JPH05286937A - Substituted pyridyloxycarboxylic acid amide derivative and agricultural bactericide containing the same - Google Patents

Abstract

PURPOSE:To provide the subject new compound having high bactericidal activity, esp. having excellent controlling effect on blast developed in paddy rice crops through its stems/leaves treatment or water surface application, while giving no chemical injuries on rice, thus useful as an agricultural bactericide. CONSTITUTION:The objective compound of formula I (pyridyl is 2-, 3- or 4- pyridyl which may be substituted with at least one CF3 and also with up to 3 halogens or lower alkyl groups; R<1> and R<2> are each lower alkyl or cycloalkyl or combined into (CH2)n (n is 4-6); R<3> and R<4> are each H or lower alkyl; Q is CN, CONR<5>R<6> or CO2R<7> (R<5>-R<7> are each H, lower alkyl or lower alkenyl)], e.g. 2-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-N-(1-cyano-12-dimethylpropyl) propionamide. The compound of the formula I can be obtained by the reaction of a halogenated pyridine with a hydroxycarboxylic acid amide derivative of formula II pref. in the presence of a deoxidizer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel substituted pyridyloxycarboxylic 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. 63-132867 discloses a novel aryloxypropionic acid derivative having antibacterial activity, represented by the following general formula (A):

[0003]

[Chemical 3]

[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 containing pyridyl in which aryl is substituted with a CF ₃ group.

[0005]

Many compounds have been used as agricultural fungicides so far, but by continuously using the same drug for many years, it is possible to obtain fungicidal effects due to the emergence of bacteria that have acquired resistance to the drug. 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 is intended to provide a novel agricultural and horticultural fungicide that satisfies these needs.

[0006]

In order to solve the above problems, the inventors of the present invention have conducted diligent research, and as a result, certain substituted pyridyloxycarboxylic acid amide derivatives substituted with a CF ₃ group were excellent. They found that they have a bactericidal action, and completed the present invention. The novel substituted pyridyloxycarboxylic acid amide derivative of the present invention is represented by the following general formula (I).

[0007]

[Chemical 4]

In the above general formula (I), at least one of pyridyl is substituted with a CF ₃ group and may be further substituted with up to 3 halogen atoms or a lower alkyl group.
-, 3- or 4-pyridyl group is shown, and examples of the pyridyl group include 3-chloro-5-trifluoromethyl-
2-pyridyl group, 5-chloro-3-trifluoromethyl-2-pyridyl group, 6-chloro-4-trifluoromethyl-2-pyridyl group, 6-chloro-5-trifluoromethyl-2-pyridyl group, 5-trifluoromethyl-2-
Pyridyl group, 3-trifluoromethyl-2-pyridyl group, 6-methyl-3-trifluoromethyl-2-pyridyl group, 6-trifluoromethyl-3-pyridyl group, 2-
Examples thereof include trifluoromethyl-4-pyridyl group.

In the above general formula (I), R ¹ and R ² represent a lower alkyl group or a cycloalkyl group, or R ¹ and R ² are both-(CH ₂ ) _n- (where n is 4 And the lower alkyl group is, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-
A C ₁ -C ₆ alkyl group such as a butyl group, an n-pentyl group, an i-pentyl group and an n-hexyl group can be exemplified, and the cycloalkyl group can be a C ₃ A C ₆ cycloalkyl group can be exemplified.

In the above general formula (I), R ³ and R ⁴ represent a hydrogen atom or a lower alkyl group, and examples of the lower alkyl group include a methyl group, an ethyl group, an n-propyl group,
Examples are C ₁ -C ₆ alkyl groups such as i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, i-pentyl group and n-hexyl group. it can.

In the above general formula (I), Q is a CN group, CON
R ⁵ R ⁶ group or CO ₂ R ⁷ group (provided that R ⁵ , R ⁶ and R
⁷ each represents a hydrogen atom, a lower alkyl group or a lower alkenyl group), and the lower alkyl includes
For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group,
t-butyl group, n-pentyl group, i-pentyl group, n-
It can be exemplified such as C ₁ -C ₆ alkyl group hexyl. Examples of the lower alkenyl group include a propenyl group, a butenyl group,
Examples thereof include C ₃ -C ₆ alkenyl groups such as pentenyl group, hexenyl group and isomers thereof, and R ⁷ is
A methyl group and an ethyl group are preferred.

As specific examples of the compound of the present invention represented by the above general formula (I), the compounds shown in Table 1 below can be exemplified.

[0013]

[Table 1]

[0014]

[Table 2]

[0015]

[Table 3]

The compound represented by the general formula (I) of the present invention is, for example, the following compound in which the pyridine ring substituent in the following compound (I) satisfies the kind and the substitution mode of the substituent specified in the compound (I). It can be formed by reacting a halogenated pyridine of (II) with a hydroxycarboxylic acid amide derivative of the following compound (III), preferably in the presence of a deoxidizing agent.

[0017]

[Chemical 5]

In the above reaction scheme, pyridyl, R ¹ ,
R ² , R ³ , R ⁴ and Q have the same meanings as described in the general formula (I).

Examples of the deoxidizing agent used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydride and potassium hydride; pyridine,
An organic base such as 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.

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. After completion of the reaction, the target compound (I) can be isolated from the reaction mixture according to a conventional method. The hydroxycarboxylic acid amide derivative (III) used in the above reaction is a compound (VI) which can be easily produced by the reaction of the acetoxycarboxylic acid chloride (IV) and the amine compound (V) represented by the following reaction formula:
It can be produced by deacetylation.

[0022]

[Chemical 6]

This reaction is preferably carried out in the presence of a solvent,
Examples of the solvent used include ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone; hydrocarbons such as hexane, benzene, toluene and xylene; dichloromethane, chloroform, carbon tetrachloride and the like. Examples thereof include halogenated hydrocarbons; esters such as methyl acetate and ethyl acetate; acetonitrile, water and the like, and mixed solvents thereof.

Examples of the deoxidizing agent include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Inorganic bases such as sodium bicarbonate; pyridine, collidine,
Organic bases such as trimethylamine, triethylamine and diazabicycloundecane; The reaction temperature is not particularly limited and may be appropriately selected. For example, the reaction temperature may be ice-cooling temperature to solvent reflux temperature. 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.

By reacting the acetoxycarboxylic acid amide compound (VI) thus obtained in the presence of a deacetylating agent, the hydroxycarboxylic acid amide derivative (III) can be easily produced. Examples of the deacetylating agent used in this reaction include sodium methylate, sodium ethylate, potassium methylate and the like. This reaction is preferably carried out in a solvent, and examples of the solvent used include alcohols such as methanol, ethanol and i-propyl alcohol. 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. The reaction time varies depending on the reaction temperature, the type of solvent used, etc., but for example, a reaction time of about 1 to about 20 hours can be exemplified. After completion of the reaction, the target compound (I) can be isolated from the reaction mixture according to a conventional method.

The fungicide of the present invention contains the novel substituted pyridyloxycarboxylic 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. It is prepared and used as a drug, emulsion, wettable powder, 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.

Examples of the carrier or diluent 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, polygloskite group and the like, specifically, pyroflight, attapulgite, sepiolite, kaolinite, bentonite, vermiculite, mica and talc; 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, ester gums, cobal gums and dumbmal gums; 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, monochrome. Chlorinated hydrocarbons such as benzene and orthochlorotoluene; ethers such as dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, 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, disintegration control, 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 sodium 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 bactericide 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 in consideration of 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 rest 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 pyridyloxycarboxylic 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.,
In the case of foliar treatment, it is 0.1 to 10,000 ppm, preferably 1 to 500 ppm, per active ingredient, although it cannot be specified unconditionally. In the case of soil treatment, it is 10 to 100,000 g / ha, preferably 200 to 20,000 g / ha.

[0036]

EXAMPLES The present invention will be specifically described below with reference to examples. Production Example 1 2- (3-chloro-5-trifluoromethyl-2-pyri
Ziroxy) -N- (1-cyano-1,2-dimethylprop
Ropyl) propionamide (Compound No. 5) 2,3-dichloro-5-trifluoromethylpyridine 2.16 g (0.01 mol) was added to 2-hydroxy-N-
(1-Cyano-1,2-dimethylpropyl) propionamide 1.84 g (0.01 mol), sodium hydride (60% in oil) 0.4 g (0.01 mol) and DMF
The mixture was added dropwise to 50 ml of the mixture at 0 ° C. with stirring, and then the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate, washed with water and dried, and the solvent was distilled off, followed by purification using column chromatography to obtain 2- (3-chloro-5-trifluoromethyl-). 2-pyridyloxy)
3.06 g of -N- (1-cyano-1,2-dimethylpropyl) propionamide was obtained (yield 84%).

(Production Example of Starting Material) 2-Hydroxy-N- (1-cyano-1,2-dimethyl)
Propyl) propionamide 2-acetoxypropionyl chloride 1.5 g (0.01
A solution of 10 mol of THF in 10 ml of 2-amino-2,3-dimethylbutyronitrile, 1.12 g (0.01 mol), 1.01 g (0.01 mol) of triethylamine and TH
A mixture of 50 ml of F was added dropwise at 0 ° C. with stirring. After dropping
The mixture was stirred at the same temperature for 30 minutes. After the reaction was completed, the reaction solution was poured into water, extracted with ethyl acetate, washed with water and dried, and the solvent was distilled off to obtain an oily product. This was dissolved in 50 ml of methanol and sodium methylate was added as a catalytic amount. After stirring for 1 hour, the solvent was distilled off and the residue was purified by column chromatography to give 2-hydroxy-N- (1-cyano-1,2-dimethylpropyl) propionamide 1.3.
g was obtained (71% yield).

The compounds of the present invention shown in Table 2 below were obtained in the same manner as in Production Example 1 above.

[0039]

[Table 4]

Next, several embodiments of formulation examples using the compound of the present invention will be shown. The "parts" in the following preparations are based on weight. 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. 5 20 parts Diatomaceous earth 70 parts Calcium lignin sulfonate 5 parts Naphthalene sulfonate formalin condensate 5 parts The above components were mixed and pulverized to obtain 100 parts wettable powder.

Formulation Example 3 (Granule) Compound No. 5 5 parts Bentonite 50 parts Talc 42 parts Sodium lignin sulfonate 2 parts Polyoxyethylene alkylaryl ether 1 part After adequately 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. 5 30 parts Di-2-ethylhexyl sulfosuccinate sodium salt 2 parts Polyoxyethylene nonylphenyl ether 3 parts Defoamer 1 part Propylene glycol 5 parts Water 59 parts or more The mixture was uniformly pulverized and mixed with a wet ball mill to obtain 100 parts of a flowable agent. According to the above-mentioned formulation examples, bactericides using the compound of the present invention can be formulated.

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 further incubate in a humid chamber at 25 ° C.
After keeping it for a day, it was sick in a 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.

[0045]

[Equation 1]

The results are shown in Table 3.

[0047]

[Table 5]

[0048]

The substituted pyridyloxycarboxylic acid amide derivative represented by the above general formula (I) of the present invention is a compound not described in the literature. This substituted pyridyloxycarboxylic acid amide derivative is characterized in that it has a pyridyl group substituted with a trifluoromethyl group and a 2-substituted alpha aminonitrile or ester moiety. It is considered that the excellent properties of the bactericide containing the acid amide derivative are exhibited. The compound and fungicide of the present invention show an excellent controlling effect against blast disease occurring in paddy rice cultivation in foliage treatment and water surface application, and show no phytotoxicity to rice.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinmitsu Sawai 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Mitsubishi Petrochemical Co., Ltd. Tsukuba Research Institute

Claims (2)

[Claims] 1. The following general formula (I): [However where each of pyridyl at least one is substituted with a CF ₃ group, may be further substituted by a halogen atom or a lower alkyl of up to three, 2, shows the 3- or 4-pyridyl group, R ¹ And R ² represent a lower alkyl group or a cycloalkyl group, or R ¹ and R ² together represent — (CH ₂ ) _n — (where n represents an integer of 4 to 6), and R ³ and R ⁴ represents a hydrogen atom or a lower alkyl group, Q represents a CN group, a CONR ⁵ R ⁶ group or a CO ₂ R ⁷ group (provided that R ⁵ , R ⁶ and R ⁷ are a hydrogen atom, a lower alkyl group or a lower alkyl group, respectively). An alkenyl group is shown). ] The substituted pyridyloxy carboxylic acid amide derivative represented by these. 2. The following general formula (I): [However where each of pyridyl at least one is substituted with a CF ₃ group, may be further substituted by a halogen atom or a lower alkyl of up to three, 2, shows the 3- or 4-pyridyl group, R ¹ And R ² represent a lower alkyl group or a cycloalkyl group, or R ¹ and R ² together represent — (CH ₂ ) _n — (where n represents an integer of 4 to 6), and R ³ and R ⁴ represents a hydrogen atom or a lower alkyl group, Q represents a CN group, a CONR ⁵ R ⁶ group or a CO ₂ R ⁷ group (provided that R ⁵ , R ⁶ and R ⁷ are a hydrogen atom, a lower alkyl group or a lower alkyl group, respectively). An alkenyl group is shown). ] The agricultural fungicide containing the substituted pyridyloxy carboxylic acid amide derivative represented by this as an active ingredient.