JPS6129339B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [] (In the formula, R represents a lower alkyl group excluding a methyl group.) The present invention relates to a novel cyanopyrrole derivative represented by the following formula and an agricultural and horticultural fungicide containing the compound as an active ingredient. Conventionally, various compounds have been known as phenylpyrrole compounds, including 3-chloro-4-(2
-Nitro-3-chlorophenyl)pyrrole (Japanese Patent Publication No. 1988-88630), 3-chloro-4-(3-trifluoromethylphenyl)pyrrole (Japanese Patent Publication No. 1988-88630)
2011) etc. are known to have antibacterial properties against plant pathogenic bacteria. However, these compounds are unstable to sunlight and have low residual efficacy.
It has poor practicality as an agricultural fungicide. The present inventors synthesized a large number of phenylpyrrole derivatives and conducted various studies on their efficacy as agricultural and horticultural fungicides. As a result, they discovered that cyanopyrroles represented by the above general formula [] have excellent residual efficacy. The present invention has now been completed. Furthermore, these compounds of the present invention can be used to treat Trichophyton
It was also discovered that it has antibacterial properties against bacteria and fungi. Among the compounds represented by the general formula [], the compounds that are excellent as agricultural and horticultural fungicides have a phenyl group.
It is a compound in which Cl is 2-Cl. To produce the compound of the present invention, the objective can be achieved by reacting a corresponding acylating agent with a 3-cyano-4-phenylpyrrole represented by the corresponding general formula []. The most common acylating agent is the corresponding carboxylic acid anhydride, but is not limited thereto.
In addition, when using an acid halide etc. as an acylating agent, the reaction can be carried out in the presence of an appropriate base, or the compound of the general formula [], which is a raw material, can be converted into a sodium salt beforehand and then reacted. It is. Further, the compound represented by the general formula [] can be produced, for example, by the following reaction formula. The method for producing the compound of the present invention will be explained in detail with reference to Examples below. Example 1 Synthesis of 1-propionyl-3-cyano-4-(2-chlorophenyl)pyrrole (compound number 1) 1 g of 3-cyano-4-(2-chlorophenyl)pyrrole was mixed with 4 ml of propionic anhydride,
Heated at 140-150°C for 4 hours. The reaction solution was added to ice water to decompose the excess acid anhydride, and then extracted with ethyl acetate. The ethyl acetate solution was washed with an aqueous sodium bicarbonate solution and then with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give a crude oil. I got it. This n-
Hexane was added to cause crystallization, and the crystals were separated and washed with methanol to obtain 490 mg of the target substance. Physicochemical properties of the obtained target substance Properties: Colorless columnar crystals Melting point: 107-108℃ Infrared absorption: 3080, 2890, 2230, 1725, 1505,
1415, 1379, 1340, 1325, 1256, 1221, 1158,
1085, 1062, 1035, 990, 916, 845, 811,
783, 751 cm ^-1 Example 2 Synthesis of 1-n-butyryl-3-cyano-4-(2-chlorophenyl)pyrrole (compound number 2) 1 g of 3-cyano-4-(2-chlorophenyl)pyrrole was dissolved in anhydrous n- Mix with 4 ml of butyric acid, 140-150
Heated at ℃ for 4 hours. The reaction solution was added to ice water to decompose excess acid anhydride, and then extracted with ethyl acetate. The ethyl acetate solution was washed with an aqueous sodium bicarbonate solution, then with brine, and dried over anhydrous sodium sulfate.
It was concentrated under reduced pressure to obtain a crude oily substance. This crude oily substance was subjected to silica gel preparative thin layer chromatography (Merck
Art 5717 Developing solvent acetone:hexane=1:
The product was purified in step 2) and dried under vacuum to obtain 1 g of the desired product. Physicochemical properties of the obtained target substance Properties: Colorless needle crystals Melting point: 64.5-69℃ Infrared absorption: 3110, 2890, 2225, 1725, 1510,
1429, 1372, 1315, 1275, 1261, 1199, 1145,
1101, 1070, 990, 940, 892, 867, 831, 806,
769cm ^-1 Example 3 Synthesis of 1-isobutyryl-3-cyano-4-(2-chlorophenyl)pyrrole (compound number 3) 1 g of 3-cyano-4-(2-chlorophenyl)pyrrole was mixed with 4 ml of isobutyric anhydride. , 140～
Heated at 150°C for 4 hours. The reaction solution was added to ice water to decompose the excess acid anhydride, and then extracted with ethyl acetate. The ethyl acetate solution was washed with an aqueous sodium bicarbonate solution and then with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give a crude oil. I got it. This crude oil was subjected to silica gel preparative thin layer chromatography (Merck art 5717 developing solvent: acetone: hexane =
1:2) and dried under vacuum to obtain 600 mg of the desired product. Physicochemical properties of the obtained target substance Properties: Colorless crystal Melting point: 73-84℃ Infrared absorption: 3230, 2930, 2220, 1724, 1505,
1442, 1428, 1365, 1315, 1201, 1177, 1128,
1093, 1042, 988, 930, 860, 830, 766, 738cm
^-1 Example 4 Synthesis of 1-pivaloyl-3-cyano-4-(2-chlorophenyl)pyrrole (chemical substance number 4) Add a small amount of ferric nitrate to 100 ml of liquid ammonia, add 450 mg of sodium, and stir. A suspension of sodium amide was obtained. In this, 3-cyano-4
-(2-chlorophenyl)pyrrole 4.05g in 40ml
The ether suspension was stirred dropwise and left to stand for two days and nights after distilling off the ammonia, the ether was decanted and discarded, the precipitate was suspended in 95 ml of 1,2-dimethoxyethane, and 3-cyano-4-(2 -chlorophenyl)pyrrole sodium salt/dimethoxyethane suspension was obtained. 500mg pivalic acid chloride 10ml 1.2
-Dissolve in dimethoxyethane, stir, and add 3
A suspension of about 0.8 g of -cyano-4-(2-chlorophenyl)pyrrole in dimethoxyethane (20 ml) of sodium salt was added dropwise, and the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into 100 ml of iced sodium bicarbonate solution, stirred for 1 hour, and then extracted with benzene. The benzene layer was washed with water, dried under reduced pressure, and washed with methanol to obtain 600 mg of target crystals. Physicochemical properties of the obtained target crystal Properties: Colorless crystal Melting point: 99-100℃ Infrared absorption: 3090, 2910, 2230, 1703, 1515,
1452, 1428, 1400, 1340, 1310, 1253, 1200,
1139, 1066, 1031, 990, 912, 843, 810, 750
cm ⁻¹ Compounds obtained in the above Examples, which are specific examples of the compounds of the present invention, are shown in Table 1.

[Table] The agricultural and horticultural sterilizer of the present invention is used in the form that common agricultural chemicals can take, ie, in the form of wettable powders, emulsions, powders, etc. As additives and carriers, fine mineral powders such as diatomaceous earth, apatite, talc, pyrofluorite, and clay, or vegetable powders such as soybean flour and wheat flour can be used as solid agents. When the purpose is to form a dosage form, kerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, alcohol, acetone, water, etc. are used as the solvent.
A surfactant can be added if necessary to obtain a uniform and stable form in these formulations. Next, some examples regarding formulations of the agricultural and horticultural fungicides of the present invention will be shown, but the additives and addition ratios are not limited to the examples and can be varied over a wide range. Example 5 Wettable powder compound 1 20 parts Diatomaceous earth 73 parts Higher alcohol sulfate ester sodium salt
Mix 7 parts or more uniformly and finely crush the active ingredients.
A 20% hydrating agent was obtained. Example 6 Emulsion Compound 2 20 parts Xylene 42 parts Dimethylformamide 30 parts Polyoxyethylene alkyl allyl ether
More than 8 parts were mixed and dissolved to obtain an emulsion containing 20% of the active ingredient. Example 7 Powder Compound 2 2 parts Talc 98 parts The above was mixed and pulverized uniformly to obtain a powder containing 2% of the active ingredient. Example 8 Granule Compound 3 5 parts Talc 40 parts Clay 39 parts Bentonite 10 parts Sodium alkyl sulfate 6 parts After uniformly mixing the above ingredients and pulverizing them finely, they were granulated into granules with a diameter of 0.5-1 mm using a granulator. 5% active ingredient
granules were obtained. Wettable powders and emulsions obtained as in the above examples can be diluted with water to form suspensions or emulsions, and powders and granules can be used as they are for use in areas where plant diseases have occurred or where plant diseases are expected to occur. Applies where applicable. In other words, it can be applied directly to plants by means such as spraying or coating to control diseases such as blast, sheath blight, gray mold, and scab, or it can be applied to the soil to control seedling blight. Diseases such as diseases can be effectively controlled. Furthermore, by applying hydrating powders and granules directly to plant seeds, or immersing the seeds in a chemical solution prepared by diluting hydrating powders and emulsions with water, rice blast, sesame leaf blight, baka-nae disease, It can also control diseases such as smut. Furthermore, the effective compound of the present invention can be added to various conventional forms of fungicides, insecticides, plant regulators, etc. to impart fungicidal properties. Next, some test examples regarding the efficacy of the fungicide of the present invention will be shown. Test Example 1 Botrytis disease leaf test True leaves of kidney bean seedlings cultured for about 3 weeks were cut and added to a chemical solution of a predetermined concentration of a hydrating powder of the compound of the present invention.
After soaking for about 30 seconds and air drying, inoculate with Botrytis cinerea mycelia and leave for 20 days for 4 days.
After keeping it in a humid room at ℃, the degree of disease onset was investigated, and the control value was calculated based on the degree of disease onset in the untreated control plot. The results are shown in Table 2.

[Table] Test Example 2 Gray mold residual effect test Potted kidney bean seedlings that had been cultured for about 3 weeks were sprayed with a predetermined concentration of a hydrating powder containing the compound of the present invention.
After leaving it in the greenhouse for a week, the treated leaves were cut off and placed in a wet room in a shear room.
After inoculating the mycelium of cinerea and keeping it at 20°C for 4 days, the degree of disease onset was investigated, and the control value was calculated based on the degree of disease onset in the untreated control plot. The results are shown in Table 3.

【table】

Claims (1)

[Claims] 1. General formula (In the formula, R represents a lower alkyl group excluding a methyl group.) A compound represented by the formula: 2 General formula (In the formula, R represents a lower alkyl group having 2 to 4 carbon atoms.) The compound according to claim 1, represented by: 3 General formula (In the formula, R represents a lower alkyl group excluding a methyl group.) An agricultural and horticultural fungicide characterized by containing a compound represented by the following as an active ingredient. 4 General formula (In the formula, R represents a lower alkyl group having 2 to 4 carbon atoms.) The agricultural and horticultural fungicide according to claim 3, which contains a compound represented by the following as an active ingredient.