JPH0570428A - Substituted phenoxycarboxylic acid amide derivative and agricultural fungicide containing the same - Google Patents

Abstract

PURPOSE:To provide a new substituted phenoxycarboxylic acid amide derivative useful as an agricultural fungicide having excellent controlling effect against rice blast, downy mildew of cucumber, etc. CONSTITUTION:The compound of formula I [X is halogen or (substituted) lower alkyl; n is integer of 0-3; R<1> and R<2> are H or lower alkyl; A is (substituted) heteroaryl], e.g. N-(cyano-3-thienylmethyl)-2-(2,4-dichloro-3-methylphenoxy) propionamide. The compound of formula I excluding the compound of formula VIII (R is H or lower alkyl) can easily be produced by reacting a compound of formula VI with a compound of formula V preferably in the presence of an acid acceptor. The compound of formula V is obtained from a compound of formula II and a compound of formula VII (Y is halogen; R<3> is lower alkyl) through the compounds of formula III and formula IV. The objective compound exhibits excellent controlling effect against rice blast generated in paddy rice field by foliar treatment and submerged application and is absolutely free from phytotoxicity to rice plant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel substituted phenoxycarboxylic acid amide derivative which has not been described in the literature, and an agricultural fungicide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art Japanese Unexamined Patent Publication No. 62-5944 discloses a new N-
The following general formula (A) as an acylamino acid derivative:

[0003]

[Chemical 3]

[In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, and R ² represents 1 to 10 carbon atoms substituted by a linear or branched alkyl group or a carboxyl group.
5 represents a straight-chain or branched alkyl group, the groups R ¹ and R ² together with the carbon atom to which they are attached form a ring, or the groups R ¹ and R ² together 1 to 1 carbon atoms
6 represents an ethylene group which may be substituted with a straight chain or branched chain alkyl group of 6, wherein R ³ is a hydrogen atom or a carbon number of 1
~ 4 alkyl groups, R ⁴ represents a halogen atom]
Although an N-acyl amino acid derivative having ## STR1 ## and a salt thereof which is acceptable in pesticides are disclosed, the patent publication does not describe a compound having a polysubstituted phenyl group and does not mention any bactericidal activity. ..

On the other hand, in Japanese Patent Laid-Open No. 63-132867, a novel aryloxycarboxylic acid derivative having antibacterial activity is represented by the following general formula (B):

[0006]

[Chemical 4]

[Wherein aryl is unsubstituted or C
_1-5 alkyl, C _1-5 alkoxy, C _1-5 alkyl-SO _n
(N = 0, 1 or 2), halogen, NO ₂ , CF ₃ ,
_{CN, CH 3 OCH 2, (} CH 3) 2 NCH 2, COO -alkyl, mono- by CONH ₂ or phenyl - or trisubstituted phenyl group, or 1- or 2-naphthyl group, optionally chlorinated substituted 2 -, 3- or 4
- or pyridyl group, a pyridyl group or quinolyl group, Q is ^{- (R 5) C (R} 6) - represents a _{(CH 2) m (m =} 0,1 or 2), R ¹ is H, _Represents C _1-6 alkyl or allyl, R ² and R ³ are H, C _1-6 alkyl (which may contain O or S atoms in the chain), C _3-7 cycloalkyl, CH ₂ —COO Represents-(C _1-5 alkyl), phenyl, or R ² and R ³ are both-(CH ₂ ) ₄ -,-
Represents (CH ₂ ) ₅ — or — (CH ₃ ) CH— (CH ₂ ) ₄ —,
R ⁴ represents CN and CONH ₂ , R ⁵ represents H, CH ₃ and C ₂ H ₅
, R ⁶ represents H, CH ₃ , and X represents O or S], but no reference is made to the compound in which R ⁴ is a heteroaryl group. ..

[0008]

Many compounds have been used as agricultural fungicides so far, but by continuously using the same drug for a number of years, the appearance of bacteria that have acquired resistance to the drug has a bactericidal effect. The decline is a problem. Therefore, regarding agricultural and horticultural fungicides, it is expected to create compounds having a new structure having a strong bactericidal effect. The present invention aims to provide a novel agricultural and horticultural fungicide that meets these needs.

[0009]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the inventors of the present invention have conducted diligent research, and as a result, have found that a certain substituted phenoxycarboxylic acid amide derivative having a polysubstituted phenyl group and a heteroaryl group. However, they found that they have an excellent bactericidal action, and completed the present invention. The novel substituted phenoxycarboxylic acid amide derivative of the present invention is represented by the following general formula (I).

[0010]

[Chemical 5]

In the above general formula (I), examples of the halogen atom for X include fluorine, chlorine and bromine, and fluorine or chlorine is preferable. The lower alkyl group which may be substituted has 1 to 1 carbon atoms.
3 are preferred, for example, methyl group, ethyl group, n-
Examples thereof include a propyl group, an i-propyl group, trifluoromethyl and the like. The lower alkyl group for R ¹ and R ² is preferably one having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group and an i-propyl group.
The optionally substituted heteroaryl group for A is preferably a 5- or 6-membered ring which may be substituted with a lower alkyl group, for example, 2-furyl, 3-furyl,
2-thienyl, 3-thienyl, 2-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2- (N-methyl) pyrrolyl and the like can be exemplified. As specific examples of the compound of the present invention represented by the general formula (I), the compounds shown in Table 1 below can be exemplified. In the table, Me represents a methyl group.

[0012]

[Table 1]

[0013]

[Table 2]

[0014]

[Table 3]

The compound represented by the general formula (I) of the present invention can be synthesized, for example, by the following method.

[0016]

[Chemical 6]

In the above synthesis method A, X, n, R ¹ and R ² have the same meanings as described in the above general formula (I), and R ³
Represents a lower alkyl group, Y represents a halogen atom, R
Represents a hydrogen atom or a lower alkyl group. In the above reaction formula, the phenoxycarboxylic acid ester derivative (III) can be easily produced by reacting the phenol (II) with the halogenated carboxylic acid alkyl ester (VII) in the presence of a deoxidizing agent. Examples of the deoxidizing agent used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium bicarbonate.

This reaction is preferably carried out in the presence of a solvent,
Examples of the solvent used include alcohols such as methanol, ethanol and i-propanol; ethers such as tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone; acetonitrile, dimethyl sulfoxide, dimethylformamide and the like, and a mixture thereof. Solvents include, especially alcohols, ethers,
Dimethylformamide is preferred.

The reaction temperature is not particularly limited and may be appropriately selected. For example, the reaction temperature may be room temperature to the reflux temperature of the solvent. It is particularly preferable to carry out the reaction at or near the reflux temperature of the solvent. The reaction time varies depending on the reaction temperature, the type of reagent used, etc., but can be exemplified by a reaction time of about 1 to about 20 hours. If desired, the ester (III) thus obtained can be isolated according to a conventional method, but it does not need to be purified and isolated, and is a crude product for use in the next hydrolysis step. It is enough.

The hydrolysis of the compound (III) into the phenoxycarboxylic acid derivative (IV) easily proceeds in the presence of an acid or an alkali. Examples of the acid used include, for example, mineral acids such as hydrochloric acid and sulfuric acid, and examples of the alkali include, for example,
Examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. The hydrolysis reaction is preferably performed in the presence of a solvent, and examples of the solvent used include alcohols such as methanol, ethanol and i-propanol;
Examples thereof include lower fatty acids such as acetic acid and propionic acid.

There are no particular restrictions on the temperature of the hydrolysis reaction, but examples include room temperature to the reflux temperature of the solvent. It is particularly preferable to carry out at or near the reflux temperature of the solvent. The reaction time varies depending on the reaction temperature, the type of acid and alkali used, and the like, but for example, a reaction time of about 1 to about 10 hours can be exemplified.

In this way, the phenoxycarboxylic acid derivative (IV) is obtained. The substituted phenol alkali metal salt (II) and halogenated carboxylic acid are hydrated with an alkali metal such as sodium hydroxide or potassium hydroxide. It is also possible to directly obtain the compound (IV) by reacting in the presence of a substance.

By treating the phenoxycarboxylic acid derivative (IV) thus obtained with a halogenating agent such as thionyl chloride, phosphorus pentachloride, phosphorus tribromide, etc., fequinoxycarboxylic acid can be easily obtained. Acid halide (V) can be produced. The substituted fequinoxycarboxylic acid amide of the present invention can be easily obtained by reacting the acid halide derivative (V) obtainable as described above with the amino compound (VI), preferably in the presence of a deoxidizing agent. The derivative (I) can be produced. Examples of the deoxidizing agent used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium bicarbonate; organic bases such as pyridine and triethylamine.

This reaction is preferably carried out in a solvent, and the solvent used is not particularly limited as long as it does not participate in the reaction. For example, ethers such as diethyl ether, tetrahydrofuran, dioxane; benzene, toluene,
Aromatic hydrocarbons such as xylene; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; acetonitrile, dimethylsulfoxide, dimethylformamide, etc. The mixed solvent of can be illustrated.

In this case, the reaction temperature is not particularly limited, but examples thereof include room temperature to the reflux temperature of the solvent.
Although the reaction time varies depending on the reaction reagent, reaction temperature, etc., the reaction time may be, for example, about 1 to several hours.
After completion of the reaction, the target compound (I) can be isolated from the reaction mixture according to a conventional method. The phenoxycarboxylic acid amide derivative (I) is a phenoxycarboxylic acid derivative (IV).
And amino compound (VI) with phosphorus pentoxide, phosphorus oxychloride,
It can also be obtained by reacting in the presence of a dehydrating agent such as dicyclohexylcarbodiimide (DCC). The amino compound (VI) used in the above reaction can be synthesized by a general method (for example, J. Chem. Soc. 1947, 1371).

[0026]

[Chemical 7]

In the above synthesis method B, X, n, R,
R ¹ , Y and A have the same meanings as described in the synthetic method A.
In the above reaction formula, the compound (VIII) is produced by reacting the acid halide derivative (V) with the amine salt (X), preferably in the presence of a deoxidizing agent. Examples of the deoxidizing agent used in this reaction include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Inorganic bases such as sodium bicarbonate; organic bases such as pyridine and triethylamine.

This reaction can be carried out in a solvent, and the solvent used is not particularly limited as long as it does not participate in the reaction, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane; benzene, toluene,
Aromatic hydrocarbons such as xylene; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; acetonitrile, dimethylsulfoxide, dimethylformamide, etc. The mixed solvent of can be illustrated. There are no particular restrictions on the reaction temperature, but examples include room temperature to the reflux temperature of the solvent. Although the reaction time varies depending on the reaction reagent, reaction temperature, etc., the reaction time may be, for example, about 1 to several hours.

The compound (VIII) thus obtained is treated with bromine in a suitable solvent to obtain a brominated intermediate (IX). Solvents that can be used in this reaction include dichloromethane, chloroform, carbon tetrachloride, 1,
Halogenated hydrocarbons such as 4-dichloroethane; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, propyl acetate and ethyl propionate; carbon disulfide and the like. Particularly, good results are obtained by using an ester solvent such as ethyl acetate. Reaction temperature is 0-12
Temperatures in the range of 0 ° C, preferably room temperature. It is more preferable to carry out this reaction in an atmosphere of an inert gas.
The bromine intermediate (IX) is unstable and is used immediately after its preparation is complete. In addition, bromine is another halogenating agent,
For example, chlorine, phosphorus oxychloride, sulfuryl chloride, phosphorus tribromide or the like can be used instead.

This bromine intermediate (IX) is reacted with a pyrrole derivative represented by the general formula (XI) (wherein R represents a hydrogen atom or a lower alkyl group). This reaction can be carried out in the presence of an acid acceptor. Examples of the acid acceptor include organic bases such as triethylamine, dimethylaniline and pyridine; inorganic bases such as ammonia, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide and ammonium carbonate; organometallic compounds such as butyllithium. be able to. This reaction is preferably carried out in a solvent or diluent. Pyridine can be used as both a solvent and an acid acceptor. This reaction does not have good intermediate stability, so too high temperature is not desirable,
Since it is an exothermic reaction, it is desirable to perform it under cooling.
At a low temperature, the reaction intermediate is likely to precipitate and the reaction rate is slow, which is not practical and therefore -30 to 50 ° C, preferably-
It is preferably carried out at 20 to 20 ° C. The desired product (I) produced by this reaction can be easily isolated and purified by a conventional method.

The fungicide of the present invention contains the novel substituted phenoxycarboxylic acid amide derivative represented by the general formula (I) as an active ingredient. When the compound of the present invention is used as a bactericidal agent, it is mixed with a carrier or diluent, an additive and an auxiliary agent by a known method, and a formulation form usually used as an agricultural chemical, for example, powder, granules, hydration. Agent, emulsion,
Used as a wettable powder, a flowable agent, etc. Further, it can be used by mixing or in combination with other pesticides such as fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers and soil conditioners. In particular, when used in combination with other fungicides, not only the pesticides used can be reduced and labor can be saved, but also a broader bactericidal spectrum due to the synergistic action of both drugs and a higher synergistic effect can be expected.

The carriers or diluents used in the preparation include solid or liquid carriers generally used. Examples of the solid carrier include clays represented by kaolinite group, montmorillonite group, illite group, polygolskite group and the like, specifically, pyroflight, attapulgite, sepiolite, kaolinite, bentonite, vermiculite, mica and talc, etc .; Plaster, calcium carbonate, dolomite, diatomaceous earth,
Other inorganic substances such as magnesium lime, phosphorus lime, zeolite, silicic acid anhydride, synthetic calcium silicate; soy flour, tobacco flour, walnut flour, wheat flour, wood flour, starch, crystalline cellulose and other plant organic substances; coumarone resin, Examples thereof include synthetic or natural polymer compounds such as petroleum resins, alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, estil gum, cobal gum, and d'ummal gum; waxes such as carnauba wax and beeswax, and urea.

Suitable liquid carriers include, for example, paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, and white oil; aromatic hydrocarbons such as xylene, ethylbenzene, cumene, methylnaphthalene; trichloroethylene, monochromatic. Chlorinated hydrocarbons such as benzene and orthochlorotoluene; ethers such as dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone and isophorone; ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate , Esters such as dibutyl maleate and diethyl succinate; methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, Alcohols such as emissions benzyl alcohol, ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, ether alcohols such as diethylene glycol butyl ether; dimethylformamide, polar solvents or water such as dimethyl sulfoxide.

Others Emulsification, dispersion, wetting, spreading, spreading, binding, regulation of disintegration, stabilization of active ingredient of the compound of the present invention,
Surfactants and other auxiliary agents can be used for the purpose of improving fluidity, preventing rust, and preventing freezing. Examples of the surfactant to be used include nonionic, anionic, cationic and zwitterionic substances, but usually nonionic and / or anionic compounds are used. Things are used.

Suitable nonionic surfactants include, for example, compounds obtained by polymerizing addition of ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol; isooctylphenol,
Compounds obtained by polymerizing addition of ethylene oxide to alkylphenols such as nonylphenol; Compounds obtained by polymerizing addition of ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol; Polymerization addition of ethylene oxide to higher fatty acids such as palmitic acid, stearic acid and oleic acid Compounds: higher fatty acid esters of polyhydric alcohols such as sorevitan, compounds obtained by polymerizing addition of ethylene oxide, compounds obtained by block-polymerizing addition of ethylene oxide and propylene oxide, and the like.

Suitable anionic surfactants include, for example, alkyl sulphate salts such as sodium lauryl sulphate, oleyl alcohol sulphate amine salts, etc., alkyl succinate dioctyl esters, sodium 2-ethylhexene sulphonate and the like. Examples thereof include aryl sulfonates such as sulfonates, sodium isopropylnaphthalene sulfonate, sodium methylenebisnaphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylbenzene sulfonate.

Further, the fungicide of the present invention contains casein, gelatin, and / or gelatin for the purpose of improving the properties of the preparation and enhancing the bactericidal effect.
High molecular compounds such as albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol and the like and other auxiliary agents can be used together. The above-mentioned carrier and various auxiliary agents are appropriately used alone or in combination depending on the purpose, taking into consideration the dosage form of the preparation, the application scene and the like.

The content of the active ingredient of the compound of the present invention in the various dosage forms thus obtained varies depending on the dosage form, but is usually 0.1 to 99% by weight, preferably 1 to 99% by weight. 60% by weight is most suitable. In the case of a wettable powder, for example, the active ingredient compound is usually 10 to 90%.
The rest is a solid carrier and a dispersion wetting agent, and a protective colloid agent, a defoaming agent and the like are added if necessary.

In the case of granules, for example, the active ingredient compound is usually contained in an amount of 1 to 35% by weight, and the balance is solid particles and surfactants. The active ingredient compound is uniformly mixed with the solid particles, or is uniformly fixed or adsorbed on the surface of the solid carrier, and the particle diameter is about 0.2 to 1.5 mm. In the case of an emulsion, the active ingredient compound is usually added in an amount of 5 to 3
The content is 0% by weight, which contains about 5 to 20% by weight of an emulsifier, and the balance is a liquid carrier, and a spreading agent, a rust preventive agent and the like are added if necessary. In the case of a flowable agent, for example, the active ingredient compound is usually contained in an amount of 5 to 50% by weight, and this contains a dispersion wetting agent in an amount of 3 to 10% by weight, and the balance is water, and if necessary, a protective colloid agent, Preservatives, defoamers and the like are added.

The substituted phenoxycarboxylic acid amide derivative of the present invention can be used as an agent in the form of the compound of the general formula (I) as it is, or in any of the above-mentioned preparation forms. The use concentration of the compound of the present invention varies depending on the target crop, method of use, formulation form, application amount, etc. and cannot be specified unconditionally, but as the amount of the compound represented by the general formula (I) (the amount of active ingredient), For processing 0.1-10,000p
pm, preferably 1 to 500 ppm, 10 to 100,000 g / ha in the case of soil treatment, preferably 200 to 20,00
It is 0 g / ha.

[0041]

EXAMPLES The present invention will be specifically described below with reference to examples. Production Example 1 N- (cyano-3-thienylmethyl) -2- (2,4-
Dichloro-3-methylphenoxy) propionamide
(Compound No. 8) 100 g of 2,4-dimethyl-3-methylphenol (0.
56 mol), ethyl 2-bromopropionate 102 g
(0.56 mol), potassium carbonate 86 g (0.62 mol), DM
A mixture of 400 ml of F was stirred at 50 ° C. for 1 hour. Pour the reaction solution into water, extract with dimethyl ether, dry,
The solvent was distilled off, and ethyl 2- (2,4-dichloro-3-
149 g of methylphenoxy) propionate was obtained (yield 95%). To a solution of 149 g (0.54 mol) of this ester in 300 ml of methanol was added 300 ml (0.68 mol) of an aqueous sodium hydroxide solution under ice cooling, and the mixture was stirred at room temperature for 1 hour. The reaction solution was poured into water, acidified with dilute hydrochloric acid, and the precipitated crystals were collected by filtration, washed with water and dried to give (2,4-dichloro-
128 g of 3-methylphenoxy) propionic acid was obtained (yield 96%).

10 g (0.14 mol) of thionyl chloride was added to 2 g (0.008 mol) of 2- (2,4-dichloro-3-methylphenoxy) propionic acid, and the mixture was heated under reflux for 1 hour. When excess thionyl chloride was distilled off from the reaction mixture, 2.1 g of crude 2- (2,4-dichloro-3-methylphenoxy) propionic acid chloride was obtained. A solution of 2.1 g of this crude acid chloride in 10 ml of diethyl ether was added to amino (3
-Thienyl) acetonitrile hydrochloride 1.39 g (0.008
Mol) and 16 g of a 5% aqueous sodium hydroxide solution (0.02
Mol) was added dropwise to the mixture under water cooling. Then, the mixture was stirred at room temperature for 1 hour and extracted with ether. The extract was washed with saturated brine, dried and the solvent was evaporated. The residue was purified by silica gel column chromatography to give the desired compound 2.17.
g was obtained (74% yield).

Production Example 2 N- (cyano-2-pyrrolylmethyl) -2- (2,4-
Dichloro-3-methylphenoxy) propionamide
(Compound No. 10) 1.12 g (12 mmol) of aminoacetonitrile hydrochloride was dissolved in 24 ml (30 mmol) of 5% aqueous sodium hydroxide solution, and 2- (2,4-dichloro-3) was added thereto.
-Methylphenoxy) propionic acid chloride 3.2 g
A mixture of (12 mmol) and 24 ml of diethyl ether was added dropwise under ice cooling, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were collected by filtration, washed with water and dried to give N-cyanomethyl-2.
3.03 g of-(2,4-dichloro-3-methylphenoxy) propionic acid was obtained (yield 88%).

2 g of this N-cyanomethyl-2- (2,4-dichloro-3-methylphenoxy) propionic acid (0.
1.23 g of bromine in 50 ml of ethyl acetate (007 mol)
(0.008 mol) was added all at once at room temperature, and the mixture was stirred at the same temperature until the color of bromine disappeared. Pyrrole 0.83 g (0.012 mol), triethylamine 4.07 g (0.04 mol),
To a mixed solution of 10 ml of dioxane, the previously prepared ethyl acetate solution of bromide was added dropwise at 10 ° C or lower. After the completion of dropping, the mixture was stirred for 130 minutes under ice cooling. 50 ml of water was added to this reaction mixture to separate the organic layer, which was washed with water and dried. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 1.2 g of the target compound (yield 4
9%). The compounds of the present invention shown in Table 2 were obtained in the same manner as in the above Production Example.

[0045]

[Table 4]

Next, several embodiments of formulation examples using the compound of the present invention will be shown. The "parts" in the following formulations are on a weight basis. Formulation Example 1 (Emulsion) Compound No. 2 10 parts Xylene 45 parts Calcium dodecylbenzene sulfonate 7 parts Polyoxyethylene styryl phenyl ether 13 parts Dimethylformamide 25 parts The above components were uniformly mixed and dissolved to obtain 100 parts of an emulsion.

Formulation Example 2 (Wettable powder) Compound No .: 2 20 parts Diatomaceous earth 70 parts Lignin sulfonate calcium 5 parts Naphthalene sulfonate formalin condensate 5 parts The above components were mixed and pulverized to obtain 100 parts wettable powder.

Formulation Example 3 (granules) Compound No .: 25 parts bentonite 50 parts talc 42 parts sodium lignin sulfonate 2 parts polyoxyethylene alkylaryl ether 1 part After thoroughly mixing the above, add an appropriate amount of water. The mixture was kneaded and granulated using an extrusion granulator to obtain 100 parts of granules.

Formulation Example 4 (flowable agent) Compound No .: 2 30 parts Sulfosuccinic acid di-2-ethylhexyl ester sodium salt 2 parts Polyoxyethylene nonylphenyl ether 3 parts Defoamer 1 part Propylene glycol 5 parts Water 59 parts The mixture was uniformly pulverized and mixed with a wet ball mill to obtain 100 parts of a flowable agent. The bactericides using the compound of the present invention can be prepared according to the above-mentioned preparation examples.

Next, according to a test example, the bactericide of the present invention was used.
The effect of controlling various plant diseases will be specifically described. Test Example (Control test against rice blast) Seven rice varieties (variety: Koshihikari) were sown in a plastic cup having a diameter of 7 cm, and grown in a greenhouse for 3 weeks. The reagent agent emulsified according to Formulation Example 1 was diluted with water so as to have a predetermined concentration, and sprayed so as to sufficiently adhere to the leaf surface of rice. One day after spraying, inoculate with a spore suspension of rice blast fungus, and then incubate in a humid chamber at 25 ° C.
After keeping it for a day, he was ill in the greenhouse. Seven days after the inoculation, the average number of lesions per leaf was investigated, and the control value was calculated by the following formula.

[0051]

[Equation 1]

The results are shown in Table 3.

[Table 5]

[0053]

The substituted phenoxycarboxylic acid amide derivative represented by the above general formula (I) of the present invention is a compound not described in the literature. The substituted phenoxycarboxylic acid amide derivative represented by the above general formula (I) of the present invention is characterized by having a polysubstituted phenyl group and an alphaaminonitrile moiety substituted with a heteroaryl, and its structural characteristics Therefore, it is considered that the excellent properties of the bactericide containing the substituted phenoxycarboxylic acid amide derivative are exhibited. The compound and fungicide of the present invention have an excellent controlling effect against blast disease that occurs in paddy rice cultivation in foliar treatment and water surface application, and show no phytotoxicity to rice. Further, the compound of the present invention and the fungicide have an excellent controlling effect against cucumber downy mildew and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C07D 213/57 6701-4C 307/54 7729-4C 333/24 7729-4C (72) Inventor Takayama Yoshihiro, 3-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Mitsubishi Petrochemical Co., Ltd. Tsukuba Research Institute

Claims (2)

[Claims] 1. The following general formula (I): [Wherein, X represents a halogen atom or an optionally substituted lower alkyl group, n represents an integer of 0 to 3,
R ¹ and R ^{2 each} represent a hydrogen atom, a lower alkyl group or, and A represents an optionally substituted heteroaryl group], a substituted phenoxycarboxylic acid amide derivative. 2. The following general formula (I): [Wherein, X represents a halogen atom or an optionally substituted lower alkyl group, n represents an integer of 0 to 3,
R ¹ and R ^{2 each} represent a hydrogen atom, a lower alkyl group or, and A represents an optionally substituted heteroaryl group], which is a fungicide for agriculture containing a substituted phenoxycarboxylic acid amide derivative as an active ingredient. ..