JPS6222753A - Oxime ether derivative, production thereof and agricultural and horticultural fungicide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [X and Y are H, halogen, lower alkyl, lower alkenyl, methoxymethyl, etc.; R is H, lower alkoxyl (which may be substituted with halogen, cyano, etc.), lower alkenyloxy or lower alkynyloxy; excluding the case that two of X, Y and R are X at the same time; R' is H, lower alkyl (which may be substituted with halogen, phenyl, etc.), lower alkynyl, etc.]. EXAMPLE:3-Chloro-4,5-diethoxybenzaldehydroxime. USE:Agricultural and horticultural fungicide. Effective to powdery mildew of cucumber, cercospora leaf spot of beet, scab of pear, rice blast, etc. PREPARATION:The compound of formula I can be produced by reacting the benzaldehyde derivative of formula I with the hydroxylamine derivative of formula R'-ONH2 in a solvent such as methanol at a temperature between 0 deg.C and the boiling point of the solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula CI) [wherein X and Y are a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkenyl group, a lower haloalkyl group, a lower alkoxyl group, a methoxymethyl group, a nitro group, acyl group, methoxycarbonyl group or methoxycarbonylamino group.

R represents a hydrogen atom, a lower alkoxyl group, a lower alkenyloxy group, a lower alkynyloxy group, or a lower alkoxyl group substituted with any one of a halogen atom, a lower alkoxyl group, and a cyano group .

However, the case where two groups among x, y and R are hydrogen atoms at the same time is excluded.

R' represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a lower alkynyl group, or a lower alkyl group substituted with any one of a halogen atom, a cyano group and a phenyl group. The present invention relates to a method for producing the oxime ether derivative C (hereinafter referred to as the compound of the present invention) and to an agricultural and horticultural fungicide containing it as an active ingredient.

The oxime ether derivatives represented by the general formula CI) include benomyl [methyl 1-(butylcarbamoyl)benzimidazole-2-ylbamate], fuberidazole (2-(2-furyl)benzimidazole), thiabendazole (2-(4 -thiazolyl)benzimidazole], carpendazim[methyl benzimidazole-2
-ylbamate], thione mononate methyl [1,2
-bis(8-methoxycarbonyl-2-thioureido)
benzene], benzimidazole/thiono 1 nate fungicides such as thiophanate [1,2-bis(8-ethoxycarbonyl-2-thioureido)benzene], procymidone (N-(a',5?-dichlorophenyl)- 1,2-dimethylcyclopropane-1,2-dicarboximide], iprodione [8-CB1.5F-dichlorophenyl)-1-isopropylcarbamoylimidazolidine-2゜4-dione], vinclozolin (8-
CB'.

51-dichlorophenyl)-5-methyl-5-vinyloxazolidine-2,4-dione], ethyl (R5)-a
- Plant diseases resistant to cyclic imide fungicides such as (s',5'-dichlorophenyl)-5-methyl-2,4-cy#-1-sooxazolidine-5-carboxylate - Protozoan and other It is characterized by a selective and strong bactericidal effect against filamentous fungi (hereinafter referred to as drug-resistant bacteria).

The inventors of the present invention have conducted extensive studies on bactericidal agents that exhibit bactericidal effects against drug-resistant bacteria, and as a result, have discovered the compound of the present invention represented by the general formula (I).

Examples of drug-resistant bacteria for which the compound of the present invention exhibits a strong bactericidal effect include powdery mildew of apples (Podosphae spp.
ra 1eoucotricha χ Vent
uria 1naequalis), pear scab fungus (
1G) (Venturia nashicola), Scl-erotinia mali, Gloeosp-orium kakiχ
Sclerotinia cfnere
a), Cladosprium carpo
p-hilum')% Botrytis gray mold fungus (Bot
rytiscinerea Eisino
e ampelina χ late rot fungus (Glomerell)
a cingulata), sugar beet brown spot fungus (Ce
rcospora beticola), Peanut '7
Cercospora arachidi
cola), Cercospora per
sonata), barley powdery mildew (Erysi
phe graminis f, sp.

hordei), eye spot fungus (Cercosp)
or-ella herpotrichoides),
Fusarium n1vale, wheat powdery mildew (Erysiphe gramin)
is f, sp, tritici), cucumber powdery mildew (Sphaerotheca fuligi)
-nea), Mycosphaerel
la melonis).

Botrytis cinerea,
Cladosporium cucumer
inumχ Tomato leaf mold fungus (Cladospor
ium fulvum), gray mold fungus (Botryt
is cinerea), strawberry powdery mildew (Sp
haerotheca humul i), Botrytis cinerea, tobacco powdery mildew (Erysiphe cichor)
acearum), rose scab 11 (Diploc)
arpon rosae), tangerine scab fungus (El
sinoe fawcetii
cillium italicumχ green mold fungus (Pe
n-icilium digitatum).

As a result of further studies, it was found that the compound of the present invention is effective against the rice blast fungus (Pyricularia), regardless of the presence or absence of drug resistance.
It was found to be effective in controlling insects such as P. oryzae).

Examples of the compounds of the present invention are shown in Table 1.

Table 1 The compounds of the present invention can be produced, for example, by the method shown in the following reaction formula.

Y [wherein X, Y, R and f<, / represent the same meanings as above. ] ■ In general formula (I), when R/ is not a hydrogen atom [■] [v] [In the formula, X, Y and R represent the same meanings as above,
Q represents a leaving group, and all represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, or a lower alkyl group substituted with any one of a halogen atom, a cyano group, and a phenyl group. represent. ] Here, the leaving group refers to a halogen atom, a mesyloxy group, or a tosyloxy group.

That is, in the method shown in reaction formula (2), a compound represented by the general formula (n) and a compound represented by the general formula (2) are reacted in an organic solvent.

Polar solvents such as methanol and ethanol are used as the organic solvent. The reaction is usually carried out in a temperature range from θ°C to the boiling point of the solvent.

Furthermore, in the method shown in Reaction Formula (2), a compound represented by general formula CI') is obtained by reacting the compounds represented by general formula 1) and (V). The reaction is usually carried out in an organic solvent in the presence of an acid binder at temperatures between O and 40°C, preferably at 5C.
The temperature range is from room temperature to room temperature.

Inert solvents such as dimethylformamide, tetrahydrofuran, acetonitrile, chloroform, and toluene are used as organic solvents, and as acid binders, hydrogenation, thorium, triethylamide, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, etc. are used. Organic or inorganic bases such as potassium carbonate are used.

Next, a production example will be given to explain the production method of the present invention.

This will be explained in more detail. , ・ Production example 1 (according to method ■) C, H, O-c.

Add 1.89 F of hydroxyamine hydrochloride to an aqueous solution of 1.1 Of sodium hydroxide and 10 txl of water at 0°C.
added. To this was added a suspension prepared by dissolving 6.20 f of 3-chloro-4,5-jethoxybenzaldehyde in 80 WIl of ethanol. After stirring at room temperature overnight, ethanol was distilled off under reduced pressure. Ethyl acetate was added, the organic layer was washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off.
8-chloro-4,6-jethoxybenzaldehydeoxy A6.14F (yield 98.0%) was obtained. Leaf
1.5682 Production Example 2 (according to method ①) 2HIIO In 20 ml of tetrahydrofuran, 8-chloro-4,
5-Jethoxybenzaldehyde oxime 1,01lf
, 1.00 t of potassium hydroxide, and t, oor of monoium bromide in tetra-n-butyl acetate were added. While stirring at room temperature, 1 wl of ethyl iodide was added thereto. After stirring at room temperature overnight, it was poured into ice water and ethyl acetate was added. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. The solvent was distilled off to give an oily 8-chloro-4,5-jethoxy-
Benzaldehyde oxime 0-ethyl ether 0.99
f (yield 89.5%) was obtained.

n2901.5829 In addition, the structure of the compound is IR, NMR.

Determined from spectrum analysis results such as MASS. Also,
The compound of the present invention includes two types of tautomers shown below,
The compounds of the present invention include any isomers.

Examples of compounds produced based on such a production method are:
As shown in Table 2.

Table 2 When actually applying the compounds of the present invention obtained as described above, they can be used as they are without adding other ingredients, or they can be mixed with a carrier to make them easier to use as fungicides. , commonly used forms such as powders, wettable powders,
It is applied in 1ζ formulations such as oils, emulsions, tablets, granules, fine granules, aerosols, and flowables.

Examples of formulations are shown below. Note that parts represent parts by weight.

Formulation Example 1 Powder 2 parts of the compound of the present invention (9), 88 parts of clay, and 1 part of talc
0 parts were thoroughly ground and mixed to obtain a powder having a base ingredient content of 2%.

Formulation Example 2 Wettable powder 80 parts of the compound of the present invention (5), 45 parts of diatomaceous earth, 20 parts of white carbon, 8 parts of a wetting agent (sodium lauryl sulfate) and 2 parts of a dispersing agent (calcium lignin sulfonate) were thoroughly ground and mixed. A hydrating agent with a base ingredient content of 80% is obtained.

Formulation Example 8 Hydrating agent The compound of the present invention (6150 parts, 45 parts of diatomaceous earth, 2.5 parts of wetting agent (calcium alkylbenzene sulfonate) and 2.5 parts of dispersing agent (calcium lignin sulfonate) are thoroughly ground and mixed to form a main ingredient. A quantity of 50% hydrating agent is obtained.

Formulation Example 4 Emulsion A compound of the present invention (7110 parts), 80 parts of cyclohexanone, and 10 parts of an emulsifier (polyoxyethylene alkyl allyl ether) are mixed to obtain an emulsion having a base agent content of 10%.

In the above formulations, the active compound is generally contained in a heavy chain of 1.0 to
96.0%, preferably 2.0 to 80.0%, and the application rate is usually 10 to 100 V per 10 are. Further, the concentration used is preferably in the range of 0,005 to 0.51%, but the amount and concentration used vary depending on the dosage form, time of application, method, location, target disease, target crop, etc., so it is not limited to the above range. There is no problem in increasing or decreasing the amount without any problem.

Furthermore, it can be used in combination with other fungicides, herbicides, plant growth regulators and insecticides.

Next, a test sample will be given to further clarify the usefulness of the compound of the present invention as a fungicide for agriculture and horticulture. Note that the control compounds are indicated by the common names shown in Table 8. .

Table 8 Test Example 1 Cucumber powdery mildew control effect 901 plastic pots were filled with sandy loam, and cucumbers (variety: Wasumi Hanshiro) were sown. This seedling was cultivated at room temperature for 8 days to obtain cucumber seedlings with expanded cotyledons. A water-diluted solution of the test compound in the form of an emulsion or permanent cutting was sprayed on the grass leaves of the seedlings until the droplets were sufficiently attached to the leaf surface. After air-drying the chemical solution, seedlings are infected with chemical-resistant or sensitive cucumber powdery mildew (Sp.
haerotheca fuliginea) (7
) Spray inoculation with conidial suspension. The plants were cultivated at room temperature for 10 days to develop the disease, and then the disease state was observed.

The disease severity was calculated using the following method.

That is, depending on the appearance of lesions on the investigated leaves, 0°0.5.1
．． The disease was classified into an index of 2.4, and the disease severity was calculated using the following formula.

(Incidence index) (Infection state) O: No bacterial flora or lesions observed on the leaf surface.

0.5: Bacterial flora or lesions are observed on the leaf surface in less than 5% of the leaf area.

l: Bacterial flora or lesions are observed on the leaf surface in less than 20% of the leaf area.

2: Bacterial flora or lesions are observed on the leaf surface in less than 50% of the leaf area.

4...Bacterial flora or lesions are observed on 50% or more of the area of the upper leaf.

Next, the control value was calculated using the following formula.

As a result, as shown in Table 4, the compound of the present invention showed an excellent control effect against drug-resistant bacteria.
Commercially available fungicides such as benomyl, thiophanate methyl, or carpendazim and commercially available herbicides with similar chemical structures showed almost no control effect.

, Table 4 Test Example 2 Sugar beet brown spot control effect A 90 g/vol plastic pot was filled with sandy loam, and sugar beet (variety: Detroit Dark Red) was sown.

After 20 days of cultivation in a greenhouse, the seedlings were sprayed with a water-diluted solution of the test compound in the form of an emulsion or a wettable powder until the droplets sufficiently adhered to the leaf surface. After air-drying the chemical solution, seedlings were infected with drug-resistant or susceptible sugar beet brown spot fungus (Cercospor).
a beticola) (A conidial suspension D was inoculated by spraying. Covered with a vinyl cover) and cultivated in a greenhouse under humid conditions for 10 days, and then the disease state was observed.

The disease onset investigation method and control value calculation were performed in the same manner as in Test Example 1.

As shown in Table 6, similar to the results of Test Example 1, the compound of the present invention showed an excellent control effect against drug-resistant bacteria 6ζ. All agents showed almost no control effect.

Table 5 Test Example 8 Pear scab control effect A 90 ml plastic pot was filled with a mixed soil of peat moss and sandy loam, and seeds collected from pear fruit (variety: Chojube) were sown. This was cultivated in a greenhouse for 20 days, and a water-diluted solution of the test compound in the form of an emulsion or a wettable powder was sprayed on the foliage of the seedlings until the droplets sufficiently adhered to the leaf surface. After air-drying the chemical solution, young seedlings were infected with drug-resistant or susceptible pear scab fungus (V
entu-ria nashicola) (7) A conidial suspension was spray inoculated. The plants were placed under humid conditions at 20°C for 8 days, and then cultivated under fluorescent lighting at 20°C for 20 days to develop the disease.

The disease onset investigation method and control value calculation were the same as in Test Example 1.

As a result, as shown in Table 6, the compounds of the present invention showed an excellent control effect against drug-resistant bacteria, but the commercially available fungicides benomyl and thiophanate methyl did not show a control effect.

Table 6 Test Example 4 Binak brown spot control effect A plastic pot of 100 se/volume was filled with sandy loam soil and
The cultivar Nichiba semi-erect) was sown. After 140 hours of cultivation in a greenhouse, the resulting seedlings were sprayed with a water-diluted solution of the test compound in the form of an emulsion or wettable powder, 10 times per pot. After the chemical solution is air-dried, the seedlings are infected with chemically resistant or susceptible Cercospora arachidicola.
) was inoculated by spraying with a spore suspension. This was covered with a vinyl cover to maintain humid conditions, and after culturing in a greenhouse for 100 days38), the disease state was observed. The disease onset investigation method and control value calculation were performed in the same manner as in Test Example 1.

As a result, as shown in Table 7, the compound of the present invention showed an excellent control effect against drug-resistant bacteria, but the commercially available fungicides, benomyl and thiophanate methyl, did not show a control effect.Table 7 Test Example 5 Cucumber gray mold control effect A plastic pot weighing 90 g/volume was filled with sandy loam, and cucumbers (variety: Wasumi Hanshiro) were sown. Cultivate this in a greenhouse for 8 days,
A cucumber with expanded cotyledons was obtained. A water diluted solution of the test compound in the form of an emulsion or wettable powder was applied to the seedlings at 10% per pot.
W No. 1 and a half was sprayed on the stems and leaves. After air-drying the chemical solution, seedlings are infected with chemical-resistant or sensitive cucumber gray mold fungus (Botryt).
is, cinerea) was pasted on the leaf surface and inoculated. This was heated to 8°C under humid conditions at 20°C.
After feigning illness for several days, the disease state was observed. The disease onset investigation method and control value calculation were performed in the same manner as in Test Example 1.

As a result, as shown in Table 8, the compound of the present invention showed an excellent control effect against drug-resistant bacteria, but the commercially available fungicides benomyl and thiophanate methyl did not show a control effect.・ Table 8 Test Example 6 ・ Cucumber vine blight control effect A 90 ml plastic pot was filled with sandy loam soil, and cucumbers (variety:
Wasumi Hanpaku) was sown. This was cultivated in a greenhouse for 8 days to obtain cucumbers with expanded cotyledons. A water-diluted solution of the test compound in the form of an emulsion or a wettable powder was sprayed onto the seedlings at a rate of 10 liters per pot. After air-drying the chemical solution, the seedlings are infected with drug-resistant or sensitive cucumber vine blight fungi (Mycosphae).
rellamelonis) (7) A bacterial flora section (diameter 51131) was pasted onto the leaf surface and inoculated. This 2
After leaving the apparatus under humid conditions at 0°C for 8 days to induce disease, the state of disease onset was observed. The disease onset investigation method and control value calculation were performed in the same manner as in Test Example 1. As a result, as shown in Table 9, the compounds of the present invention showed a good control effect against drug-resistant bacteria, but the commercially available fungicides benomyl and thiophanate methyl did not show any control effect.

Table 9 Test Example 7 Effect on controlling tangerine blue mold After thoroughly washing tangerine fruit (variety: Unshu) with water and air-drying, immerse for 1 minute in a chemical solution made by diluting an emulsion of the compound of the present invention or a control commercially available drug with water to a predetermined concentration. did. After air-drying, drug-resistant or susceptible tangerine blue mold fungus (Pencil)
l-urn italicum) conidia were suspended in water and inoculated by spraying onto the fruit surface.

After being kept in a greenhouse for 14 days after inoculation, the degree of disease onset was investigated using the disease index of 0.1.2.8.4°6 as shown below.

(Disease condition) (Infection index) No lesions observed 0 Lesions observed on less than 20% of fruit surface area 1 = Lesions observed on less than 20-40% 2 = 40-60%
3 is 60-80
% 480% or more lesions were observed 5 The severity and control value were calculated in the same manner as in Test Example 1.

As a result, as shown in Table 1θ, the compounds of the present invention showed an excellent control effect against drug-resistant bacteria, whereas the commercially available fungicides benomyl and thiophanate methyl did not show a control effect.

Table l O Test Example 8 Test for phytotoxicity on crops 150 ml plastic pots were filled with sandy loam and wheat (variety: Norin No. 61) and apple (variety: Kogyoku)
and Beenuts (variety: Chiba semi-erect) were sown and cultivated in a greenhouse. A water-diluted solution of the test compound in the form of an emulsion or wettable powder was sprayed on the stems and leaves of the obtained seedlings. After spraying, the plants were placed in the greenhouse again, and after cultivation for 10 days, the presence or absence of phytotoxicity was investigated according to the following criteria.

Standards for degree of drug damage Grade C) (symptoms) -No abnormality.

10. Abnormalities due to chemical damage are observed in some of the crops.

Ox: Abnormalities caused by chemical damage are observed throughout the crop.

+1) The plant will wither and die due to chemical damage.

As a result, as is clear from Table 11, the compound of the present invention had no harmful effect on crops, and the commercially available herbicide with a chemical structure similar to that used as a control had a phytotoxic effect.

Table 11 (41 completed)

Claims (4)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X and Y are hydrogen atoms, halogen atoms, lower alkyl groups, lower alkenyl groups, lower haloalkyl groups, lower alkoxyl groups, methoxymethyl groups, nitro group, acyl group, methoxycarbonyl group or methoxycarbonylamino group. R represents a hydrogen atom, a lower alkoxyl group, a lower alkenyloxy group, or a lower alkynyloxy group, or a lower alkoxyl group substituted with any one of a halogen atom, a lower alkoxyl group, and a cyano group. However, the case where two groups among X, Y and R are hydrogen atoms at the same time is excluded. R' represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, or a lower alkyl group substituted with any one of a halogen atom, a cyano group, and a phenyl group. ] An oxime ether derivative represented by (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X and Y are hydrogen atoms, halogen atoms, lower alkyl groups, lower alkenyl groups, lower haloalkyl groups, lower alkoxyl groups, methoxymethyl groups, R represents a hydrogen atom, a lower alkoxyl group, a lower alkenyloxy group, or a lower alkynyloxy group, or a halogen atom, a lower alkoxyl group, or a cyano group. Represents a lower alkoxy group substituted with any one of these groups. However, this excludes the case where two groups among X, Y, and R are hydrogen atoms at the same time.] A benzaldehyde derivative represented by the following and the general formula R '-ONH_2 [In the formula, R' represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, or a lower alkynyl group, or a lower [In the formula, X, Y, R and R' are the same as above. ] A method for producing an oxime ether derivative. (3) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X and Y are hydrogen atoms, halogen atoms, lower alkyl groups, lower alkenyl groups, lower haloalkyl groups, lower alkoxyl groups, methoxymethyl groups, nitro group, acyl group, methoxycarbonyl group or methoxycarbonylamino group. R represents a hydrogen atom, a lower alkoxyl group, a lower alkenyloxy group, or a lower alkynyloxy group, or a lower alkoxyl group substituted with any one of a halogen atom, a lower alkoxyl group, and a cyano group. However, the case where two groups among X, Y and R are hydrogen atoms at the same time is excluded. ) and a benzaldehyde oxime derivative represented by the general formula R''-Q [wherein R'' represents a lower alkyl group, a lower alkenyl group, or a lower alkynyl group, or any one of a halogen atom, a cyano group, and a phenyl group. represents a lower alkyl group substituted with one group, and Q represents a leaving group. ] General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X, Y, R and R'' have the same meanings as above.] A method for producing oxime ether derivatives. (4) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X and Y are hydrogen atoms, halogen atoms, lower alkyl groups, lower alkenyl groups, lower haloalkyl groups, lower alkoxyl groups, methoxymethyl groups, nitro group, acyl group, methoxycarbonyl group or methoxycarbonylamino group. R represents a hydrogen atom, a lower alkoxyl group, a lower alkenyloxy group, or a lower alkynyloxy group, or a lower alkoxyl group substituted with any one of a halogen atom, a lower alkoxyl group, and a cyano group. However, the case where two groups among X, Y and R are hydrogen atoms at the same time is excluded. R' represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, or a lower alkyl group substituted with any one of a halogen atom, a cyano group, and a phenyl group. ] An agricultural and horticultural fungicide characterized by containing an oxime ether derivative as an active ingredient.