JPS62120372A - Triazole derivative - Google Patents

Abstract

NEW MATERIAL:A triazole derivative expressed by the formula (X is Cl or F; n is 0, 1 or 2) or a salt thereof. EXAMPLE:4-Chlorobenzyl N-(2,4-dichlorophenyl)-2-(1,2,4-triazol-4-yl)ethane thioimidate. USE:Useful as an agricultural and horticultural germicide, having a wide antimicrobial activity and capable of exhibiting controlling effect on a wide range of plant blights, particularly rust and powdery mildew of gramineous grains, helminthosporium leaf spot of rice plants and corns, rust and powdery mildew of apples, etc., in fruit trees and further BAKANAE disease (cause by Gibberella fujikuroi), etc., of rice plants by using as a seed disinfectant and safe for useful plants, humans, animals and fishes without toxicity thereto. PREPARATION:As shown in the reaction formula, a compound expressed by formula II is reacted with phosphorus pentachloride to give a compound expressed by formula III, which is then reacted with a benzyl mercaptan expressed by formula IV to afford the aimed compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel triazole derivatives or salts thereof, which are useful as fungicides in the field of agriculture and horticulture. be.

Until now, as a compound similar to the present invention,
In JP 26391, a compound represented by the following general formula is known as an agricultural and horticultural fungicide.

General Formula However, as in the present invention, 1°2,4-triazol-4-ylisothio fatty acid anilide derivatives are not known.

3 (-ru, to) Conventional triazole derivatives are effective in controlling wheat rot and powdery mildew on cucumbers and barley, but depending on how they are used, they may cause phytotoxicity. The present invention has the drawback that the control effect rapidly decreases and no practical effect can be obtained. The object of the present invention is to provide a highly practical 1,2,4-triazole derivative that exhibits a high control effect on rust and powdery mildew, has no chemical damage, and is highly practical.

The present inventors synthesized various triazoles in order to solve the above-mentioned object, and conducted extensive studies on their practicality in the field of agriculture and horticulture.

As a result, the general formula CI) (wherein X is a chlorine atom or a fluorine atom, n is 0, l
It has been found that the triazole derivatives represented by (or 2) or their salts are novel compounds that have not been described in literature, and are useful as agricultural and horticultural fungicides.

Representative compounds of general formula (I) of the present invention are shown below.

In addition, the manufacturing method and Examples of these compounds are as described later.

1" The compound of the present invention is represented by the general formula CI).

It has superior bactericidal activity compared to known similar compounds.

In other words, the compound of the present invention is highly effective against cucumber powdery mildew, wheat rust, etc. with an extremely low treatment concentration of 6.25 ppm, and it does not cause any chemical damage to crops, making it safe to use. can.

The preparation of the compound of general formula (I) according to the present invention is carried out by the following formula (I
1.2.4-) Riazol-4-yl acetic acid anilide of I) is reacted with phosphorus pentachloride to produce imidoyl chloride of the following formula (m), and benzyl mercaptan of the following formula (mV) It can be produced by reacting.

(rI) (m) CI) (In the formula, X and n are the same as above) This imidoyl chloride reaction, ie.

C] The reaction between the general formula 11 and phosphorus pentachloride 1 can usually be carried out in various solvents, but chlorinated hydrocarbons such as chloroform and dichloroethane, phosphorus oxytrichloride, etc. are preferable.
Although the reaction proceeds at room temperature, it is preferable to heat it up to the boiling point of the solvent used. After the reaction is complete, the solvent used is completely distilled off under reduced pressure to obtain the formula [■] or its hydrochloride. However, the following condensation reaction with benzyl mercaptans is usually carried out without isolation and purification.

Condensation reactions usually use organic solvents. As the organic solvent, hydrocarbons, ethers, esters, ketones, nitriles, acid amides, dimethyl sulfoxide, etc. can be used. It is preferred to use acid binders in this reaction, examples of which may include organic amines such as triethylamine and pyridine, or inorganic bases such as potassium carbonate. This reaction proceeds even at room temperature, but it can be completed within a short period of time by heating. After the reaction is complete, the salts of the acid binder precipitated in the reaction solution are filtered off, and the solvent in the filtrate is distilled off. Then, the compound of the present invention can be obtained. In some cases, 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.

Note that the compound of formula [■] which is the starting material of this production method is itself a new compound, but one compound is a compound of the above-mentioned known compound 1,2,4-h riazol-4-yl acetic acid hydrochloride. 1,2.4- by reacting with thionyl chloride in a conventional manner
) It can be easily produced by reacting the lyazole acetic acid chloride hydrochloride with the corresponding aniline in an organic solvent in the presence of an acid binder.

A method for producing the compound of formula (U) is shown in Reference Production Example.

Salts of the compound of formula (I), which is the compound of the present invention, include inorganic acid salts, organic acid salts, and metal complex salts. Here, those that can be used as non-11 acids are hydrogen halides,
Examples include sulfuric acid, nitric acid, perchloric acid, phosphoric acid and sulfamic acid. To produce an a-free salt, compound CI)
This is done by dissolving or suspending the acid in water or an organic solvent, and adding a stoichiometric amount of the acid, either as is or diluted with an organic solvent. In addition, when the acid is obtained in the form of a gas, the reaction can also be obtained by directly blowing the acid into the reaction mixture.The reaction is generally rapid and proceeds at room temperature or under cooling, but it can be heated in some cases. When the inorganic acid salts precipitate as crystals, the compound of the present invention can be separated by filtration, but in some cases, the compound of the present invention can be obtained by distilling off the solvent.

Example 2 shows an example of producing an inorganic acid salt.

Organic acids that can be used include substituted or unsubstituted saturated or unsaturated fatty acids, arylcarboxylic acids, alkyl or arylsulfonic acids, mono- or di-substituted alkyl or arylsulfamic acids, phosphoric or phosphorous acids, including sulfur congeners. Examples include esters and amides. Examples of specific acids include 1.

Dichloroacetic acid, trichloroacetic acid, oxalic acid, maleic acid, 2
, 4.6-dolinitrobenzoic acid, methanesulfonic acid, octylsulfonic acid, benzenesulfonic acid, toluenesulfonic acid, dimethylsulfamic acid, cyclohexylsulfamic acid, phenylsulfamic acid, 0.0-diethylphosphoric acid, o.

-Gel monothiophosphoric acid, 0.0-diethyldithiocap 10
Examples include -ethyl phenylphosphonic acid, 0-ethylphosphonic acid, and phenylphosphonic acid. The production of salts of organic acids is accomplished by dissolving or suspending the compound of formula (I) in water or an organic solvent, and adding a stoichiometric amount of the acid, optionally diluted in water or an organic solvent. The process is generally rapid and proceeds at room temperature or under cooling, but can be heated if necessary. When the salts of IjJa acid precipitate as crystals, the compound of the present invention can be isolated by filtration. In some cases, the compound of the present invention can be obtained by distilling off the solvent and the like.

Organic 1% 111! Example 3 shows a similar production example.

As cations of gold FAk8 class, cations such as copper, manganese, zinc, cobalt, nickel, iron, aluminum, silver, magnesium, tin, and calcium can be used, and as anions, chlorine, bromine, iodine, Non-molecular anions such as fluorine, sulfuric acid, nitric acid or phosphoric acid, or organic anions such as formic acid, acetic acid, methanesulfonic acid or toluenesulfonic acid can be used. The production of metal complex salts is carried out by mixing the compound of formula (1) and metal salts, usually in an inert solvent. Inert solvents include ice,
methanol, acetonitrile, dioxane, ether,
It is most appropriate to mix the compound of formula 0 (CI), in which dichloromethane, chloroform or hexane is used, and the metal salt in a close stoichiometric molar ratio, and depending on the metal cation used, the ligand 6. The reaction normally proceeds at room temperature and there is no need to particularly heat it. If the metal complex salt precipitates as crystals, the compound of the present invention can be isolated by filtration. . In some cases, the compound of the present invention can be obtained by distilling off the solvent and the like.

Example 4 shows an example of producing a metal complex salt.

Although not specifically mentioned in this specification, the compound of formula CI) may have geometric isomers because it has a C═N bond, but the present invention covers all single isomers or It is intended to include mixtures thereof in any ratio.

N-(2,4-dichlorophenyl)-2-(1,2,4
-) 27.1 g of lyazol-4-yl) acetic acid amide is dissolved in 100 m of phosphorus oxytrichloride, and 20.9 g of phosphorus pentachloride is added under water cooling. 30 minutes at room temperature, then 60 minutes
After cooling the reaction solution which had been stirred for 1 hour at °C, the solvent was completely distilled off under reduced pressure. Acetonitrile loOmM to the residue, 4
-16.0 g of chlorobenzyl mercaptan and 21.2 g of triethylamine were added and stirred at 60°C for 1 hour. After cooling the reaction solution to room temperature, the precipitated crystals were filtered off, the filtrate was condensed, and toluene and water were added to the residue to separate the organic layer. This organic layer was treated with IN-sodium hydroxide.
Then, after washing with water, it was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 39.5 g of the title compound as pale yellow crystals. When this crude crystal is recrystallized with a mixed solvent of n-hexane/ethyl acetate, white crystals are obtained.
It showed a melting point of 138.5-139.5°C.

1.2.4-) Suspend 16°4g of lyazole acetic acid hydrochloride in 100mM benzene, and add thionyl chloride under water cooling.
15.5 g was added dropwise, and after one drop, the mixture was gradually heated and allowed to react at the boiling point of the solvent until no gas was generated. After cooling,
The solvent was distilled off under reduced pressure, and 100ml of chloroform was added to the residue.
9. ．． Add 16.2 g of 2.4-dichloroaniline,
After one drop of 22.2 g of triethylamine was added under water cooling, the mixture was stirred at room temperature for 20 minutes, water was added, and the organic layer was separated. After drying the organic layer with anhydrous sodium sulfate,
The solvent was distilled off under reduced pressure to obtain 24.9 g of the title compound as pale brown crystals. When the crude crystals were recrystallized from a mixed solvent of cyclohexane/acetone, they became white crystals with a melting point of 141.5-142.5°C.

Benzyl N-(2,4-dichlorophenyl)-2-(
Dissolve 3.8 g of 1,2,4-)riazol-4-yl)ethanethioimidate in 50 m fL of acetone, and add 2 m of 5N hydrochloric acid solution to this solution.
+nJ1 and added. After this mixture was left at room temperature for 1 hour, the precipitated crystals were filtered off and washed with acetone to obtain 3.3 g of the title compound as white crystals.

This had a melting point of 193.5-195°C (d e c).

Dissolve 4.1 g of 4-chlorobenzyl N-(2,4-dichlorophenyl)-2-(1,2,4-)lyazol-4-yl)ethanethioimidate in 100 m of ether, and add to this solution. Ig oxalate was dissolved in 100 ml of ether and added.

After the mixture was left at room temperature for 2 hours, the precipitated crystals were filtered and washed with ether to obtain 4.5 g of the title compound as white crystals. This thing has a melting point of 147-1
It showed 48°C.

1 2 4-) lyazol-4-yl ethanethioimidate jl n24-chlorobenzyl N-(2,4-dichlorophenyl)-2-(1,
4.1 g of 2,4-1-riazol-4-yl)ethanethioimidate was dissolved in 100 mL of ethanol, and 0.8 g of anhydrous cupric chloride was added to this solution. After the mixture was left at room temperature for 1 hour, the precipitated crystals were filtered off.

After washing with ethanol, 4.0 g of the title compound was obtained as old colored crystals. This product has a melting point of 18B-190℃ (
dec) was shown.

To use the compound of the invention as an agricultural and horticultural fungicide, the compound of general formula (1) may be used as it is, or with a liquid carrier such as water or an organic solvent, or with a solid powder or other suitable carrier. If necessary, add auxiliary agents such as wetting agents, spreading agents, dispersing agents, emulsifiers, and fixing agents to produce wettable powders, oils, liquids, emulsions, sols (flowables), powders, and DL. (Driftless) type powder, fine granules, granules, etc. may be used. Liquid carriers used in formulation include:
For example, water, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, esters, ketones, acid amides,
Solvents such as 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, wood flour, and other mineral powders. As adjuvants, nonionic, anionic, cationic, and amphoteric surfactants, ligninsulfonic acid or its salts, gums, aliphatic salts, and glues such as methylcellulose can be used.

Preparations such as wettable powders, solutions and emulsions contain from 1 to 10% of the active ingredient.
It can be contained in an amount of 95% by weight, usually in the range of 2 to 75% by weight. These formulations are generally diluted with water to a concentration of 0.0001-
Used at 10% by weight.

Powders, microgranules 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 dilution. Furthermore, to use it as a seed disinfectant, you can apply the wettable powder or powder directly to crop seeds, or dilute the wettable powder, sol, or emulsion with water and soak the seeds for 90 minutes. It is effective to do so.

Furthermore, when using the compound of the present invention as a fungicide for agriculture and horticulture, it is possible to expand its applicability by mixing it with insecticides, fungicides, herbicides, plant growth regulators, etc. A synergistic effect can also be expected by using these in combination.

Next, specific examples of formulations of the triazole derivatives of the present invention or agricultural and horticultural fungicides containing them will be shown, but the present invention is not limited to these formulation examples only. All indicate the t position.

Part 11 Medical blood 1 20 parts of compound No. 3, 5 parts of polyoxyethylene alkylaryl ether, 3 parts of calcium lignin sulfonate, and 7 parts of diatomaceous earth are uniformly ground and mixed to obtain a wettable powder containing 20% of the active ingredient. .

30 parts of compound No. 7, 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.

LLfL!楌-1 Compound No. 1 50 parts and ethyl cellosolve 5
0 parts are uniformly dissolved and mixed to obtain an oil agent containing 50% of the active ingredient.

40 parts of compound No. 6 pulverized to less than 10 μm of sol flowable,
Two parts of lauryl sulfate, two parts of sodium alkylnaphthalene sulfonate, one part of hydroxypropyl cellulose, and 55 parts of water are uniformly mixed to obtain a sol containing 40% of the active ingredient.

On a plate - 1 1 part of compound No. 5, 0.5 parts of silicic anhydride fine powder, 0.5 parts of calcium stearate, 50 parts of clay, and 48 parts of talc were uniformly mixed and ground to obtain 1% of the active ingredient. Obtain a powder containing.

Viewing plate utLJJ 3 parts of compound No. 4, 1 part of calcium lignin sulfonate, 30 parts of bentonite, and 6 parts of clay
6 parts were uniformly mixed and pulverized, water was added and granulated, dried and sieved to obtain granules containing 3% of the active ingredient.

The compound of the present invention has a wide range of antibacterial activity and exhibits control effects against a wide range of plant diseases, in particular, sedation of cereals, powdery mildew, and sesame leaf blight of rice and corn. , among legumes, pain relief in soybeans and broad beans, charcoal stain disease in kidney beans and beans,
Among vegetables, powdery mildew (on cucumbers, watermelons, eggplants, green peppers, etc.);
It is effective against vine blight and as a pain reliever for green onions. Also, in fruit trees, it is effective against powdery mildew, powdery mildew of apples, powdery mildew of two pears, analgesia of grapes, rotten rot, etc., and is especially effective against powdery mildew of L crops, powdery mildew, etc. In contrast, treatment with an extremely low concentration of 6.25 ppm resulted in a reduction of 1.
00% control effect, and when used as a seed disinfectant, it has excellent effects on rice sesame leaf blight, rice fungus, wheat smut, and smut. Furthermore, the compounds of the present invention exhibit superior control effects against these diseases compared to conventional compounds, and are particularly excellent in preventive effects. Furthermore, although the compounds of the present invention have strong antibacterial effects, they hardly cause any phytotoxicity to useful plants and can be used safely without toxicity to animals or fish. As described above, the compound of the present invention has excellent safety as an agricultural and horticultural fungicide and exhibits high control effects against various diseases, and is therefore considered to make a great contribution to the agricultural and horticultural fields.

Next, the usefulness of the compound of the present invention as an agricultural and horticultural fungicide,
Specific examples of the effects will be shown using test examples.

Placed on the left 1 yu Wheat - 1■ The first wheat was cultivated in soil in an unglazed pot with a diameter of 9 cm in a greenhouse. A diluted solution of a predetermined concentration of a hydrating powder prepared according to Example 1 was sprayed onto wheat seedlings (variety Norin No. 61) at the leaf stage at a concentration of 20 ml per 3 pots. One day later, the wheat red spores that had been formed in advance on the wheat leaves were examined under a microscope with a magnification of 150 times, and the spore concentration per field of view was approximately 50.
The suspension was suspended in sterile water to which 50 ppm of Tween 20 (trade name of polyoxyethylene sorbitan monolaurate manufactured by Kao Soap Co., Ltd.) was added, and spray S was inoculated onto leaves sprayed with the drug. - After being kept in a greenhouse at 20°C at night, they were 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 a linear equation. In addition, chemical damage to wheat was investigated using the following indicators.

This test was conducted using three pots per concentration of chemical solution, and the average control value (%) was determined. The results are shown in Table 2.

Indicator for investigation of drug damage 5;
Cucumbers grown in soil using the unglazed firing method with a diameter of 9cm (
A diluted solution of a predetermined concentration of an emulsion prepared according to Example 2 was sprayed onto first leaf stage seedlings of the cultivar Wasumi Hanshiro (variety Wasumi Hanshiro), and after being left overnight, a spore suspension of cucumber powdery mildew was spray inoculated. Ten days after inoculation, the cucumber powdery mildew lesion area ratio (%) 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.

This test was conducted using 3 pots per 1 chemical solution concentration, and the average control value (%) was determined. The results are shown in Table 3.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X is a chlorine atom or a fluorine atom, and n is 0, 1
or 2) or a salt thereof.