JPS6035348B2 - Thiophene derivatives and agricultural and horticultural fungicides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel thiophene derivatives and agricultural and horticultural fungicides containing these derivatives as active ingredients.

The novel thiophene derivative in the present invention has the general formula (1)
It is represented by However, in the formula, × is a hydrogen atom, lower alkylcarbonyl group, halogen-substituted lower alkylcarbonyl group, lower alkenylcarbonyl group, lower alkoxy lower alkylcarbonyl group, lower alkylthio lower alkylcarbonyl group, cycloalkylcarbonyl group, group, group, lower Alkylthio group, lower alkylcarbonyloxy lower alkylcarbonyl group, lower alkylcarbamoyl group, di-lower alkylcarbamoyl group, cycloalkylcarbamoyl group, lower alkoxycarbonyl group, phenoxycarbonyl group, halogen-substituted penzoyl group, benzyloxycarbonyl group, toluene R represents a lower alkoxy lower alkyl group or a phenyl group.

The present inventors synthesized a large number of thiophene derivatives and conducted extensive studies on their practicality as agricultural and horticultural fungicides.

As a result, the novel compound represented by the general formula (1) was found to be effective for rice blast, rice sesame leaf blight, rice sheath blight, domato late blight, rice sclerotium, rice bakanae disease, and cucumber vine blight. Diseases, tomato mold, grape rot, pear black spot, apple rot, vegetable soft rot, cucumber spot late fungus, corn holly blight, cucumber downy mildew, cucumber powdery mildew, We have discovered that scales exhibit control activity against cucumber anthracnose and other diseases and can be widely used as a fungicide for agriculture and horticulture. The compound of general formula (1) of the present invention can be produced by the method of the following reaction formula.

Example 1 3,4-dihydroxy-2,5-di-2-ethoxyshethoxycarbonylthiophene (Compound No. 1) 2-ethoxyethanol 150% and dimethylformamide (
18 (0.45 mol) of NaH (60%) powder was added to 100% DMF) under ice-cooling, and then heated from room temperature to 80oC.
Then, a mixed solution of thiodiglycolic acid diethoxyethyl ester 549 (0.2 mol) and oxalic acid diethoxyethyl ester 63 mol (0.3 mol) was added dropwise to the filtrate.

After 1 hour rope pestle at 60-80q0, 50 units of concentrated hydrochloric acid [
(0.5 mol) and 500 ml of water, and the precipitated crystals were separated in a furnace.

When this is recrystallized from methanol-water, the melting point is 79-80.
33.2 hours (yield 48%) of 0.00 yellow powder are obtained.
Elemental analysis value (C, 4 days as 2.08S) Calculated value C 48.27 days 5.79 Measured value C 50.00 days 5.90 Example 2 3,4-dimethylcarbamoyloxy-2,5-di2 -ethoxyethoxycarbonylthiophene (compound N
o. 3) 3,4-dihydroxy-2,5-di-2'-ethoxyethoxycarponylthiophene 3.5 hours (0.0
1 mole) and 1.2 moles of methyl isocyanate (0.0
2 mol) of dioxane was dissolved in 15% of dioxane, 0.1% of triethylamine was added, and the mixture was incubated at room temperature for 7 hours.

Next, the reaction solution was poured into 100 g of water, and the precipitated crystals were separated in a furnace and recrystallized from a mixed solvent of n-hexane and benzene to produce 2.1 g of white needle-shaped crystals with a melting point of 87.5 mm (yield: 46%). ) was obtained. Elemental analysis value (C, 8 days 26N20, o
S) Calculated value C 46.75 days 5.63N 6
．． 06 measurement value C 46.90 days 5.65N 5.7
0 Example 33,4-dimethoxymethylcarbonyloxy-2,5-di-2'-methoxyethoxycarbonylthiophene (Compound No. 12) 3,4-dihydroxy-2,5-di2'-methoxy 3.2 moles (0.01 mol) of ethoxycarbonylthiophene and 3.0 moles (0.028 mol) of methoxyacetyl chloride were dissolved in 50 mol of dioxane, and 10 ml of triethylamine was added dropwise under ice cooling for 30 minutes. After stirring, the mixture was allowed to react at room temperature for an additional hour.

The reaction solution was poured into 200 g of water, and the precipitated crystals were separated in a furnace and then recrystallized from ethanol to obtain 1.6 g of white needle-like crystals (yield: 35%) with a melting point of 81.2°C. Elemental analysis value (C, 8 days, 240, 2S) Calculated value C 46.
55 days 5.17 Measured value C 46.55 days 5.10 Example 4 3,4-dimethoxycarbonyloxy-2,5-dibenzyloxycarponylthiophene (compound No. 2
1) 3,4-dihydroxy-2,5-dibenzyloxycarbonylthiophene 3.8 moles (0.01 mol) and methyl chloroformate 2.2 moles (0.023 mol)
was dissolved in 20 parts of dioxane, 5 parts of pyridine was added to the resulting solution, and the mixture was heated at 60 parts for 2 hours with shaking.

After the reaction, the reaction solution was poured into 150 mL of water, and the precipitated crystals were separated in a furnace and recrystallized from ethanol to give a melting point of 103.4.
3.2 hours of white plate-like crystals (yield: 64%) were obtained. Elemental analysis value (C24th day 2.

○, as oS) Calculated value C 57.60 days 4.00
Measured value C 57.60 days 4.00 Next, the compounds of the present invention obtained according to the method of Examples are illustrated in Table 1.

Note that the compound numbers in the table are referred to in Examples and Test Examples. Table 1 General formula Table 1 (Continued) When the compound of the present invention is used as an agricultural and horticultural fungicide, it may be used as a powder, wettable powder, emulsion, granule, fine granule, or other commonly used forms of the compound. It is possible to use.

The carrier used in the present invention may be either solid or liquid, and is not limited to a specific carrier. Examples of solid carriers include various clays, kaolin, clay,
Examples of the liquid carrier include those that serve as a solvent for the active ingredient compound according to the present invention, and even non-solvents that can disperse or dissolve the active ingredient compound with the aid of an auxiliary agent. You can use it if it is.
Examples include benzene, xylene, toluene, kerosene, alcohols, ketones, dimethyl sulfoxide, dimethylformamide, and the like. It can be used as an aqueous solution or emulsion by mixing a suitable surfactant and other auxiliary agents such as a spreading agent and a fixing agent. Furthermore, the compound of the present invention can be used in combination with other fungicides, insecticides, herbicides, plant growth regulators, etc. to ensure labor-saving and pesticidal effects. Next, some examples of using the compounds of the present invention as agricultural and horticultural fungicides will be shown, but the main compounds and additives are not limited to the following examples.

Example 5 (Powder) Compound No. By uniformly mixing and pulverizing 2 parts of the compound No. 4 and 98 parts of clay, a powder containing 2% of the active ingredient is obtained.

Example 6 (hydrating agent) Compound No. 30 parts of the compound of No. 5, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylene nonyl phenyl ether, and 62 parts of clay are uniformly mixed and ground to obtain a water containing 30% of the active ingredient in the form of a fine powder with a uniform composition. Obtain Japanese medicine.

When using this product, dilute it 600 to 100 parts with water and spray it on plants. Example 7 (Emulsion) Compound No. By mixing and dissolving 30 parts of the compound No. 7, 55 parts of methyl ethyl ketone, and 15 parts of polyoxyethylesononylphenyl ether, an emulsion containing 30% of the active ingredient is obtained.

When using this product, dilute it with water to a concentration of 600-100% and spray it on plants. Example 8 (granules) Compound No. 15 parts of water was added to 5 parts of the compound No. 15, 1.5 parts of lauryl sulfate, 1.5 parts of calcium lignosulfonate, 25 parts of bentonite, and 67 parts of Shirashi, and the mixture was kneaded in a mixer, then granulated and fluidized. 5% when dried in a dryer
Granules are obtained.

Next, the pesticidal effect when the compound of the present invention is used as an agricultural and horticultural fungicide will be explained using test examples.

Test example 1 Rice blast control effect test Paddy rice (variety:
A test chemical solution prepared by diluting a hydrating powder prepared according to Example 6 to a predetermined concentration was sprayed on third hollyhock stage seedlings of Asahi (Asahi).

One day after the spraying, a spore suspension of the blast fungus was inoculated by spraying.
After inoculation, leave overnight under humid room conditions (humidity 95-100%, temperature 24%).
~250C). Five days after inoculation, the number of lesions per species on the third leaf was investigated, and the control value (%) was calculated using the following formula. In addition, chemical damage to rice was investigated using the following indicators.
The results are shown in Table 2. Indicator for drug damage investigation 5: Severe 4: Severe 3: Much 2: Little 1: Slight 0: None Table 2 Test Example 2 Paddy rice sesame leaf blight control effect test Cultivated in soil in a clay pot with a diameter of 9 arcs in a greenhouse Paddy rice (variety:
A drug solution diluted to a predetermined concentration was sprayed on seedlings at the fourth true leaf stage of Asahi (Asahi), and one day after the spraying, a conidial suspension of the rice sesame leaf blight fungus was inoculated with a fin mist.

Five days after inoculation, the number of lesions per plant on the fourth leaf was investigated, and the control value was calculated using the following formula. In addition, chemical damage to rice was investigated using the same method as in Test Example 1. The results are shown in Table 3. Table 3 Test Example 3 Tomato late blight control effect test Tomato seedlings (variety: Sekai Ichi, No. 2 millet stage seedlings) grown in soil in a clay pot with a diameter of 9 cm in a greenhouse were prepared according to Example 6. A chemical solution prepared by diluting a wettable powder with water to a predetermined concentration was sprayed using a pressure sprayer.

Three days after the spraying, zoospores of the tomato Phytophthora fungus formed on potato tubers were diluted and suspended in water, and the suspension was inoculated onto tomato leaves by drip. After inoculation, the plants were kept in a humid room (humidity 95 to 98%) for 2000 hours and investigated after 3 days to calculate the control value (%) using the following formula. In addition, chemical damage to tomatoes was investigated using the same method as in Test Example 1. The results are shown in Table 4. Attack rate (
%)=Korenha Kaoru X・〇.

Table 4 Test Example 4 Cucumber Downy Mildew Control Effect Test Cucumbers (second true-leaf stage seedlings of Sagami Hanshiro variety) grown in a greenhouse in a clay pot with a diameter of 9 mm were prepared according to Example 6. A wettable powder was diluted with water to a predetermined temperature and then sprayed using a pressurized sprayer, and one day after the spraying, a suspension of conidial spores of downy mildew was inoculated.

Seven days after inoculation, the lesion area ratio (%) on the first leaf was investigated, and the control value (%) was calculated using the following formula. The test was conducted using 1 plot and 3 lotuses, and the average control value was calculated. In addition, chemical damage to cucumbers was investigated using the same method as in Test Example 1. The results are shown in Table 5. Table 5 Test Example 5 Cucumber Powdery Mildew Control Efficacy Test Cucumbers (
A chemical solution diluted to a predetermined concentration was sprayed onto the first leaf stage seedlings of Sagami Hanjiro (variety: Sagami Hanshiro), and the next day, the powdery mildew spore suspension was spray inoculated.

Ten days after inoculation, the lesion area ratio (%) was investigated and the control value was calculated using the following formula. Control value (%) i The results are shown in Table 6.

Table 6

Claims (1)

[Claims] 1 Thiophene derivative represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (wherein, X is a hydrogen atom, a lower alkylcarbonyl group, a halogen-substituted lower alkylcarbonyl group, a lower alkenylcarbonyl group) , lower alkoxy lower alkyl carbonyl group, lower alkylthio lower alkyl carbonyl group, cycloalkyl carbonyl group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ groups, lower alkylthio carbonyl groups, lower Alkylcarbonyloxy lower alkylcarbonyl group, lower alkylcarbamoyl group, di-lower alkylcarbamoyl group, cycloalkylcarbamoyl group, lower alkoxycarbonyl group, phenoxycarbonyl group, halogen-substituted benzoyl group, benzyloxycarbonyl group, toluenesulfonyl group, lower represents an alkylsulfonyl group, a di-lower alkylsulfamoyl group or a di-lower alkylthionophosphoryl group, and R represents a lower alkoxy-lower alkyl group or a phenyl group). 2 An agricultural and horticultural fungicide characterized by containing as an active ingredient a thiophene derivative represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. Substituted lower alkylcarbonyl group, lower alkenylcarbonyl group, lower alkoxy lower alkylcarbonyl group, lower alkylthio lower alkylcarbonyl group, cycloalkylcarbonyl group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ Numerical formulas, chemical formulas, tables, etc. There are ▼ groups, lower alkylthiocarbonyl group, lower alkylcarbonyloxy lower alkylcarbonyl group, lower alkylcarbamoyl group, di-lower alkylcarbamoyl group, cycloalkylcarbamoyl group, lower alkoxycarbonyl group, phenoxycarbonyl group, halogen-substituted benzoyl group, a benzyloxycarbonyl group, a toluenesulfonyl group, a lower alkylsulfonyl group, a di-lower alkylsulfamoyl group or a di-lower alkylthionophosphoryl group, and R represents a lower alkoxy lower alkyl group or a phenyl group).