JPH023785B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to new azole derivatives and their use as agricultural and horticultural fungicides. More specifically, the present invention is based on the general formula [] (In the formula, X is the same or different and is a halogen atom, a lower alkyl group, a lower alkoxy group, or a trifluoromethyl group, n is an integer from 0 to 3, Y is a nitrogen atom or a methine group, The present invention also relates to an agricultural and horticultural fungicide containing one or more azole derivatives represented by (A is a linear or branched alkylene group) as an active ingredient. The present inventors synthesized a large number of azole derivatives and conducted extensive studies on their practicality in order to develop a low-toxic, safe, and versatile fungicide. As a result, it has been found that the azole derivative represented by the above general formula [] has extremely excellent properties as a fungicide for agricultural and horticultural use. Until now, it was disclosed in Japanese Patent Application Laid-Open No. 52-1979 that esters, anilides and imines of 1,2,4-triazol-1-yl fatty acids could be used as fungicides for agricultural and horticultural purposes.
It is known from the publication No. 27767. However, the amidines provided by the present invention are novel compounds whose composition has not yet been described. Furthermore, the bactericidal activity of these compounds of the present invention is significantly superior to that of conventionally known compounds. That is, the compounds of the present invention have a wide range of antibacterial activity and exhibit control effects against a wide range of plant diseases, but are particularly effective against mildew and powdery mildew of cereals, beans, vegetables, or fruit trees. Furthermore, the compounds of the present invention have almost no phytotoxicity to useful crops, and can be used safely without toxicity to animals or fish. Furthermore, when the compound of the present invention is reacted with alcohols and thiols, 1,2,4-triazole-1, which is an excellent bactericidal agent, is
The compound of formula [] is also an important synthetic intermediate because it can be easily derived into -yl fatty acid isoanilides and isothioanilides. In addition, since the compound of formula [] contains a 1,2,4-triazole ring and in some cases an imidazole ring,
It can also be used in the form of an inorganic acid salt, an organic acid salt, or a metal complex salt. In addition, the compound of formula [] may have geometric isomers because it has a -C=N- double bond, and stereoisomers such as optical isomers depending on the type of A, but the present invention is intended to include all single isomers or mixtures thereof in any ratio. The compound of formula [] of the present invention can be produced by the method of the following reaction formula (a) or (b). Reaction formula (a) In the general formula [], X, n, Y and A have the same meanings as above, and Hal represents a halogen atom. The compound of the general formula [] is the compound of the general formula []
Since it has an azole group like the compound described above, it can also be used in the form of inorganic acid salts, organic acid salts, and metal complex salts. The compound of formula [] can be easily produced by the reaction of imidoyl halides obtained by the reaction of halofatty acid anilides with phosphorus pentahalides and azoles. The compound of formula [] is 1,
It is a 2,4-triazole and can be easily produced by known methods. It is usually preferable to use an organic solvent when reacting the compound of formula [] with the compound of formula [] according to reaction formula (a). Examples of organic solvents include hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, and dichloroethane, ethyl ether,
Ethers such as tetrahydrofuran, esters such as methyl acetate and ethyl acetate, ketones such as acetone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide and N-methylformamide, and dimethyl sulfoxide. etc. can be used. The acid binder does not necessarily need to be used because the compounds of formulas [], formulas [], and [] are bases, but if necessary, organic amines such as triethylamine and pyridine, or inorganic bases such as potassium carbonate may be used. can be used. Further, the compound of the formula [] can be used in advance by converting it into a sodium salt or potassium salt with metallic sodium, sodium amide, sodium hydride, or the like. The reaction can be carried out at any temperature from cooling to the boiling point of the solvent, but usually a temperature from 0°C to about 100°C under ice-water cooling, preferably from room temperature to 85°C. The reaction time varies depending on the solvent used, reaction temperature, etc., but is usually completed within 3 hours. After completion of the reaction, when an acid binder is used, the salts of the acid binder precipitated in the reaction solution are separated and the solvent of the solution is distilled off to obtain the compound of the present invention.
Further, depending on the case, the desired product can be obtained by adding a solvent such as benzene, chloroform, ether or tetrahydrofuran and water, separating the organic layer, and distilling off the organic solvent. Example 1 shows a method for producing the compound of the present invention according to reaction formula (a). Reaction formula (b) In the general formula [], X, n and A have the same meanings as above, and Hal represents a halogen atom. Since the compound of the general formula [] has a 1,2,4-triazole group like the compound of the general formula [], it can also be used in the form of an inorganic acid salt, an organic acid salt, or a metal complex salt. The compound of formula [] is 1,
It can be easily produced by reacting 2,4-triazol-1-yl fatty acid anilide with phosphorus pentahalide. In the general formula [], Y has the same meaning as above, imidazole or 1,2,
4-triazole. All of these can be easily manufactured by known methods. It is usually preferable to use an organic solvent in the reaction between the compound of formula [] and the compound of formula [] according to reaction formula (b). Examples of organic solvents include hydrocarbons similar to those produced by reaction formula (a), halogenated hydrocarbons, ethers, esters, ketones, nitriles,
Amides, dimethyl sulfoxide, etc. can be used. Since the compounds of formula [], formula [], and formula [] are bases, acid binders do not necessarily have to be used, but if necessary, amines and inorganic bases as described in reaction formula (a) can be used. Alternatively, the compound of formula [] can be used in advance in the form of sodium salt or potassium salt. The reaction can be carried out at any temperature from cooling to the boiling point of the solvent. Usually, the reaction temperature is selected from 0°C to about 100°C under ice-water cooling, preferably from 0°C to 85°C. Although the reaction time varies depending on the solvent used, reaction temperature, etc., the reaction is relatively quick and is usually completed within one hour. Treatment after completion of the reaction can be carried out according to the method described in reaction formula (a). Example 2 shows a method for producing the compound of the present invention according to reaction formula (b). Furthermore, when Y is a nitrogen atom in the compound [ ] of the present invention, the reaction route is shown by reaction formula (a) or (b), but the reaction formula shown below is
(c) can be advantageously produced. That is, two equivalents of 1,2,
This is a method of reacting 4-triazole. Reaction formula (c) In the general formula [], X, n and A have the same meanings as above, and Hal represents a halogen atom, which may be the same or different from each other. General formula [] represents a group of compounds in which Y is a nitrogen atom. It is preferable to use an organic solvent in the reaction of the compound of formula [] and the compound of formula [] according to reaction formula (c). Examples of organic solvents include hydrocarbons similar to those produced by reaction formula (a), halogenated hydrocarbons, ethers, esters, ketones, nitriles,
Amides, dimethyl sulfoxide, etc. can be used. Since the compounds of formula [] and formula [] are bases, acid binders do not necessarily need to be used, but amines and inorganic bases as described in reaction formula (a) may be used if necessary. Alternatively, the compound of formula [] can be used in the form of sodium salt or potassium salt in advance. The reaction can be carried out at any temperature from cooling to the boiling point of the solvent, but usually a temperature from 0°C to about 100°C, preferably from room temperature to 85°C is selected. The reaction time varies depending on the solvent used, reaction temperature, etc., but is usually completed within 3 hours. The treatment after the reaction can be carried out according to the method described in reaction formula (a). Examples 3 and 4 show a method for producing the compound of the present invention according to reaction formula (c). Example 1 Production of compound No. 12 (method a) 1-[N-(2,4,5-trichlorophenyl)
-2-chloro-ethanimidoyl]-1,2,4
A mixture of 32.4 g of -triazole, 7.3 g of 1,2,4-triazole, 14.5 g of anhydrous potassium carbonate and 200 ml of acetone was refluxed for 2 hours with stirring.
After cooling, the precipitated salt was removed by suction filtration, and the liquid was concentrated under reduced pressure to yield 1-[N-(2,4,5-trichlorophenyl)-2-(1,2,4-triazol-1-yl). )-ethanimidoyl]-1,2,4-
32.4 g of triazole was obtained as pale yellow crystals. Recrystallization from a mixed solvent of n-hexane/ethyl acetate gave white crystals with a melting point of 114.5-6°C. Example 2 Production of compound No. 5 (method b) 14.0 g of imidazole and 100 ml of chloroform
A mixture of 29.0 g of N-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)-ethanimidoyl chloride and 100 ml of chloroform was added dropwise to the mixture under water cooling over 10 minutes. After the dropwise addition, the mixture was refluxed with stirring for 30 minutes. After cooling, add water,
The organic layer was separated, further washed with water, and then dried over anhydrous sodium sulfate. When the solvent is distilled off under reduced pressure, 1-
[N-(2,4-dichlorophenyl)-2-(1,
30.8 g of 2,4-triazol-1-yl)-ethanimidoyl]-imidazole was obtained as light brown crystals. Recrystallization from a mixed solvent of cyclohexane/acetone gives white crystals with a melting point of 175-176.
℃ was shown. Example 3 Production of Compound No. 6 N-(2,4-dichlorophenyl)- was added to a mixture of 15.2 g of 1,2,4-triazole, 30.4 g of anhydrous potassium carbonate, and 100 ml of acetonitrile under water cooling.
A mixture of 25.7 g of 2-chloroethanimidoyl chloride and 100 ml of acetonitrile was added dropwise over 30 minutes.
After the dropwise addition, the mixture was refluxed for 1 hour while stirring. After cooling, the precipitated salt was removed by suction filtration, the liquid was concentrated under reduced pressure, benzene and water were added to the residue, and the organic layer was separated. After drying over anhydrous sodium sulfate and removing the solvent under reduced pressure, 1-[N-(2,4,-dichlorophenyl)
-2-(1,2,4-triazol-1-yl)
ethanimidoyl]-1,2,4-triazole
30.6 g was obtained as pale yellow crystals. White crystals were obtained by recrystallization with a mixed solvent of n-hexane/acetone, and the melting point was 100.5 to 102°C. Example 4 Production of Compound No. 8 1,2,4-triazole 15.2g, anhydrous sodium carbonate 23.3g and tetrahydrofuran 100ml
A mixture of 24.1 g of N-(2-chloro-4-fluorophenyl)-2-chloroethanimidoyl chloride and 100 ml of tetrahydrofuran was added dropwise to the mixture under water cooling over 30 minutes. After dropping, add 2 while stirring.
Refluxed for an hour. After cooling, the precipitated salt was removed by suction filtration, benzene and water were added to the solution, and the organic layer was separated. The organic layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to give 1-[N-(2-chloro-4-fluorophenyl)-2-(1,2,4
-triazol-1-yl)-ethanimidoyl]
28.1 g of -1,2,4-triazole was obtained as pale yellow crystals. Recrystallization from a mixed solvent of cyclohexane/ethyl acetate showed a melting point of 114-115.5°C. Table 1 shows representative examples of compounds of general formula [] produced by the same method as in the above examples.

[Table] In order to use the compound of the present invention as a fungicide for agriculture and horticulture, the compound of the present invention may be used as it is or diluted with a liquid carrier such as water or an organic solvent, a solid powder or other suitable carrier, and as required. Wetting agent,
By adding auxiliary agents such as spreading agents, dispersants, emulsifiers, and fixing agents, we can produce wettable powders, oils, liquids, emulsions, sols (flowables), powders, DL (driftless) powders, fine granules, granules, etc. It can be formulated and used. Liquid carriers used in formulation include, for example, water,
Solvents such as aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, esters, ketones, acid amides, and dimethyl sulfoxide can be used. Examples of solid carriers include mineral powders such as clay, talc, kaolin, bentonite, diatomaceous earth, calcium carbonate, and silicic acid, and organic powders such as wood flour. In addition, as adjuvants, nonionic, anionic, cationic and amphoteric surfactants,
Glues such as ligninsulfonic acid or its salts, gums, aliphatic salts, and methylcellulose can be used. Preparations such as wettable powders, solutions and emulsions may contain active ingredients in the range of 1 to 95% by weight, usually 2 to 75% by weight. These preparations are commonly diluted with water.
Used at 0.0001-10% by weight. Powders and granules also generally contain from 0.1 to 10% by weight of active ingredient. In addition, concentrated liquids such as oils, emulsions, and sols (flowables) can be used as they are as micro-dose dispersants without being diluted. Furthermore, as a seed disinfectant, a hydrating powder or a powder can be applied directly to crop seeds, or a hydrating powder, a sol, an emulsion, etc. can be diluted with water and the seeds can be immersed. Furthermore, when the compound of the present invention is used as a fungicide for agriculture and horticulture, it is possible to expand the applicability by mixing it with insecticides, fungicides, herbicides, plant growth regulators, etc., and in some cases synergistic effects may be obtained. You can also expect good results. Next, examples will be shown regarding the method for formulating the agricultural and horticultural fungicide of the present invention, but the present invention is not limited to these examples. Note that parts in the examples indicate parts by weight. Example 5 Wettable powder Wettable powder containing 20% of the active ingredient by uniformly pulverizing and mixing 20 parts of Compound No. 6, 5 parts of polyoxyethylene alkylaryl ether, 3 parts of calcium lignin sulfonate, and 72 parts of diatomaceous earth. get. Example 6 Emulsion 30 parts of compound No. 8, 50 parts of xylene and 20 parts of polyoxyethylene alkylaryl ether
The components were uniformly dissolved and mixed to obtain an emulsion containing 30% of the active ingredient. Example 7 Oil agent 50 parts of compound No. 1 and 50 parts of ethyl cellosolve
A liquid solution containing 50% of the active ingredient is obtained by uniformly dissolving and mixing the two parts. Example 8 Sol agent (flowable agent) 40 parts of compound No. 5 pulverized to 10μ or less,
2 parts of lauryl sulfate, 2 parts of sodium alkylnaphthalene sulfonate, 1 part of hydroxypropyl cellulose and 55 parts of water are mixed uniformly to prepare the active ingredients.
A sol containing 40% is obtained. Example 9 Powder 0.5 part of compound No. 11, 0.5 part of silicic anhydride fine powder
0.5 parts of calcium stearate, 50 parts of clay, and 48.5 parts of talc are uniformly mixed and ground to obtain a powder containing 1% of the active ingredient. Example 10 Granules 3 parts of Compound No. 12, 1 part of calcium lignin sulfonate, 30 parts of bentonite and clay
66 parts were uniformly mixed and pulverized, water was added and granulated, dried and sieved to obtain granules containing 3% of the active ingredient. Test example 1 Wheat rot disease control test Wheat seedlings in the first true leaf stage grown in clay pots with a diameter of 9 cm in a greenhouse (variety Norin No. 61)
A predetermined concentration diluted solution of a hydrating powder prepared according to Example 5 was sprayed in an amount of 20 ml per three pots. One day later, the summer spores of the wheat rot fungus that had been formed on the wheat leaves were examined using a microscope with a magnification of 150 times, using Tween 20 [Polyoxyethylene (manufactured by Kao Atlas Co., Ltd.)] so that the spore concentration was approximately 50 per field of view. [trade name of sorbitan monolaurate] was suspended in sterile water to which 50 ppm was added, and the suspension was sprayed and inoculated onto leaves sprayed with the drug. After keeping it in a humid room at 20°C overnight, it was transferred to a greenhouse at 20°C to induce disease onset. Ten days after inoculation, the leaves were taken out, the number of infected pedicelium per leaf was investigated, and the control value (%) was calculated using the following formula. In addition, chemical damage to wheat was investigated using the following indicators. The test was conducted using three pots at one concentration, and the average control value (%) was determined. The results are shown in Table 2. Control value (%) = (1 - number of diaspores in the sprayed area / number of diaspores in the untreated area) x 100 Survey indicators for chemical damage 5: Severe, 4: Severe, 3: Many, 2: Little, 1: Slight, 0: None Test Example 2 Powdery mildew prevention test on cucumber Powdery mildew test On the first leaf stage seedlings of cucumber (cultivar Sagami Hanshiro) grown in clay pots with a diameter of 9 cm in a greenhouse,
A predetermined concentration chemical solution of an emulsion prepared according to Example 6 was
After spraying 10 ml and leaving it overnight, a powdery mildew spore suspension was sprayed and inoculated. Ten days after inoculation, the area ratio (%) of powdery mildew lesions on cucumber was investigated, and the control value (%) was calculated using the following formula. Furthermore, chemical damage to cucumbers was investigated using the same criteria as in Test Example 1. The results are shown in Table 2. Control value (%) = (1 - percentage of lesion area in sprayed area/ percentage of lesion area in non-sprayed area) x 100

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Claims (1)

[Claims] 1. General formula [In the formula, X is the same or different and is a halogen atom, a lower alkyl group, a lower alkoxy group, or a trifluoromethyl group, n is an integer from 0 to 3, Y is a nitrogen atom or a methine group, and A is a linear or branched lower alkylene group). 2 General formula (In the formula, X is the same or different and is a halogen atom, a lower alkyl group, a lower alkoxy group, or a trifluoromethyl group, n is an integer from 0 to 3, Y is a nitrogen atom or a methine group, and A is a linear or branched lower alkylene group) as an active ingredient.