JPS604829B2 - Imidazole derivatives, their production methods, and agricultural and horticultural fungicides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (where A is or a naphthyl group, R is an alkyl group, and x is a lower alkylthio group, a phenyl group, a phenoxy group, or a halo-substituted phenoxy group).

), its production method, and an agricultural and horticultural fungicide containing the acid compound as an active ingredient.

In the cultivation of agricultural and horticultural crops, a large number of pesticides are used to control crop diseases, but their control efficacy may be insufficient, or their use may be restricted due to the emergence of drug-resistant bacteria. In addition, many fungicides are not necessarily satisfactory because they cause phytotoxicity or contamination of plants or are highly toxic to animals, animals, and fish.

Therefore, there is a strong demand for a drug that has fewer such drawbacks and can be used safely. The present inventors conducted research on a large number of compounds with the above-mentioned drawbacks in mind, and found that the group of compounds represented by the above general formula exhibits excellent control effects against various plant diseases. Furthermore, the present invention was completed through pharmaceutical research, and a novel fungicide for agricultural and horticultural use was now provided. The fungicide of the present invention exhibits control effects against a wide range of plant diseases, but is particularly effective against gray mold, sclerotium, seedling blight, powdery mildew, and sesame leaf blight of corn. It has excellent efficacy.

In the production of the compound of the present invention, the general formula (〇) (wherein R and A have the same meanings as defined above) is used.

) and imidazole are reacted in an inert solvent in the presence of an acid binder.

Inert solvents include chloroform, dichloromethane,
Polar solvents such as chlorobenzene, acetonitrile, acetone, dimethyl sulfoxide, and tetrahydrofuran are used, and as acid binders, sodium carbonate, potassium carbonate, sodium hydroxide, sodium methylate, trimethylamine, triethylamine, pyridine, and the like are used.

The reaction is carried out at 0° C. to 80 qo, preferably room temperature to 60° C., and usually requires a reaction time of 30 minutes to 3 hours. After the reaction is completed, the reaction mixture is allowed to cool, washed with water, dried, and the solvent is distilled off to obtain a crude product of the desired product. This can be purified by column chromatography, solvent washing, etc. to obtain a substantially pure compound of the present invention. The structure of the compound of the present invention was determined from the analysis results of elemental analysis, infrared absorption spectrum, nuclear magnetic resonance spectrum, mass vector, etc.

In addition, the raw material compounds represented by the general formula (0) are obtained by reacting the corresponding acetamides with a chlorinating agent such as phosgene, thionyl chloride, phosphorus pentachloride, phosphorus oxytrichloride, etc. The compounds of the present invention are produced by reacting imidyl chlorides with imidazole without isolating them.

Next, the method of the present invention will be explained in more detail with reference to Examples. Example 1 Synthesis of 1-[N-(2-methylthiophenyl)-2-methylbentaimidoyl]imidazole: Compound No. 1N
500 mg of 1-(2-methylthiophenyl)-21-methylbentanamide and 4.8 mm of phosphorus pentachloride were heated under reflux in 50°C of benzene for 1 hour.

After distilling off benzene and by-product phosphorus oxychloride under reduced pressure,
Dissolve in 30' of acetonitrile, add 1.6' of imidazole, heat at 50-60°C for 3 minutes, then slowly add 10' of triethylamine solution in acetonitrile for 2.3' of ice-cooling. Ta. The mixture was heated at 50 to 60°C for 3 minutes, and after removing the acetonitrile, it was dissolved in 100ml of methylene chloride, washed with water, and dried, and then the methylene chloride was removed.

The obtained oil was purified by silica gel column chromatography to obtain the desired product. n customers 1-5
962 Example 2 1-{N-[4-(4-chlorophenoxy)phenyl)
Synthesis of 2-methylbentanimidoyl}imidazole: Compound No. 2N-[4-(4-chlorophenoxy)phenyl]-2-methylbentanamide and 2.9 phosphorus pentachloride were combined in 50' The mixture was heated under reflux in benzene for 1 hour.

After distilling off benzene and the generated phosphorus oxychloride under reduced pressure,
Dissolved in 30 ml of acetonitrile, added imidazole for 1 night, heated at 50 to 6 mph for 30 minutes, then cooled on ice for 1 night.
．． 5 ml of a solution of triethylamine in acetonitrile was slowly added. The mixture was heated at 50-60 pm for 30 minutes, and after distilling off the acetonitrile, it was dissolved in 100 methylene chloride, washed with water, and dried, and then the methylene chloride was distilled off.

The obtained oil was purified by silica gel column chromatography to obtain the desired product. n answer 1.5
976 Example 3 Synthesis of 1-[N-(2-phenylphenyl)-2-methylbentanimidoyl]imidazole: Compound No. 3N
1-(2-Phenylphenyl)-2-methylbesotanamide (4 mol) and phosphorus pentachloride (3.4 mol) were heated under reflux for 1 hour in 50 ml of benzene.

After removing benzene and phosphorus oxychloride under reduced pressure,
The mixture was dissolved in 30 ml of acetonitrile, added with 1.1 ml of imidazole, heated at 50 to 6,000 ℃ for 30 minutes, and then slowly added 1.7 ml of a solution of triethylamine in acetonitrile under ice. The mixture was heated at 50 to 60° C. for 3 minutes, and after removing the acetonitrile, it was dissolved in 100% methylene chloride, and after washing and drying, the methylene chloride was removed.

The obtained oil was purified by silica gel column chromatography to obtain the desired product (4.2%). n sound 1-5
930 Example 4 Synthesis of 1-[N-(1-naphthyl)-2-methylbentanimidoyl]imidazole: Compound No. 4N-(1-
7 days of (naphthyl)-121 methylbentanamide and 6.7 days of phosphorus pentachloride were heated to reflux in 50°C of benzene for 1 hour.

After removing benzene and by-product phosphorus oxychloride under reduced pressure,
Dissolved in 30% acetonitrile, added 2.2% imidazole, heated at 50-60°C for 30 minutes, and gradually added 3.2% solution of triethylamiso in acetonitrile under ice cooling. . The mixture was heated at 50 to 60 qo for 3 minutes, and after removing the acetonitrile, it was dissolved in 100 methylene chloride, and after washing and drying, the methylene chloride was removed.

The obtained oily substance was purified by silica gel column chromatography to obtain the desired product. n total. 61
64 Next, the structural formulas and physical constants of representative compounds of the present invention are shown in Table 1. Table 1 The fungicide of the present invention can be used as a pure active ingredient compound, and for the purpose of use as an agricultural chemical, it can be used in the form that general agricultural chemicals can take, such as wettable powders, granules, powders, etc. emulsion,
It can also be used in the form of an aqueous solvent, an arosol, or the like.

As additives and carriers, if the purpose is a solid agent,
Vegetable powders such as soybean flour and wheat flour, and mineral fine powders such as diatomite, apatite, gypsum, talc, pyrophyllite, and clay are used. For liquid formulations, use kerosene, key oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide,
Dimethyl sulfoxide, alcohol, acetone, water, etc. are used as solvents. In these preparations, a surfactant may be added if necessary to obtain a uniform and stable form. The hydrating agent obtained in this way is
Emulsions can be diluted with water to a predetermined concentration to form a suspension or
Emulsions, powders, and granules are used as they are by spraying them on plants. Next, some examples of compositions of the present invention will be shown, but the additives and their addition ratios should not be limited to these examples and can be varied over a wide range.

Example 5 Wettable powder compound 1 4 Ikarito coralline algae ±
5$ Japanese higher alcohol sulfate ester 4 parts Alkylnaphthalene sulfonic acid 3 or more parts are uniformly mixed and finely ground to obtain a wettable powder containing 40% of the active ingredient.

Example 6 Emulsion compound 2 3 parts xylene 3 parts dimethylformamide 3 parts Polyoxyethylene alkyl allyl ether 7 or more parts are mixed and dissolved to obtain an emulsion containing 30% of the active ingredient.

Example 7 Emulsion Compound 3 1 Ikarito Talc
By uniformly mixing 8 $ parts and 1 part or more of polyoxyethylene alkyl allyl ether and finely pulverizing the mixture, a powder containing 10% of the active ingredient is obtained.

Next, some test examples regarding the efficacy of the fungicide of the present invention will be shown.

Test Example 1 Cucumber Powdery Mildew Pot Test A solution of a predetermined concentration of a hydrating agent of the compound of the present invention was sprayed at a rate of 5 drops per pot at the single-leaf stage of the pot, and after air-drying, powdery mildew fungi (Sphaerotheca
ignea) and cultured in a greenhouse.

The onset of disease was investigated after 10 days, and the control value was calculated based on the onset of disease in the control plot.

The results are shown in Table 2.

Table 2: 6-Methyl-1,2,3-quinoxaline dithiol cyclic carbonate test example 2. Fresh leaf test for preventing gray mold disease.True leaves of kidney bean seedlings grown for about 3 weeks were cut and After soaking in a chemical solution of a predetermined concentration of wettable powders for about 30 minutes and air drying,
After inoculating the mycelium of the genus rea) and keeping it in a greenhouse at 20°C for 4 days, the degree of disease onset was investigated, and the control value was calculated based on the disease onset in the untreated control plot.

The results are shown in Table 3. Table 3 *2,4kawa dichlor-6-(orthochloraniliha-S
- Triazine Test Example 3 Corn Sesame Blight Pot Test A predetermined amount of the hydrating agent of the compound of the present invention was applied to seedlings of corn (variety "Golden Cross Vandum J") 12 days after sowing, which were sown at 5 grains each in 4-inch pots. After spraying a concentrated chemical solution and air drying, the corn sesame leaf blight fungus (Helminthosporlu) obtained by culturing at 28°C for 6 days
After inoculating the plants with a spore suspension of S. mmaydis and keeping them in a 2800 greenhouse for 3 days, the degree of disease onset was investigated, and the control value was calculated based on the degree of disease onset in the non-sprayed control area.

The results are shown in Table 4. Table 4 × Ethylene pis (dithiocarbamide rut manganese test example 4)
'Cucumber seedling damping-off pot test 2
．． Cucumbers (variety "Yotsuba") sown with 7 seeds in 5-inch pots
The seedlings (7 days after sowing) were infected with the cucumber seedling blight fungus (Rhizocto blight), which had been cultured in advance on a sowing-rice husk medium.
niasolani), and a chemical solution of a predetermined concentration of a hydrating powder of the compound of the present invention was applied to the soil, and four days later, 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 5. Table 5 Loss of pentachloronitrobenzene

Claims (1)

[Claims] 1 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A is ▲ Numerical formulas, chemical formulas, tables, etc. ▼ or naphthyl group, R is an alkyl group, and X is lower alkylthio ), phenyl group, phenoxy group, or halo-substituted phenoxy group. 2 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or naphthyl group, R is an alkyl group, X is a lower alkylthio group, phenyl group, phenoxy or a halo-substituted phenoxy group) and imidazole are reacted in the presence of an acid binder. There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. A has the same meaning as defined above.) A method for producing a compound represented by. 3 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A is ▲ Numerical formulas, chemical formulas, tables, etc. ▼ or naphthyl group, R is an alkyl group, X is a lower alkylthio group, phenyl group, phenoxy or a halo-substituted phenoxy group.