JPH0314827B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [] (However, in the formula, Y represents a halogen atom or a lower alkyl group, and n represents an integer of 0 to 2. When n is 2 in Yn, the two Y's may be the same or different from each other. R is Indicates a hydrogen atom, alkyloxy group, alkynyloxy group, alkylthio group, or alkenylthio group.However, when R is a hydrogen atom and Y is a halogen atom, and when R is a hydrogen atom and n is 0 4H-3,1-benzoxazine derivatives represented by
The present invention relates to a method for producing the same and an agricultural and horticultural fungicide containing the same. Many synthetic organic compounds and antibiotics with bactericidal properties have already been discovered, and many substances have been developed as fungicides for agriculture and horticulture. However, these compounds often have plant growth inhibitory and herbicidal effects, and have the drawback that they cannot necessarily be said to be safe to use. In order to compensate for these shortcomings, the present inventors have worked diligently to develop a drug that has a novel skeleton and is highly effective even in small amounts, and have completed the present invention. The compound of the present invention represented by the general formula does not show any adverse effects. The compound of the present invention represented by the general formula [] is widely applicable as an agricultural and horticultural fungicide for both prevention and treatment against various pathogenic bacteria belonging to the fungi, ascomycetes, basidiomycetes, and deuteromycetes. You can. Powdery mildew and rust of particularly useful plants;
It shows excellent efficacy against downy mildew, seedling damping off, etc. The method for producing the compound of the present invention represented by the general formula [] is as follows. Already known benzophenone derivatives (for example, described in JP-A-55-139306) [] (However, in the formula, Y and n have the same meanings as above) are mixed with a suitable halogenating agent, such as thionyl chloride, thionyl bromide, etc., without a solvent or in an inert solvent, such as methylene chloride, chloroform, benzene, toluene, etc. The desired compound is obtained by reacting the resulting reaction product with a corresponding alcohol (in this case, branched alcohols proceed particularly smoothly) and thiols. (However, in the formula, Y and n have the same meanings as above, and R represents an alkyloxy group, an alkynyloxy group, an alkylthio group, or an alkenylthio group.) For this reaction, a suitable deoxidizing agent such as triethylamine, pyridine, caustic soda, caustic potash,
By using sodium alkoxide etc.
The reaction proceeds more smoothly. The reaction temperature is 0~90℃, and the reaction time is 1~6
It's time. In addition, known methods (for example, JP-A-57-1999) for the benzophenone derivative represented by the general formula []
Benzhydrol derivatives that can be produced by the method described in Publication No. 59867 [] (However, in the formula, Y and n have the same meanings as above), an appropriate halogenating agent such as thionyl chloride, thionyl bromide, phosphorus trichloride, etc., and an appropriate inert solvent such as benzene, toluene, etc., if necessary. The desired compound can be easily obtained by ring-closing in chloroform, etc. (However, in the formula, Y and n have the same meanings as above, and R represents a hydrogen atom. However, cases where Y is a halogen atom and cases where n is 0 are excluded) are obtained. Although room temperature is sufficient without requiring any special operation, the reaction temperature is generally -5°C to 30°C, preferably 0°C to 20°C, and the reaction time is 3 to 5 hours. Next, a manufacturing example will be shown and explained. Production example 1 4-(4-chlorophenyl)-4-isopropyloxy-2-(4-pyridyl)-4H-3,1-
Benzoxazine (Compound No. 3) 11.2 g of 2-(4-chlorobenzoyl)-isonicotine anilide was added to 100 ml of thionyl chloride and refluxed for 4 hours. After the reaction is complete, thionyl chloride is distilled off under reduced pressure, and the resulting product is mixed with isopropyl alcohol.
After adding 100 ml, 15 ml of triethylamine was slowly added dropwise while stirring under ice cooling. After the dripping is finished,
After continuing stirring at room temperature for an additional 2 hours, water was added to the reaction product, and the mixture was extracted with ethyl acetate. The obtained ethyl acetate layer was dried with magnesium sulfate. After filtering out the magnesium sulfate,
Ethyl acetate was distilled off under reduced pressure, and the resulting product was recrystallized from a mixed solvent of ethyl sulfate and n-hexane to obtain 10.1 g (yield: 80%) of the desired product. Melting point 114-115℃. Elemental analysis value: C ₂₂ H ₁₉ ClN ₂ O ₂ molecular weight 378.85 C H N Calculated value (%) 69.75 5.05 7.39 Actual value (%) 69.71 5.08 7.42 Production example 2 4-(4-chlorophenyl)-4-ethylthio-
2-(4-pyridyl)-4H-3,1-benzoxazine (Compound No. 4) Produced in the same manner as in Production Example 1 except that a solution of 100 ml of tetrahydrofuran in which 10 ml of ethyl mercaptan was dissolved was used instead of isopropyl alcohol. The reaction was carried out to obtain 10.8 g (yield: 85%) of the target product.
Melting point 138-139°C Elemental analysis value: C ₂₁ H ₁₇ ClN ₂ OS Molecular weight 380.88 C H N Calculated value (%) 66.22 4.50 7.35 Actual value (%) 66.14 4.48 7.39 The compound of the present invention thus obtained was It is shown in Table 1. The positional representation (numbering) of the skeleton of the compound of the present invention [] is as follows. However, the compounds in Table 1 do not limit the compounds of the present invention. In addition, the compound numbers in the table are also applied to test examples and formulation examples.

【table】

[Table] Since the compound of the present invention thus obtained has systemic transferability to plants, any treatment method is possible, such as above-ground foliage treatment, seed treatment, water surface treatment, or soil treatment. . In addition, since the compounds of the present invention do not have any adverse effects on the target useful plants, the compounds of the present invention can be used at any stage of the useful plants, including before sowing, during the sowing period, during the seedling stage, during the growing season, and during the fruiting stage. It can be used in When actually using the compound of the present invention, it is possible to use it as it is without adding other ingredients, but in order to make it more convenient to use, various solid and liquid carriers that are used in the preparation of general agricultural chemicals can be used. It can be mixed with powders to produce wettable powders, emulsions, oils, powders, granules, flowables, etc. Furthermore, auxiliary agents such as dispersants, diluents, emulsifiers, spreading agents, wetting agents, adsorbents, thickeners, antifoaming agents, and antifreezing agents can be added to the drug. The carrier referred to herein may be either solid or liquid, or a combination thereof. Examples of these include talc, clay, bentonite,
Kaolin, diatomaceous earth, calcium carbonate, wood flour, starch, gum arabic, water, alcohol, kerosene,
Examples include naphtha, xylene, cyclohexanone, methylnaphthalene, benzene, acetone, dimethylformamide, glycol ether, and N-methylpyrrolidone. Examples of adjuvants include polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan monooleate, ethylene oxide propylene oxide copolymer, lignin sulfonate, sorbitan ester, soaps, sulfated oils, alkyl sulfate ester salts, Petroleum sulfonates, dioctyl sulfosuccinate salts, alkylbenzene sulfonates, aliphatic amide salts, quaternary ammonium salts, alkylpyridinium salts, alkylaminoethylglycine, alkyldimethylbetaine, polyglycol sulfate esters,
Examples include alkylamine sulfonic acid, isopropyl phosphate, carboxymethyl cellulose, polyvinyl alcohol, hydroxypropyl cellulose, ethylene glycol, xanthan gum, and the like. It can also be used as an aerosol agent by mixing it with a propellant such as fluorotrichloromethane or dicyclodifluoromethane, or with a suitable blowing agent,
It can also be used as a fumigant or smoke agent by mixing with combustion agents. In formulation, the mixing ratio is generally 0.05 to 95%, preferably 0.1% by weight of the compound of the present invention.
~80%, particularly preferably 1~70%, optimally 70~99% as a carrier and 0~20% as an adjuvant. Furthermore, by mixing with other fungicides, herbicides, plant growth regulators, insecticides, acaricides, and other pesticides, fertilizers, etc., a wider range of effects can be expected. When actually using the compound of the present invention, it is natural that the concentration should be selected appropriately depending on the time of use, weather conditions, method of use, dosage form, place of use, target disease, target crop, etc. In general
0.5-1000ppm, preferably 3-500ppm,
The amount used (as the compound of the present invention) is generally 0.5 to 500 g per 10 ares, preferably 1 to 250 g per 10 ares. Next, the usefulness of the compound of the present invention as a fungicide for agriculture and horticulture will be explained using test examples. Test Example 1 Powdery mildew control test on cucumber (preventive effect) A clay pot with a diameter of 15 cm was filled with granular soil for horticulture, and 10 seeds of cucumber (variety: Takasago) were sown. This was cultivated in a greenhouse for 10 days, and the young seedlings with expanded cotyledons were used as samples. The hydrating powder of the compound of the present invention obtained in Formulation Example 2 was diluted with water to a predetermined concentration on these seedlings, and 15% of the powder was added per pot.
ml was sprayed. After the chemical solution was air-dried, a conidial suspension of Sphaerotheca fuliginea was spray inoculated onto the shoots and leaves. After inoculation, 23-26℃
After cultivating for 10 days under greenhouse conditions, the disease state was investigated. After the onset of illness, it was calculated by the following method. That is, depending on the lesion area after investigation, the lesions were classified into disease severity indexes of 0, 1, 2, 3, 4, and 5 as shown below.

【table】

[Table] Based on the disease severity index thus obtained, the disease severity was calculated using the formula below, and the control value was further calculated from the comparison with the disease severity in the untreated area using the formula below. Disease severity (%) = Σ (Infection severity index) × (Number of leaves) / 5 × (Number of inspected leaves) ×
100 Control value (%) = (Incidence level in untreated area) - (Incidence level in treated area) / (Incidence level in untreated area) x 100 The results are shown in Table 2.

[Table] Test example 2 Powdery mildew control test on cucumber (therapeutic effect) A clay pot with a diameter of 15 cm was filled with horticultural soil, 10 seeds of cucumber (variety: Takasago) were sown, and the seeds were cultivated in a greenhouse for 10 days until the cotyledons grew. Fully expanded young seedlings were tested. This young seedling is infected with the powdery mildew fungus (Sphaerotheca).
fuliginea) was spray-inoculated with a conidial suspension of 23
After being left in a greenhouse at ~26°C for one day, the emulsion of the compound of the present invention obtained in Formulation Example 3 was diluted with water to a predetermined concentration and sprayed at 15 ml per pot. After air drying, 23-26
After cultivation for 10 days under greenhouse conditions at ℃, the disease state was investigated. The disease state index, disease severity, and control value are as in Test Example 1.
According to. The results are shown in Table 3.

[Table] Test Example 3 Wheat powdery mildew control test (preventive effect) A clay pot with a diameter of 12 cm was filled with Arakida soil, and 15 grains of wheat (variety: Norin No. 61) were sown. Do this in a greenhouse
The seedlings were grown for 12 days and the first leaf had developed. The emulsion of the compound of the present invention obtained by the method of Formulation Example 4 was diluted with water to a predetermined concentration on the seedlings, and 15 ml was added to each pot.
was sprayed. After air drying, wheat powdery mildew (Erysiphe
graminis) was inoculated by spraying with a conidial suspension.
After inoculation, the seeds were cultured for 10 days at a temperature of 20 to 24°C, and then the disease state was investigated. The disease severity index, disease severity, and control value are as in Test Example 1.
According to. The results are shown in Table 4.

【table】

[Table] Test example 4 Wheat powdery mildew control test (therapeutic effect) Fill a clay pot with a diameter of 12 cm with Arakida soil, sow 15 grains of wheat (variety: Norin No. 16), and cultivate it in a greenhouse for 12 days. Young seedlings with expanded leaves were tested. These seedlings are infected with wheat powdery mildew (Erysiphe).
graminis), and after inoculation, leave it for 1 day under greenhouse conditions at 20 to 23°C, and then add a hydrating powder of the compound of the present invention obtained by the method of Formulation Example 2 to a predetermined amount with water. Dilute to a specific concentration and spray 15ml per pot.
After air-drying, the plants were cultivated in a greenhouse at 20-24°C for 10 days, and then the disease state was investigated. The disease severity index, disease severity, and control value are as in Test Example 1.
According to. The results are shown in Table 5.

[Table] Test Example 5 Cucumber Powdery Mildew Control Test (Preventive Effect) A low dose test was conducted in the same manner as Test Example 1.
The results are shown in Table 6.

[Table] Test Example 6 Control effect (therapeutic effect) on cucumber powdery mildew A low dose test was conducted in the same manner as Test Example 2.
The results are shown in Table 7.

[Table] Test example 7. Effect on controlling downy mildew on cucumber (preventive effect) A clay pot with a diameter of 12 cm was filled with soil culture (manufactured by Kureha), and cucumber (variety: Ochiai Aocho Kusei) was sown.
Young cucumber seedlings that had been grown in a greenhouse for 10 days and had developed cotyledons were used. The emulsion of the compound of the present invention obtained by the method of Formulation Example 3 was diluted with water to a predetermined concentration and sprayed onto the seedlings so that the chemical solution was sufficiently attached to the leaf surface. After spraying the chemical solution,
The plants were cultivated in a greenhouse for 2 days and inoculated by spraying with a conidial suspension of Pseudoperonospora cubensis. The plants were placed under humid conditions at 21-22°C for 3 days, and then cultivated for 3 days under 21-22 fluorescent light illumination to develop the disease, and then the disease state was investigated. The disease severity was calculated by the following method. In other words, 0, 1, 2,
Expressed as an index of 3, 4, 5.

[Table] Using this index, the disease severity was calculated using the following formula. Disease severity (%) = Σ (sickness index) × (number of leaves) / number of investigated leaves × 5 × 100 Next, the control value was calculated using the following formula. Control value (%) = (Incidence level in untreated area) - (Incidence level in treated area) / Incidence level in untreated area x 100 The results are shown in Table 8.

[Table] Test Example 8 Effect on controlling Pythium aphanidernatum Pythium aphanidernatum Field soil was filled in a Norabawell pot, and disease source soil in which Pythium aphanidernatum was cultured was mixed and inoculated to a depth of 2 cm from the surface layer. Thereafter, the sample was kept in a superhumidified state for 24 hours in a greenhouse at 28°C, and then the wettable powder of the test drug obtained by the method of Formulation Example 2 was diluted with water, and a predetermined amount of the solution was sprinkled onto the soil. On top of that, add 1 seed of Kiyu (variety: Ochiai Aonaga Setsu).
Ten seeds were sown per pot and covered with soil. After cultivating for two weeks in a greenhouse, the disease state was examined and the percentage of healthy seedlings was calculated. Healthy seedling rate (%) = Number of healthy seedlings in each treated area/Number of germination in untreated and non-inoculated areas x 100 The results are shown in Table 9.

[Table] Examples of formulations are shown below. "Parts" in the examples are "parts by weight"
shows. Formulation Example 1 Powder Compound No. 8 2 parts Clay 98 parts or more are mixed and pulverized to obtain a powder. Formulation Example 2 Wettable powder Compound No. 14 10 parts Sodium alkylsulfonate 5 parts Clay 85 parts or more are mixed and pulverized to obtain a wettable powder. Formulation Example 3 Emulsion Compound No. 3 5 parts Calcium alkylbenzene sulfonate 4 parts Polyoxyethylene alkyl phenyl ether
11 parts cyclohexanone 10 parts xylene 70 parts or more are mixed to obtain an emulsion. Formulation Example 4 Emulsion Compound No. 5 10 parts Calcium alkylbenzenesulfonate 3 parts Polyoxyethyleakyl phenyl ether
12 parts dimethylformamide 10 parts xylene 65 parts or more are mixed to obtain an emulsion. Formulation Example 5 Granules Compound No. 1 2 parts Calcium ligninsulfonate 2 parts Bentonite 30 parts Talc 66 parts The above ingredients are mixed, water is added, kneaded, granulated and dried to obtain granules. Formulation Example 6 Flowable Compound No. 15 10 parts ethylene glycol 5 parts xanthan gum 0.2 parts polyoxyethylene sorbitan monooleate
5 parts water 79.8 parts Wet grind the above to obtain a flowable agent.

Claims (1)

[Claims] 1. General formula (In the formula, Y represents a halogen atom or a lower alkyl group, and n represents an integer of 0 to 2. In Yn, n
When is 2, the two Y's may be the same or different. R represents a hydrogen atom, an alkyloxy group, an alkynyloxy group, an alkylthio group, or an alkenylthio group. However, cases 8 in which R is a hydrogen atom and Y is a halogen atom, and cases in which R is a hydrogen atom and n is 0 are excluded. ) is expressed as
4H-3,1-benzoxazine derivative. 2 General formula (In the formula, Y represents a halogen atom or a lower alkyl group, and n represents an integer of 0 to 2. In Yn, n
When is 2, the two Y's may be the same or different. ) is reacted with a halogenating agent, and the resulting product is reacted with a corresponding alcohol or thiol. (In the formula, Y and n have the same meanings as above,
R is an alkyloxy group, an alkynyloxy group,
Indicates an alkylthio group or an alkenylthio group. )
A method for producing a 4H-3,1-benzoxazine derivative represented by 3 General formula (In the formula, Y represents a halogen atom or a lower alkyl group, and n represents an integer of 0 to 2. In Yn, n
When is 2, the two Y's may be the same or different. ) A general formula characterized by ring-closing a benzhydrol derivative represented by (In the formula, Y and n have the same meanings as above,
R represents a hydrogen atom. However, cases where R is a hydrogen atom and Y is a halogen atom, and cases where R is a hydrogen atom and n is 0 are excluded. ) is expressed as
Method for producing 4H-3,1-benzoxazine derivative. 4 General formula as an active ingredient (In the formula, Y represents a halogen atom or a lower alkyl group, and n represents an integer of 0 to 2. In Yn, n
When is 2, the two Y's may be the same or different. R represents a hydrogen atom, an alkyloxy group, an alkynyloxy group, an alkylthio group, or an alkenylthio group. However, R is a hydrogen atom and Y
Except when is a halogen atom, and when R is a hydrogen atom and n is 0. ) 4H expressed as
-1 or 2 of 3,1-benzoxazine derivatives
An agricultural and horticultural fungicide characterized by containing seeds or more.