JP2723554B2 - Novel acylated triazole derivative, process for producing the same and agricultural / horticultural fungicide containing the derivative as an active ingredient - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an acylated triazole derivative having utility as an active ingredient having a function of controlling plant diseases, a method for producing the same, and the acylated triazole derivative as an active ingredient. The present invention relates to an agricultural and horticultural fungicide to be contained.

2. Description of the Related Art At present, the damage of crops caused by various plant diseases is enormous, and the problem of environmental pollution caused by pesticides has often been taken up as a topic, and has attracted people's attention. Therefore, it has low toxicity to humans, birds and fish, low phytotoxicity to useful plants, high safety in immediate handling, little impact on the environment, and excellent control of a wide range of plant diseases. Horticultural fungicides have been sought.

It has been shown that triazole derivatives have excellent effects as such agricultural and horticultural fungicides. (JP
62-149667, JP-A-63-156782. The present inventors have further studied azole derivatives having low toxicity to humans and animals, high safety in handling, and an excellent control effect on a wide range of plant diseases,
As a result of synthesizing a large number of azole derivatives and examining their practicality, they have found that acylated triazole derivatives have the above-described properties, and have accomplished the present invention.

That is, an object of the present invention is to provide a novel acylated triazole derivative useful as an active ingredient of an agricultural and horticultural fungicide, a method for producing the same, and excellent control of a wide range of plant diseases containing the acylated triazole derivative as an active ingredient. It is an object of the present invention to provide an agricultural and horticultural fungicide which is effective.

Means for Solving the Problems The present invention relates to an acylated triazole derivative represented by the following general formula (I): (Wherein, X is a halogen atom, an alkyl group of C ₁ -C _4, a phenyl group. The R represents an alkyl group of C ₁ -C _3.) The triazole derivative represented by the following general formula (II) (In the formula, X represents a halogen atom, a C ₁ -C ₄ alkyl group, or a phenyl group.) By reacting with an acid anhydride represented by the following general formula (III) in the presence of a catalyst, method (wherein, R represents an alkyl group of _{C 1 ~C 3.) R-} CO-O-CO-R (III) to produce the acylated triazole derivative represented by formula (I) and the general formula (I ) Is an agricultural and horticultural fungicide containing an acylated triazole derivative represented by the formula (1) as an active ingredient.

The above-mentioned acylated triazole derivative according to the present invention is a novel compound not described in any literature, and examples thereof are shown in Table 1, but are not limited thereto.

 The physicochemical properties are also shown in Table 1.

The NMR spectrum of each compound shown in Table 1 was measured using TMS as an internal standard, and indicated by the following symbols.

s: singlet, d: doublet, t: triplet, m: multiplet,
b: Broad line, J: Coupling constant (unit, H
z) The infrared absorption spectrum of each compound exemplified in Table 1 is shown in the attached drawings (FIGS. 1 to 6).

The acylated triazole derivative represented by the above general formula (I) according to the present invention is produced by the following method.

By reacting the triazole derivative represented by the general formula (II) with an acid anhydride represented by the general formula (III) in the presence of a diluent and a catalyst, the objective compound represented by the general formula (I) is obtained. An acylated triazole derivative is obtained.

The triazole derivative represented by the general formula (II) used as a starting material here is a known compound and is disclosed in
The compounds described in -149667 may be used.

The compound represented by the general formula (I) according to the present invention is preferably reacted with the compounds represented by the general formulas (II) and (III) in the presence of a diluent. As the compound represented by the general formula (II), acetic anhydride, propionic anhydride, butyric anhydride and the like are preferably used. Examples of the diluent include hydrocarbons such as benzene, toluene, xylene, and hexane; halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; and ethers such as diethyl ether, diisopropyl ether, and tetrahydrofuran.

It is also possible to use an acid anhydride represented by the general formula (III) as a solvent without using a diluent. In this case, it is necessary to use an appropriate excess of the acid anhydride represented by the general formula (III).

In the production method of the general formula (I) according to the present invention, it is preferable to use a catalyst such as, for example, triethylamine, pyridine, N, N-dimethyl-4-pyridineamine, and in particular, triethylamine and N, N-dimethyl-4. It is preferable to use both of -pyridineamine.

In order to carry out the production method according to the present invention, for example, a triazole represented by the above general formula (II) is dissolved in the above diluent and an acid anhydride represented by the above general formula (III) is mixed with the acid anhydride represented by the above general formula (II). It is preferable to add 1.0 to 3.0 equivalents of the compound represented by the formula (1) and 0.04 to 2.0 equivalents of the above-mentioned catalyst, respectively, to carry out the reaction. Further, an acid anhydride represented by the general formula (III) may be used in place of the diluent.

The reaction temperature at this time may be any temperature from the freezing point to the boiling point of the diluent as a solvent, but the reaction is preferably performed at a temperature in the range of 0 ° C to 50 ° C. The reaction time is in the range of 10 to 30 hours, and the reaction is preferably performed with stirring.

After the completion of the above reaction, the obtained reaction mixture was poured into ice water, extracted with an organic solvent such as ethyl acetate, chloroform, benzene or the like to separate an organic layer. After washing with a saline solution and drying, the solvent is distilled off under reduced pressure, and the obtained residue is purified to obtain the target compound. The purification treatment can be performed by subjecting to silica gel column chromatography or the like.

Next, the usefulness of the acylated triazole derivative having the general formula (I) according to the present invention as an active ingredient of an agricultural and horticultural fungicide will be described.

The acylated triazole derivative exhibits an excellent controlling effect on a wide range of plant diseases shown below.

Rice blast (Pyricularia oryzae), rice sesame leaf blight (Cochliobolus miyabeanus), rice white blight (Xanthomonas oryzae), rice sheath blight (Rhizoctonia solani), rice small scab (Helminthosporium sigmoideum) , Rice idiot disease (Gibberella fujikuroi), Apple powdery mildew (Podosphaera leucotricha) Apple scab (Venturia inaequalis), Apple monilia disease (Monilinia mali), Apple spot leaf rot (Alternaria mali), Apple Rot rot (Valsa mali), Pear black spot (Alternaria kikuchiana), Pear powdery mildew (Phyllactinia pyri), Pear scab (Gymnosporangium asiaticum), Pear scab (Venturia nashicola), Grape powdery mildew (Uncinula necator), Grape rust (Phakopsora ampelopsidis), Grape late rot (Glomerella cingulata), Barley powdery mildew (Erysiphe graminis f.sp.horde)
i), barley scald (Rhynchosporium secalis f.sp.hord)
ei), black rust of barley (Puccinia graminis), yellow rust of barley (Puccinia striiformis), red rust of wheat (Puccinia recondita), leaf wilt of wheat (Septoria tritici), yellow rust of wheat (Puccinia striiformis) ), Wheat powdery mildew (Erysiphe graminis f.sp.tritic)
i), Powdery mildew on cucumber (Sphaerotheca fuliginea), Anthracnose on cucumber (Colletotrichum lagenarium), Fusarium wilt on watermelon (Fusarium oxysporum f.sp.niveu)
m), Cucumber vine disease (Fusarium oxysporum f.sp.cucume
rinum), yellow radish of radish (Fusarium oxysporum f.sp.raphan)
i), Tomato powdery mildew (Erysiphe cichoracearum), Tomato blight (Alternaria solani), Eggplant powdery mildew (Erysiphe cichoracearum), Strawberry powdery mildew (Sphaerotheca humuli), Tobacco powdery mildew (Erysiphe) cichoracearum), tobacco scab (Alternaria longipes), sugar beet brown spot (Cercospora beticola), potato summer blight (Alternaria solani), soybean brown spot (Septoria glycines), soybean purple spot (Cercospora kikuchii), It has activity against ash disease (Monilinia fructicola) on drupe fruits, gray mold disease (Botrytis cinerea) on various crops, and sclerotinia (Sclerotinia sclerotiorum).

To apply the compound of the acylated triazole derivative represented by the general formula (I) as a fungicide for agricultural and horticultural use, the compound may be used as it is or mixed with a carrier (diluent), powder, wettable powder, granule , Emulsions, and liquid preparations. Further, if necessary, in addition to the above-mentioned carrier, an auxiliary agent such as a spreading agent, an emulsifier, a wetting agent, and a fixing agent may be added to further ensure the effect.

The type of the carrier (diluent) and the auxiliary agent, and the mixing ratio with the acylated triazole derivative can be selected in a wide range.

Incidentally, since the present compound contains a 1,2,4-triazole ring, it can be used in the form of an inorganic acid salt, an organic acid salt or a metal complex salt.

In addition, the present compound has 1-position and 2-position of the cyclopentane skeleton.
Since there is an asymmetric carbon at the position, stereoisomers such as geometric isomers of cis- and trans-forms and optical isomers may exist. In the present invention, all of these single isomers and any of the respective isomers are optional. And the mixture in the ratio of

Therefore, it should be understood that the agricultural and horticultural fungicides according to the present invention include those containing these isomers alone or as a mixture as active ingredients.

Effect of the Invention The acylated triazole derivative of the present invention has the general formula (II)
Of the OH group Is a novel triazole derivative substituted with These compounds can be used as agricultural or horticultural fungicides as they are or in a mixture with various carriers in various forms. The agricultural and horticultural fungicide of the present invention has an excellent control effect on an extremely wide range of plant diseases, as is apparent from the examples described later. In addition, some of the plant diseases have not only a preventive control effect but also a therapeutic effect.

Hereinafter, the effect of the acylated triazole derivative according to the present invention will be described with reference to a specific production method and a specific example of an agricultural and horticultural fungicide using the derivative as an active ingredient.

Example 1 c-2-[(4-chlorophenyl) methyl] -1- (1H
-1,2,4-triazol-1-ylmethyl) -r-1-
Preparation of cyclopentyl acetate (compound No. 1 shown in Table 1) c-2-[(4-chlorophenyl) methyl] -1-
(1H-1,2,4-triazol-1-ylmethyl) -r-
To 500 mg of 1-cyclopentanol, 0.6 ml of acetic anhydride, 0.6 ml of triethylamine, and 16 mg of N, N-dimethyl-4-pyridineamine were added, and the mixture was stirred at room temperature for 14 hours.

The obtained reaction mixture was poured into ice water and extracted with ethyl acetate to obtain an organic layer. The organic layer was washed with 1N hydrochloric acid, a saturated aqueous solution of sodium bicarbonate, and saturated saline, and dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure.

The obtained residue was purified by silica gel column chromatography (developing solvent: n-hexane: ethyl acetate = 1: 1) to obtain 270 mg of the title compound. (Yield 47.6%) The NMR spectrum data of the compound thus obtained is shown in Table 1, and the infrared absorption spectrum is shown in FIG.

Example 2 c-2-[(4-chlorophenyl) methyl] -1- (1H
-1,2,4-triazol-1-ylmethyl) -r-1-
Preparation of cyclopentyl propionate (compound No. 6 shown in Table 1) c-2-[(4-chlorophenyl) methyl] -1-
(1H-1,2,4-triazol-1-ylmethyl) -r-
1-cyclopentanol 500 mg, propionic anhydride 0.5
ml, 0.5 ml of triethylamine and 10 mg of N, N-dimethyl-4-pyridineamine were added, and the mixture was stirred at room temperature for 25 hours.

The obtained reaction mixture was poured into ice water and extracted with ethyl acetate to obtain an organic layer. The organic layer was washed with 1N hydrochloric acid, a saturated aqueous solution of sodium bicarbonate, and saturated saline, and dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure.

The obtained residue was purified by silica gel column chromatography to obtain 330 mg of the title compound. (Yield 55.9
%).

The NMR spectrum data of the compound thus obtained is shown in Table 1, and the infrared absorption spectrum is shown in FIG.

Next, the formulation of an agricultural and horticultural fungicide containing the acylated triazole derivative as an active ingredient and a test example for controlling pathogenic bacteria will be described.

Example 3: Powder by weight Compound of the present invention (Compound No. 1) 3 Clay 40 Talk 57 is pulverized and mixed and used as dusting.

Example 4: wettable powder (parts by weight) The compound of the present invention (compound No. 1) 50 ligninsulfonate 5 alkylsulfonate 3 diatomaceous earth 42 is pulverized and mixed to obtain a wettable powder, which is diluted with water and used.

Example 5: Granules (parts by weight) Compound of the present invention (Compound No. 3) 5 Bentonite 43 Cray 45 Lignin sulfonate 7 is uniformly mixed, further added with water, kneaded, and processed into granules by an extrusion granulator and dried. Into granules.

Example 6: Emulsion Part by weight The compound of the present invention (Compound No. 6) 20 polyoxyethylene alkyl allyl ether 10 polyoxyethylene sorbitan monolaurate 3 xylene 67 are uniformly mixed and dissolved to form an emulsion.

Example 7: Wheat Leaf Rust Control Test The second leaf stage young seedling wheat (cultivar: Norin 64, 16 / pot, using three pot treatment areas) cultivated using a 10 cm diameter unglazed pot,
The wettable powder shown in Example 4 was diluted and suspended with water at a predetermined concentration, and sprayed at a ratio of 5 ml / pot. After air-spraying of the sprayed leaves, a suspension of euspores of wheat leaf rust collected from the diseased leaves was spray-inoculated and kept at 20 to 23 ° C. under high humidity for 24 hours. Then, it was left in a glass greenhouse, 7 to 10 days after the inoculation, the lesion area ratio of wheat leaf rust was investigated, and the control value was calculated by the following formula.

The results are shown in Table 2.

Example 8: Wheat Powdery Mildew Control Test Young seedling wheat of the second leaf stage cultivated using an unglazed body having a diameter of 10 cm (variety: Norin 64, 16 / pot, using three pots in the treatment area)
Then, the wettable powder in the form of Example 4 was diluted and suspended with water to a predetermined concentration, and sprayed at 5 ml per pot. After air-spraying of the sprayed leaves, a suspension of wheat powdery mildew spores collected from the diseased leaves was spray-inoculated, kept at 20 to 24 ° C. under high humidity for 24 hours, and then left in a greenhouse. 9 to 11 days after the inoculation, the lesion area ratio of wheat powdery mildew was investigated, and the control value was calculated by the following formula.

The results are shown in Table 3.

Example 9 Test of antibacterial activity against various pathogenic bacteria This example shows the results of testing the antibacterial activity of the compound of the azole derivative according to the present invention against various plant pathogenic bacteria.

Test method: The compound of the present invention was dissolved in dimethyl
The solution was dissolved in sulfoxide, and 0.6 ml of the solution was well mixed with 60 ml of a PSA medium at about 60 ° C. in a 100 ml Erlenmeyer flask. The mixture was poured into a petri dish and solidified. On the other hand, test bacteria previously cultured on a plate medium were punched out with a cork borer having a diameter of 4 mm, and inoculated on the above-mentioned drug-containing plate medium. After inoculation, each strain was cultured at an appropriate growth temperature for 1 to 3 days, the growth of the bacteria was measured by the diameter of the bacteria, and the rate of inhibition of hyphal elongation was determined according to the following formula in comparison with the growth of the bacteria in the drug-free group. .

 R = 100 (dc-dt) / dc In the equation, R = inhibition rate of hyphal elongation (%) dc = bacterial cell diameter on untreated plate dt = bacterial cell diameter on drug-treated plate

Based on the results, the degree of growth inhibition was evaluated in five steps according to the following criteria.
The results are shown in Table 4.

Growth inhibition 5 Hyphal elongation inhibition rate of 100% to 90% or more 4 Hyphal elongation inhibition rate of less than 90% to 70% or more 3 Hyphal elongation inhibition rate of less than 70% to 40% or more 2 Hyphal elongation Inhibition rate of less than 40% to 20% or more 1. Hyphal elongation inhibition rate of less than 20%

[Brief description of the drawings]

The attached drawings show the infrared absorption spectra of the compounds Nos. 1 to 6 in Table 1 according to the present invention. 1 is Compound No. 1, FIG. 2 is Compound No. 2, FIG. 3 is Compound No. 3, FIG. 4 is Compound No. 4, FIG. 5 is Compound No. 5, and FIG. 3 shows an infrared absorption spectrum.

Claims (3)

(57) [Claims] 1. The compound of the general formula (I) (Wherein X represents a halogen atom, a C ₁ -C ₄ alkyl group or a phenyl group, and R represents a C ₁ -C ₃ alkyl group). 2. A compound of the general formula (II) (Wherein, x represents a halogen atom, an alkyl group of C ₁ -C _4, a phenyl group.) In the general formula of the triazole derivative in the presence of a catalyst represented (III) R-CO-O -CO-R ( III) (wherein R represents a C ₁ -C ₃ alkyl group), and reacted with an acid anhydride represented by the following general formula (I): (Wherein, X represents a halogen atom, a C ₁ -C ₄ alkyl group or a phenyl group. R represents a C ₁ -C ₃ alkyl group.) A process for producing an acylated triazole derivative represented by the formula: 3. A compound of the general formula (I) (In the formula, x represents a halogen atom, a C ₁ -C ₄ alkyl group or a phenyl group. R represents a C ₁ -C ₃ alkyl group.) Agricultural and horticultural fungicides.