JPH0445507B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a carbothioamide derivative represented by the following general formula and an agricultural and horticultural fungicide containing the compound as an active ingredient. (R ₁ and R ₂ are methyl, ethyl, or a combination of R ₁ and R ₂ to form an alkylene group having 4 to 5 carbon atoms or an oxyalkylene group having 4 carbon atoms (however, the oxygen atom of the oxyalkylene group) ), and R ₃ is benzyl or naphthyl which may be substituted with an alkyl, cycloalkyl, alkenyl or halogen atom having 1 to 8 carbon atoms; or

[Formula] (where X is a halogen atom such as chlorine, fluorine, bromine, alkyl having 1 to 6 carbon atoms, cycloalkyl, alkoxy, haloalkoxy, phenoxy,
A carbothioamide derivative represented by )) representing alkylthio, trifluoromethyl and haloalkyl. The compound of the present invention can be synthesized, for example, by the following method. Sodium sulfinate represented by the formula R ₃ --SO ₂ Na is dissolved in water, and a solution of N,N-dialkylthiocarbamoyl chloride dissolved in an aromatic hydrocarbon such as benzene or toluene is added dropwise at room temperature. After dropping, the reaction is carried out at a temperature from room temperature to the boiling point of the solvent. After the reaction, the organic layer is separated, washed with saturated brine, and dried over anhydrous calcium chloride. The solvent is distilled off under reduced pressure and the residue is subjected to silica gel column chromatography and eluted with benzene or recrystallized from an alcoholic solvent such as methanol or ethanol. Typical synthesis examples will be shown below and explained in more detail. Synthesis Example 1 p-Fluorobenzenesulfonyl N,N-dimethylcarbothioamide 34.3 g (0.157 M) of dihydrate of sodium p-fluorobenzenesulfinate was dissolved in 150 c.c. of water, and N,N- was dissolved with stirring at room temperature. A solution of 18.6 g (0.15 M) of dimethylthiocarbamoyl chloride in 150 c.c. of benzene is added dropwise over 10 to 15 minutes. After dropping, the solution was vigorously stirred while refluxing the solvent for 3 hours. After cooling to room temperature, the benzene layer was separated, washed twice with saturated brine, dried over anhydrous calcium chloride, and the solvent was distilled off under reduced pressure. The desired product (compound 20) is obtained by recrystallizing the residue from methanol. Yield 9.9g Synthesis Example 2 p-difluoromethoxybenzenesulfonyl N,N-dimethylcarbothioamide Dissolve 9.2g (0.04M) of sodium p-difluoromethoxybenzenesulfinate dihydrate in 70cc of water and stir at room temperature. Meanwhile, 70 c.c. of a benzene solution containing 5 g (0.04 M) of N,N-dimethylthiocarbamoyl chloride and 0.1 g of tetra-n-butylammonium bromide was added dropwise over 10 to 15 minutes. After dropping, stir vigorously at 50°C for 5 hours. After cooling to room temperature, the benzene layer was separated and washed twice with saturated saline.
Dry over anhydrous calcium chloride. The solvent is distilled off under reduced pressure and the residue is recrystallized from methanol to obtain the desired product (Compound 15). Yield: 3.6g Synthesis Example 3 p-Phenoxybenzenesulfonyl-N,N-
Tetramethylenecarbothioamide Dissolve 8.8g (0.03M) of sodium p-phenoxybenzenesulfinate dihydrate in 50cc of water and stir at room temperature to dissolve 4.5g (0.03M) of N,N-tetramethylenethiocarbamoyl chloride. 50 ml of a benzene solution containing 0.1 g of M) and tetra n-butylammonium bromide was added dropwise over 10 minutes. After dripping 3
Stir vigorously while refluxing the solvent for an hour.
After cooling to room temperature, the benzene layer was separated and diluted with saturated saline.
Wash twice, dry over anhydrous calcium chloride, and remove the solvent under reduced pressure. The desired product (compound 7) is obtained by recrystallizing the residue from methanol. Yield 3.0g Synthesis example 4 m-trifluoromethylbenzenesulfonyl
N,N-dimethylcarbothioamide Dissolve 16 g (0.06 M) of sodium m-trifluoromethylbenzenesulfinate dihydrate in 100 ml of water, and while stirring at room temperature, add 8 g (0.06 M) of N, N-dimethylcarbamoyl chloride to toluene.
Add 100ml solution dropwise. After dropping, the solution was vigorously stirred while refluxing the solvent for 3 hours. After cooling to room temperature, the toluene layer was separated, washed twice with saturated brine, and dried over anhydrous calcium chloride. The solvent was distilled off under reduced pressure and the residue was subjected to silica gel column chromatography and eluted with benzene (Compound 28) Yield: 4.8 g Synthesis Example 5 n-Butanesulfonyl N,N-dimethylcarbothioamide Dihydrate of sodium n-butanesulfinate
10.8 g (0.06 M) is dissolved in 100 c.c. of water, and while stirring at room temperature, a benzene solution (100 ml) containing 7.4 g (0.06 M) of N,N-dimethylcarbamoyl chloride is added dropwise. After dropping, the mixture was stirred at 30-40°C for 2 hours, and then vigorously stirred for 2 hours while refluxing the solvent. After cooling to room temperature, the benzene layer is separated, washed twice with saturated brine, and dried over anhydrous calcium chloride. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography and eluted with benzene:n-hexane (1:2) to obtain the desired product (compound 36). Yield: 4.8g Various compounds of the present invention represented by the above general formula are synthesized by similar methods, and representative compounds are shown in Table 1. However, in compounds (1) to (47), R ₁ and R ₂ are CH ₃ ,
CH ₃ ; In (48) to (54), R ₁ and R ₂ are −(C ₂ H ₄ )O
(C ₂ H ₄ ) −; In (55) to (68), R ₁ and R ₂ are −
( _CH2 ) _4- ; (69) to ( ₈₁ ) represent _{C2H5 and C2H5} .

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[Table] The compounds of the present invention are effective in controlling a wide range of diseases in agricultural and horticultural crops, and the main ones include the following. Paddy rice blast, sheath blight, sesame leaf blight; wheat
Spot disease, powdery mildew, yellow rust, sclerotium; Phytophthora late blight, summer blight, scab, black bruise; soybean
Downy mildew, leaf spot, brown spot, sclerotinia, rust; Tobacco red star blight, late blight; brown net blast, rice blast, anthracnose, ring spot; beet downy mildew, brown spot, seedlings Damping-off; Vegetables Tomato Phytophthora, gray mold, leaf mold, wilt, sclerotium, seedling damping-off, ring spot; cucumber downy mildew, gray blight, gray mold, sclerotinia, sclerotium , seedling damping off, anthracnose, vine blight, vine splitting disease,
Powdery mildew; radish downy mildew, yellow spot, black spot; onion downy mildew, gray rot, rust; lettuce downy mildew, sclerotium; fruit trees citrus gray mold, black spot, scab ; Apple monilia disease, black spot disease,
Leaf spot disease, powdery mildew; Persimmon gray mold, Enboshi leaf blight, anthracnose, horn spot leaf leaf disease; Pear red leaf blight,
Scotch blight, black spot; Peach gray blight, scabrous rot, Phuomopsis rot; grape downy mildew, black pox, gray mold, rust, powdery mildew, late rot; It is used as a fungicide for agriculture and horticulture, but it can also be used as it is or mixed with a carrier (diluent) as a powder, granule, wettable powder, emulsion, oil, or other suitable agent commonly used in agrochemical formulations. In this case, spreading agents, emulsifiers, wetting agents, fixing agents, etc. are used as necessary, and they can also be used in combination or mixed with other types of fungicides, insecticides, herbicides, fertilizers, etc. . Example 1 Powder Compounds listed in the table 3 parts Clay 40 parts Talc 57 parts Example 2 Wettable powder Compounds listed in the table 75 parts Polyoxyethylene alkyl allyl ether
9 parts White carbon 16 parts There is not necessarily a limit on the amount of spraying, but usually when spraying on fields where crops are grown, the active ingredient compound (AI) is 50 to 1000g/10a, and
When applied in soil, approximately 2 to 8 KgA.I/10a is appropriate. Of course, this is just a guideline, and it may be adjusted as necessary, taking into account factors such as the type of crop, the type and degree of damage, the season, the weather, and the dosage form of the drug. Hereinafter, typical test examples will be shown to specifically explain the effects of the compounds of the present invention. However, these are merely examples, and it goes without saying that the application examples of the present invention are not limited to these. Test example 1 Antibacterial activity test against plant pathogenic bacteria <Test method> Conidia of plant pathogenic bacteria cultured in a specified medium
Mix it evenly with the PSA medium and pour a certain amount into a designated container to create a uniform plate. After solidification, paper with a diameter of 8 mm that has absorbed a certain amount of a drug at a predetermined concentration and air-dried is placed on the plate, and the diameter of the inhibition circle produced after 48 hours of culture is measured. However, the number of stations shall be two.

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[Table] Test Example 2 Spore germination inhibition test against pear spot fungus <Test method> Alternaria cultured on apricot medium for 7 to 10 days
Mix the conidia of kikuchiana with the drug solution and microscopy.
Adjust so that there are approximately 20 pieces per 100x field of view.
Drop 0.02 ml of this mixed suspension onto a slide glass, keep it at 27°C and 100% humidity for 20 hours, and then examine it with a microscope to check for spore germination. Each test is repeated twice, and the presence or absence of germination of approximately 200 spores and the degree of germination are examined.

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[Table] Test Example 3 Pear black spot efficacy test <Test method> A chemical solution diluted to a predetermined concentration was sprayed onto the expanded leaves of pear (variety: Nijusseiki) at 20 ml per 5 leaves and air-dried indoors. After air drying, it was cultured on apricot medium.
Conidia of Alternaria kikuchiana were inoculated by spraying, and immediately left to stand for 3 days at 25°C and 100% humidity, and the diseased area was examined after 3 days. However, the number of runs shall be 5.

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[Table] Test example 4 Spore germination inhibition test against citrus black spot fungus <Test method> Diaporthe citri conidia cultured on dead citrus branches and a chemical solution were mixed and adjusted so that the number of conidia was about 20 per field of view under a microscope at 100x magnification. do. Place 0.02ml of this mixed suspension on a glass slide.
After dropping it and keeping it at 27℃ and 100% humidity for 20 hours, examine it with a microscope to check for spore germination. Each test is repeated twice, and the presence or absence of germination of approximately 200 spores and the degree of germination are examined.

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[Table] Test Example 5 Citrus Black Spot Fungal Efficacy Test <Test Method> At the time of development of new shoots of potted mandarin oranges (variety: Natsukan), a sufficient amount of a chemical solution diluted to a predetermined concentration was sprayed and then air-dried in a greenhouse. Cultured with mandarin orange branches
Immediately after spray inoculation with Diaporthe citri conidia, the cells were kept in the dark at a temperature of 23° C. and a humidity of 100% for 2 days. Two days later, the plants were left in a greenhouse, and the degree of disease onset was investigated 30 days after inoculation. However, the number of runs shall be three. Disease severity = Σnf/Σ4N f: Disease severity n: Number of leaves by disease severity N: Total number of leaves investigated

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[Table] Test Example 6 Rice Blast Efficacy Test <Test Method> Spray an amount equivalent to 200/10a of a chemical solution at a prescribed concentration at the 3-leaf stage of potted rice (variety: Jukoku).
Rice blast fungus (Pyricularia
oryzae) per field of view at 100x magnification.
A suspension adjusted to 40 seeds was spray inoculated. Immediately after inoculation, keep it under dark conditions at 23℃ and 100% humidity for 48 hours, then leave it in a greenhouse and inoculate.
After 10 days, the degree of disease onset was examined using the following criteria, and the degree of disease onset was calculated. However, the number of runs shall be three. Disease severity = Σnf / Σ4N × 100 n: Number of leaves by disease severity f: Index by disease severity N: Number of leaves examined

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[Table] Test Example 7 Rice sheath blight efficacy test <Test method> Cut the primary leaves of green beans (variety: Masterpiece), spray 20ml of a chemical solution diluted to a specified concentration on 10 primary leaves, and air dry indoors. did. After air-drying, a fungus of rice sheath blight (Rhizoctoria solari IA) previously cultured on a PDA medium was punched out on a cork board and inoculated. Immediately after inoculation, temperature 28
After keeping it in a constant temperature room at ℃ and 100% humidity for 4 days, the diseased area was investigated. However, the number of rows was 10, and 10 primary leaves were examined.

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[Table] Test Example 8 Bean Sclerotinia Efficacy Test <Test Method> Primary leaves of green beans (variety: Masterpiece) were cut, and 20 ml of a chemical solution diluted to a specified concentration was sprayed onto 10 primary leaves and air-dried indoors. Afterwards, fungi of legume sclerotiorum (Sclerotivia sclerotiorum), which had been cultured in PDA medium in advance, were punched out on a cork board and inoculated. Immediately after inoculation, temperature 28
After keeping it in a constant temperature room at ℃ and 100% humidity for 4 days, the diseased area was investigated. However, the number of rows was 10 and 10 primary leaves were examined.

[Table] Test Example 9 Radish Yellowing Disease Efficacy Test <Test Method> Radish Yellowing Disease Fungus (Fusarium oxysporum 5)
Soil artificially contaminated with chlamydospores of A. raphani is placed in clay pots with a diameter of 15 cm. Sow 10 pre-germinated radish seeds (variety: Aokubi Miyaju) per pot on the surface and cover with contaminated soil. Immediately, a chemical solution diluted to a predetermined concentration is uniformly applied to the surface, and then lightly sprinkled with water. The pots are then left in the greenhouse and watered accordingly. 60 days after treatment, the presence or absence of disease onset and its severity will be investigated according to the following criteria. Disease severity = number of wilted seedlings x 1 + number of duct browned seedlings x 0.5 / number of surveyed seedlings However, the number of rows was 5, and 50 seedlings were surveyed.

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[Table] Test Example 10 Tomato Phytophthora Efficacy Test <Test Method> An amount equivalent to 200/10a of a chemical solution diluted to a predetermined concentration was sprayed at the two-leaf stage of potted tomatoes (variety: Daiyo Fukuju). After air-drying, zoospores of Phytophthora infestars cultured in advance were inoculated by spraying, and immediately kept in a constant temperature room at 20° C. and 100% humidity for 7 days, and the degree of disease onset was examined using the following criteria. However, the number of rows was 20, and 40 leaves were investigated. Disease severity = Σnifi / Σ3N × 100 ni: Number of leaves by disease severity fi: Index by disease severity N: Number of investigated leaves Index by disease severity Disease area 0 0% 1 1~25 2 26~50 3 51~

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Claims (1)

[Claims] 1. General formula (However, R ₁ and R ₂ are methyl, ethyl, or R ₁ and R ₂
together represent an alkylene group having 4 to 5 carbon atoms or an oxyalkylene group having 4 carbon atoms (excluding cases where the oxygen atom of the oxyalkylene group is adjacent to a nitrogen atom), R ₃ is benzyl or naphthyl which may be substituted with an alkyl, cycloalkyl, alkenyl or halogen atom having 1 to 8 carbon atoms; 6 alkyl, cycloalkyl, alkoxy, haloalkoxy, phenoxy,
Represents alkylthio, trifluoromethyl and haloalkyl. )) Carbothioamide derivative. 2 General formula (However, R ₁ and R ₂ are methyl, ethyl, or R ₁ and R ₂
together with an alkylene group having 4 to 5 carbon atoms or an oxyalkylene group having 4 carbon atoms (however,
The case where the oxygen atom of the oxyalkylene group is adjacent to the nitrogen atom is excluded. ), R ₃ is benzyl or naphthyl which may be substituted with an alkyl, cycloalkyl, alkenyl or halogen atom having 1 to 8 carbon atoms or the formula [Formula] (where X is a halogen such as chlorine, fluorine or bromine); atom, alkyl having 1 to 6 carbon atoms, cycloalkyl, alkoxy, haloalkoxy, phenoxy,
Represents alkylthio, trifluoromethyl and haloalkyl. )) An agricultural and horticultural fungicide containing a carbothioamide derivative as an active ingredient.