JPH04164084A - Triazole derivative and agricultural and horticultural germicide - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X and Y are H, halogen, lower alkyl or lower alkoxy; Z is 0, S or NH; n is 1 or 2). EXAMPLE:6-Chloro-2-[1-(triazol-1-yl)-2-(p-chlorophenyl) ethyl] benzothiazole. USE:An agricultural and horticultural germicide. PREPARATION:An alpha-(triazol-1-yl)phenylpropionic acid derivative [e.g. alpha-(triazol-1- yl)-p-chlorophenylpropionic acid] expressed by formula II is converted into an acid chloride in the presence of a chlorinating agent (e.g. thionyl chloride) in a solvent and the resultant acid chloride is subsequently reacted with an amine derivative (e.g. 4-chloro-2-mercaptoaniline) expressed by formula III in the presence of an acid binder to afford the compound expressed by formula I. Furthermore, the starting raw material expressed by formula II is a new substance.

Description

DETAILED DESCRIPTION OF THE INVENTION OBJECTS OF THE INVENTION 1) Industrial Field of Application The present invention relates to novel triazole derivatives. More specifically, the present invention relates to a triazole-substituted heterofused ring derivative represented by the general formula (1) described later, and an agricultural and horticultural fungicide containing the derivative as an active ingredient. Then,
INDUSTRIAL APPLICABILITY The present invention is useful in the chemical industry and agricultural and horticultural fields, particularly in the agricultural chemical manufacturing field.

2) Prior Art Until now, no derivatives having a chemical structure similar to the compound of the present invention have been known. That is, the triazole-substituted heterofused ring derivative of the present invention represented by the general formula (1) below has not been described in the literature.

3) Problems to be solved by the invention Various drugs have been used to treat important diseases of fruit trees, vegetables, and grains such as downy mildew, late blight, powdery mildew, and rust. Due to resistance issues, their use has become unusable or has been restricted. Therefore, in these fields, there is a demand for a fungicide having a new chemical structure different from that of conventional drugs. The present invention aims to provide a novel disinfectant that meets these needs.

In order to achieve the above object, the present inventors synthesized a large number of compounds and conducted extensive studies on their usefulness. As a result, it was discovered that the triazole derivative represented by the following general formula (I) is a new compound that has not been described in any literature, and that it has high activity and safety as an agricultural and horticultural fungicide.

Therefore, the first gist of the present invention is the following general formula (I), where X and Y are the same or different hydrogen atoms,
represents a halogen atom, a lower alkyl group or a lower alkoxy group, Z represents an oxygen atom, a sulfur atom or NH,
n represents l or 2. ) is a triazole derivative represented by

The lower alkyl group referred to herein may be linear or branched. Moreover, the term "lower" as used herein refers to those having 1 to 6 carbon atoms.

The second gist of the present invention is the above - general formula (I)
O is an agricultural and horticultural fungicide characterized by containing a triazole derivative as an active ingredient.Next, specific examples of the present compound of the general formula (1) are shown in Table 1.

In addition, compound No. is also referred to in the following examples and test examples.

Table 1 2) Effect The compound of general formula (I) of the present invention is a new compound. This compound of general formula (I) acts as an active ingredient of a fungicide for agricultural and horticultural use.

The compound of general formula (1) according to the present invention can be produced by the method described below. That is, the a-(triazol-1-yl)phenylpropionic acid derivative represented by the general formula (I1) is converted into an acid chloride in a solvent in the presence of a chlorinating agent, and then the a-(triazol-1-yl)phenylpropionic acid derivative represented by the general formula (I[I) It can be produced by reacting the amine derivative represented by the formula in the presence of an acid binder.

(■) (+) (In the formula, X%YSZsn has the same meaning as above.

) Chlorinating agents used in this reaction include thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, and phosgene. Examples of the solvent include hydrocarbons such as toluene and hexane, halogenated hydrocarbons such as chloroform and chlorobenzene, ethers such as dioxane and tetrahydrofuran, and nitriles such as acetonitrile and zlopionitrile.

Although the reaction proceeds at room temperature, the reaction time can be shortened by heating up to the boiling point of the solvent. After the reaction is complete, add water and an organic solvent such as benzene, toluene, tetrahydro7rane, or chloroform to separate the desired product.
The compound of the present invention can be obtained by distilling off the solvent.

An example of production by this method is shown in Example 1-2.

The starting material, the compound of the formula (I[[), is a known compound, but the compound of the formula (I[) is a new intermediate that has not been described in the literature and can be produced by the following route, and the specific method is described in the reference example. Indicated.

-do' (II) (Y has the same meaning as above.) Example 1 σ-(triazole-t-
25.29 g of p-chlorophenylpropionic acid and 200 IIQ of chloroform were added thereto, and 12.59 g of thionyl chloride was added dropwise to this mixture. After the dropwise addition, the mixture was stirred at 60° C. for 1 hour. After cooling, 16.09 g of 4-chloro-2-mercaptoaniline was added to the reaction mixture, and the mixture was stirred at 60°C for 2 hours. After the reaction, the organic layer was washed with water and dried over anhydrous sodium sulfate.
The solvent was distilled off under reduced pressure to obtain 37.89% of the title compound as brown crystals. Recrystallization from a mixed solvent of ethyl acetate and hexane gave light brown crystals (yield: 28.3 g) with a melting point of 149-150°C.

Example 2 σ-(triazole-1
25.2 g of p-chlorophenylpropionic acid and 200 rIII of toluene were added, and 12.5 g of thionyl chloride was added dropwise to this mixture.
Stir for 1 minute. After cooling, add 2-hydroxyaniline 1 to the reaction solution.
0.9 g was added and the mixture was further stirred at 110°C for 1 hour. After cooling, the mixture was treated in the same manner as in Example 1 to obtain 32.8 g of the title compound as brown crystals. When this was recrystallized from a mixed solvent of ethyl acetate and hexane, light brown crystals (yield: 2
1.9 g) and showed a melting point of 211-213°C.

Triazole 16. 'ht
, potassium carbonate 16.6g and acetonitrile 200g
m<2 and add diethyl bromo malonate 23.
99 was added thereto, and the mixture was stirred at 80°C for 2 hours. After the reaction, insoluble matter was separated from the furnace and the solvent was distilled off under reduced pressure to give diethyltriazole-1.
-ilmalonate was obtained as an oil. Put this material and dimethylformamide room < 1 in a 300s + 4 Q flask, add 1.6 g of sodium hydride (60% mineral oil paste) under water cooling, and after hydrogen generation has finished, add 16.19 g of p-chlorobenzyl chloride. 1
The reaction mixture was stirred at 00°C for 30 minutes. After cooling, 300 mff of ethyl acetate was added and washed twice with water. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain diethyl (p-chlorobenzyl, triazol-1-yl) malonate as an oil. Ta. Add this to 40 mQ of potassium hydroxide and 200 mQ of 50% ethanol water.
Four pieces of 0rtrQ were placed in a flask and stirred at 80°C for 30 minutes. Ethanol was distilled off from the reaction solution under reduced pressure, and the po of the remaining aqueous solution was adjusted to around 3 with concentrated hydrochloric acid to obtain 10.6 g of the title compound as pale brown crystals. This thing has a melting point of 2
It showed 09-210°C.

Moreover, the agricultural and horticultural fungicide of the second present invention has the general formula (
The compound of I) can be formulated and used according to a conventional formulation. That is, by blending the compound of general formula (1) with appropriate carriers and auxiliary agents, such as surfactants, binders, stabilizers, etc., preparations such as aquariums, emulsions, solutions, and sols (including floor preparations) can be prepared. The content of the compound of the present invention in
In the case of wettable powders, emulsions, sols, and oils, 1 to 1 can be used.

The method of using the agricultural and horticultural fungicide of the present invention is generally as follows. In other words, wettable powders, liquids, emulsions, and sols (
For flowable agents) and oil agents, add 500 to 20 with water.
When diluted 1:00, the active ingredient is generally l = 1100
The solution is prepared at a concentration of 0.00 pp. Then, add 50 to 500 (2, usually 100 to 3
00Q is sprayed on the stems and leaves of the plant where the disease occurs.

In addition, liquids, emulsions, and sol (flowables) can be used as concentrated liquids without diluting them with water, or by diluting them up to 10 times with water. UL
V spraying agent), 50 to 3000 m (
The amount of 2 will be sprayed using a helicopter etc.

In addition, powders, DL coarse powders, fine granules, and coarse powders are applied at a dose of 2 to 5 kgC per 10 ares (approximately 50 to 5,009 active ingredients) to the foliage, soil surface, soil, or water surface of the diseased site of the plant. .

A method for formulating the compound of the present invention represented by general formula (1) as an agricultural and horticultural fungicide is shown in Examples 3 to 6 below.

Example 3 Two parts of the bag - 2 parts of Compound No. 12, 1 part of PAP (physical properties modifier) and 97 parts of clay are mixed uniformly and pulverized to obtain a powder containing 2% of the active ingredient.

Example 4 20 parts of the wettable powder compound N008, 3 parts of potassium alkynebenzene sulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 72 parts of arsenic clay were uniformly mixed and pulverized to obtain a composition containing 20% of the active ingredient. Obtain an irrigation agent.

Example 511 Compound No. 9, 30 parts of compound, methyl ethyl ketone 4
By mixing and dissolving 0 parts of polyoxyethylene nonylphenyl ether and 30 parts of polyoxyethylene nonylphenyl ether, an emulsion containing 30% of the active ingredient is obtained.

Example 6 A sol containing 40% of the active ingredient was prepared by uniformly mixing 40 parts of compound No. 016, 2 parts of lauryl sulfate, 2 parts of sodium alkylnaphthalene sulfonate, 1 part of acetoxypropyl cellulose, and 55 parts of water. obtain.

Effects of the Invention The novel compound of the present invention is useful as an agricultural and horticultural fungicide because it exhibits high control effects against downy mildew, late blight, powdery mildew, and rust, which are important diseases of fruit trees, vegetables, and grains. It is.

Next, the usefulness and specific examples of the compound of the present invention represented by the general formula (1) are shown in Test Examples 1 to 4.

Test example 1 Cucumber and disease control effect test In a greenhouse with a diameter of 9
Cucumber seedlings at the second leaf stage (variety: Sumo Hanshiro) grown in soil in clay pots with a size of cm were sprayed with a diluted solution of a predetermined concentration of a hydrating powder prepared according to Example 4 at 2QtQ per pot. .

Then, use a damp brush to remove cucumbers and pathogens (Pseudo).
Spores were scraped off from diseased leaves of Peronospora cubenis and suspended in a 50 ppm aqueous solution of a spreading agent (polyoxyethylene alkyl ether). Then, the spore concentration was adjusted to 5XlO' spores (spores/m12), and a spore suspension of cucumber and disease fungi was sprayed and inoculated one day after the chemical spraying. Then, 2
The cucumbers were allowed to stand still for several days, allowing the cucumbers to develop the disease. Six days after inoculation, the diseased spot area ratio (%) of cucumber per leaf was investigated, the average diseased spot area ratio was determined, and the control value (C%) was calculated using the following formula.
was calculated, and the evaluation value was obtained according to the following criteria.

This test was conducted in duplicate per drug solution concentration area.

In addition, chemical damage to cucumbers was investigated according to the following criteria. The results are shown in Table 2.

In addition, the evaluation value of bactericidal effect and the investigation index of chemical damage were similarly used in Test Examples 2 to 4 below.

5 100% 4 Less than 80 to 100% 360 to less than 80% 240 to less than 60% 1 Less than 20 to 40% 0 Less than 20% Investigation indicator for drug damage 5: Microbacterium 4 2 Very 3: Many 2: Slightly 1: Slightly 0: None Table 2 Note: Values within 0 for non-sprayed plots indicate the average lesion area ratio per leaf.

(Generic name: Chlorothalonil) Test Example 2 Tomato late blight control effect test Example 4 was applied to 5th leaf stage seedlings of tomatoes (variety: Raikou K) grown in soil in a greenhouse with a vinyl pot 9 cm in diameter.
A predetermined concentration diluted solution of a hydrating powder prepared according to the above was sprayed at 30 mQ per 3 pots using an automatic spraying device. The day after the chemical treatment, the potato soil sliced in advance was cultured at 20°C for 3 days.
Zoospore sacs of hLhorainfestans (Phytophthora infestans) were scraped (adjusted so that the concentration of zoospores was 10 5 7'aQ), and spray inoculated onto a tomato plant using a tin gun. And 20°
C1 After being stored in a greenhouse with 100% humidity for 5 days, the 1st to 4th true leaves were investigated for the area ratio (%) of tomato late blight disease spots, the average lesion area ratio was determined, and the control value was determined by comparing with the non-sprayed area. (
%) was calculated and converted into an evaluation value of bactericidal effect.

This test was conducted in duplicate per drug solution concentration area.

In addition, phytotoxicity to tomatoes was investigated using the same criteria as in Test Example 1. The results are shown in Table 3.

Table 3 Note 1) Comparative drug A is the same compound shown in Table 2. .

Note 2) Values within 0 for non-sprayed plots indicate the percentage of lesion area per leaf.

Test Example 3 Barley Powdery Mildew Control Effect Test Hydration prepared according to Example 4 was applied to first leaf stage seedlings of barley (variety: Azuma Golden) cultivated in clay pots with a diameter of 9 cm in a greenhouse. 1 0r per 3 pots of a prescribed concentration of chemical solution
After spraying the powdery mildew (Erysiphegramimis) at night, a spore suspension of barley powdery mildew (Erysiphegramimis) was spray inoculated. Seven days after inoculation, the number of diseased spots of barley powdery mildew was investigated, and no spraying was performed. The control value (%) was calculated from comparison with the ward and converted into an evaluation value of bactericidal effect.

This test was conducted in duplicate per drug concentration area.

In addition, the degree of drug damage to barley was investigated using the same criteria as in Test Example 1, and displayed. The results are shown in Table 4 (Note) The numbers within 0 for non-sprayed plots indicate the number of diseased spots per f leaf.

(Generic name: Kinomethionate) Test Example 4 Wheat rot disease control effect test Example A predetermined concentration diluted solution of an irrigation agent prepared according to 4 was sprayed at 20 m+ (2) per 3 pots.One day later, wheat rot fungus (Puccinia), which had been formed on wheat leaves in advance,
recondita: Puccinia recondita) using a microscope with a magnification of 150 times, the spore concentration per field of view was approximately 5.
Tween 20 (trade name of polyoxyethylene sorbitan monolaurate manufactured by Kao Seki # Co., Ltd.) 5 so that the number is 0.
The spore suspension was suspended in sterilized water to which 0 ppm was added, and the leaves to be rounded were sprayed and inoculated with the spore suspension. 20℃, humidity 100%
After keeping it in a greenhouse overnight, it was transferred to a greenhouse at 20°C to induce disease onset. The leaves were taken out 10 days after inoculation, the number of diseased pedicels per leaf was investigated, the average number of pedicel spores was determined, the control value (%) was calculated, and the result was converted into an evaluation value of the bactericidal effect.

This test was conducted in three pots per drug solution concentration area.

In addition, the degree of drug damage to wheat was investigated and displayed using the same criteria as Test Example 1, and the results are shown in Table 5.

Defense L Table 5 Note) Numbers within 0 in non-sprayed plots indicate the number of lesions per leaf.

Patent applicant: Hokuko Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X and Y are the same or different hydrogen atoms,
represents a halogen atom, a lower alkyl group or a lower alkoxy group, Z represents an oxygen atom, a sulfur atom or NH,
n represents 1 or 2. ) A triazole derivative represented by 2) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X and Y are the same or different hydrogen atoms,
represents a halogen atom, a lower alkyl group or a lower alkoxy group, Z represents an oxygen atom, a sulfur atom or NH,
n represents 1 or 2. ) An agricultural and horticultural fungicide characterized by containing a triazole derivative represented by the following as an active ingredient.