JPH11180954A - O-phenacyloxime derivatives and production of the same and bactericide for agriculture and horticulture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound having bactericidal activity for agriculture and horticulture. SOLUTION: This compound is expressed in formula I [R<1> is H or a halogen or an 1-4C alkyl and the like; m is 1-4; R<2> is H or an 1-4C alkyl and the like; R<3> and R<4> are each H or an 1-4C alkyl or a (substituted)phenyl; R<5> is H or a halogen or an 1-4C alkoxy and the like; n is 1-5C], for example, O-phenacyl 2-(6-methylpyridyl)aldehydeoxim. The compound of the formula I is obtained by reacting 1.0-1.5 mole times of the compound expressed by formula III (X is a releasable group) and a mole of the compound expressed by formula II, in a solvent (e.g.; benzene and toluene and tetrahydrofuran and the like), under the presence of a base (e.g.; triethylamine and the like), preferably, at 10-110 deg.C, for 0.5-5 hours. The preferable amount of the solvent used in the reaction is 10-70 wt.%. The amount of the base used in the reaction is 1.0-1.5 molar times based on the compound of the formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel O-phenacyl oxime derivative useful as a fungicide for agricultural and horticultural use.

[0002]

BACKGROUND OF THE INVENTION As a compound similar to the present invention,
9-3047 and JP-A-7-19617 describe a ketone oxime ether derivative, but do not disclose an O-phenacyl oxime derivative as in the present invention. Accordingly, the O of the present invention
-Phenacyl oxime derivatives are novel compounds and are not known to have fungicidal activity for agricultural and horticultural purposes.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel O-phenacyl oxime derivative, a process for producing the same, and a fungicide for agricultural and horticultural use containing the same as an active ingredient.

[0004]

Means for Solving the Problems The present inventors have conducted studies to solve the above problems, and as a result, have found that a novel O-phenacyl oxime derivative has a remarkable agricultural and horticultural fungicidal activity. The present invention has been completed. That is, the present invention is as follows. According to a first aspect, the following formula (1):

[0005]

Embedded image

Wherein R ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted; m represents an integer of 1 to 4; Is an integer of 2 to 4, R ¹ may be the same or different; R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms. Represents a phenyl group which may be substituted; R ³ and R ⁴ are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted; R ⁵ may be bonded to each other to form a saturated or unsaturated 3- to 6-membered ring; R ⁵ is a hydrogen atom, a halogen atom,
Alkyl group of 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, nitro group, cyano group, amino group which may be substituted,
Represents an optionally substituted phenyl group or an optionally substituted phenoxy group; n represents an integer of 1 to 5;
When R is an integer, R ⁵ may be the same or different. )
The present invention relates to an O-phenacyl oxime derivative represented by the formula: The second invention provides the following formula (2):

[0007]

Embedded image

(Wherein R ¹ , R ² and m are as defined above) and the following formula (3):

[0009]

Embedded image

Wherein R ^{3 to} R ⁵ and n have the same meanings as above; and X represents a leaving group. O indicated by
The present invention relates to a method for producing a phenacyl oxime derivative. The third invention relates to an agricultural and horticultural fungicide containing the O-phenacyl oxime derivative represented by the above formula (1) as an active ingredient.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The various substituents represented by the above compounds are as follows. [R ¹ ] R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an optionally substituted phenyl group. R ¹ may be the same or different when m (representing an integer from 1 to 4) is an integer from 2 to 4. And R ¹
Is not particularly limited; however, is preferably at position 4 or / and 6.

Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; a chlorine atom is preferred. The substitution position is not particularly limited, but is preferably at the 6-position. Alkyl groups can include straight or branched ones; preferably a methyl group. And the substitution position is not particularly limited, but is preferably at position 4 or / and 6. The substitution position of the phenyl group is not particularly limited, but is preferably the 6-position. [R ² ] R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group which may be substituted. As the alkyl group,
A straight or branched one may be mentioned; preferably, a methyl group. As the cycloalkyl group,
Preferred are those having 3 to 6 carbon atoms; more preferred is cyclopropyl group.

[R ³ and R ⁴ ] R ³ and R ⁴ may be the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Further, they may combine with each other to form a ring. Alkyl groups can include straight or branched ones; preferably a methyl group.
Examples of the ring formed by bonding R ³ and R ⁴ to each other include a saturated or unsaturated 3- to 6-membered ring; preferably a saturated 3- to 6-membered ring; Is a four-membered ring.

[R ⁵ ] R ⁵ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms.
Four alkoxy groups, nitro groups, cyano groups, optionally substituted amino groups, optionally substituted phenyl groups, and optionally substituted phenoxy groups. When n (representing an integer of 1 to 5) is an integer of 2 to 5, R ⁵ may be the same or different. And the substitution position of R ⁵ is not particularly limited; however, it is preferably at the 2,3,4 or / and 5-position.

Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; a chlorine atom, a bromine atom and a fluorine atom are preferred. And the substitution position is preferably the 3 or 4 position. Alkyl groups can include straight or branched ones; preferably a methyl group. And
The substitution position is preferably at the 4-position. Alkoxy groups can include straight or branched ones; preferably OCH ₃ . And the substitution position is preferably the 2, 4 or / and 5 position. The substitution position of the nitro group is preferably the 4-position. The substitution position of the cyano group is preferably the 4-position. The substitution position of the amino group is preferably the 4-position. The substitution position of the phenyl group is preferably the 4-position. The substitution position of the phenoxy group is preferably the 4-position.

[M] m represents an integer of 1 to 4, preferably 1 or 2. [N] n represents an integer of 1 to 5; preferably 1 or 2. [X] X represents a leaving group; although not particularly limited, a halogen atom (a chlorine atom, a bromine atom, an iodine atom, etc.) or an alkane sulfonyl group (a methane atom) which is a leaving group in a general aromatic nucleophilic substitution reaction. Sulfinyl basic, ethanesulfinyl group, etc.), arylsulfonyl group (benzenesulfonyl group, p-toluenesulfonyl group, etc.), arylsulfinyl group (benzenesulfinyl group, p-toluenesulfinyl group, etc.) and the like; A halogen atom; more preferably a chlorine atom or a bromine atom. As the compound (1), compounds obtained by combining the above-mentioned various substituents can be mentioned, and preferable compounds from the viewpoint of drug efficacy are as follows.

(1) (R ¹ ) _m is (alkyl group having 1 to 4 carbon atoms) ₁ , R ² is an alkyl group having 1 to 4 carbon atoms, and R ³ , R ⁴ and (R ⁵ ) _n is a hydrogen atom. (2) (R ¹ ) _m is (an alkyl group having 1 to 4 carbon atoms)
₁ , R ² is an alkyl group having 1 to 4 carbon atoms, R ³ and R ⁴ are hydrogen atoms, and (R ⁵ ) _n is (halogen atom) ₁ . (3) (R ¹ ) _m is (alkyl group having 1 to 4 carbon atoms)
₁ , R ² is an alkyl group having 1 to 4 carbon atoms, R ³ and R ⁴ are hydrogen atoms, and (R ⁵ ) _n is (alkoxy group having 1 to 4 carbon atoms) ₁ What is.

(4) (R¹)_mIs (with 1 to 4 carbon atoms
Alkyl group)₁And R^TwoHas 1 to 4 carbon atoms.
A alkyl group;^ThreeAnd R^FourIs a hydrogen atom, and (R
^Five)_nIs the same or different A 1 -C 4
Lucoxy group)_TwoWhat is. (5) (R¹)_mIs (alkyl group having 1 to 4 carbon atoms)
₁And R^TwoIs an alkyl group having 1 to 4 carbon atoms
R^ThreeAnd R^FourIs a hydrogen atom, and (R^Five)_nGa (charcoal
An alkyl group having 1 to 4 elementary atoms)₁What is. (6) (R¹)_mIs (alkyl group having 1 to 4 carbon atoms)
₁And R^TwoIs an alkyl group having 1 to 4 carbon atoms
R^ThreeIs a phenyl group, and R^FourAnd (R^Five) _nBut water
Those that are elementary atoms. (7) (R¹)_mIs (phenyl group) 1 and R^TwoIs carbon
An alkyl group having 1 to 4 atoms;^Three, R^Fouras well as
(R^Five)_nIs a hydrogen atom.

[Synthesis of Compound (1)] Compound (1)
Is a method of reacting compound (2) with compound (3) in a solvent in the presence of a base to obtain compound (1). The type of the solvent is not particularly limited as long as it does not directly participate in the reaction.For example, benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, chloroform, dichloroethane, Chlorinated or non-chlorinated aromatic, aliphatic and alicyclic hydrocarbons such as trichloroethylene; nitriles such as tetrahydrofuran, siloxane, acetonitrile, propionitrile and the like;
Aprotic polar solvents such as N, N-dimethylformamide, dimethylsulfoxide, N, N-dimethylimidazolidinone, N-methylpyrrolidone; and mixtures of the above solvents.

The amount of the solvent used is such that the compound (2)
Weight percent can be used; however, 10
~ 70% by weight is preferred. The type of base is not particularly limited, and organic and inorganic bases, for example, tertiary amines such as triethylamine, organic bases such as DBU, hydrides, hydroxides, carbonates of alkali metals and alkaline earth metals, Mention may be made of inorganic bases such as bicarbonates; inorganic bases are preferred. The amount of the base to be used is 1 to 5 moles per 1 mole of Compound (2);
Double molar is preferred.

The reaction temperature is not particularly limited, but is in the range from room temperature to the boiling point of the solvent used or less;
110 ° C. is preferred. The reaction time varies depending on the concentration and temperature in the previous period; it is usually 0.5 to 5 hours. The amount of the starting compound used is the compound (3) based on the compound (2).
Is 1.0 to 5 moles; preferably 1.0 to 1.5 moles. Compound (2) used in the present invention is disclosed in
It can be manufactured by the method described in JP-A-258223. Compound (3) can be produced by various known methods. Chem. Soc.
Jpn. , 60, 1159-1160 (1987). In addition, commercially available products can also be used. After completion of the reaction, the target compound (1) produced as described above is subjected to ordinary post-treatments such as extraction, concentration and filtration, and if necessary, by known means such as recrystallization and various types of chromatography. It can be refined appropriately.

[Control effect] The pathogens for agricultural and horticultural use which are effective in controlling the compound (1) of the present invention include, for example,
Wheat red rust fungus, barley powdery mildew, cucumber gray mold, cucumber downy mildew, rice blast fungus, tomato late blight fungus and the like.

(Pest control agent) The fungicide for agricultural and horticultural use of the present invention contains at least one compound (1) as an active ingredient. Compound (1) can be used alone, but usually, a carrier, a surfactant,
It is preferable to use a dispersant, an adjuvant, and the like compounded (for example, prepared as a composition such as a powder, emulsion, fine granule, granule, wettable powder, oily suspension, and aerosol).

Examples of the carrier include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea, etc .; hydrocarbons (kerosene, mineral oil, etc.), aromatic hydrocarbons Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), water, etc .; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection) out and the like.

Surfactants and dispersants that can be used to improve the performance of the agent, such as adhesion to animals and plants, absorption, and dispersion, emulsification, and spreading of drugs include alcohol sulfates and alkyls. Sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like can be mentioned. In order to improve the properties of the preparation, for example, carboxymethylcellulose, polyethylene glycol, gum arabic and the like can be used as an auxiliary agent. In the production of the present agent, the above-mentioned carrier, surfactant, dispersant, and auxiliary can be used alone or in appropriate combination according to the respective purposes. When the compound (1) of the present invention is formulated, the concentration of the active ingredient is usually 1 to 50% by weight for emulsions, usually 0.3 to 25% by weight for powders, and usually 1 to 90% for wettable powders.
% By weight, usually 0.5 to 5% by weight for granules, 0.5 to 5% by weight for oils and 0.1 to 5% by weight for aerosols. These preparations can be diluted to an appropriate concentration and applied to various uses by spraying them on plant foliage, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.

[0026]

The present invention will be specifically described below with reference to examples. Note that these do not limit the scope of the present invention. Example 1 [Synthesis method of compound (1)] (1) O-phenacyl 2- (6-methylpyridyl) aldehyde oxime (compound 2) 2- (6-methylpyridyl) aldehyde oxime (0.
Phenacyl bromide (0.73 g) and then sodium carbonate (0.40
g) was added and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, toluene (80 ml) and water (100 ml) were added to the reaction solution, and after liquid separation, the organic layer was dried over sodium sulfate.
It was concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 4: 1) to obtain 0.40 g of the target compound as a pale yellow crystalline solid (yield 43%). .

¹ H-NMR (CDCl ₃ , δ ppm) 2.57 (s, 3H), 5.45 (s, 2H), 7.5
0 to 7.70 (m, 2H), 8.00 (m, 2H),
8.33 (s, 1H)

(2) O-3'-bromophenacyl 2-
(6-Methylpyridyl) methylketone oxime (compound 5) N, N-dimethylformamide of 2- (6-methylpyridyl) methylketone oxime (0.30 g) and 3-bromophenacyl bromide (0.55 g)
Potassium carbonate (0.20 g) was added to the
Stirred at room temperature for minutes. After the reaction was completed, toluene (60 ml) and water (100 ml) were added to the reaction solution, and the mixture was separated. The organic layer was dried over sodium sulfate and concentrated under reduced pressure.
The obtained residue is subjected to silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 4:
1 elution) to give 0.25 g of the desired product (yield 36).
%).

(3) O-3'-bromophenacyl 2-
(6-Methylpyridyl) phenylketone oxime (compound 6) N, N-dimethylformamide of 2- (6-methylpyridyl) phenylketone oxime (0.30 g) and 3-bromophenacyl bromide (0.39 g)
Potassium carbonate (0.20 g) was added to the
Stirred at room temperature for minutes. After the reaction was completed, toluene (60 ml) and water (100 ml) were added to the reaction solution, and the mixture was separated. The organic layer was dried over sodium sulfate and concentrated under reduced pressure.
The obtained residue is subjected to silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 4:
1 elution) to obtain 0.55 g of the desired product (yield: 97).
%).

(4) O-4'-chlorophenacyl 2-
(6-Methylpyridyl) aldehyde oxime (compound 8) 2- (6-methylpyridyl) aldehyde oxime (0.
70 g) in a solution of N, N-dimethylformamide in 10 ml of 4-chlorophenacyl bromide (1.20 g),
Then potassium carbonate (0.80 g) was added, and for 30 minutes,
Stirred at room temperature. After the completion of the reaction, toluene (80
ml) and water (100 ml) were added, and after liquid separation, the organic layer was dried over sodium sulfate and concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 4: 1) to give 0.53 g of the desired product as a pale yellow solid (36% yield).

(5) Synthesis of other compound (1) in Tables 1 and 2 According to the method described in the above (1) to (4), other compounds (1) in Tables 1 and 2 were synthesized. did. The compounds (1) synthesized as described above and their physical properties are shown in Tables 1 and 2.

[0032]

[Table 1]

[0033]

[Table 2]

Example 2 [Preparation of preparation] (1) Preparation of granules 5 parts by weight of compound (1), 35 parts by weight of bentonite, 57 parts by weight of talc, Neorex powder (trade name; manufactured by Kao Corporation) 1 Parts by weight and 2 parts by weight of sodium ligninsulfonate were uniformly mixed, and then a small amount of water was added and kneaded, followed by granulation and drying to obtain granules.

(2) Preparation of wettable powder 10 parts by weight of compound (1), 70 parts by weight of kaolin, 18 parts by weight of white carbon, 1.5 parts by weight of Neolex powder (trade name, manufactured by Kao Corporation), and 0.5 part by weight of Demol (trade name; manufactured by Kao Corporation) is uniformly mixed,
Then, it was pulverized to obtain a wettable powder.

(3) Preparation of emulsion Compound (1) was added to 20 parts by weight of xylene and 70 parts by weight of xylene.
Toxanone (trade name; manufactured by Sanyo Chemical Industry Co., Ltd.) (10 parts by weight) was added, mixed uniformly, and dissolved to obtain an emulsion.

(4) Preparation of Dust A powder was obtained by uniformly mixing 5 parts by weight of the compound (1), 50 parts by weight of talc and 45 parts by weight of kaolin.

Example 3 [Efficacy test] (1) Control effect test against cucumber gray mold (preventive effect) Paper wetted with water was spread in a container (35 cm x 25 cm) and cucumber (cultivar: Sagami) Half-white) cotyledons, and then a spore suspension (10 ⁵
Spores / ml, 5% sucrose-1% yeast
xtract solution) was dropped on the cotyledon, and a paper disk (diameter: 7 mm) was superimposed on the cotyledon. Immediately, the target compound (1) shown in Tables 1 and 2
Acetone solution containing one of the above is added to a surfactant (0.0
(5%), and diluted with water to 40 ppm, and 90 μl was dropped from the top of the paper disk. Then, after keeping at 20 ° C in the dark for 4 days, the degree of cucumber gray mold spots appearing on cotyledons was examined.

The evaluation of the drug effect was evaluated in six stages (0: the whole diseased, 1: the lesion area was about 60%, and 2: the lesion area was about 40%, as compared with the degree of the lesion in the untreated plot. 3: The lesion area is about 20%, 4: The lesion area is 10% or less, 5: No lesion). Table 3 shows the results.

[0040]

[Table 3]

(2) Test for controlling efficacy against rice blast (preventive effect) Ten rice plants (variety: Nipponbare) were grown per pot in a plastic flowerpot having a diameter of 6 cm. One of the target compounds (1) shown in Tables 1 and 2
500ppm seed solution (containing 0.05% surfactant)
Was sprayed in an amount of 20 ml per pot. Cultivation was performed in a glass greenhouse until the inoculation after spraying the chemicals. On the day after the drug application, a rice blast fungal conidia spore suspension (3 × 10 ⁵ spores / ml) was prepared.
This was sprayed and inoculated uniformly on the plant body. 4 days after inoculation, 2
5 ° C, wet room (dark for the first 3 days, illuminated for the next 1 day)
And the degree of rice blast spots on the leaves was investigated. In the evaluation of the drug effect, the control effect was determined by a 6-point evaluation of 5 to 0 in the same manner as in the above (1), in comparison with the degree of the lesion in the untreated section. Table 4 shows the results.

[0042]

[Table 4]

[0043]

The novel O-phenacyl oxime derivative of the present invention has an excellent agricultural and horticultural bactericidal effect.

Claims (3)

[Claims] (1) The following formula (1): (Wherein, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted; m represents an integer of 1 to 4; When an integer of 4, R ¹ may be the same or different; R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, R ³ and R ⁴ are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may be substituted; R ⁵ may form a saturated or unsaturated 3- to 6-membered ring;
A hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro group,
Represents a cyano group, an optionally substituted amino group, an optionally substituted phenyl group, or an optionally substituted phenoxy group;
n represents an integer of 1 to 5; when n is an integer of 2 to 5, R ⁵ may be the same or different. O)
-Phenacyl oxime derivatives. 2. The following formula (2): (Wherein R ¹ , R ² and m have the same meanings as in claim 1) and a compound represented by the following formula (3): (Wherein, R ^{3 to} R ⁵ and n are as defined in claim 1;
X represents a leaving group. 2) reacting the compound represented by the formula (1) with the compound represented by the formula (1).
-Preparation of phenacyl oxime derivatives. 3. The method according to claim 1, wherein the compound represented by the formula (1)
A fungicide for agricultural and horticultural use containing a phenacyl oxime derivative as an active ingredient.