JPH0123472B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [] (In the formula, X represents a hydrogen atom or a halogen atom, Y represents a halogen atom, and m represents an integer of 0 to 2.) A 4H-3,1-benzoxazine derivative represented by The present invention relates to an agricultural and horticultural fungicide characterized by containing one or more of these 4H-3,1-benzoxazine derivatives. 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, in recent years, the emergence of resistant bacteria and environmental pollution due to mass spraying have become problems. In addition, in recent years, many inventions related to so-called azole compounds as agricultural and horticultural fungicides have been announced.
For example, JP-A-56-152446, JP-A-57-16870, JP-A-57-48982, JP-A-57-120579, JP-A-57-
There are 126479. However, these compounds often have plant growth-inhibiting and herbicidal effects, and have the drawback that they cannot necessarily be said to be safe to use. In order to compensate for these drawbacks, 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. In particular, it shows excellent efficacy against powdery mildew, rust, etc. of useful plants. The compound of the present invention represented by the general formula [] (However, in the formula, X represents a hydrogen atom or a halogen atom, Y represents a halogen atom, and m represents an integer of 0 to 2.) It can be produced by ring-closing the aminobenzhydrol derivative represented by I can do it. The aminobenzhydrol derivative represented by the general formula [] is known, for example, from JP-A-57-59867. The aminobenzhydrol derivative represented by the general formula [] is ring-closed by using a so-called halogenating agent, such as thionyl chloride, thionyl bromide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, etc., to form 4H- 3,1-benzoxazine derivative []
can be manufactured. In order to carry out this ring-closing reaction with good yield, it is more preferable to use a deoxidizing agent such as pyridine, triethylamine, dialkylamine, or the like. Furthermore, an appropriate solvent may be used to allow the reaction to proceed smoothly. All of the deoxidizing agents mentioned above are liquids, and it is natural that they can act as a solvent as well as acting as a solvent if used in excess. For example, benzene, toluene, chloroform, etc. can be used as a material that gives a . 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. Next, a manufacturing example will be shown and explained. In addition, the position indication (numbering) of the bone nucleus of the compound of the present invention [] is as follows. Production example 1 4-(4'-chlorophenyl)-2-(4-pyridyl)-4H-3,1-benzoxazine (compound number 4) 2-(4-chloro-α) was added to 200 ml of pyridine under ice cooling.
-hydroxybenzyl)-isonicotine anilide
11.3 g was added thereto, and further 4 g of thionyl chloride was gradually added and stirred for 1 hour. After the reaction was further stirred at room temperature, the reaction mixture was poured into water to precipitate crystals. The obtained crystals were separated, dissolved in ethyl acetate, washed with water, and the ethyl acetate solution was dried over anhydrous awn crystals. Separate the anhydrous awn crystals and distill off the acetic acid ethyl ester under reduced pressure.
Recrystallization from a mixed solvent of n-hexane gave 9.8 g (yield: 92%) of the desired product. Melting point 116-117℃. Elemental analysis value: C ₁₉ H ₁₃ ClN ₂ O molecular weight 320.77 C H N Calculated value (%) 71.14 4.08 8.73 Actual value (%) 71.19 4.01 8.70 Production example 2 4-(4'-chlorophenyl)-6-fluoro-2
-(4-pyridyl)-4H-3,1-benzoxazine (compound number 11) 2-(4-chloro-α-hydroxybenzyl)-
Using 11.9 g of 4-fluoro-isonicotine anilide, the same procedure as in Production Example 1 was carried out to obtain 10.2 g of the desired product (yield: 90
%) was obtained. Melting point 144-145℃. Elemental analysis value: C ₁₉ H ₁₂ ClFN ₂ O molecular weight 338.77 C H N Calculated value (%) 67.36 3.57 8.27 Actual value (%) 67.31 3.62 8.23 Production example 3 6-chloro-4-(4'-chlorophenyl)-2 −
(4-pyridyl)-4H-3,1-benzoxazine (compound number 8) 4-chloro-2-(4-
12.4 g of chloro-α-hydroxybenzyl)-isonicotine anilide and 5.0 ml of triethylamine were dissolved, and 9.1 g of phosphorus tribromide was gradually added under ice-cooling and stirring, followed by continued stirring for 1 hour. After further stirring for 3 hours at room temperature, the reaction mixture is poured into water.
The chloroform layer was thoroughly washed with water and then dried. After chloroform was completely distilled off under reduced pressure, the product was recrystallized from a mixed solvent of ethyl acetate and n-hexane to obtain 10.1 g (yield: 85%) of the desired product. Melting point 140~
141℃. Elemental analysis value: C ₁₉ H ₁₂ Cl ₂ N ₂ O molecular weight 352.23 C H N Calculated value (%) 64.24 3.41 7.89 Actual value (%) 64.29 3.38 7.91 Production example 4 6-bromo-4-phenyl-2-(4 -pyridyl)-4H-3,1-benzoxazine (compound number 3) 4-bromo-2-(α
-hydroxybenzyl)-isonicotine anilide
Using 12.8g, react with 6.0ml of diethylaniline instead of triethylamine to obtain the desired product.
10.3g (85% yield) was obtained. Melting point 161-162℃. Elemental analysis value: C ₁₉ H ₁₃ BrN ₂ O molecular weight 365.22 C H N Calculated value (%) 62.49 3.59 7.67 Actual value (%) 62.43 3.61 7.65 The compounds of the present invention thus obtained are shown in Table 1. 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] 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 is possible to use 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 amine salts,
Quaternary ammonium salts, alkylpyridinium salts, alkylaminoethylglycine, alkyldimethylbetaine, polyglycol sulfate, alkylamine sulfonic acid, isopropyl phosphate, carboxymethyl cellulose, polyvinyl alcohol, hydroxypropyl cellulose,
Examples include ethylene glycol and xanthan gum. It can also be used as an aerosol agent by mixing with a propellant such as fluorotrichloromethane or dichlorodifluoromethane, or as a fumigant or smoke agent by mixing with an appropriate blowing agent or combustion agent. 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
The amount is 0.5 to 1000 ppm, preferably 3 to 500 ppm, and the amount used (as the compound of the present invention) is generally 0.5 to 500 g per 10 are, preferably 1 to 1 to 500 g per 10 are.
It is 250g. 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 young seedlings, and 15% of the powder was added per pot.
ml was sprayed. After the chemical solution was air-dried, a conidial aqueous solution 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. The disease severity was calculated by the following method. That is, the lesions were classified into disease severity indexes of 0, 1, 2, 3, 4, and 5 as shown below, depending on the lesion area of the investigated leaves.

[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 ( disease severity index ) × ( number of investigated leaves ) / 5 × ( number of investigated leaves ) × 100 Control value ( % ) = ( disease severity in untreated area ) - ( disease severity in treated area ) / ( Disease severity in untreated plot) ×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 an aqueous solution of conidia.
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
Seedlings that had been cultivated for 12 days and had developed their first leaves were used as samples. 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 an aqueous solution of conidia.
After inoculation, the plants were cultivated 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] 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. 61), and cultivate it in a greenhouse for 12 days. Young seedlings with expanded leaves were tested. This young seedling is infected with wheat powdery mildew fungus (Erysiphe).
After inoculation by spraying with an aqueous solution of conidia of P. graminis and leaving it for 1 day at a temperature of 20 to 23°C, add a wettable powder of the compound of the present invention obtained by the method of Formulation Example 2 to a predetermined concentration with water. Dilute 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] 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 The above ingredients are mixed and pulverized to obtain a powder. Formulation Example 2 Wettable powder Compound No. 2 10 parts Sodium alkylsulfonate 5 parts Clay 85 parts The above ingredients are mixed and pulverized to obtain a wettable powder. Formulation Example 3 Emulsion Compound No. 4 5 parts Calcium alkylbenzenesulfonate 4 parts Polyoxyethylene alkyl phenyl ether
Mix 11 parts cyclohexanone 10 parts xylene 70 parts to obtain an emulsion. Formulation Example 4 Emulsion Compound No. 12 10 parts Calcium alkylbenzenesulfonate 3 parts Polyoxyethylene alkyl phenyl ether
12 parts dimethylformamide 10 parts xylene 65 parts Mix the above 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 agent Compound number 4 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 formulation.

Claims (1)

[Claims] 1. General formula (However, in the formula, X represents a hydrogen atom or a halogen atom, Y represents a halogen atom, and m represents an integer of 0 to 2.) 4H-3,1-benzoxazine derivative represented by: 2 General formula (However, in the formula, X represents a hydrogen atom or a halogen atom, Y represents a halogen atom, and m represents an integer of 0 to 2.) A general product characterized by ring-closing an aminobenzhydrol derivative represented by formula (However, in the formula, X represents a hydrogen atom or a halogen atom, Y represents a halogen atom, and m represents an integer of 0 to 2.) A method for producing a 4H-3,1-benzoxazine derivative represented by the formula: 3 General formula (However, in the formula, X represents a hydrogen atom or a halogen atom, Y represents a halogen atom, and m represents an integer of 0 to 2.) One or two of the 4H-3,1-benzoxazine derivatives represented by An agricultural and horticultural fungicide characterized by containing seeds or more.