4-chlorophenyl) ethyl] -2-cyanoacetamide 1.11 g (5 mmol), bivalaldehyde.
52 g (6 mmol) was dissolved in 5 ml of dioxane, 2 drops of piperidine was added with stirring at room temperature, and the mixture was stirred at room temperature for 12 hours. After the reaction, dioxane was distilled off, and silica gel column chromatography (eluting solvent; hexane: ethyl acetate =)
Purification by 5: 1) gave 0.76 g of N- [1- (4-chlorophenyl) ethyl] -2-cyano-4,4-dimethyl-2-pentenoic acid.

mp 95-98 ° ¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 1.24 (s, 9H), 1.50 (d, J = 7Hz, 3H), 4.85-5.40 (m, 1H), 6.6-. 95 (br d, 1H), 7.15 to 7.4 (m, 4H), 7.63 (s, 1H) Production Example 2 (Compound (15)) N- [1- (4-trifluoromethylphenyl) ethyl] -2 -Cyanoacetamide 1.28 g (5 mmol), 3-pentanone 2.5 ml, glacial acetic acid 0.1 g, benzene 10 ml and p-
Aminophenol (14 mg) was mixed, and the mixture was heated under reflux for 3 hours while removing water produced using a water separator. After the reaction solution was concentrated, it was purified by silica gel column chromatography (elution solvent; hexane: ethyl acetate = 5: 1), and N
-[1- (4-trifluoromethylphenyl) ethyl]
2-Cyano-3-ethyl-2-pentenoic acid (0.85 g of compound (15) was obtained.

mp 72 to 74 ° C ¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 0.8 to 1.3 (m, 6H), 1.49 (d, J = 7Hz, 3H), 2.15 to 2.95 (m, 4H), 4.75 -5.35 (m, 1H), 6.25-6.7 (brd, 1H), 7.1-7.65 (m, 4H) Table 1 shows some of the compounds of the present invention produced by such a production method.

Next, production examples of the cyanoacetic acid amide compound represented by the general formula [II] will be shown.

Reference Production Example 3.65 g (30 mmol) of ethyl dicyanoacetate and 1
-(4-Bromophenyl) ethylamine 6.0 g (30 mmol)
While the resulting mixture was mixed with the mixture to remove the produced ethanol, the mixture was heated and stirred at a bath temperature of 180 ° C. for 2 hours and then cooled. The resulting crystals were recrystallized from ethanol to give 5.11 g of N- [1- (4-bromophenyl) ethyl] -2-cyanoacetamide (yield 64
%) Was obtained.

mp 136-139 ° C ¹ H-NMR (CDCl ₃ / DMSO-d ₆ , δ (ppm)) 1.31 (d, J = 7 Hz, 3H) 3.31 (s, 3H), 3.59 (s, 2H), 4.5-5.1 (M, 1H), 6.95 to 7.6 (m, 4H), 8.3 to 8.8 (br d, 1H) General formula [I
Some of the cyanoacetic acid amide compounds represented by [I] are shown below.

Compound shown by Next, a production example will be described. The compounds of the present invention are shown by the compound numbers in Table 1. Parts represent parts by weight.

Production Example 1 50 parts each of the compounds (1) to (15) of the present invention, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide were well pulverized and mixed, and a wettable powder for each of the compounds of the present invention was prepared. To get

Formulation Example 2 25 parts of each of the present compounds (1) to (15), 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and water
69 parts were mixed and wet-milled until the particle size of the active ingredient was 5 microns or less to obtain a suspension agent for each of the compounds of the present invention.

Formulation Example 3 2 parts of each of the compounds (1) to (15) 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 of each of the compounds (1) to (15) 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 prepare an emulsion of each of the compounds of the present invention. obtain.

Formulation Example 5 2 parts of each of the compounds (1) to (15) 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, it is shown in Test Examples that the compound of the present invention is useful as a plant disease controlling agent. The compounds of the present invention are shown by the compound numbers in Table 1, and the compounds used for comparison and control are shown by the compound symbols in Table 2.

Moreover, the control efficacy is "5", about 10% if the disease state of the test plant at the time of the survey, that is, the flora of leaves, stems, etc. If it is recognized, "4", about 30% is recognized as "3", about 50% is recognized as "2", about 70% is recognized as "1". If no difference from the state was observed, it was evaluated as "0" and evaluated in 6 levels, and shown as 5, 4, 3, 2, 1, 0, respectively.

Test Example 1 Rice blast control test (preventive effect) Sand loamy soil was filled in a plastic pot, and rice (Nihonbare)
Were sown and grown in a greenhouse for 20 days. A rice seedling was diluted with water as a wettable powder according to Formulation Example 1 to a predetermined concentration and sprayed on foliage so that it was sufficiently adhered to the leaf surface. After spraying, the plants were sprayed and inoculated with an air-dried spore suspension of blast fungus. After inoculation, the plant was grown at 28 ° C. in the dark and in high humidity for 4 days, and the control efficacy was investigated. The results are shown in Table 3.

Test Example 2 Rice blast control test (permeation transfer effect) Sand loamy soil was filled in a plastic pot, and rice (Nihonbare)
Was sown and grown 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, 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 pest control efficacy was investigated after leaving for 4 days at 28 ° C. in darkness and high humidity. The results are shown in Table 4.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yoshitaka Takano 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd. (56) Reference JP-A-60-32702 (JP, A) US Patent 4104273 (US, A)

Claims (2)

(57) [Claims] 1. A general formula [In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or R ¹ and R ² are bonded to each other to have 3 to 6 carbon atoms. Represents an alkylene group. X and Y are the same or different and each represents a hydrogen atom or a chlorine atom, and Z represents a chlorine atom, a bromine atom or a trifluoromethyl group. ] The cyanoacetic acid amide derivative shown by these. 2. General formula [In the formula, X and Y are the same or different and each represents a hydrogen atom or a chlorine atom, and Z represents a chlorine atom, a bromine atom or a trifluoromethyl group. ] The cyanoacetic acid amide compound shown by these.