JPS6160064B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention includes (1) General formula [] [In the formula, R represents an alkenylene group having 4 to 6 carbon atoms, a cycloalkylene group having 5 to 7 carbon atoms, or a cycloalkenylene group having 5 to 7 carbon atoms. ] N-(3,5-dichlorophenyl)pyrrolidine-2,5-dione derivative represented by these. (2) General formula [] [In the formula, R represents an alkenylene group having 4 to 6 carbon atoms, a cycloalkylene group having 5 to 7 carbon atoms, or a cycloalkenylene group having 5 to 7 carbon atoms. ] Dibasic acid or its anhydride represented by 3,
A method for producing an N-(3,5-dichlorophenyl)pyrrolidine-2,5-dione derivative represented by the general formula [], which comprises reacting with 5-dichloroaniline and cyclizing dehydration. (3) Formula〔〕 N-(3,5-dichlorophenyl)itaconimide represented by and 1 having 4 to 6 carbon atoms,
General formula ['] characterized by reacting with a 3-alkadiene or a 1,3-cycloalkadiene having 5 to 7 carbon atoms [In the formula, R' represents an alkenylene group having 4 to 6 carbon atoms or a cycloalkenylene group having 5 to 7 carbon atoms. ] A method for producing an N-(3,5-dichlorophenyl)pyrrolidine-2,5-dione derivative represented by: (4) General formula [″] [In the formula, R″ represents a cycloalkenylene group having 5 to 7 carbon atoms.] Characterized by adding hydrogen to the N-(3,5-dichlorophenyl)pyrrolidine-2,5-dione derivative represented by General formula [] [In the formula, R represents a cycloalkylene group having 5 to 7 carbon atoms. ] Process for producing N-(3,5-dichlorophenyl)pyrrolidine-2,5-dione derivative represented by (5) General formula [] [In the formula, R represents an alkenylene group having 4 to 6 carbon atoms, a cycloalkylene group having 5 to 7 carbon atoms, or a cycloalkenylene group having 5 to 7 carbon atoms. ] This is an agricultural and horticultural fungicide characterized by containing an N-(3,5-dichlorophenyl)pyrrolidine-2,5-dione derivative represented by the following as an active ingredient. The present inventors have so far discovered certain 1-phenylpyrrolidine-2,5-dione derivatives (for example, Japanese Patent Publication No. 18156-1980, Publication No. 13633-1982, Publication No. 21598-1980, Publication No. 21598-1980, No. 47-43817, Special Publication 1977
55 and Japanese Patent Publication No. 48-2328) have been found to exhibit bactericidal activity against certain fungi. As a result of long-term research to develop fungicides with even better efficacy and practicality, we have now discovered a series of derivatives that have a spiro structure at the 3-position of the pyrrolidine ring, such as the compound of the present invention.
It was discovered that it is incomparably more powerful than conventional related compounds and exhibits a wide range of bactericidal activity. To explain in more detail the fungicidal activity of the compounds of the present invention, the compounds of the present invention can be used to treat rice blast, sesame leaf blight and sheath blight, sclerotia, gray mold, powdery mildew, and seedling blight in agricultural and horticultural crops. diseases, black spot of pears and cruciferous crops, ring spot of tomatoes, anthracnose and vine blight of cucumbers, red star blight, leaf spot blight, monilia blight and scab blight of apples, gray blight of peaches,
It is widely effective against black spot, blue mold, and green mold of mandarin oranges, and has excellent properties as a plant disease control agent, such as being able to control two or more diseases at the same time. On the other hand, rice, green beans, adzuki beans, soybeans, potatoes, tobacco, cucumbers,
Tomatoes, peas, eggplants, green peppers, fava beans,
Even if the compound of the present invention is applied to a wide range of plants such as melons, lettuce, onions, watermelons, strawberries, daikon radish, cabbage, Chinese cabbage, apples, pears, mandarin oranges, grapes, peaches, plums, and persimmons at a concentration sufficient to control diseases, no harm is caused. No effect was observed, and therefore, the compound of the present invention can be safely used as a disease control agent without causing any phytotoxicity to various crops. In addition, the compounds of the present invention have extremely low toxicity, have no harmful effects on humans, livestock, fish, and shellfish, are preferable in terms of public health, and have no risk of causing environmental destruction. In the production of the compounds of the present invention, the general formula [] [In the formula, R represents an alkenylene group having 4 to 6 carbon atoms, a cycloalkylene group having 5 to 7 carbon atoms, or a cycloalkenylene group having 5 to 7 carbon atoms. ] Dibasic acid or its anhydride represented by 3,5
- By reacting with dichloroaniline and cyclizing dehydration, N-
(3,5-dichlorophenyl)pyrrolidine-2,
A 5-dione derivative is obtained. More specifically, method A: α-substituted succinic acid represented by the general formula [ ] or its anhydride and 3,5-dichloroaniline are mixed and heated, or a suitable solvent such as benzene, toluene, xylene, or chlorobenzene is used. , dichlorobenzene, methyl isobutyl ketone, cyclohexane, etc., preferably in xylene and optionally a suitable basic catalyst, such as triethylamine, tributylamine, triethanolamine, pyridine, N-methylmorpholine, potassium carbonate, sodium carbonate. The desired N-(3,5-
dichlorophenyl)pyrrolidine-2,5-dione derivatives can be obtained. Method B: The above α-substituted succinic anhydride and dichloroaniline are reacted in a suitable solvent such as benzene, toluene, xylene, tetrahydrofuran, dioxane, isopropyl ether, chlorobenzene, etc., preferably toluene to obtain the corresponding α- The above-mentioned target product is obtained by dehydrating the substituted succinic acid monoanilide and treating it with a suitable dehydrating agent such as acetic anhydride, phosphorus pentoxide, phosphorus oxychloride, acetyl chloride, thionyl chloride, etc., preferably acetic anhydride. It can be obtained in pure form and in good yield. Method C: N-(3,5-dichlorophenyl)itaconimide and 1,3-alkadiene or 1,3-cycloalkadiene are mixed without solvent or in a suitable solvent such as benzene, toluene, xylene, chlorobenzene,
The desired N-
(3,5-dichlorophenyl)pyrrolidine-
2,5-dione derivatives can be obtained. Method D: N-(3,5-
dichlorophenyl)pyrrolidine-2,5-dione derivative in a suitable solvent such as ethanol, methanol, dioxane, tetrahydrofuran, acetic acid, ethyl acetate, benzene, toluene, etc., preferably dioxane, with platinum oxide, platinized activated carbon, or The target N-(3,5-dichlorofluoride) is purified and produced in a good yield by hydrogenation using palladium-coated activated carbon, preferably palladium-coated activated carbon, as a catalyst under normal pressure or increased pressure, preferably under a hydrogen atmosphere at normal pressure. (enyl)pyrrolidine-2,5-dione derivatives can be obtained. When actually applying the compound of the present invention obtained in this way, it can be used in pure form without adding other ingredients, or it can be mixed with a carrier to make it easier to use as a fungicide. It can be used in any of the commonly used forms, such as powders, wettable powders, oils, emulsions, tablets, granules, fine granules, and aerosols. The formulations generally contain 0.1 to 95.0%, preferably 0.2 to 90.0%, by weight of the active compound (including mixed ingredients), and a suitable application amount is usually 10 to 1000 g per 10 ares. Furthermore, the concentration used is preferably in the range of 0.001 to 1.0%, but the amount and concentration used vary depending on the dosage form, application time, method, location, target disease, target crop, etc., so do not limit yourself 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, such as N-(3,5-dichlorophenyl)-
1,2-dimethylcyclopropane-1,2-dicarboximide, S-n-n-butyl S'-paratertiarybutylbenzyldithiocarbonimidate, O,O-dimethyl-O-2,6-dichloro-4-methyl Phenyl phosphorothioate, methyl-N-benzimidazol-2-yl-N-
(Butylcarbamoyl)carbamate, N-trichloromethylthio-4-cyclohexene-1,2
-dicarboximide, cis-N-(1,1,
2,2-tetrachloroethylthio)-4-cyclohexene-1,2-dicarboximide, polyoxin, streptomycin, zinc ethylene bis(dithiocarbamate), zinc dimethylthiocarbamate, manganese ethylene bis(dithiocarbamate), bis( dimethylthiocarbamoyl) disulfide, tetrachloroisophthalnitrile, 8-hydroxyquinoline, dodecylguanidine acetate, 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide, N'-dichlorofluoromethylthio-N ,N
-dimethyl-N'-phenylsulfamide, 1-
(4-chlorophenoxy)-3,3-dimethyl-1
-(1,2,4-triazol-1-yl)-2-
It can be used in combination with butanone, 1,2-bis(3-methoxycarbonyl-2-thioureido)benzene, etc., and neither of them will reduce the control effect of each agent alone. It can also be used in combination with insecticides. For example, O,O-dimethyl-O-(4-
nitro-meth-tolyl) phosphorothioate, O
-para-cyanophenyl-O,O-dimethylphosphorothioate, O-para-cyanophenyl-O
-ethylphenylphosphonothioate, O,O-
Dimethyl-S-(N-methylcarbamoylmethyl)phosphorodithioate, 2-methoxy-4H
-1,3,2-Benzodioxaphosphorine-2-
Sulfide, O,O-dimethyl-S-(1-ethoxycarbonyl-1-phenylmethyl)phosphorodithioate, α-cyano-3-phenoxybenzyl-2-(4-chlorophenyl)isovalerate, 3-phenoxy It can be used in combination with benzyl-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate, 3-phenoxybenzyl chrysanthemate, etc., and both have the same pesticidal effect as each single agent. It never decreases. Example 1 Production method Method A-1; Bicyclo[2,2,1]hept-5-ene-
8.9 g of 2-ylspiro-3'-succinic anhydride,
8.1 g of 3,5-dichloroaniline, 0.5 g of triethylamine, and 120 ml of xylene were placed in a 200 ml four-necked flask equipped with a water separator and refluxed for 4 hours. After cooling, xylene was distilled off, and separation was performed using silica gel column chromatography, followed by recrystallization with ethanol to obtain 7.0 g of pure bicyclo[2,2,1]heptan-5-en-2-ylspiro-3'-[ 1'-(3'',5''-dichlorophenyl)pyrrolidine-2',5'-dione] was obtained. Melting point 86.5-88.0℃ Elemental analysis value C (%) H (%) N (%) Cl (%) Calculated value 59.7 4.1 4.4 22.0 (as C ₁₆ H ₁₃ NO ₂ Cl ₂ ) Actual value 59.5 4.3 4.3 22.1 Method A- 2; 4-carboxymethyl-4-carboxy-
1,2-dimethylcyclohexene 12.0g, 3,
9.2 g of 5-dichloroaniline, 0.5 g of triethylamine and 150 ml of xylene were placed in a 200 ml four-necked flask equipped with a water separator and refluxed for 5 hours. After cooling, xylene was distilled off, separated using silica gel column chromatography, and recrystallized with a mixed solvent of ethanol and acetone.
g of pure 3,4-dimethylcyclohexa-3
-Enspiro-3'-[1'-(3'',5''-dichlorophenyl)pyrrolidine-2',5'-dione] was obtained. Melting point 158.0-159.0℃ Elemental analysis value C (%) H (%) N (%) Cl (%) Calculated value 60.4 5.1 4.1 21.0 (as C ₁₇ H ₁₇ NO ₂ Cl ₂ ) Actual value 60.6 5.0 3.9 21.0 Method B; Bicyclo[2,2,2]oct-5-en-2-yl spiro-3'-succinic anhydride 5.0
Pour 4.2 g of 3,5-dichloroaniline and 120 ml of toluene into a 200 ml four-necked flask.
Refluxed for an hour. After cooling, 20 g of acetic anhydride and 0.7 g of sodium acetate were added to the reaction mixture, and the mixture was refluxed for 3 hours. After cooling, 100 ml of water was added and stirred for 1 hour.
The precipitated crystals are collected with lacquer and dried under reduced pressure.4.1
pure bicyclo[2,2,2]octa-5 of g
-en-2-ylspiro-3′-[1′-(3″,5″-
dichlorophenyl)pyrrolidine-2',5'-dione] was obtained. Melting point 83.0-84.0℃ Elemental analysis value C (%) H (%) N (%) Cl (%) Calculated value 60.7 4.5 4.2 21.1 (as C ₁₇ H ₁₅ NO ₂ Cl) Actual value 60.5 4.4 4.4 21.0 Method C; N 7.7 g of -(3,5-dichlorophenyl)itaconimide, 2.4 g of cyclohexadiene and 150 ml of toluene were charged into an autoclave and reacted at 130°C for 8 hours. After cooling, toluene was distilled off, separated using silica gel column chromatography, and recrystallized with a mixed solvent of acetone and hexane to yield 3.7 g of pure bicyclo[2,2,2].
Oct-5-en-2-ylspiro-3'-
[1'-(3'',5''-dichlorophenyl)pyrrolidine-2',5'-dione] was obtained. Melting point 82.5-83.5℃ Elemental analysis value C (%) H (%) N (%) Cl (%) Calculated value 60.7 4.5 4.2 21.1 (as C ₁₇ H ₁₅ NO ₂ Cl) Actual value 60.8 4.7 4.1 21.0 Method D; Bicyclo [2,2,1]hept-5-ene-
2-ylspiro-3′-[1′(3″,5″-dichlorophenyl)pyrrolidine-2′,5′-dione] 2.5 g
A solution of 0.1 g of palladium-coated activated carbon in 60 ml of dioxane was subjected to normal pressure catalytic reduction. After the reaction, the palladium-attached activated carbon was separated, the solvent was distilled off, and the mixture was recrystallized from a mixed solvent of acetone and hexane.
g of pure bicyclo[2,2,1]heptyl spiro 3′[1′-(3″,5″-dichlorophenyl)
Pyrrolidine-2',5'-dione was obtained. Melting point 141.0
~142.0℃ Elemental analysis value C (%) H (%) N (%) Cl (%) Calculated value 59.3 4.7 4.3 21.9 (as C ₁₆ H ₁₅ NO ₂ Cl ₂ ) Actual value 59.3 4.8 4.4 21.7 Obtained in the same way Although the results are shown in Tables 1 and 2, it goes without saying that the present invention is not limited to these.

【table】

【table】

[Table] The present invention will be explained in more detail with reference to examples and formulation examples below, but the present invention is of course not limited to these. Example 2 Effect test on controlling green bean sclerotium disease When green beans (variety: Taisho Kintoki) grown in a flower pot with a diameter of 9 cm began to develop their third true leaves, a test chemical in the form of a wettable powder was applied with water. Dilute to 10ml per pot
It was distributed at a rate of One day later, agar pieces containing Sclerotinia sclerotiorum (diameter 5
mm) was inoculated onto the leaves, and the disease state was observed 3 days later. The degree of morbidity was investigated using the following method. In other words, the disease severity is determined by calculating the percentage of diseased area of the investigated leaves, and depending on the degree, 0, 1, 2, 3, 4, etc.
The number of leaves classified into 5 indices and corresponding to each disease index n ₀ ,
n ₁ , n ₂ , n ₃ , n ₄ , and n ₅ were investigated and calculated using the following formula.

[Table] The results of this test are shown in Table 3. As is clear from the results, the compound of the present invention exhibits a superior pesticidal effect compared to the control compound.

[Table] Example 3 Botrytis gray mold control effect test When the cucumber (variety: Sagami Hanshiro) grown in a 9 cm diameter flower pot had finished developing its cotyledons, the test drug in emulsion form was diluted with water. It was sprayed at a rate of 7 ml per needle. One or seven days after spraying, agar pieces containing Botrytis cinerea (diameter 5
mm) was inoculated onto the leaves, and the disease state was observed 3 days later. Incidentally, the disease severity was determined in the same manner as in Example 2. The results of this test are shown in Table 4, and as is clear from these results, the compound of the present invention exhibited a superior pest control effect compared to the control compound and did not cause any chemical damage.

【table】

[Table] Example 4 Chinese cabbage black spot control effect test When Chinese cabbage (variety: Nozaki No. 2) grown on planting needles with a diameter of 9 cm reached the second true leaf stage, a test chemical in the form of a wettable powder was added to the water. The solution was diluted with water and sprayed at a rate of 7 ml per needle. One day later, Alternaria
The leaf surface was inoculated with a spore suspension of Brassicicola by spraying. After inoculation, the plants were left in a dark and humid environment for 1 day, and then placed under light for 2 days to investigate the disease state. The degree of morbidity was investigated using the following method. That is, the disease severity is determined by calculating the percentage of diseased area of the investigated leaves, classifying them into indices of 0, 1, 2, 3, and 4 according to the degree, and calculating the number of leaves n ₀ , n ₁ , n corresponding to each disease index. ₂ , n ₃ and n ₄ were investigated and calculated using the following formula.

【table】 The results of this test are shown in Table 5.

[Table] Test Example 4 Apple Spot Leaf Disease Control Efficacy Test Three-year-old apple seedlings (variety: India) grown in clay pots with a diameter of 30 cm were used as test plants. A single seedling is allowed to sprout 3 to 4 new shoots, and when 10 to 20 new leaves have developed, the test drug in emulsion form is diluted with water.
30 ml of a chemical solution with a predetermined concentration was sprayed per bottle. After spraying, the seedlings were cultivated in a greenhouse for 6 days, and then a conidial suspension of Alternaria mali was spray-inoculated all over the seedlings. After inoculation, the plants were kept in a humid room for 24 hours, and then kept in a greenhouse for 2 days, after which the disease state was investigated. The degree of morbidity was investigated using the following method. In other words, the disease severity is calculated by calculating the percentage of diseased area of the investigated leaves and assigning it as 0, 1, 2, or 2 depending on the severity.
The number of leaves n ₀ , n ₁ , n ₂ , n ₃ , n ₄ , n ₅ corresponding to each disease index was investigated and calculated using the following formula.

[Table] The results of this test are shown in Table 6. As is clear from the results, the compound of the present invention exhibits a superior pesticidal effect compared to the control compound.

【table】

[Table] Formulation example 1 Powder 2 parts of the compound of the present invention (2), 88 parts of clay, and talc
By thoroughly grinding and mixing 10 parts, a powder with a base ingredient content of 2% can be obtained. Formulation example 2 Wettable powder 30 parts of the present compound (3), 45 parts of diatomaceous earth, 20 parts of white carbon, 3 parts of wetting agent (sodium lauryl sulfate) and dispersant (calcium lignin sulfonate)
By thoroughly grinding and mixing the two parts, a hydrating agent with a base ingredient content of 30% can be obtained. Formulation Example 3 Hydrate 50 parts of the present compound (5), 45 parts of diatomaceous earth, 2.5 parts of wetting agent (calcium alkylbenzenesulfonate) and dispersing agent (calcium ligninsulfonate)
By thoroughly grinding and mixing 2.5 parts, a hydrating agent with a base ingredient content of 50% can be obtained. Formulation example 4 Emulsion 10 parts of the present compound (4), 40 parts of dimethyl sulfoxide
By thoroughly mixing 40 parts of xylene and 10 parts of an emulsifier (polyoxyethylene alkyl allyl ether), an emulsion with a base agent content of 10% is obtained.

Claims (1)

[Claims] 1. General formula [In the formula, R represents an alkenylene group having 4 to 6 carbon atoms, a cycloalkylene group having 5 to 7 carbon atoms, or a cycloalkenylene group having 5 to 7 carbon atoms. ] N-(3,5-dichlorophenyl) represented by
Pyrrolidine-2,5-dione derivative. 2 General formula [In the formula, R represents an alkenylene group having 4 to 6 carbon atoms, a cycloalkylene group having 5 to 7 carbon atoms, or a cycloalkenylene group having 5 to 7 carbon atoms. ] The dibasic acid shown or its anhydride and 3,5-
A general formula characterized by reacting with dichloroanilines and cyclizing dehydration. [In the formula, R represents the same meaning as above. ] N-(3,5-dichlorophenyl) represented by
A method for producing a pyrrolidine-2,5-dione derivative. 3 formulas N-(3,5-dichlorophenyl) represented by
Itaconimide and 1,3-alkadiene having 4 to 6 carbon atoms or 1,3-alkadiene having 5 to 7 carbon atoms
General formula characterized by reacting with cycloalkadiene [In the formula, R' represents an alkenylene group having 4 to 6 carbon atoms or a cycloalkenylene group having 5 to 7 carbon atoms. ] N-(3,5-dichlorophenyl) represented by
A method for producing a pyrrolidine-2,5-dione derivative. 4 General formula [In the formula, R″ represents a cycloalkenylene group having 5 to 7 carbon atoms.] N-(3,5-dichlorophenyl) represented by
General formula characterized by adding hydrogen to a pyrrolidine-2,5-dione derivative [In the formula, R represents a cycloalkylene group having 5 to 7 carbon atoms. ] N-(3,5-dichlorophenyl) represented by
A method for producing a pyrrolidine-2,5-dione derivative. 5 General formula [In the formula, R represents an alkenylene group having 4 to 6 carbon atoms, a cycloalkylene group having 5 to 7 carbon atoms, or a cycloalkenylene group having 5 to 7 carbon atoms. ] N-(3,5-dichlorophenyl) represented by
An agricultural and horticultural fungicide characterized by containing a pyrrolidine-2,5-dione derivative as an active ingredient.