JPH0551363A - Utilization of o-acylformaldoxime pyridines as agricultural germicide - Google Patents

Abstract

PURPOSE:To obtain new compounds useful as an agricultural and horticultural germicide, especially a germicide capable of exhibiting excellent activity against oomycetes. CONSTITUTION:Compounds expressed by formula I (R<1> is halogen; R<2> is H or halogen; R<3> is 1-4C alkyl, 1-4C alkoxy, halogen or nitro), e.g. 0-(4-chloro-3- nitrobenzoyl)-3-(2-chloro-formaldoxime)-pyridine. The compounds expressed by formula I are obtained by reacting a compound expressed by formula II with a compound expressed by formula III (M is halogen) 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 compound expressed by formula III is used in a molar amount of 1-1.5 times based on 1 mol compound expressed by formula II and the acid binder is used in a molar amount of 1-1.5 times based on 1 mol compound expressed by formula II. The resultant compounds are useful for late blight of tomato, 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 use as agricultural fungicides.

[0002]

It is already known that O-acyl (α-nitroformaldoxime) or (α-haloformaldoxime) pyridines have bactericidal activity. (US Patent USP 4,244,959)

[0003]

DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention
The following O-acylformaldoxime pyridines of formula (I) were found.

Expression

[Chemical 2] In the formula, R ¹ represents a halogen atom, R ² represents a hydrogen atom or a halogen atom, and R ³ represents a C _1-4 alkyl group,
C _{1-4 represents an} alkoxy group, a halogen atom or nitro.

The compound of the formula (I) of the present invention can be prepared, for example, by the following method: a) Formula:

[Chemical 3] In the formula, R ¹ and R ² are the same as above, and a compound represented by the formula:

[Chemical 4] Wherein R ³ is the same as above and M is a halogen atom, or

B) Formula:

[Chemical 5] In the formula, R ² and R ³ are the same as defined above, and can be obtained by reacting a halogenating agent.

The O-acylformaldoxime pyridines of the formula (I) of the present invention exhibit a strong bactericidal action as agricultural bactericides. According to the present invention, the O-acylformaldoxime pyridines of formula (I) are prepared according to USP 4,2 above.
44,959 is conceptually included, but is not specifically disclosed at all. The compound of the present invention surprisingly exhibits a remarkable bactericidal action as compared with the compound disclosed in the US patent, and in particular, Oomyc for plant diseases.
It exhibits an excellent control effect against etes (oomycetes).

In the compounds of the formula (I) of the present invention and the intermediates (II) and (III) for the production thereof, the halogen atom is fluoro, chloro, bromo or iodo, preferably fluoro or chloro. , Brom, especially chlor. The alkyl moiety of the C _1-4 alkyl group and the C _1-4 alkoxy group represents methyl, ethyl, n-propyl, isopropyl, n- (iso-, sec- or tert-) butyl, preferably methyl or ethyl. , Especially methyl.

In the compound of the formula (I) of the present invention, preferred examples thereof are where R ¹ represents chloro, R ² represents a hydrogen atom or chloro, and R ³ represents methyl, methoxy, chloro or nitro. Compounds of More particularly preferred examples are where R ¹ represents chloro, R ² represents a hydrogen atom, R ³ represents methyl, methoxy, chloro or nitro, and the O-acylformaldoxime residue is at the 3-position of the pyridine ring. The compound that binds can be mentioned.

As the compounds of the formula (I) of the present invention, the following compounds can be listed in addition to the compounds mentioned in the examples below. O- (4-methoxy-3-nitrobenzoyl) -2- (α-chloro-formaldoxime) -pyridine, O- (4-methoxy-3-nitrobenzoyl)-
3- (α-chloro-formaldoxime) -pyridine,
O- (3-methoxy-4-nitrobenzoyl) -3-
(Α-chloro-formaldoxime) -pyridine, O-
(3,5-Dinitrobenzoyl) -3- (α-chloro-
Formaldoxime) -pyridine,

O- (2-methyl-6-nitrobenzoyl) -3- (α-chloro-formaldoxime) -pyridine, O- (2-methyl-3-nitrobenzoyl) -3
-(Α-chloro-formaldoxime) -pyridine, O
-(2-Methyl-5-nitrobenzoyl) -3- (α-
Chloro-formaldoxime) -pyridine, O- (3-
Methyl-4-nitrobenzoyl) -3- (α-chloro-
Formaldoxime) -pyridine, O- (3-methoxy-2-nitrobenzoyl) -4- (α-chloro-formaldoxime) -pyridine, O- (4-methyl-3-nitrobenzoyl) -3- ( α-chloro-formaldoxime) -pyridine, O- (2-chloro-5-nitrobenzoyl) -2- (α-chloro-formaldoxime)-
Pyridine,

O- (4-chloro-2-nitrobenzoyl) -3- (α-chloro-formaldoxime) -pyridine, O- (2-chloro-4-nitrobenzoyl) -3
-(Α-chloro-formaldoxime) -pyridine, O
-(5-Methyl-2-nitrobenzoyl) -3- (α-
Chloro-formaldoxime) -pyridine, O- (4-
Chloro-3-nitrobenzoyl) -3- (α-chloro-
Formaldoxime) -pyridine, O- (3-methoxy-2-nitrobenzoyl) -2- (α-chloro-formaldoxime) -pyridine, O- (3-methoxy-2-)
Nitrobenzoyl) -3- (α-chloro-formaldoxime) -pyridine, O- (2-chloro-5-nitrobenzoyl) -3- (α-chloro-formaldoxime)
-Pyridine,

O- (2-chloro-3-nitrobenzoyl) -3- (α-chloro-formaldoxime) -pyridine, O- (5-chloro-2-nitrobenzoyl) -3
-(Α-chloro-formaldoxime) -pyridine, O
-(2-chloro-5-nitrobenzoyl) -4- (α-
Chloro-formaldoxime) -pyridine, O- (3-
Chloro-2-nitrobenzoyl) -3- (α-chloro-
Formaldoxime) -pyridine, O- (3,4-dinitrobenzoyl) -3- (α-chloro-formaldoxime) -pyridine.

In the production method a), for example, as raw materials,
Using 2- (α-chloro-formaldoxime) -pyridinium hydrochloride and 4-methoxy-3-nitrobenzoyl chloride, the reaction formula is shown below.

[Chemical 6]

In the production method b), for example, as raw materials,
O- (4-methoxy-3-nitrobenzoyl) -3-
Using (formaldoxime) -pyridine and N-chloro-succinimide, the reaction formula is shown below.

[Chemical 7]

The compounds of formula a) in at material of formula (II) represents those in accordance with the definition of R ¹ and R ^2, preferably, based on the R ¹ and R ² each preferably defined Shows The compound of formula (II) is a known compound described in U.S. Pat. No. 4,244,959 and Japanese Patent Application No. 2-251840, and specific examples thereof include 3- (α-chloroform aldo). Oxime) -pyridinium hydrochloride, 4- (α-chloroformaldoxime) -pyridinium hydrochloride, 2-
Examples include (α-chloroform aldoxime) -pyridinium hydrochloride and the like.

The starting compound of formula (III) in the production method a) has the same meaning as defined for R ³ and M above, preferably chloro which is a preferred definition of R ³ and preferred definition of M. Based on. Compounds of formula (III) are well known in the field of organic chemistry, for example 4-methoxy-3-nitrobenzoyl chloride, 3-
Methoxy-2-nitrobenzoyl chloride, 4-chloro-3-nitrobenzoyl chloride, 3-methoxy-
4-nitrobenzoyl chloride, 2-methyl-6-nitrobenzoyl chloride, 2-methyl-3-nitrobenzoyl chloride, 2-methyl-5-nitrobenzoyl chloride, 3-methyl-4-nitrobenzoyl chloride, 4-methyl- 3-nitrobenzoyl chloride, 2-chloro-5-nitrobenzoyl chloride, 4
-Chloro-2-nitrobenzoyl chloride, 2-chloro-4-nitrobenzoyl chloride, 5-methyl-2
Examples include -nitrobenzoyl chloride, 2-chloro-3-nitrobenzoyl chloride, 5-chloro-2-nitrobenzoyl chloride, 3-chloro-2-nitrobenzoyl chloride and 3,4-dinitrobenzoyl chloride.

[0018] Compounds of formula b) in in starting materials of the formulas (IV) represents those in accordance with the definition of the R ² and R ^3, preferably, to each of the preferred definitions of R ² and R ³ Based on. The compound of formula (IV) can be synthesized according to the method shown in the above-mentioned production method a).

Specific examples of the compound of the formula (IV) include O-
(4-Methoxy-3-nitrobenzoyl) -2- (formaldoxime) -pyridine, O- (4-chloro-2-
Nitrobenzoyl) -3- (formaldoxime) -pyridine, O- (3-methoxy-2-nitrobenzoyl)
-3- (formaldoxime) -pyridine etc. can be illustrated. Examples of the halogenating agent in the production method b) include N-chloro-succinimide, N-bromo-succinimide, chlorine gas and the like.

In carrying out the process a) mentioned above, use may be made, as suitable diluent, of all inert organic solvents. Examples of such diluents are water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated), for example hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene. , Methylene chloride, chloroform, carbon tetrachloride,
Ethylene chloride, chlorobenzene; Other ethers such as diethyl ether, methyl ethyl ether, di-iso-propyl ether, dibutyl ether, propylene oxide, dioxane, tetrahydrofuran; Other ketones such as acetone, methyl ethyl ketone, methyl- iso-propyl ketone, methyl-iso-butyl ketone; other, nitriles such as acetonitrile, propionitrile, acrylonitrile; other, esters such as ethyl acetate, amyl acetate; other, acid amides such as dimethylformamide, Dimethylacetamide; other, sulfolane,
Sulfoxides, such as dimethyl sulfoxide, sulfolane; Others, bases, such as pyridine; Others,
Etc. can be mentioned.

The production method a) can be carried out in the presence of an acid binder, and examples of the acid binder include hydroxides, carbonates, bicarbonates and alcoholates of alkali metals, and Secondary amines such as triethylamine,
Tributylamine, 1,1,4,4-tetramethylethylenediamine, N, N-diethylaniline, pyridine,
4-dimethylaminopyridine, 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,8-diazabicyclo [5,4,0] undec-7-ene (DB
U) etc. can be mentioned. The production method a) can be carried out within a substantially wide range. In general,
It can be carried out at a temperature of about -10 to about 80 ° C, preferably about 0 to about 25 ° C. Further, it is desirable that the reaction is carried out under normal pressure, but it can be operated under pressure or under reduced pressure.
In carrying out the production method a), for example, 1 to 1.5 times the molar amount of the compound of the formula (III), 1 to 1.5 times the molar amount of the compound of the formula (II), and 1 to 1.5 times the amount of the acid binder relative to the compound of the formula (II) are used. The compound can be obtained by reacting in a 1.5-fold molar amount, or in the case where the compound of the formula (II) is a salt, in a 2-2.5-fold molar amount in an inert solution, for example, in the presence of methylene chloride.

In carrying out the process b) mentioned above, use may be made, as suitable diluent, of any inert organic solvent. Examples of such diluents are water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated), for example hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene. , Methylene chloride, chloroform, carbon tetrachloride,
Ethylene chloride, chlorobenzene; Other ethers such as diethyl ether, methyl ethyl ether, di-iso-propyl ether, dibutyl ether, propylene oxide, dioxane, tetrahydrofuran; Other ketones such as acetone, methyl ethyl ketone, methyl- iso-propyl ketone, methyl-iso-butyl ketone; other, nitriles such as acetonitrile, propionitrile, acrylonitrile; other, esters such as ethyl acetate, amyl acetate; other, acid amides such as dimethylformamide, Dimethylacetamide; other, sulfolane,
Sulfoxides, such as dimethyl sulfoxide, sulfolane; Others, bases, such as pyridine; Others,
Etc. can be mentioned.

Process b) can be carried out within a substantially wide range. Generally, about -10 to about 80
C., preferably between about 0 and about 25.degree. Further, it is desirable that the reaction is carried out under normal pressure, but it can be operated under pressure or under reduced pressure. In carrying out the production method b), for example, with respect to the compound of the formula (IV), a halogenating agent in an amount of 1 to 1.5 mol, in an inert solution, for example,
It can be obtained by reacting in the presence of methylene chloride. 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,
Zygomycetes, Ascomycetes, Basidiomycetes
It can be used against various plant diseases caused by (Basidiomycetes) and Deuteromycetes, and in particular, exhibits excellent bactericidal effect against Ohmicetes. As a bactericidal agent, Pseudomonadaceae (Pseudomonadace)
ae), Rhizobiaceae,
Enterobacteriaceae (Enterobacteria)
ceae), Corynebacterium (Coryneba)
cteriaceae) and Streptomycetes (St
It can be used against various plant diseases caused by reptomyceceae.

Since the active compound of the present invention shows good compatibility with a plant at the concentration of the active compound required for controlling phytopathogenic fungi, the active compound of the present invention can be applied to the above-ground part of the plant at the time of use. It enables chemical treatment, 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 compound of the present invention can be formulated into a usual formulation. And as such forms, liquid preparations, emulsions, wettable powders, suspensions, powders, foams, pastes, granules, aerosols, active compound infiltration-natural and synthetic products, microcapsules, seed coatings, combustion devices (Eg as a combustion device, fumigation and fumes cartridges, cans and coils), and UL
V [cold mist (warm mist)] can be mentioned.

These preparations can be manufactured by a known method. Such a process comprises, for example, applying an active compound to a developing agent, ie a liquid diluent; a liquid gas diluent; a solid diluent or carrier, optionally a surfactant, ie an emulsifier and / or dispersant and / or foam. It is carried out by mixing with a forming agent. If water is used as the developing agent, for example, organic solvents can also be used as cosolvents. Liquid diluents or carriers typically 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, paraffins (eg, mineral oil fraction) Etc.)], alcohols (eg, butanol, glycol and their ethers, esters, etc.), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strong polar solvents (eg, dimethylformamide, dimethyl sulfoxide, etc.) )
And we can mention water.

The liquefied gas diluent or carrier is a gas at room temperature and atmospheric pressure, examples of which include butane, propane, nitrogen gas, carbon dioxide, and aerosol propellants such as halogenated hydrocarbons. be able to. Solid diluents include soil natural minerals (eg, kaolin,
Clay, talc, chalk, quartz, attapal guide, montmorillonite, diatomaceous earth, etc.) and soil synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.). 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 the emulsifier and / or foaming agent include nonionic and anionic emulsifiers [eg, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid alcohol ether (eg, alkylaryl polyglycol ether, alkyl sulfonate, alkyl sulfate). , Aryl sulfonates, etc.)], and albumin hydrolysis products. Examples of the dispersant include lignin sulfite waste liquid, and methyl cellulose. 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 , Trace elements such as iron, manganese, boron, copper, cobalt, molybdenum, zinc and their salts. The formulation generally comprises from 0.1 to 0.1 of the active ingredient.
It may be contained in an amount of 95% by weight, preferably 0.5 to 90% by weight.

The active compound of the present invention can be used in the above-mentioned preparations or in various use forms 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.

For seed treatment, the active compound is seeded 1
0.001 to 50 g, preferably 0.01 to 1 per kg
0 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.

[0031]

【Example】

 Synthesis example

[Chemical 8] Triethylamine (2.3 g) was added dropwise to a solution of 3- (α-chloro-formaldoxime) -pyridine (3 g) in methylene chloride (100 ml) at 0 ° C. Keep 0 ℃ 30
After stirring for a minute, a solution of 4-chloro-3-nitro-benzoyl chloride (4.6 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)
Desired O- (4-chloro-3-nitrobenzoyl) -3
-(Α-Chloro-formaldoxime) -pyridine is obtained. mp. 134-138 ° C

The compounds obtained in the same manner as in the above-mentioned synthesis example are shown in Table 1 below.

[Chemical 9]

[Chemical 10] But

[Chemical 11] To indicate *,

[Chemical formula 12] But

[Chemical 13] To indicate **,

[Chemical 14] But

[Chemical 15] Is indicated as ***.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

Biological test examples; -Comparison compounds

[Chemical 16]

Test Example 1 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 Emulsion above It is prepared by diluting the prescribed amount of the above with water.

Test method: Tomatoes (cultivar: Kurihara) cultivated in a 9 cm unglazed pot were sprayed with a spray gun using the test compound in emulsion form prepared according to the above method. One day after spraying, inoculate with a spore suspension of this disease fungus, 20 ° C, humidity 90%
After keeping it in the above-mentioned constant temperature room 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.

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

[Equation 1] The results are shown in Table 2.

[0040]

[Table 4] Table 2 Compound active ingredient concentration Control value No. ppm% ────────────────────────── 15 500 100 17 17 500 100 100 18 500 100 21 500 100 ────────────────────────── C-1 500 53 ─────────────── ─────────────

Test Example 2 Foliar spraying efficacy test against rice sesame leaf blight Rice paddy rice (cultivar: Kusabue) was cultivated in a clay pot with a diameter of 12 cm and prepared according to Test Example 1 at the 3 to 4 leaf stages. 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 morbidity Degree of illness 0 No illness 1 Fine 2 Small 3 Medium 4 Large 5 5

[0043]

[Equation 2] The results are shown in Table 3.

[0044]

[Table 5] Table 3 Compound active ingredient concentration Control value No. ppm% ────────────────────────── 15 500 100 16 16 500 100 17 500 100 18 500 100 ────────────────────────── C-1 500 73 73 ────────────── ──────────── In the above Test Examples 1 and 2, no chemical damage to the crops was observed.

[0045]

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] 0038

[Correction method] Change

[Correction content]

Test method: Tomatoes (cultivar: Kurihara) grown in 9 cm plastic pots were sprayed with a test compound in the form of an emulsion prepared according to the above method using a spray gun. One day after spraying, inoculate with a spore suspension of this disease fungus, and
After keeping it in a temperature-controlled room at ℃ and humidity of about 100% overnight, 5
After a day, the disease level was classified and evaluated according to the following criteria by the lesion area ratio, and the control value was obtained.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

Test Example 2 Foliar spraying efficacy test for rice sesame leaf blight Paddy rice (variety: Kusabue) made of plastic with a diameter of 9 cm
Cultivated in pots, according to Test Example 1 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.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Haruhiko Sakuma 1-5-7 Minamimachi, Oyama-shi, Tochigi Prefecture (72) Inventor Michiaki Shita 39-15 Namikimachi, Hachioji-shi, Tokyo

Claims (4)

[Claims] 1. The formula: In the formula, R ¹ represents a halogen atom, R ² represents a hydrogen atom or a halogen atom, and R ³ represents a C _1-4 alkyl group,
A C _1-4 alkoxy group, a halogen atom or nitro,
O-acylformaldoxime pyridines represented by: 2. The compound according to claim 1, wherein R ¹ represents chloro, R ² represents a hydrogen atom or chloro, and R ³ represents methyl, methoxy, chloro or nitro. 3. R ¹ represents chloro, R ² represents a hydrogen atom, R ³ represents methyl, methoxy, chloro or nitro, and an O-acylformaldoxime residue is bonded to the 3-position of the pyridine ring. The compound of claim 1, wherein 4. An agricultural fungicide containing the O-acylformaldoxime pyridine according to claim 1 as an active ingredient.