JPH03284659A - Oxime ether derivative, production thereof and germicide - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R is phenyl which may have any substituent group of 1-6C alkyl, halogen, NO2, 1-4C alkoxy, substitutive phenoxy, methylenedioxy, CN, 1-4C haloalkyl and 1-6C alkylsufonyl]. EXAMPLE:Methyl alpha-methoxymethylene-O- phenylcyanomethaneiminoxymethylphenylacetate. USE:A germicide having powerful germicidal activity even at a low concentration with excellent preventive and treating effects on plant pathogenic germs. PREPARATION:A compound expressed by formula II is reacted with a compound expressed by formula III (X is leaving group) in the presence of a base in an organic solvent to afford the compound expressed by formula I.

Description

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

C. Prior art] 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, R is a CrA-s alkyl group or a halogen atom.

Nitro group, CI-4 alkoxy group, phenoxy group which may have a substituent, methylenedioxy group.

Cyano group, C+~4 haloalkyl group or C, ~.

Represents a phenyl group which may have any of the substituents of an alkylsulfonyl group. ) Compound (2) A compound represented by the following formula (wherein R has the same meaning as above) and a compound represented by the following formula (wherein, X represents a leaving group) in an alkaline solution. The present invention relates to a method for producing the compound of formula (1), characterized in that the reaction is carried out under conditions (3), and a bactericide 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 (1) 1 which is the target compound and the compounds (■) and (III) which are the raw materials for its production, R is a C1-6 alkyl group, a halogen atom (for example, a chlorine atom, fluorine atom, bromine atom, iodine atom, etc.), nitro group, CI~4 alkoxy group (e.g., methoxy group, ethoxy group, propoxy group, butoxy group, etc.),
Phenoxy group, methylenedioxy group, cyano group, C+~4 haloalkyl group (e.g., chloromethyl group, fluoromethyl group, trifluoromethyl group, l- or 2-chloroethyl group, l- or 2-chloroethyl group, which may have a substituent) -or 2-
A phenyl group which may have a substituent of either a fluoroethyl group, etc.) or a C]-6 alkylsulfonyl group can be mentioned.

As the substituent in the phenyl group which may have a substituent, in the case of a Clya alkyl group, linear or branched ones can be mentioned; preferably C-4 ones. is preferred; more preferably a methyl group.

Ethyl group, i-propyl group, l-butyl group, 1-butyl group, etc. are preferable.

In the case of a nitro group, the substitution position is preferably the 2.3 or 4 position.

In the case of a halogen atom, a chlorine atom, a bromine atom or an iodine atom is preferred; more preferably, the substitution position is the 2.3 or 4 position.

In the case of C, -, alkoxy groups, linear or branched ones can be mentioned; methoxy groups are preferred; more preferably, the substitution position is at the 2-position.

In the case of a C, ~, haloalkyl group, a trifluoromethyl group is preferred; more preferably, the substitution position is 4
It is better to be in the same position.

In the case of a cyano group, the substitution position is preferably the 3rd or 4th position.

The C~.alkyl group in the C1~@alkylsulfonyl group may be linear or branched; preferably C~, the latter being more preferred: methyl group.

Ethyl group is good.

X is a leaving group, and is not particularly limited. lomethanesulfonyloxy, etc.), arylsulfonyloxy groups (benzenesulfonyloxy, p-toluenesulfonyloxy, etc.);
Preferably a halogen atom; more preferably a bromine atom.

Compound (I) of the present invention is obtained as a mixture of geometric isomers and can be separated into individual isomers if necessary.

The raw material compound (II) used in the present invention is, for example, Org
anic Reaction Vol. 7, p. 327, J
ohn Wiley & 5ons, INC, (195
According to the method described in 9), the following formula; R-CH2C
A compound represented by N (wherein R has the same meaning as above) is added to methyl nitrite or isoamyl nitrite in the presence of a suitable acid such as hydrogen chloride or a suitable base such as sodium ethylate. It can be easily produced by treatment with an appropriate alkyl nitrite.

The raw material compound (■) used in the present invention is, for example,
Methyl-
2-Methoxy-1-(2-methylphenyl)-acrylate can be easily prepared by treating it with a halogenating agent such as N-bromsuccinimide.

The target compound (I) can be produced by reacting starting compound (II) and starting compound (III) 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. I can list many things, but
It is preferable to use an aprotic solvent such as acetonitrile, and examples of the base include potassium carbonate, sodium carbonate, sodium hydride, etc., and it is preferable to use potassium carbonate.

The method for producing the target compound (1) requires a reaction concentration of 01 to 40%.
It can be done with

In the production method, the raw material compounds (II) and (III)
The ratio of using is based on mole of raw material compound (■),
The raw material compound (III) can be added in a proportion of 0.1 to 4 moles, preferably 05 to 1.5 moles.

The reaction temperature in the production method can be carried out at -10 to 130°C, but preferably 0 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, late blight, grape downy mildew, blast, wheat rust, powdery mildew, scab, and brown spot of satsamum vegetables. 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 fungicide of the present invention contains one or more types of compound (I) as an active ingredient.

Although compound (I) can be used alone, it is usually added to a carrier or a surfactant by a conventional method.

It is preferable to use the composition by adding a dispersing agent or an adjuvant (for example, preparing a composition such as a powder, an emulsion, a single fine granule, a wettable powder, an oily suspension, or an aerosol).

Examples of carriers include talc and bentonite.

Clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate.

Solid carriers such as urea; hydrocarbons such as kerosene and mineral oil;
Aromatic hydrocarbons such as benzene, toluene, xylene,
Chlorinated hydrocarbons such as chloroform and carbon tetrachloride, ethers such as dioxane and tetrahydrofuran, ketones such as acetone and cyclohexanone isophorone, esters such as ethyl acetate, ethylene glycol acetate dibutyl maleate, methanol, and n-hexanol.

Examples include alcohols such as ethylene glycol, polar solvents such as dimethylformamide, dimethyl sulfoxide, or liquid carriers such as water; gaseous carriers such as air, nitrogen, carbon dioxide, and freon (in this case, they can be mixed and injected) Something happens.

Examples of surfactants and dispersants that can be used to improve the adhesion and absorption of this drug to animals and plants, as well as drug dispersion, emulsification, and spreading, include alcohol sulfate esters, alkyl sulfonate salts, etc. , 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 production of this agent, the carrier, surfactant 9, dispersant, and auxiliary agent 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 single granules, usually 0.5 to 5% by weight for oil solutions, 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)] p-methylphenylacetonitrile (4 g) and i-amyl nitride (10 m/) were mixed with ethanol (30 m/
), sodium ethoxide (2.2 g) was added thereto, and the mixture was stirred at room temperature for 8 hours.

Water (50i) was added to this, extracted with ether, dried over anhydrous magnesium sulfate, removed the solvent, and subjected to silica gel column chromatography (Wakogel C-200,
By purifying with toluene:ethyl acetate=5:1), 2.7 g of colorless crystal α-oximino-p-methylphenylacetonitrile was obtained.

■ [Synthesis of raw material compound (III)] Methyl-1-(2-methylphenyl)-2-methoxyacrylate (8.83 g) and N-bromsuccinimide (7.6 g) were dissolved in carbon tetrachloride (60 m/). The mixture was dissolved, benzoyl peroxide (0.3 g) was added, and the mixture was heated under reflux for 4 hours. This was cooled to room temperature, filtered, concentrated, and n-
By crystallizing from hexane, 11.6 g of methyl α-(2-bromomethylphenyl)-β-methoxy acrylate was obtained as colorless crystals (melting point: 85-87°C).
.

Example 1 ■Methyl α-methoxymethylene-〇-phenylcyanomethaniminooxymethylphenylacetate (Compound 2
) synthesis of methyl-2-C2-(bromomethyl)phenyl]-3-
Methoxypropenoate (0.57 g.

2mmoA) and α-oximino-acetonitrile (0,
33g, 2.06mmol) and acetonitrile (
15yd), and potassium carbonate (0.33g
, 2.4 mmon) and heated at 60° C. for 4 hours. This was cooled to room temperature, water (5011/) was added thereto, and the organic solvent layer was extracted with ether. The organic solvent layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off.

The resulting residue was subjected to silica gel column chromatography (
Wakogel C-200, toluene: ethyl acetate = 5:
1) to obtain 0.6 g of an amber target compound (shown as Compound 2 in Table 1).

■ [Synthesis of Compounds 1, 3 to 28 in Table 1] Starting compound (II) consisting of the substituents (Q and R) as shown in Table 1 obtained according to the synthesis method in Reference Examples and (III
I) to prepare the target compound (I) as shown in Table 1.
) (In Table 1, Compounds (In Table 1, Compounds 1, 3 to
It was shown as 28. ) was able to be obtained.

Example 2 ■ [Preparation of finely powdered wettable powder] 10 parts by weight of Compound 2, 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 1, 30 parts by weight of xylene, 10 parts by weight of Agelisil P-300 (trade name; manufactured by Kao Atlas Co., Ltd.), 5 parts by weight of Emulgen A-90 (trade name; manufactured by Kao Atlas Co., Ltd.), Rheosol 460 (product name; manufactured by 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 (1) shown in Table 1 was applied to the seedlings at the 1.5 leaf stage. The hydrating agent prepared according to 2 was diluted to 50 ppm with water containing a surfactant (001%) 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
bensiS) zoosporangia were prepared from diseased leaves and uniformly spray-inoculated onto the underside of the plant leaves.

After inoculation, the plants were kept in the dark at 20°C for 1 day and 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.

The evaluation is given on a 6-level scale of 5.4.3.2.1.0, with 5 being no lesions and 10% of the lesion area compared to the untreated area.
Below, approximately 4.20%, 3.40%, and 2.60% were indicated as 1, and those in which the entire population was affected were indicated as 0. The control compound includes 4-(4-chlorobenzoyloxyimino)-1,3-dimethyl-2- shown in the following formula (C).
Pyrazolin-5-one Hs was used at 250 ppm. The results are shown in Table 2.

(Hereinafter, blank space) 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 rice plants at the 1.5 leaf stage were grown. A hydrating agent prepared according to Example 2 containing the target compound (1) shown in Table 1 was applied to a young plant, diluted to 200 ppm with water containing a surfactant (001%) (however, the compound 25 was prepared (the 50% solution was diluted to 500 pprn before use) and sprayed at 20y#l 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 (7x 10m spores, /
ml') was evenly spray 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%
It was used in ppm.

(Hereinafter, blank spaces) Table 3 Table 6 [Control efficacy test (preventive effect) against barley powdery mildew] Ten barley plants (variety: black wheat) were grown per pot in plastic flower pots with a diameter of 6 cm, and 15 leaves were grown. A wettable powder prepared according to Example 2 containing the target compound (I) shown in Table 1 was applied to young plants at the stage of the treatment, diluted to 200 ppm with water containing a surfactant (0.01%). , sprayed 20 yards per pot.

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/m/m) 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 the barley powdery mildew lesions that appeared at No.-i 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 Table 5 Ten wheat plants (variety: Kobushi wheat) were grown per pot 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 1.5 leaf stage. A hydrating agent prepared according to Example 2 was mixed with a surfactant (0.01%
) diluted to 200ppm with water containing 20% per pot.
- sprayed.

After spraying, the plants were cultivated in a glass greenhouse for 2 days, and then a spore suspension (7XIO' spores/rnl) 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%
Used in pprn.

Grow one cucumber (variety: Sumo Hanshiro) per pot in a plastic flower pot with a diameter of 6 cm.
Spora cubensis) zoosporangia were prepared from diseased leaves and uniformly spray-inoculated onto the underside of the leaves of the plants.

After keeping it in the dark at 20°C for one day, a wettable powder prepared according to Example 2 for the target compound (I) shown in Table 1 was mixed with water containing a surfactant (0.01%). It was diluted to 500 ppm and sprayed at 2 o- per pot.

After spraying, the plants were cultivated 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.

The results are shown in Table 6 using the same evaluation method as in ■. In addition, as a control compound, compound (C) shown in (■) was added at 500%
It was used in ppm.

Table 6 [Effects of the Invention] According to the present invention, an oxime ether derivative having an excellent bactericidal effect can be provided.

Claims (3)

[Claims] (1) The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R is a C_1_ to_6 alkyl group, a halogen atom, a nitro group, a C_1_ to_4 alkoxy group, even if it has a substituent. Good phenoxy group, methylenedioxy group, cyano group, C_1_~_4 haloalkyl group or C_1_~
_6 Represents a phenyl group which may have any substituent of an alkylsulfonyl group. ). (2) There is a compound represented by the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (In the formula, R has the same meaning as described in claim 1) and the following formula ▲ Numerical formula, chemical formula, table, etc. A method for producing a compound of formula (I) according to claim 1, characterized in that the compound represented by ▼(III) (wherein X represents a leaving group) is reacted under alkaline conditions. (3) A fungicide containing the compound of formula (I) according to claim 1 as an active ingredient.