JPH03275659A - Oxime ether derivative, its production and fungicide - Google Patents

Abstract

NEW MATERIAL:The oxime ether derivative of formula I [R is 1-6C alkyl when Q is phenyl having two substituents selected from 1-4C alkoxy, F and 1-4C haloalkyl, phenyl having 1-6C alkylsulfonyl at 3-site, phenyl having phenylthio group, (substituted) naphthyl or 3-6C cycloalkyl and R is 1-10C alkylthio when Q is 1-6C alkyl or (halogen-substituted) phenyl]. EXAMPLE:Methyl alpha-methoxymethylene-O-[1-(2,5-dimethoxy) ethaniminoxy]methylphenylacetate. USE:Useful as a fungicide. It is effective at a low concentration for the remedy and prevention of downy mildew of cucumber, rice blast, etc. PREPARATION:The compound of formula I can be produced by reacting a compound of formula II with a compound of formula III (X is eliminable group) under alkaline condition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to oxime ether derivatives, a method for producing the same, and a fungicide containing the same as an active ingredient.

[Conventional technology]

Among oxime ether derivatives, for example,
Publication No. 0-258166, JP-A-62-114971
It is known that compounds such as those shown in Japanese Patent Application Publication No. 62-283962, and (2) Cruzate (trade name; manufactured by DuPont) have bactericidal activity.

However, the compounds shown in ■ to ■ do not have a bactericidal effect sufficient to suppress the onset of disease, and furthermore, no bactericidal effect can be expected at low concentrations, and the cruzate shown in ■ does not allow plants to grow healthy without developing disease. Almost no preventive effect has been observed.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a novel oxime ether derivative, a method for producing the same, and a fungicide containing the same as an active ingredient.

[Means for solving problems]

As a result of intensive research to solve the above-mentioned problems, the present inventors found that a new oxime ether derivative has strong bactericidal activity even at low concentrations, and therefore has excellent preventive and therapeutic effects against plant pathogens. This discovery led to the completion of the present invention.

That is, the present invention (1) The following formula: (In the formula, Q is a C1-4 alkoxy group and a fluorine atom.

A phenyl group having two substituents selected from CI~4 haloalkyl groups, a phenyl group having CI~, an alkylsulfonyl group at the 3-position, a phenyl group having a phenylthio group, a naphthyl group which may have a substituent , 03-6 cycloalkyl group, R represents 01-6 alkyl group; when Q represents a CI-6 alkyl group or a phenyl group which may have a halogen atom, R represents 01-1° alkylthio represents a group. ) Compound (2) A compound represented by the following formula: (wherein, Q and R have the same meanings as above) and a compound represented by the following formula: (wherein, X represents a leaving group) (3) A method for producing the compound of formula (I), characterized by reacting the compound with a compound of formula (I) under alkaline conditions (3) A disinfectant containing the compound of formula (I) as an active ingredient.

The present invention will be explained in detail below.

In the novel oxime ether derivative (I) which is the target compound, and the compounds (n) and (III) which are the raw materials for its production, Q is a C1-4 alkoxy group, a fluorine atom, a C+
A phenyl group having two substituents selected from ~4 haloalkyl groups, C! A phenyl group having a ~6 alkylsulfonyl group at the 3-position, a phenyl group having a phenylthio group,
Examples include a naphthyl group and a Cs-6 cycloalkyl group which may have a substituent; R at this time is C
Mention may be made of 1 to 6 alkyl groups.

Further, examples of Q include a C+ to 6 alkyl group and a phenyl group which may have a halogen atom; examples of R in this case include a C and to 10 furkylthio group.

01-4 Alkoxy groups include linear or branched ones (eg, methoxy group, ethoxy group).

Propoxy group, butoxy group, etc.) are preferable, preferably those having 2 to 2 carbon atoms, and more preferably methoxy group.

Examples of the halogen atom include 1, for example, a chlorine atom, a fluorine atom, a bromine atom, an iodine atom, etc., and preferably a chlorine atom or a fluorine atom.

CI44 haloalkyl groups include linear or branched ones (e.g., chloromethyl group, fluoromethyl group, trifluoromethyl group, 1-chloroethyl group, 2-chloroethyl group, l-fluoroethyl group, 2-fluoroethyl group). (eg, trifluoromethyl group), but trifluoromethyl group is preferable.

01~. As the alkyl group of the C7-6 alkylsulfonyl group in the phenyl group having an alkylsulfonyl group at the 3-position, linear or branched ones of 01-B can be mentioned, but preferably C1- , more preferably C~2.

Examples of the C, -6 cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and preferably a cyclopropyl group.

01~. Examples of the alkyl group include linear or branched ones (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, 1 hexyl group, etc.), but preferably those with C1 to 3 More preferably, a methyl group is used.

CI~yo. As the alkylthio group, straight chain or branched ones can be mentioned, but those of 01 to 8 are preferable.

X is a leaving group, and is not particularly limited. sulfonyloxy, etc.), arylsulfonyloxy groups (henzensulfonyloxy, p-toluenesulfonyloxy, etc.),
A halogen atom is preferred, and a bromine atom is more preferred.

The raw material compound (n) used in the present invention can be obtained by adding a ketone and hydroxylamine hydrochloride to a suitable solution such as potassium acetate, for example, according to the method described in Shin Jikken Kagaku Koza, Vol. 14, I, p. 1301 (Maruzen). It can be easily produced by using a suitable solvent such as toluene, ethanol, methylene chloride, water, etc. in the presence of a base, and heating if necessary.

The raw material compound (III) used in the present invention can be prepared by converting methyl-2-methoxy-1-(2-methylphenyl)-acrylate into N-bromsuccinimide, for example, according to the method described in JP-A-61-280452. It can be easily produced by treating with a halogenating agent such as.

The target compound (I) can be produced by reacting the starting compound (n) and the starting compound (II[) in an organic solvent in the presence of a base.

Examples of organic solvents that can be used in the manufacturing method include aprotic solvents such as acetonitrile and dimethylformamide, ethereal solvents such as tetrahydrofuran, diethyl ether, and dioxane, and polar solvents such as acetone. Solvents can be mentioned, but
It is preferable to use an aprotic solvent such as acetonitrile, and examples of the base include potassium carbonate, sodium carbonate, sodium hydride, and it is preferable to use potassium carbonate.

The method for producing target compound (I) requires a reaction concentration of 001 to 40
It can be done in %.

In the production method, the raw material compounds (n) and (III) can be added at a ratio of 0.1 to 4 moles of the raw material compound (III) per 1 mole of the raw material compound (■). , preferably 0.5 to 1.5 mol.

The reaction temperature in the production method can be carried out at -10 to 130°C, but preferably 10 to 80°C.

The manufacturing method varies depending on the concentration and temperature mentioned above, but
It can usually be carried out in 0.5 to 8 hours.

The target compound (I) can be isolated by simply removing the solvent from the reaction mixture after the completion of the reaction to obtain the crude target compound (I) of the present invention, which is further subjected to recrystallization, chromatography, etc. A highly pure target compound (I) can be obtained by a conventional purification method.

The compound (I) of the present invention can be used for the prevention and treatment of plant diseases such as downy mildew of rat vegetables, late blight, grape downy mildew, blast, wheat rust, powdery mildew, scab, and brown spot. In particular, it has a remarkable bactericidal effect in the prevention and treatment of cucumber mildew, rice blast, barley powdery mildew, and wheat rust.

The disinfectant of the present invention contains one or more types of compound (I) as an effective acid.

Compound (I) can be used alone, but it is usually mixed with a carrier, a surfactant, a dispersant, or an auxiliary agent (e.g., powder, emulsion, fine granule, granule, water, etc.) by a conventional method. It is preferable to prepare a composition such as a Japanese powder, an oil-based suspension, or an aerosol.

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

Examples of surfactants and dispersants that can be used to improve properties such as adhesion to animals and plants, absorption, dispersion, emulsification, and spreading of drugs include alcohol sulfate esters, alkyl sulfonates, lignin sulfonate,
Examples include polyoxyethylene glycol ether.

In order to improve the properties of the preparation, carboxymethyl cellulose, polyethylene glycol, gum arabic, etc. can be used as adjuvants.

In the standard production, the carrier, surfactant, dispersant, and auxiliary agent described above may be used alone or in appropriate combinations depending on the purpose.

When the compound (I) of the present invention is formulated, the concentration of the active ingredient is usually 1 to 50% by weight in an emulsion, and usually 0.3% in a powder.
-25% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, usually 0.5 to 5% by weight for oils, and usually 0.1 to 5% by weight for aerosols. be.

These preparations can be diluted to an appropriate concentration and sprayed on plant foliage, soil, or the water surface of paddy fields, depending on the purpose.
Alternatively, it can be applied directly for various purposes.

〔Example〕

Hereinafter, the present invention will be illustrated by reference examples and examples.

Note that these Examples do not limit the scope of the present invention.

Reference Example 1 ■ [Synthesis of raw material compound (II)] (a12.5-Dimethoxyacetophenone oxime synthesis 2.5-dimethoxyacetophenone (1.8 g) and hydroxylamine hydrochloride (2.1 g) were mixed in toluene (30 g).
The mixture was dissolved in a mixture of mj and water (30 mA), sodium acetate (2 g) was added, and the mixture was heated and stirred for 1 hour.

The organic solvent layer was separated, and the aqueous layer was extracted with toluene, dried over anhydrous magnesium sulfate, and the solvent was removed to obtain 1.7 g of colorless crystals of 2.5-dimethoxyacetophenone oxime. Ta.

(b) Synthesis of α-methylthio-2-fluorobenzaldoxime 2-fluorobenzaldoxime (7 g) was dissolved in chloroform (250 mff), and chlorine gas was blown into the solution at 0° C. for 15 minutes.

Next, excess chlorine was decomposed with an aqueous IN sodium thiosulfate solution, washed with water, dried, and then concentrated.

The obtained residue was dissolved in THF (20 m/), and a 15% aqueous solution of methyl mercaptan sodium salt (25-) was added at room temperature.

After stirring this for 1 hour, it was extracted with ether, washed with water, dried, and purified by silica gel column chromatography to obtain a colorless oily product of α-methylthio-2-
6.8 g of fluorobenzaldoxime was obtained.

■ [Synthesis of raw material compound (III)] (a) Synthesis of α-(2-bromomethylphenyl)-β-methoxyacrylate Methyl-1-(2-methylphenyl)-2-methoxyacrylate (8.83g) N-bromsuccinimide (7.6 g) was dissolved in carbon tetrachloride (60 ml), benzoyl peroxide (0.3 g) was added, and the mixture was heated under reflux for 4 hours. This was cooled to room temperature, filtered and concentrated, n-
By crystallizing with hexane, 11.6 g of colorless crystal methyl α-(2-bromomethylphenyl)-β-methoxy acrylate was obtained.

Example 1 ■ [Methyl α-methoxymethylene-o-(1-(2,5
Synthesis of -dimethoxy)ethaniminooxycomethylphenylacetate (compound 1)] Methyl-2-C2-(bromomethyl)phenyl-3-methoxypropenoate (0.57 g, 2 mm, ol) and 2.5-dimethoxy Acetophenone oxime (0.43g12.2mm
”ol) in acetonitrile (15 mff),
Potassium carbonate (0.33 g, 2.4 mmol) was added to this and heated at 60° C. for 6 hours. The mixture was cooled to room temperature, water (50 mj) was added, and the organic solvent layer was extracted with ether. The organic solvent layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off. It was isolated by column chromatography (Wako Gel C-200, toluene:ethyl acetate-50:1) to obtain a colorless target compound (shown as Compound 1 in Table 1).

■Synthesis of methyl-3-methoxy 2-[methylthio(2-fluorophenyl)]methyliminooxymethylphenylacrylate (compound 6) α-methylthio-2-fluorobenz, the raw material compound (n) obtained in Reference Example 1 Aldoxime (0,56) g, potassium carbonate (0,4
The raw material compound (■) obtained according to the method shown in Reference Example 2 was added to a mixture of 1g) and acetonitrile (10m/).
3-methoxy-2-(2-bromomethylphenyl)acrylate (0.57 g) was added thereto, and the mixture was stirred at 50°C for 3 hours.

After cooling the mixture to room temperature, water (10 m/h) was poured into the mixture, and the mixture was extracted with ethyl acetate. This was then concentrated after drying.

The resulting residue was isolated by silica gel column chromatography to give a colorless oil of methyl-3-methoxy-2
-[Methylthio(2-fluorophenyl)]methyliminooxymethylphenylacrylate (shown as Compound 6 in Table 1) was obtained in an amount of 0.70 g.

■ [Synthesis of compounds 2-5.7-12 in Table 1] Starting compound (n ) and (II
I) to prepare the target compound (I) as shown in Table 1.
) (shown as compounds 2-5, 7-I2 in Table 1) could be obtained.

Table 1 Example 2 ■ [Preparation of finely powdered wettable powder] 10 parts by weight of Compound 1, 69.75 parts by weight of kaolin, 18 parts by weight of white carbon, Neoperex powder (
Product name: Kao Atlas) 1.8 parts by weight and Demol E
0.45 parts by weight of P (trade name; manufactured by Kao Atlas Co., Ltd.) was uniformly mixed and ground to obtain a finely powdered wettable powder.

■ [Preparation of emulsion] 50 parts by weight of Compound 2, 30 parts by weight of xylene, 10 parts by weight of Agelisil P-300 (product name; manufactured by Kao Atlas Co., Ltd.), 5 parts by weight of Emulgen A-90 (product name; manufactured by Kao Corporation) , Rheosol 460 (product name: Kao Atlas) 5
Parts by weight were mixed and dissolved to obtain an emulsion.

Example 3 ■ [Control efficacy test against cucumber and disease (preventive effect)
] One cucumber (variety: Sumo Hanshiro) per pot was grown in a plastic flower pot with a diameter of 6 cm, and the target compound (I) shown in Table 1 was applied to the seedlings at the 1st and 5th leaf stages. The hydrating agent prepared according to 2 was diluted to 50 ppm with water containing a surfactant (0.01%) and sprayed at 20 ppm per pot.

After spraying, cultivation was carried out in a glass greenhouse for 2 days, and then cucumbers and diseased bacteria (Pseudoperonospora cu
Z. bensis) zoosporangia were prepared from diseased leaves and uniformly spray-inoculated onto the underside of the leaves of the plants.

After inoculation, the cucumbers were kept in the dark at 20°C for 1 day, then grown in a glass greenhouse for 5 days, and the extent of cucumbers and lesions that appeared on the first leaves was examined.

The drug effect was determined by comparing the degree of lesions in the untreated plot.

Evaluation is given on a 6-point scale as shown in 5.4.3.2.10, with no lesions being 5, lesions less than 10% compared to the untreated area being 4, and 20% being 3.40. The percentage was 2.60% was expressed as 0 if all 11 patients were affected. In addition,
As a control compound, 4-(4-chlorobenzoyloxyimino)-1,3-dimethyl-2-pyrazolinone shown in the following formula (C) was used at 250 ppm. The results are shown in Table 2.

Table 2 ■ [Control efficacy test against rice blast disease (preventive effect)] Ten rice plants (variety: Nipponbare) were grown per pot in plastic flower pots with a diameter of 6 cm, and seedlings at the 1.5 leaf stage were grown. A wettable powder containing the target compound (I) shown in Table 1 prepared according to Example 2 was diluted to 200 ppm with water containing a surfactant (001%) and sprayed at 2 Od per pot.

After spraying, the rice blast fungus (Pyriculariao nigra) prepared from diseased leaves was cultivated in a glass greenhouse for 2 days.
ryZae) conidial suspension (7X10' spores/-)
was evenly sprayed and inoculated onto the leaves of the plants.

After inoculation, the plants were grown in a humid room at 28°C for 5 days, and the extent of rice blast lesions that appeared on the leaves was examined.

The drug effect was determined by comparing the degree of lesions in the untreated plot.

The results are shown in Table 3 using the same evaluation method as in ■. In addition, as a control compound, the compound (C) shown in ■ was added at 200%
1) Used at pm.

(The following is a blank space) Table 3 Preventive effect of compounds against rice blast ■ [Control efficacy test against barley powdery mildew (preventive effect)] Ten barley plants (variety: black wheat) per pot were placed in plastic flower pots with a diameter of 6 cm. A hydrating agent containing the objective compound (H) shown in Table 1 prepared according to Example 2 was added to a young plant at the 1.5 leaf stage after being grown in water containing a surfactant (0.01%). Dilute to 200ppm with 201rl per 1 pot.
It was sprayed one by one.

After spraying, the barley powdery mildew fungus (Erysiphe) was cultivated in a glass greenhouse for 2 days, and then infected with barley powdery mildew (Erysiphe) prepared from diseased leaves.
A conidial suspension (7 x 104 spores/ml) of S. graminis was uniformly inoculated onto the plant by spraying.

After inoculation, the plants were grown in a glass greenhouse for one week, and the extent of barley powdery mildew lesions that appeared on the first leaves was examined.

The drug effect was determined by comparing the degree of lesions in the untreated plot.

The results are shown in Table 4 using the same evaluation method as in ■. In addition, as a control compound, the compound (C) shown in ■ was added at 200%
It was used in ppm.

Table 4 ■ [Control efficacy test against wheat rust (preventive effect)
] 10 wheat plants (variety: Kovushi wheat) per pot were grown in plastic flower pots with a diameter of 6 cm, and the target compound (I) shown in Table 1 was added to the seedlings at the 15-leaf stage in Example 2.
A surfactant (0.01%) was added to the hydrating agent prepared according to
diluted to 200 ppm with water containing 2 (7
It was dispersed.

After spraying, the plants were cultivated in a glass greenhouse for 2 days, and then a spore suspension (7 x 10' spores/-) of wheat rust (Puccinia dispersa) was spray-inoculated uniformly onto the plants.

After inoculation, the plants were grown in a glass greenhouse for one week, and the extent of wheat rust lesions that appeared on the first leaves was examined.

The drug effect was determined by comparing the degree of lesions in the untreated plot.

The results are shown in Table 5 using the same evaluation method as in ■. In addition, as a control compound, the compound (C) shown in ■ was added at 200%
It was used in ppm.

(Hereinafter, blank spaces) C [Effects of the Invention] According to the present invention, it is possible to provide an oxime ether derivative having an excellent bactericidal effect.

Claims (3)

[Claims] (1) The following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, Q has two substituents selected from a C_1_ to_4 alkoxy group, a fluorine atom, and a C_1_ to_4 haloalkyl group) When representing a phenyl group, a phenyl group having a C_1_-_6 alkylsulfonyl group at the 3-position, a phenyl group having a phenylthio group, a naphthyl group which may have a substituent, a C_3_-_6 cycloalkyl group, R is C_1_-_6 Represents an alkyl group; Q is C_1_-_6
When representing an alkyl group or a phenyl group which may have a halogen atom, R represents a C_1_ to_1_0 alkylthio group. ). (2) The following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, Q and R have the same meanings as described in claim 1.) The compound represented by the following formula: ▲ Numerical formula, chemical formula, There are tables etc.▼(III) (In the formula, X represents a leaving group.) A compound of formula (I) according to claim 1, characterized in that it is reacted with a compound represented by the formula (I) under alkaline conditions. Manufacturing method. (3) A fungicide containing the compound of formula (I) according to claim 1 as an active ingredient.