JPH0588224B2 - - Google Patents

Description

[Detailed description of the invention]

This invention is based on the general formula

[Formula] (In the formula, R ¹ represents COOR ⁴ or OR ⁵ , R ⁴ represents a hydrogen atom, an alkyl group, or an aryl group,
R ⁵ represents a hydrogen atom or a lower alkanoyl group.
R ² and R ³ represent lower alkyl groups. X and Y are the same or different and represent an oxygen atom, a sulfur atom or =NR ⁶ , and R ⁶ represents a hydrogen atom or a lower alkyl group. However, X and Y are never oxygen atoms at the same time. ) and an agricultural and horticultural fungicide containing the same as an active ingredient. In the definition of the general formula () above, lower alkyl groups include methyl, ethyl, n-propyl,
Isopropyl, n-butyl, isobutyl, sec-
Examples include straight-chain or branched alkyl groups having 1 to 4 carbon atoms such as butyl or t-butyl, and examples of alkyl groups include the above-mentioned lower alkyl groups as well as carbon atoms such as octyl or dodecyl. Examples include linear or branched alkyl groups having 1 to 12 alkyl groups. Examples of lower alkanoyl groups include alkanoyl groups having 2 to 5 carbon atoms such as acetyl, propionine, butynyl, isobutyryl or valeryl. Examples of the aryl group include phenyl and 3-methoxyphenyl. Examples of the novel isoindoline derivatives of this invention include the following. 1 2-(2,6-diisopropylphenyl)-5
-Carboxy-3-thioxo-1-isoindolinone 2 2-(2,6-diisopropylphenyl)-6
-Carboxy-3-thioxo-1-isoindolinone 3 2-(2,6-diisopropylphenyl)-5
-methoxycarbonyl-3-thioxo-1-isoindolinone 4 2-(2,6-diisopropylphenyl)-6
-methoxycarbonyl-3-thioxo-1-isoindolinone 5 2-(2,6-diisopropylphenyl)-5
-carboxyisoindoline-1,3-dithione 6 2-(2,6-diisopropylphenyl)-5
-methoxy-carbonylisoindoline-1,
3-diotin 7 2-(2-ethyl-6-sec-butylphenyl)-5-hydroxy-3-thioxo-1-isoindolinone 8 2-(2-ethyl-6-sec-butylphenyl)-6-hydroxy- 3-thioxo-1-isoindolinone 9 2-(2-ethyl-6-sec-butylphenyl)-5-acetoxy-3-thioxo-1-isoindolinone 10 2-(2-ethyl-6-sec-butylphenyl) )-6-acetoxy-3-thioxo-1-isoindolinone 11 2-(2-ethyl-6-sec-butylphenyl)-5-acetoxyisoindoline-1,3
-dithion 12 2-(2,6-diisopropylphenyl)-5
-Carboxy-3-imino-1-isoindolinone 13 2-(2,6-diisopropylphenyl)-6
-Carboxy-3-imino-1-isoindolinone 14 2-(2,6-diisopropylphenyl)-5
-methoxycarbonyl-3-imino-1-isoindolinone 15 2-(2,6-diisopropylphenyl)-6
-methoxycarbonyl-3-imino-1-isoindolinone 16 2-(2,6-diisopropylphenyl)-5
-methoxycarbonyl-3-methylimino-1
-isoindolinone 17 2-(2,6-diisopropylphenyl)-6
-methoxycarbonyl-3-methylimino-1
-isoindolinone 18 2-(2-ethyl-6-sec-butylphenyl)-5-hydroxy-3-imino-1-isoindolinone 19 2-(2-ethyl-6-sec-butylphenyl)-6-hydroxy -3-imino-1-isoindolinone 20 2-(2-ethyl-6-sec-butylphenyl)-5-hydroxy-3-methylimino-1
-isoindolinone 21 2-(2-ethyl-6-sec-butylphenyl)-6-hydroxy-3-methylimino-1
-isoindolinone 22 2-(2,6-diisopropylphenyl)-5
-Butoxycarbonyl-3-thioxo-1-isoindolinone23 2-(2,6-diisopropylphenyl)-6
-Butoxycarbonyl-3-thioxo-1-isoindolinone24 2-(2,6-diisopropylphenyl)-5
-butoxycarbonylisoindoline-1,3
-dithion25 2-(2,6-diisopropylphenyl)-5
-butoxycarbonyl-3-methylimino-1
-isoindolinone 26 2-(2,6-diisopropylphenyl)-6
-butoxycarbonyl-3-methylimino-1
-isoindolinone 27 2-(2,6-diisopropylphenyl)-5
-dodecyloxycarbonyl-3-thioxo-
1-isoindolinone 28 2-(2,6-diisopropylphenyl)-6
-dodecyloxycarbonyl-3-thioxo-
1-isoindolinone 29 2-(2,6-diisopropylphenyl)-5
-dodecyloxycarbonyl-3-imino-1
-isoindolinone 30 2-(2,6-diisopropylphenyl)-6
-dodecyloxycarbonyl-3-imino-1
-isoindolinone 31 2-(2,6-diisopropylphenyl)-5
-(3-methoxyphenoxycarbonyl)-3-
Thioxo-1-isoindolinone 32 2-(2,6-diisopropylphenyl)-6
-(3-methoxyphenoxycarbonyl)-3-
Thioxo-1-isoindolinone33 2-(2,6-diisopropylphenyl)-5
-(3-methoxyphenoxycarbonyl)-isoindolinone-1,3-dithione34 2-(2,6-diisopropylphenyl)-5
-(3-methoxyphenoxycarbonyl)-3-
Methylimino-1-isoindolinone 35 2-(2,6-diisopropylphenyl)-6
-(3-methoxyphenoxycarbonyl)-3-
Methylimino-1-isoindolinone The novel compound () according to the present invention can be produced by the method shown below.

[Chemical formula] (In the formula, R ⁶ represents COOR ⁷ or OR ⁸ , R ⁷ represents a lower alkyl group, and R ⁸ represents a lower alkanoyl group. R ⁹ represents COOH or OH. R ² ,
R ³ and R ⁴ have the same meanings as above. ) Step 1 is an isoindoline represented by formulas 1 to 1.
1,3-Diones and LAWESSON
This is a step in which a reagent or phosphorus pentasulfide is reacted in an appropriate solvent. The solvent is not particularly limited as long as it does not participate in the reaction, but examples include aromatic hydrocarbons such as benzene, toluene, and xylene, and ethers such as dioxane and tetrahydrofuran. The reaction is usually carried out under heating, at 40 to 150°C for 30 minutes to 20 minutes.
It takes time. In particular, when the reaction is difficult to proceed, the reaction time can be shortened by adding a catalytic amount of dimethylformamide. Step 2 is a step of hydrolyzing compound Ia or Ia', and is carried out by heating in a suitable solvent in the presence of hydrohalic acid, preferably concentrated hydrobromic acid. Suitable solvents include, for example, dimethylimidazolone, acetic acid/water, dioxane, and the like. Steps 3 and 4 are steps in which Ia or Ia'' obtained in Step 1 or Step 2 is reacted with amines in an appropriate solvent to lead to Ia.As long as the solvent does not participate in the reaction, any solvent may be used. Although not particularly limited, halogenated hydrocarbons such as methylene chloride or alcohols such as methanol and ethanol are preferred.The reaction usually proceeds at room temperature or under heating and takes from 1 hour to 5 days. , in the above step 1, when only one of the two carbonyl groups is thiocarbonylated, the substitution position of the group R ⁶ varies depending on which one is thiocarbonylated. The compound of formula () of the invention, as an agricultural and horticultural fungicide, exhibits a therapeutic and protective effect against plant diseases by soil application or foliar spraying.In particular, it exhibits therapeutic and protective effects against plant diseases occurring in Brassicaceae plants and The compound of the present invention is highly effective against clubroot disease, which has been difficult to control.The compound of the present invention is also effective against strangle blight, which is an important disease in rice cultivation, and is effective against beet, cotton, and cucumber caused by Rhizoctonia fungi. It is also effective against seedling blight of various crops such as.The compound of the present invention can be mixed with a carrier and other adjuvants as necessary to form a formulation commonly used as an agricultural and horticultural fungicide, such as: It is prepared and used in powders, coarse powders, fine granules, granules, wettable powders, emulsions, suspensions, aqueous solutions, etc.The carrier here refers to
Synthetic or natural inorganic or organic substances that are mixed into agricultural and horticultural fungicides to aid in the access of the active ingredient to the area to be treated and to facilitate storage, transport or handling of the active ingredient. means. Suitable solid carriers include clays such as kaolinite group, montmorillonite group, or attapulgite group, talc, mica, phyllite, pumice, vermiyquilite, gypsum, calcium carbonate, dolomite, diatomaceous earth, and magnesium. Inorganic substances such as lime, phosphoric lime, zeolite, anhydrous silicic acid, synthetic calcium silicate, vegetable organic substances such as soybean powder, tobacco powder, walnut powder, wheat flour, wood flour, starch, crystalline cellulose, coumaron resin,
Examples include synthetic or natural polymeric compounds such as petroleum resins, alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, ester gums, cobal gums, and dammar gums, waxes such as carnauba wax and beeswax, and urea. Suitable liquid carriers include paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalene, carbon tetrachloride, chloroform, etc. , chlorinated hydrocarbons such as trichloroethylene, monochlorobenzene, 0-chlorotoluene, ethers such as dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone, ethyl acetate, amyl acetate, Esters such as ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate, alcohols such as methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, benzyl alcohol, ethylene glycol ethyl ether, ethylene glycol phenyl ether , ether alcohols such as diethylene glycol ethyl ether and diethylene glycol butyl ether, dimethylformamide,
Examples include polar solvents such as dimethyl sulfoxide, water, and the like. Emulsification, dispersion, wetting, spreading, binding, disintegration control,
Surfactants used for the purpose of stabilizing active ingredients, improving fluidity, and preventing rust can be nonionic, anionic, cationic, or amphoteric, but usually used are nonionic and/or anionic. Suitable nonionic surfactants include, for example, those obtained by polymerizing and adding ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol, and oleyl alcohol, and those obtained by polymerizing and adding ethylene oxide to alkyl phenols such as isooctylphenol and nonylphenol. products obtained by polymerizing and adding ethylene oxide to alkylnaphthols such as butylnaphthrel and octylnaphtholle, products obtained by polymerizing and adding ethylene oxide to higher fatty acids such as palmitic acid, stearic acid, and oleic acid, stearyl phosphoric acid, and dilauryl phosphoric acid. Products obtained by polymerizing and adding ethylene oxide to moles of acids or dialkyl phosphoric acids, products obtained by polymerizing and adding ethylene oxide to amines such as dodecylamine and stearic acid amide, higher aliphatic esters of polyhydric alcohols such as sorbitan, and those obtained by adding ethylene oxide to them. Examples include those obtained by polymerization and addition, and those obtained by polymerization and addition of ethylene oxide and propylene oxide. Suitable anionic surfactants include, for example, sodium lauryl sulfate, alkyl sulfate salts such as oleyl alcohol sulfate amine salts, alkyl sulfonates such as sodium sulfosuccinate dioctyl ester, and sodium 2-ethylhexene sulfonate. , aryl sulfonates such as sodium isopropylnaphthalene sulfonate, sodium methylene bisnaphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylbenzenesulfonate. Furthermore, the agricultural and horticultural fungicide of the present invention contains high-containing ingredients such as casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, and polyvinyl alcohol, in order to improve the properties of the preparation and increase its biological effects. molecular compounds and other adjuvants,
For example, activated carbon, cyclodextrin, solid paraffin, higher fatty acids such as stearic acid, etc. can also be used in combination. The above-mentioned carriers and various auxiliary agents are used in the dosage form of the preparation,
They are used alone or in combination as appropriate depending on the purpose, taking into consideration the application situation. Powders usually contain, for example, 0.1 to 25 parts by weight of the active ingredient compound, with the remainder being a solid carrier. Wettable powders usually contain, for example, 5 to 90 parts by weight of the active ingredient compound, with the remainder being a solid carrier and a dispersing wetting agent, with protective colloid agents, thixotropic agents, antifoaming agents, etc. being added as necessary. Powders, for example, usually contain 0.1 to 35 parts by weight of the active ingredient compound, with the remainder being mostly solid carrier. The active ingredient compound is homogeneously mixed with the solid carrier, or is uniformly fixed or adsorbed on the surface of the solid carrier, and the particle size is approximately 0.05 mm.
It is about 1.7mm. Emulsions, for example, usually contain 5 to 5 active ingredients.
This includes approximately 5 to 20 parts by weight of an emulsifier, the remainder being a liquid carrier, and other auxiliary agents may be added as necessary. The agricultural and horticultural fungicides of the present invention prepared in various dosage forms in this way are sprayed on the leaves and leaves of crops, or applied to the soil or water surface, for example, before or after disease outbreaks in crops in fields or paddy fields. In such cases, diseases can be effectively controlled by applying 1 to 5,000 g, preferably 10 to 1,000 g of the active ingredient per 10 acres. In addition, when the agricultural and horticultural fungicide of the present invention is used for seed treatment, for example, as a seed dressing, the active ingredient is preferably 0.01% to 2% per seed weight.
By applying 0.1 to 0.5% powder, you can effectively improve the soil,
Or it can control seed-borne diseases. The agricultural and horticultural fungicide of the present invention is preferably blended with other agricultural and horticultural fungicides in order to broaden the bactericidal spectrum, and in some cases a synergistic effect can be expected. Examples of such other fungicides include, for example, thiophanate, thiophanate methyl, penomyl, carbendazole, hymexazole,
Tecroftalam, chlorothalonil, fuentin hydroxide, captan, captafor, sarum, edeifuenfos, tricyclazole,
IBP, PCNB, fusaride, kasugamycin, vinclozolin, procymidone, isoprothiolane, propenazole, pyroquilone, clobenthiazone (S-1901), metalaxyl, eclomesol, iprodione, propiconazole, ecotanazole, triadimefon, brochloratsu, 4-
Examples of fungicides include methylsulfonyloxyphenyl, N-methylthiol carbamate (NK-191), and N-(1-butoxy-2,2,2-trichloroethyl) salicylamide (NK-483) dazomet. It is not limited to.
Furthermore, if necessary, other insecticides, such as isoxathion, fenitrothion, diazinon, trichlorfon, daisulfoton, acephate, carbaryl, propoxyur, methomyl, thiocyclam, cartap, presrin, allethrin, fenvalerate, etc., and acaricides,
Herbicides, plant growth regulators, nematicides, bactericides, soil conditioners, improvement materials, paper pots,
It can also be used by appropriately mixing with synthetic soil, compost, chemical fertilizer, etc. The agricultural and horticultural fungicide of the present invention, especially for rice cultivation, rice root blight, sesame leaf blight, leaf blight agent, and mealworm,
Combination with a planthopper and/or leafhopper repellent has great labor-saving benefits. The drugs that can be combined with the fungicide of the present invention as a simultaneous control agent are as described above. The amount to be blended varies depending on the target to be controlled and the formulation form, and is adjusted to contain the amount of active ingredient required for pest control. Example 1 2-(2,6-diisopropylphenyl)-5- Next, the method for producing the novel isoindoline derivative of the present invention will be explained in more detail with reference to examples.
Methoxycarbonylisoindoline-1,3-
dithione and 2-(2,6-diisopropylphenyl)-5-methoxycarbonyl-3-thioxo-1-isoindolinone or 2-(2,
6-diisopropylphenyl)-6-methoxycarbonyl-3-thioxo-1-isoindolinone (compound numbers 6 and 3 or 4) 2-(2,6-diisopropylphenyl)-5-
2 g of methoxycarbonylisoindoline-1,3-dione, 2 g of phosphorus pentasulfide and 20 g of dry toluene
ml of the suspension was heated to reflux for 20 hours with stirring. After the reaction was completed, 60 ml of ethyl acetate was added to the reaction mixture and filtered, the residue was washed with ethyl acetate (20 ml x 5), the washings were combined with the previous solution, washed with water, and then dried. After evaporation of the solvent, the residue was subjected to silica gel column chromatography (developing solvent: toluene) for fractional purification to yield 2-(2,6-diisopropylphenyl)-5-methoxycarbonylisoindoline- with a melting point of 188-190°C. 0.26 g of 1,3-dithione and melting point
2-(2,6-diisopropylphenyl)-5-methoxycarbonyl-3-thioxo-1-isoindolinone or 2-(2,6-diisopropylphenyl)-6-methoxycarbonyl-3 at 163-165°C -thioxo-1-isoindolinone 1.0g
was gotten. Example 2 2-(2,6-diisopropylphenyl)-5-
Carboxy-3-thioxo-1-isoindolinone or 2-(2,6-diisopropylphenyl)-6-carboxy-3-thioxo-1-isoindolinone (compound number 1 or 2) 2-(2,6 -diisopropylphenyl)-5-
1.34 g of methoxycarbonyl-3-thioxo-1-isoindolinone or 2-(2,6-diisopropylphenyl)-6-methoxycarbonyl-3-thioxo-1-isoindolinone was dissolved in 5 ml of dimethylimidazolinone. After that, 3 ml of 47% aqueous hydrobromic acid solution was added, and the mixture was heated and stirred at 130 to 140°C for 3 hours. After cooling, filter the reaction mixture and add about 100ml of water.
After washing with water and drying, a red solid was obtained. When this product was purified by silica gel column chromatography (developing solvent: hexane: ethyl acetate = 1:1), the target compound 1.2 with a melting point of 210-214°C was obtained.
g was obtained. The following compound was produced according to the method of Example 1 or 2 above. Exemplary compound NO Melting point (℃) 5 248-250 7 or 8 190-193 9 or 10 59.5-65.5 11 97.5-100 Example 3 2-(2,6-diisopropylphenyl)-5-
Carboxy-3-imino-1-isoindolinone or 2-(2,6-diisopropylphenyl)-6-carboxy-3-imino-1-isoindolinone (compound number 12 or 13) 2-(2,6 -diisopropylphenyl)-5-
Carboxy-3-thioxo-1-isoindolinone or 2-(2,6-diisopropylphenyl)
After dissolving 0.5 g of -6-carboxy-3-thioxo-1-isoindoline in 5 ml of methylene chloride, 2 ml of concentrated aqueous ammonia was added, and the mixture was stirred at room temperature for 4 days. After the reaction, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent: hexane: ethyl acetate: acetic acid = 50:50:1).
The target compound 64 with a melting point of 281-283℃
mg was obtained. The following compound was produced according to the method of Example 3 above. Exemplary Compound NO Melting Point (° C.) 14 or 15 149-151 16 or 17 202-203 Next, production examples of the agricultural and horticultural fungicides of the present invention will be given. In the text, all parts simply refer to parts by weight. Formulation Example 1 Powder 2.5 parts of compound number 12 or 13, talc
47.5 parts of clay, 47 parts of clay, and 3 parts of white carbon were uniformly mixed in a mixer and ground in a hammer mill to obtain a powder. Formulation Example 2 Granules 5 parts of Compound No. 1 or 2, 20 parts of bentonite, 1 part of calcium lignosulfonate, and 74 parts of clay were mixed, and an appropriate amount of water was added and kneaded.
After granulation using a screw extrusion type granulator, the mixture was dried and sized to obtain granules. Formulation Example 3 Wettable powder 50 parts of Compound No. 6, 5 parts of white carbon, 5 parts of Solhole AC-2495G (trade name of Toho Chemical Co., Ltd.) and 40 parts of clay were mixed uniformly in a mixer, and ground in a hammer mill. A wettable powder was obtained. Formulation Example 4 Emulsion 10 parts of compound number 12 or 13, xylene
10 parts, Baracol PS-2 (Nippon Nyukazai Co., Ltd. product name)
12 parts and 68 parts of cyclohexanone were mixed and uniformly dissolved to obtain an emulsion. Next, a test example showing the effect of the compound of the present invention as an agricultural and horticultural fungicide will be given. Test Example 1 Chinese cabbage clubroot control test (soil mixture) Clubroot (pathogen Plasmodiophra brassicae)
Chinese cabbage roots infected with clubroot were crushed and mixed with soil to create clubroot-contaminated soil. The test compound was mixed with the pathogen-contaminated soil at a concentration of 12.5 ppm to the soil, and placed in a 300 ml pot.
(5 seeds were sown per pot, and one seedling was made after germination). After growing the seedlings in a greenhouse for 45 days, they were taken out, and the degree of disease on the roots was examined using the following criteria, and the average degree of disease for 5 pots per section is shown in Table 1. Disease severity: 0 Root galls are not formed. 1 Root galls are formed on the lateral roots, but they are small and few. 〃 2. Creates many small root galls on the lateral roots, or creates large root galls. 〃 3. Creates small root galls on the tap root, with few root galls on the lateral roots. 〃 4. Creates large root galls on the tap root, lateral root galls. Moderate 〃 5 Creates many large root galls on the taproot and lateral roots.

[Table] Example 2 Rice monge disease control test (preventive spraying) 3 pots of rice seedlings (variety: Nipponbare) at the 4th to 5th leaf stage
Spray 50ml of 300ppm test chemical solution and leave it at room temperature for 24 hours. Place 4 to 5 oat grains on which Rhizoctonia solani has been cultured in advance near the rice stalks and heat at 25 to 27℃. Seven days after inoculation, the degree of disease onset was examined by the height (cm) of lesion formation. The results are shown in Table 2.

[Table] Example 3 Kiyu cucumber seedling damping-off control test (soil irrigation) Seedling damping-off fungus (Rhizoctonia solani) cultured on bran at 28°C for 2 weeks was uniformly mixed into the soil.
Put this soil in a pot with a diameter of 12 cm, sow 20 seeds of cucumber (variety: Sagami Hanshiro), and then
A 250 ppm test chemical solution was irrigated at a rate of 3/m ² .
The pots were kept in a greenhouse at 25°C for two weeks, and the number of seedlings (plants) affected by seedling damping-off was investigated. Each ward will be divided into three series, and the total values are shown in Table 3.

【table】

【table】

Claims (1)

[Claims] 1 General formula [Formula] (wherein R ¹ represents COOR ⁴ or OR ⁵ , R ⁴ represents a hydrogen atom or an alkyl group, and R ⁵ represents a hydrogen atom or a lower alkanoyl group. R ² and
R ³ represents a lower alkyl group. X and Y are the same or different; oxygen atom, sulfur atom or =NR ⁶
and R ⁶ represents a hydrogen atom or a lower alkyl group. However, X and Y are never oxygen atoms at the same time. ) or a salt thereof. 2 General formula [Formula] (In the formula, R ¹ represents COOR ⁴ or OR ⁵ , R ⁴ represents a hydrogen atom or an alkyl group, and R ⁵ represents a hydrogen atom or a lower alkanoyl group. R ² and
R ³ represents a lower alkyl group. X and Y are the same or different; oxygen atom, sulfur atom or =NR ⁶
and R ⁶ represents a hydrogen atom or a lower alkyl group. However, X and Y are never oxygen atoms at the same time. ) An agricultural and horticultural fungicide containing an isoindoline derivative or its salt as an active ingredient.