JPH0551364A - Germicidal o-acylformaldoxime pyridines - Google Patents

Abstract

PURPOSE:To obtain compounds useful as an agricultural and horticultural germicide. CONSTITUTION:Compounds expressed by formula I (R<1> is halogen; R<2> is H, halogen or 1-3C alkyl; R<3> is trifluoromethyl, cyano, hydroxy, etc.; R<4> is chloro or methoxy; m is 1-4; n is 0-2), e.g. o-(2-chloro-4-trifluoromethylbenzoyl)-3-(alpha- chloroformaldoxime)-pyridine. The compounds expressed by formula I are obtained by reacting a compound expressed by formula II with a compound expressed by formula III (hal is chloro or bromo) in the presence of an acid binder (e.g. triethylamine) in an inert organic solvent (e.g. methylene chloride) at -10 to +80 deg.C. The compounds are useful for late blight of tomato, anthracnose of cucumber, helminthosporium leaf spot of rice plant, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel O-acylformaldoxime pyridines, a process for producing the same, and an agricultural / horticultural fungicide containing the compound as an active ingredient.

[0002]

2. Description of the Related Art U.S. Pat.
No. 59 is bactericidal (α-halo-formaldoxime)
-Pyridines are described.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a novel active compound useful as an active ingredient of a fungicide and a method for producing the same.

[0004]

The O-acylaldoxime pyridines of the compound of the present invention are represented by the following formula (I). formula:

[Chemical 2] In the formula, R ¹ represents halogen, R ² represents a hydrogen atom, halogen or C _1-4 alkyl, R ³ represents trifluoromethyl, trifluoromethoxy, cyano or hydroxy, R ⁴ represents chloro. Or represents methoxy, m
Indicates 1, 2, 3 or 4 and n is 0, 1
Or 2, but the sum of m and n does not exceed 5.

The compound of formula (I) of the present invention can be obtained by the following method, and the present invention also relates to the production method thereof.

Manufacturing method a)

[Chemical 3] In the formula, R ¹ and R ² are the same as defined above,

[Chemical 4] In the formula, R ³ , R ⁴ , m and n are the same as above, and hal is chloro or bromine. A method for producing a compound represented by the formula (I), which comprises reacting with a compound represented by:

Manufacturing method b)

[Chemical 5] In the formula, R ² , R ³ , R ⁴ , m and n are the same as the above, and a method for producing a compound represented by the formula (I), which comprises reacting a compound represented by ..

The O-acylaldoxime pyridines of the formula (I) of the present invention show a strong bactericidal action. According to the invention, the O-acylaldoxime pyridines of formula (I) are surprisingly surprisingly compared to the compounds described, for example, in said US Pat. No. 4,244,959,
It has an extremely excellent bactericidal action.

In the compound (I) of the present invention, preferably R ¹ represents chloro, R ² represents a hydrogen atom, chloro or methyl, and R ³ represents trifluoromethyl, trifluoromethoxy, cyano or hydroxy. Indicates
R ⁴ represents chloro or methoxy, m represents 1 or 2 and n represents 0 or 1.

In the compound (I) of the present invention, it is particularly preferable that R ¹ represents chloro, R ² represents a hydrogen atom and R ² represents a hydrogen atom.
³ represents trifluoromethyl, trifluoromethoxy or cyano, m represents 1 and n represents 0.

The following compounds may be mentioned as specific examples of the compound (I) of the present invention. O
-(2-chloro-4-trifluoromethylbenzoyl)
-3- (α-chloro-formaldoxime) -pyridine, O- (2-hydroxy-4-methoxybenzoyl)
-3- (α-chloro-formaldoxime) -pyridine, O- (2-hydroxy-5-methoxybenzoyl)
-3- (α-chloro-formaldoxime) -pyridine, O- (3-chloro-4-trifluoromethylbenzoyl) -3- (α-chloro-formaldoxime) -pyridine, O- (2-chloro) -4-Trifluoromethylbenzoyl) -3- (α-chloro-formaldoxime)
-6-chloropyridine, O- (2-hydroxy-4-methoxybenzoyl) -3- (α-chloro-formaldoxime) -6-methylpyridine, O- (3-trifluoromethoxybenzoyl) -3- ( α-chloro-formaldoxime) -pyridine, O- (4-cyanobenzoyl) -2- (α-chloro-formaldoxime) -pyridine, O- (4-cyanobenzoyl) -3- (α-chloro- Formaldoxime) -pyridine, O- (2-hydroxybenzoyl) -3- (α-chloro-formaldoxime) -pyridine, O- (2-hydroxy-5-chlorobenzoyl) -2- (α-chloro- Formaldoxime) -pyridine, O- (3-cyanobenzoyl) -2-
(Α-chloro-formaldoxime) -pyridine, O-
(4-cyanobenzoyl) -3- (α-chloro-formaldoxime) -6-chloropyridine, O- (3-hydroxybenzoyl) -2- (α-chloro-formaldoxime) -5-methylpyridine,

O- (4-cyanobenzoyl) -4- (α
-Chloro-formaldoxime) -pyridine, O- (3
-Trifluoromethylbenzoyl) -3- (α-chloro-formaldoxime) -pyridine, O- (3-hydroxybenzoyl) -3- (α-chloro-formaldoxime) -pyridine, O- (3-hydroxy Benzoyl)
-2- (α-chloro-formaldoxime) -pyridine, O- (3-trifluoromethoxybenzoyl) -2
-(Α-chloro-formaldoxime) -pyridine, O
-(3-Hydroxybenzoyl) -4- (α-chloro-
Formaldoxime) -pyridine, O- (3-trifluoromethylbenzoyl) -2- (α-chloro-formaldoxime) -pyridine, O- (2-trifluoromethylbenzoyl) -3- (α-chloro- Formaldoxime) -pyridine, O- (4-trifluoromethylbenzoyl) -3- (α-chloro-formaldoxime) -pyridine, O- (2-trifluoromethylbenzoyl)-
3- (α-chloro-formaldoxime) -6-chloro-pyridine, O- (5-chloro-2-hydroxybenzoyl) -4- (α-chloro-formaldoxime) -pyridine, O- (3- Cyanobenzoyl) -3- (α-chloro-formaldoxime) -pyridine, O- (5-chloro-2-hydroxybenzoyl) -3- (α-chloro-formaldoxime) -pyridine, O- (2- Chloro-4-trifluoromethylbenzoyl) -3- (α-fluoro-formaldoxime) -pyridine,

O- (2-hydroxy-4-methoxybenzoyl) -3- (α-bromo-formaldoxime)-
Pyridine, O- (2-hydroxy-5-methoxybenzoyl) -3- (α-bromo-formaldoxime) -pyridine, O- (3-chloro-4-trifluoromethylbenzoyl) -3- (α-fluoro -Formaldoxime) -pyridine, O- (3-trifluoromethoxybenzoyl) -3- (α-bromo-formaldoxime)-
Pyridine, O- (4-cyanobenzoyl) -2- (α-
Bromo-formaldoxime) -pyridine, O- (4-
Cyanobenzoyl) -3- (α-fluoro-formaldoxime) -pyridine, O- (2-hydroxybenzoyl) -3- (α-fluoro-formaldoxime) -pyridine, O- (2-hydroxy-5- Chlorobenzoyl) -2- (α-fluoro-formaldoxime) -pyridine, O- (3-cyanobenzoyl) -2- (α-bromo-formaldoxime) -pyridine, O- (3-hydroxybenzoyl)- 3- (α-bromo-formaldoxime) -6-chloropyridine, O- (4-cyanobenzoyl) -4- (α-bromo-formaldoxime)
-Pyridine, O- (3-trifluoromethylbenzoyl) -3- (α-fluoro-formaldoxime) -pyridine, O- (3-cyanobenzoyl) -2- (α-bromo-formaldoxime) -5 -Methylpyridine, O
-(3-Hydroxybenzoyl) -3- (α-bromo-
Formaldoxime) -pyridine, O- (3-hydroxybenzoyl) -2- (α-fluoro-formaldoxime) -pyridine,

O- (3-trifluoromethoxybenzoyl) -2- (α-bromo-formaldoxime) -pyridine, O- (3-hydroxybenzoyl) -4- (α-
Bromo-formaldoxime) -pyridine, O- (3-
Trifluoromethylbenzoyl) -2- (α-bromo-
Formaldoxime) -pyridine, O- (2-trifluoromethylbenzoyl) -3- (α-fluoro-formaldoxime) -pyridine, O- (4-trifluoromethylbenzoyl) -3- (α-bromo- Formaldoxime) -pyridine, O- (5-chloro-2-hydroxybenzoyl) -4- (α-fluoro-formaldoxime) -pyridine, O- (3-cyanobenzoyl) -3-
(Α-Bromo-formaldoxime) -pyridine, O-
(5-chloro-2-hydroxybenzoyl) -3- (α
-Bromo-formaldoxime) -pyridine.

In the production method a), 2- (α
Using -chloro-formaldoxime) -pyridine and 3-trifluoromethoxybenzoyl chloride is represented by the following reaction formula.

[Chemical 6]

In the production method b), O- (3
-Trifluoromethylbenzoyl) -3-formaldoxime-pyridine and N-chlorosuccinimide are represented by the following reaction formula.

[Chemical 7]

In the above production method a), the compound of formula (II) is
It means that it is based on the definition of R ¹ and R ² , and preferably has the same meaning as the above-mentioned preferred definition. The compound of formula (II) may be a salt. The compound of the formula (II) is a compound known in the field of organic chemistry, and can be prepared by a method similar to the method described in US Pat. No. 4,244,959. As typical examples thereof, the following compounds can be mentioned. 4- (α-chloro-formaldoxime) -pyridine, 3- (α-chloro-formaldoxime) -pyridine, 3- (α-chloro-formaldoxime) -pyridinium hydrochloride, 2-
(Α-chloro-formaldoxime) -pyridine and the like. In the above-mentioned production method a), the compound of the formula (III) is the above-mentioned m, n, R
³ , based on the definition of R ⁴ and hal,
In m, n, R ³ and R ⁴ , preferably hal has the same meaning as defined above, hal represents chloro or bromine. The compound of formula (III) is a compound well known in the field of organic chemistry. As typical examples thereof, the following compounds can be mentioned. 3-cyanobenzoyl chloride, 4-trifluoromethoxybenzoyl chloride and the like.

In the above production method b), the compound of the formula (IV) is
Means based on the definition of R ¹ , R ³ , R ⁴ , m and n above, and preferably has the same meaning as the above preferred definition. The compound of the formula (IV) can be produced, for example, by a method similar to the above production method a). The following compounds may be mentioned as examples of the compound of the formula (IV). O- (4-trifluoromethoxybenzoyl) -4-formaldoxime-pyridine, O- (4-trifluoromethylbenzoyl) -2-formaldoxime-pyridine, O- (3
-Cyanobenzoyl) -3-formaldoxime-pyridine. Examples of the halogenating agent in the above production method b) include the following compounds. N-chlorosuccinimide (NCS), N-bromosuccinimide (NB
S), chlorine, etc.

In carrying out the process a) mentioned above, use may be made, as suitable diluent, of any inert solvent. Examples of such diluents include aliphatic, cycloaliphatic and aromatic hydrocarbons (which may optionally be chlorinated) such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene,
Xylene, methylene chloride, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, ethylene chloride, chlorobenzene, dichlorobenzene;
Other ethers such as diethyl ether, methyl ethyl ether, di-iso-propyl ether, dibutyl ether, propylene oxide, dioxane, dimethoxyethane (DME), tetrahydrofuran (TH
F), diethylene glycol dimethyl ether (DG
M); ketones such as acetone, methyl ethyl ketone (MEK), methyl-iso-propyl ketone, methyl-iso-butyl ketone (MIBK); nitriles such as acetonitrile, propionitrile, acrylonitrile; alcohols such as methanol, ethanol,
iso-propanol, butanol, ethylene glycol; esters such as ethyl acetate, amyl acetate; acid amides such as dimethylformamide (DMF), dimethylacetamide (DMA); sulfones, sulfoxides such as dimethyl sulfoxide (DMSO), sulfolane; And bases such as pyridine.

The production method a) can be carried out in the presence of an acid binder, and examples of such an acid binder include alkali metal hydroxides, carbonates, bicarbonates and alcoholates as inorganic bases such as carbonic acid. Sodium hydrogen, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide,
Examples thereof include sodium hydroxide, potassium hydroxide, and calcium hydroxide. Tertiary amines, dialkylaminoanilines and pyridines as organic bases such as triethylamine, tributylamine, 1,1,
4,4-Tetramethylethylenediamine (TMED
A), N, N-dimethylaniline, N, N-diethylaniline, pyridine, 4-dimethylaminopyridine (DM
AP), 1,4-diazabicyclo [2,2,2] octane (DABCO) and 1,8-diazabicyclo [5,5].
4,0] undec-7-ene (DBU) and the like can be mentioned.

Process a) can be carried out within a substantially wide temperature range. Generally, about -10 to about 8
It can be carried out at 0 ° C, preferably between about 0 and about 25 ° C.
Further, the reaction is preferably carried out under normal pressure, but it may be operated under increased pressure or reduced pressure. In carrying out the production method a), for example, 1 mol to 1.5 mol of the formula (III) and 1 to 1 mol of the acid binder to the formula (II) are used per 1 mol of the compound of the formula (II). The target compound can be obtained by reacting the compound of formula (II) in a molar amount of 2.5 times, or in the case of a salt of the compound of the formula (II), in a molar amount of 2 to 2.5 times in a diluent such as methylene chloride.

In carrying out the process b) mentioned above, use may be made, as suitable diluent, of any inert solvent. Examples of such diluents are water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated), for example pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene. , Xylene, methylene chloride, dichloromethane,
Chloroform, carbon tetrachloride, 1,2-dichloroethane,
Ethylene chloride, chlorobenzene, dichlorobenzene; other ethers such as diethyl ether, methyl ethyl ether, di-iso-propyl ether,
Dibutyl ether, propylene oxide, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM); ketones such as acetone, methyl ethyl ketone (MEK), methyl-iso-propyl ketone, methyl-iso-butyl ketone (MIBK). Nitriles such as acetonitrile, propionitrile, acrylonitrile; alcohols such as methanol, ethanol, iso-propanol, butanol, ethylene glycol; esters such as ethyl acetate, amyl acetate;
Acid amides such as dimethylformamide (DMF),
Examples thereof include dimethylacetamide (DMA); sulfone, sulfoxides such as dimethyl sulfoxide (DMSO), sulfolane; and bases such as pyridine.

Process b) can be carried out within a substantially wide temperature range. Generally, about -10 to about 8
It can be carried out at 0 ° C, preferably between about 0 and about 25 ° C.
Further, the reaction is preferably carried out under normal pressure, but it may be operated under increased pressure or reduced pressure. In carrying out the production method b), for example, 1 mol of the compound of the formula (IV) is reacted with a halogenating agent in a diluent, for example, DMF, in an amount of 1 to 1.2 mol to obtain the target compound. be able to.

The active compounds according to the invention show a strong bactericidal action and can in fact be used for controlling unwanted phytopathogenic fungi. The active compounds according to the invention are generally used as fungicides in Plasmodiophoromycete.
s), Oomycetes, Chitridiomycetes,
It can be used against various plant diseases caused by Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes, and as a fungicide (bacterial) agent, Pseudomonads.
ae), Rhizobiaceae,
Enterobacteriaceae (Enterobacteria)
ceae), Corynebacterium (Coryneba)
cteriaceae) and Streptomycetes (St
It can be used against various plant diseases caused by reptomyceceae. The active compound of the present invention, at a concentration of the active compound required for controlling phytopathogenic fungi, shows good compatibility with plants, and therefore, in use, a drug treatment to the above-ground part of the plant, It enables chemical treatment of rootstocks and seeds and soil treatment. Further, the compound of the present invention has low toxicity to warm-blooded animals and can be safely used.

The active compounds according to the invention can be in the usual pharmaceutical forms. And as such a form, a liquid agent, a wettable powder, an emulsion, a suspension agent, a powder agent, a foam agent, a paste,
Granules, aerosols, active compound infiltration-natural and synthetic,
Microcapsules, coatings for seeds, preparations with a combustion device (for example, fumigation and fumes cartridges, cans and coils as combustion devices), and ULVs (cold mist, warm mist).
m mist)]. These formulations can be manufactured by a known method. Such a method
For example, the active compound may be combined with a spreading agent, ie a liquid diluent; a liquefied gas diluent; a solid diluent or carrier, optionally a surfactant, ie an emulsifier and / or dispersant and / or a foam former. , By mixing.
If water is used as the developing agent, for example, organic solvents can also be used as cosolvents. Liquid diluents or carriers generally include aromatic hydrocarbons (eg, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (eg,
Chlorobenzenes, ethylene chloride, methylene chloride, etc.), aliphatic hydrocarbons [eg, cyclohexane, etc.,
Paraffins (for example, mineral oil fractions)], alcohols (for example, butanol, glycol and their ethers, esters, etc.), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strong polar solvents (for example, , Dimethylformamide, dimethylsulfoxide, etc.) and water. The liquefied gas diluent or carrier is a gas at room temperature and atmospheric pressure, examples of which include butane, propane,
There may be mentioned aerosol propellants such as nitrogen gas, carbon dioxide and halogenated hydrocarbons.

As the solid diluent, soil natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapal guide, montmorillonite, diatomaceous earth, etc.), soil synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.) ) Can be mentioned. Solid carriers for granules include ground and fractionated rocks (eg, calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic particles of inorganic and organic powders, and organic substances (eg sawdust, Coconut seeds, corn cobs and tobacco stems, etc.) can be mentioned as fine granules. Examples of emulsifiers and / or foaming agents include nonionic and anionic emulsifiers [eg, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid alcohol ether (eg, alkylaryl polyglycol ether, alkyl sulfonate, alkyl sulfate, aryl sulfone). Acid salt, etc.)], and albumin hydrolysis products. As a dispersant,
Examples include lignin sulfite waste liquor, and methylcellulose. Adhesives can also be used in the formulation (powder, granules, emulsions), such adhesives including carboxymethyl cellulose and natural and synthetic polymers (eg gum arabic, polyvinyl alcohol and polyvinyl acetate). You can It is also possible to use colorants, which include inorganic pigments (for example iron oxide, titanium oxide and Prussian blue) and organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes and also iron, Mention may be made of trace elements such as manganese, boron, copper, cobalt, molybdenum, zinc and their salts. The formulation may generally contain from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight, of the active ingredient.

The active compounds of the present invention can be used in the above-mentioned preparations or in various forms of use in other known active compounds such as fungicides (fungiside, bactericide), insecticides, acaricides, nematicides, herbicides, birds. A repellent, a growth regulator, a fertilizer and / or a soil conditioner can also be present together. When the active compound of the present invention is used, it may be used directly as it is, or may be used in the form of preparation such as preparation liquid for dispersion, emulsion, suspension, powder, paste and granule, or further diluted. It can be used in the specified usage form. And the active compound is treated in the usual way, for example by
Water spraying, dipping, spraying
Ying, atomizing, misting, vaporing, irrigation, suspension formation, application, dusting, dusting, dressing, moistening, wet coating, pasty coating, or coat coating. In the treatment of each part of the plant, the concentration of active compound in the actual use form can be varied within a substantial range. And generally 0.0001-1% by weight, preferably 0.001-
It is 0.5% by weight. In seed treatment, the active compound is present in an amount of 0.001 to 50 g, preferably 0.
01-10 g can generally be used. In soil treatment, active compounds can generally be used in concentrations of 0.00001 to 0.1% by weight, in particular 0.0001 to 0.02% by weight, based on the point of action. Next, the contents of the present invention will be specifically described with reference to examples, but the present invention should not be limited to these.

[0028]

【Example】

 Synthesis example 1

[Chemical 8] Triethylamine (2.3 g) was added dropwise at 0 ° C. to a solution of 4- (α-chloro-formaldoxime) -pyridine (3 g) in methylene chloride (100 ml). Keep 0 ℃ 30
After stirring for a minute, a solution of 4-trifluoromethoxybenzoyl chloride (2.9 g) in methylene chloride (20 ml) was added and the temperature was gradually raised to room temperature, followed by stirring for 3 hours. After washing with water and drying over anhydrous sodium sulfate, methylene chloride is distilled off under reduced pressure. Purification by silica gel column chromatography (eluent chloroform: ethanol 50: 1) gives the desired O- (4-trifluoromethoxybenzoyl) -4- (α-chloro-formaldoxime) -pyridine. mp. 171 to 175 ° C. Table 1 below shows compounds synthesized in the same manner as in the above Synthesis Example.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

Biological test: Example 2 Control test against corn blight of tomato Drug preparation method Test compound: 30 parts Organic solvent (xylene): 55 parts Emulsifier; Polyoxyethylene alkylphenyl ether: 8 parts Calcium alkylbenzene sulfonate: 7 Parts Prepared by diluting the specified amount of the above emulsion with water. Test method: Tomatoes (variety: Kurihara) cultivated in a 9 cm unglazed pot were sprayed with a test compound in the form of an emulsion prepared by the above method using a spray gun. One day after spraying, inoculate with a spore suspension of the disease fungus and keep it overnight in a temperature-controlled room at 20 ° C and a humidity of 90% or more, and then after 5 days, evaluate the morbidity according to the lesion area ratio according to the following criteria. , The control value was determined.

Degree of morbidity Lesion area ratio (%) 0 0 less than 0.5 2 12 less than 5 less than 25 less than 15 3 less than 15 30 4 less than 30 less than 50 5 50 or more

[0034]

[Equation 1]

The results are shown in Table 2.

[Table 4] Table 2 Compound active ingredient concentration Control value No. ppm% 5 500 100 7 500 500 100 10 500 100 100 11 500 100 100 15 500 500 100 21 500 500 ──────────────── ───────────

Example 3 Control test for anthracnose of cucumber Test method Cucumber (variety: Yohba) cultivated in a 9 cm biscuit pot was prepared according to Example 2 according to Example 2, and a diluted solution of the test compound at a predetermined concentration was prepared. 25 ml was sprayed per 3 pots. One day after spraying, the spore solution of this pathogen was spray-inoculated and kept in a thermostatic chamber at 23 ° C and a humidity of 90% or more for one day. 6 days after leaving, according to the following criteria,
The degree of morbidity was categorized and evaluated by the lesion area ratio, and the control value (%) was obtained.

Degree of morbidity Lesion area ratio (%) 0 0 less than 0.5 2 1 2 less than 5 2 5 less than 15 3 less than 15 30 4 less than 30 50 less than 5 50 or more

[0038]

[Equation 2]

The results are shown in Table 3.

[Table 5] Table 3 Compound active ingredient concentration Control value No. ppm% 16 500 100 17 17 500 100 21 500 500 100 ───────────────────────── ──

Example 4 Foliar spraying efficacy test against rice sesame leaf blight The paddy rice (cultivar: Kusabue) was cultivated in a clay pot with a diameter of 12 cm and prepared according to Example 2 at the 3 to 4 leaf stage. 50 ml of a predetermined concentration diluted solution of the test compound was sprayed per 3 pots. Next day, a suspension of rice sesame leaf blight fungus spores artificially cultured on the next day was spray-inoculated (twice) and kept in a wet room at 25 ° C. and 100% relative humidity for infection. Seven days after the inoculation, the degree of morbidity per pot was classified and evaluated according to the following criteria, and the control value (%) was determined.

Degree of illness Degree of illness 0 No illness 1 Minor 2 Minor 3 Medium 4 High 5

[0042]

[Equation 3]

The results are shown in Table 4.

[0044]

[Table 6] Table 4 Compound active ingredient concentration Control value No. ppm% 5 500 100 10 10 500 100 20 500 500 100 ───────────────────────── ──

In the above Examples 2, 3 and 4, no phytotoxicity to crops was observed.

[0046]

INDUSTRIAL APPLICABILITY As shown in the above examples, the compound of the present invention has excellent activity as an active ingredient of an agricultural and horticultural fungicide.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 13, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

In the above-mentioned production method b), the compound of the formula (IV) means a compound based on the above definitions of R ² , R ³ , R ⁴ , m and n, and preferably has the same meaning as the above preferred definition. Show. The compound of formula (IV) can be produced, for example, by a method similar to the above production method a). The following compounds may be mentioned as examples of the compound of formula (IV). O-
(4-trifluoromethoxybenzoyl) -4-formaldoxime-pyridine, O- (4-trifluoromethylbenzoyl) -2-formaldoxime-pyridine,
O- (3-cyanobenzoyl) -3-formaldoxime-pyridine. Examples of the halogenating agent in the above production method b) include the following compounds. N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS), chlorine and the like.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

Biological test: Example 2 Control test against corn blight of tomato Drug preparation method Test compound: 30 parts Organic solvent (xylene): 55 parts Emulsifier; Polyoxyethylene alkylphenyl ether: 8 parts Calcium alkylbenzene sulfonate: 7 Parts Prepared by diluting the specified amount of the above emulsion with water. Test method: Tomatoes (cultivar: Kurihara) cultivated in a 9 cm plastic pot were sprayed with the test compound in emulsion form prepared according to the above method using a spray gun. Scatter 1
After a day, inoculate a spore suspension of the disease fungus, at 20 ° C, humidity of about 1
After keeping it in a constant temperature room of 00% overnight, after 5 days, the morbidity was classified and evaluated according to the following criteria by the lesion area ratio, and the control value was obtained.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

Example 3 Control test for anthracnose of cucumber Test method Cucumber (variety: Yohba) cultivated in a plastic pot of 9 cm was prepared according to Example 2, and a predetermined concentration of the test compound in emulsion form was prepared. 50 ml of the diluted solution was sprayed per 3 pots. One day after spraying, spray inoculate the spore fluid of this pathogen, and
It was kept in a thermostatic chamber at a humidity of about 100% for one day. After 6 days of standing, the degree of morbidity was categorized by the lesion area ratio according to the following criteria, and the control value (%) was obtained.

[Procedure amendment 4]

[Document name to be amended] Statement

[Item name to be corrected] 0040

[Correction method] Change

[Correction content]

Example 4 Foliar spraying efficacy test against rice sesame leaf blight Paddy rice (variety: Kusabue) made of plastic with a diameter of 9 cm
Cultivated in pots, in accordance with Example 2 in the 3-4 leaf stage, 3 pots per a predetermined concentration dilutions of the test compound prepared 50ml
Sprayed. Next day, a suspension of rice sesame leaf blight fungus spores artificially cultured on the next day was spray-inoculated (twice) and kept in a wet room at 25 ° C. and 100% relative humidity for infection. Seven days after the inoculation, the degree of morbidity per pot was classified and evaluated according to the following criteria, and the control value (%) was determined.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Katsuhiko Shibuya 1-9-31 Wakagicho, Oyama City, Tochigi Prefecture (72) Inventor Michiaki Shita 39-15 Namikicho, Hachioji City, Tokyo

Claims (4)

[Claims] 1. The formula: In the formula, R ¹ represents halogen, R ² represents a hydrogen atom, halogen or C _1-3 alkyl, R ³ represents trifluoromethyl, trifluoromethoxy,
Represents cyano or hydroxy, R ⁴ represents chloro or methoxy, m represents 1, 2, 3 or 4, and n represents 0, 1 or 2, provided that the sum of m and n is 5
O-acylformaldoxime pyridines represented by the formula: 2. R ¹ represents chloro, R ² represents a hydrogen atom, chloro or methyl, R ³ represents trifluoromethyl, trifluoromethoxy, cyano or hydroxy, and R ⁴ represents chloro or methoxy. , M is 1 or 2, and n is 0 or 1.
The O-acylformaldoxime pyridines according to claim 1. 3. R ¹ represents chloro, R ² represents a hydrogen atom, R ³ represents trifluoromethyl, trifluoromethoxy, or cyano, m represents 1 and n represents 0. 1. The O-acylformaldoxime pyridines described in 1. 4. A fungicide for agricultural and horticultural use containing the O-acylformaldoxime pyridines represented by claim 1 as an active ingredient.