JPH03264564A - Imidazoleamidoxime derivative and fungicide - Google Patents

Abstract

NEW MATERIAL:An imidazolemidoxime derivative shown by formula I (R<1> and R<2> are alkyl; R<3> is H or halogen R<4> is phenyl which may be replaced or not). EXAMPLE:4-Chloro-1-dimethylsulfamoyl-5-phenyl-imidazole-2-amidoxime. USE:Useful as an agricultural and horticultural fungicide. Having preventing and treating effects on late blights, downy mildews, etc., of various kinds of plants and no phytotoxicity to crops. PREPARATION:For example, an imidazolenitrile derivative shown by formula II is reacted with hydrxylamine to give a compound shown by formula I. As another method, an imidazolenitrile derivative shown by formula III is reacted with hydroxylamine and the reaction product is sulfamoylated to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel imidazole amidoxime derivative and an agricultural and horticultural fungicide containing the derivative as an active ingredient.

[Conventional technology]

One of the important problems in agricultural production, particularly in the cultivation of fruit trees and cane vegetables, is diseases caused by plant pathogenic bacteria belonging to the fungal family (eg, downy mildew, late blight, etc.).

Diseases caused by these bacteria are difficult to control due to the physiological and ecological special characteristics of the bacteria, and the development of excellent control agents is desired. Many crops are affected by head rot and late blight, and the damage caused is extremely large.

Currently, cabtan (common name), captafor (common name),
Dithiocarbamate fungicides such as zineb (generic name) and chlorothalonil (generic name) are widely used. However, these fungicides mainly have a preventive effect and can hardly be expected to have a curative effect, so they have the major drawback that if they are used only when a disease outbreak is observed, sufficient effects cannot be expected. There is. Recently developed acylalanine compound fungicides that have been put into practical use, such as metalaxyl (generic name), have both preventive and curative effects, but resistant bacteria have already emerged. However, its control effect has been considerably reduced.

Conventionally, as a prior art that includes a compound that is chemically similar to the compound of the present invention, Japanese Patent Application Laid-Open No. 63255269
JP-A No. 1-131163 is known.

, [Problems to be Solved by the Invention] The present invention has a preventive effect and a curative effect against diseases caused by plant pathogenic bacteria belonging to the fungal family (e.g., downy mildew, late blight, etc.), and is also useful. The purpose is to provide a fungicide that does not cause chemical damage to crops, and there is a demand for the development of such an excellent fungicide.

[Means to solve the problem]

In order to solve the above-mentioned problems, as a result of various exploratory research, it was found that the compound group of general formula [1] shown below has both preventive and curative effects against late blight, downy mildew, etc. of various plants. The present inventors have completed the present invention by discovering that the present invention exhibits the following characteristics: and extremely low phytotoxicity to crops.

The compound of the present invention, which is the active ingredient of the agricultural and horticultural fungicide of the present invention, is a new compound that has not been described in any literature.

The present invention provides: (1) General formula [l]: 5O2NR'R2 [wherein R1 and R2 represent an alkyl group which may be the same or different, R3 represents a hydrogen atom or a halogen atom, and R4 represents a phenyl group which may be unsubstituted or substituted. ] An imidazole amidoxime derivative represented by

(2) In the above (1), an agricultural and horticultural fungicide containing an imidazole amidoxime derivative represented by general formula (1) as an active ingredient.

(3) General formula [2]: [In the formula, R3 represents a hydrogen atom or a halogen atom, and R
4 represents a phenyl group which may be unsubstituted or substituted. ] An imidazole amidoxime derivative represented by

It is related to.

(Hereinafter, blank spaces) Next, the production method of the present invention will be shown with a reaction scheme and explained below.

Reaction scheme ■ SO□NR'R2 [3] ■ [4] ■ [5] JP-A-63-255269 or JP-A-1-131163
Imidazole nitrile derivative obtained by the production method [
The desired imidazoleamide oxime derivative [1] can be easily obtained by reacting [3] with hydroxylamine.

5O2NR'R2 [1] JP-A-63-255267 or JP-A-1-131163
Imidazole nitrile derivative obtained by the production method [
4] by reacting with hydroxylamine [
5] was obtained, and further [5] was obtained in JP-A-63-25526.
The desired imidazole amidoxime derivative [1] can be obtained by sulfamoylation according to the method disclosed in 7 or JP-A-1-13116.

Next, the method for producing the compound of the present invention will be explained using specific examples, but the present invention is not limited to these.

Example 1 (Synthesis of compound Nα6) rρ 5O2NR'R2 Cρ 1.1 g of hydroxylamine hydrochloride was dissolved in 50 n of methanol.
+4? Inside, 1.0 g of sodium methoxide was added, and the mixture was stirred for 1 hour from ice temperature to room temperature to neutralize.

Subsequently, 2-cyano-4-chloro-1-
Dimethylsulfamoyl-5-phenylimidazole 3
．． 1g to methanol 50+nj? A solution dissolved in was added and refluxed for 3 hours.

After the reaction was completed, the solvent was distilled off under reduced pressure, and water and chloroform were added to the resulting residue for extraction. After removing insoluble matter by filtration, the aqueous layer and chloroform layer were separated, and the chloroform layer was further washed with water and then dried over anhydrous sodium sulfate. Furthermore, by concentrating this chloroform solution, the desired 4
2.4 g of -chloro-1-dimethylsulfamoyl-5-phenyl-imidazolyl-2-amidoxime were obtained.

Compounds of the present invention that can be synthesized in a similar manner to have a melting point of 59 to 61°C are shown in Tables 1 to 4 below.

SO□NR'R2 11 SO□NR'R2 5O□NR'R2 The present invention further provides an agricultural product containing the amidoxime derivative represented by the general formula (1) according to the present invention as an active ingredient. The present invention provides a horticultural fungicide.

The agricultural and horticultural fungicide of the present invention is not only effective against downy mildew and late blight of various crops, but also effective against other diseases.

The main diseases include cucumber downy mildew, grape downy mildew, lettuce downy mildew, Chinese cabbage downy mildew, hops downy mildew, potato late blight, tomato late blight, cucumber gray late blight, pepper late blight, and tomato, cucumber and rice blight caused by Pythium blight. Examples include seedling damping off and beet seedling damping off caused by Aphanomyces bacteria.

Application methods for the agricultural and horticultural fungicide of the present invention include seed treatment, foliage spraying, soil application, and the like.

The amount and concentration of application will vary depending on the target crop, target disease, degree of disease occurrence, application method, etc., but when spraying, the amount of active ingredient should be 2 to 2 per hectare.
Applicable at 2000g, preferably 10-1000g.

The spray concentration can be applied at 11-1000 pI), and preferably 5 to 500 ppm.

In addition, since the agricultural and horticultural fungicide of the present invention has both preventive and curative effects, it can be applied both preventively and after the onset of disease, and there is a wide range of suitable times for its application. have.

The agricultural and horticultural fungicides of the present invention may optionally contain other biologically active compounds, such as similar or complementary fungicides, or agricultural chemicals such as insecticides, herbicides, plant growth regulators, and fertilizers. Not only can it be used in combination with effective substances, soil conditioners, etc., but also mixed formulations with these are also possible.

The agricultural and horticultural fungicide of the present invention can be carried out using a suitable carrier, such as a solid carrier such as clay, talc, bentonand, diatomaceous earth, or water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.). ), chlorinated hydrocarbons, ethers, ketones, esters (
ethyl acetate, etc.).

It can be applied in combination with a liquid carrier such as acid amides (dimethylformamide, etc.), and if desired, emulsifiers, dispersants, suspending agents, penetrating agents, spreading agents, stabilizers, etc. may be added. Emulsions, oils, hydrating agents, powders.

It can be put to practical use in any dosage form such as granules or flowables.

Next, the range of each component and the type of each component in formulation examples of these compositions will be shown, but the agricultural and horticultural fungicide of the present invention is not limited to these.

In addition, in the following formulation examples, "1 part" means part by weight.

(1) Wettable powder Compound of the present invention: 5 to 75 parts Solid carrier: 9 to 86 parts Surfactant
・・・・・・ Parts 5 to 10 Others
...0 to 5 parts As the solid carrier, calcium carbonate, kaolinite, gicrite A1 dicrite PPP.

Examples include diatomaceous earth and talc.

As surfactants, Lunox 100OC, Tsurupol 5039, Tsurupol 5050, Tsurupol 0050 are used.
Examples include ゜Turupol 5029-0, calcium sulfonate, sodium dodecyl sulfonate, and the like.

Other components include Carplex #80.

(2) Emulsion Compound of the present invention: 5 to 50 parts Liquid carrier: 35 to 90 parts Surfactant
・・・・・・ 5 to 15 parts As a liquid carrier,
xylene, dimethylformamide, methylnaphthalene,
Examples include isophorone.

Examples of the surfactant include Tsurupol 2680, Tsurupol 3005X, and Tsurupol 3346.

(3) Flowable agent Compound of the present invention: 5 to 75 parts Liquid carrier: 14.5 to 68 parts Surfactant: 5 to 10 parts Others
...1 to 10 parts Water is used as the liquid carrier.

Examples of the surfactant include Lunox 100OC, Solpol 3353, Sorbohol PL, Nippol, Agrisol S-710, sodium ligninsulfonate, and the like.

Other ingredients include ethylene glycol, propylene glycol, xanthan gum, and the like.

(4) Powder Compound of the present invention: 0.03 to 20 parts Solid carrier: 94 to 98.97 parts Others: 0 to 3 parts As solid carrier: , calcium carbonate, kaolinite, gicrite, talc and the like.

Other ingredients include diisopropyl phosphate,
Examples include Carplex #80.

(5) Granules Compound of the present invention: 0.3 to 10 parts Solid part: 92 to 98.7 parts Others: 0 to 5 parts As a hedral carrier: , calcium carbonate, kaolinite, bentonite, talc, etc.

Other ingredients include calcium lignin sulfonate, polyvinyl alcohol, and the like.

Next, specific formulation examples of the agricultural and horticultural fungicide containing the oxime derivative represented by the general formula [1] as an active ingredient according to the present invention will be shown. It is not limited only to these. In addition, in the following formulation examples, "parts" mean parts by weight.

Formulation Example 1 Wettable powder Compound of the present invention 5 parts Sieglite PFP 87
Part (Mixture of kaolinite and sericite: Sieglite Industries ■Product name) Tsurupol 5039 5039
Part Carplex #80 ・・・・・・
3 parts (white carbon: Shionogi & Co., Ltd. product name) or more are uniformly mixed and pulverized to make a wettable powder. When using, dilute the above wettable powder 100 to 10.000 times and add the active ingredient. The amount is 10-1000 per hectare
Spread it so that it becomes g.

Formulation Example 2 Wettable powder Compound of the present invention 25 parts Sieglite PPP 69
Part (Mixture of kaolinite and sericite: Siegrite Industrial Co., Ltd.) Product name) Tsurupol 50
39 ...... 3 parts (mixture of anionic surfactant and white carbon: Toho Chemical ■trade name) Carplex #80 ...... 3 parts (white carbon: Shionogi & Co., Ltd. ■trade name) The above is uniformly mixed and pulverized to form a wettable powder. When using, add the above hydrating agent to 500~
It is diluted 50,000 times and sprayed so that the amount of active ingredient is 10 to 1000 g per hectare.

Formulation Example 3 Wettable powder Compound of the present invention 20 parts Calcium carbonate (powder) 69 parts Tsurupol 5050 10 parts Carplex #80 At least 1 part (white carbon: Shionogi & Co., Ltd. trade name) is mixed and pulverized uniformly to make a wettable powder. When used, the above-mentioned hydrating agent is diluted 400 to 40,000 times and sprayed so that the amount of active ingredient is 10 to 1000 g per hectare.

Formulation Example 4 Emulsion Compound of the present invention 5 parts Xylene 70 parts N
, N-dimethylformamide 20
Part Tsurupol 2680 ・・・・・・
At least 5 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■ trade name) are mixed uniformly to form an emulsion. When using the above emulsion,
It is diluted 0 to 10,000 times and applied so that the amount of active ingredient is 10 to 1000 g per hectare.

Formulation Example 5 Emulsion Compound of the present invention 50 parts 2 Xylene 25 parts N,N-dimethylformamide 1
Part 0 crane pole 3346...
- 15 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■trade name) The above is mixed uniformly to form an emulsion. When used, the above emulsion is diluted 500 to 50,000 times and applied so that the amount of active ingredient is 10 to 1000 g per hectare.

Formulation Example 6 Flowable agent Compound of the present invention... 5 parts Tsurupol 3353...
5 parts (Nonionic surfactant: Toho Chemical Co., Ltd. trade name)
Lunox 100Oc...
3 parts (Anionic surfactant: Toho Chemical ■Product name) 1% aqueous solution of xanthan gum 20 parts (
Natural polymer) Water ・・・・・・
57 parts ethylene glycol ・・・・・・
The above components except for 100 parts of the active ingredient (the compound of the present invention) are uniformly dissolved, and then the compound of the present invention is added, thoroughly stirred, and then wet-pulverized in a sand mill to obtain a flowable agent. When using, add the above flowable agent to 100 to 10
．． It is diluted 1,000 times and sprayed so that the amount of active ingredient is 10 to 1,000 g per hectare.

Formulation Example 770 Compound of the present invention 75 parts Tsurpol 3353 3353
5 parts (Nonionic surfactant: Toho Chemical ■Product name) Lunox 100OC...0.5 parts (Anionic surfactant: Toho Chemical@Product name) Xanthan gum 1
% aqueous solution ・・・・・・ 10 parts (natural polymer) Water ・・・・・・
4.5 parts propylene glycol...
- 5 parts The above components except for the active ingredient (the compound of the present invention) are uniformly dissolved, then the compound of the present invention is added, and after stirring well, wet grinding is carried out in a sand mill to obtain a flowable agent. When used, the above three flowable agents are diluted 1,500 to 150,000 times and sprayed at an amount of active ingredient of 10 to 1000 g per hectare.

Formulation Example 8 Powder Compound of the present invention: 10 parts Clay: 90 parts or more are mixed uniformly to obtain a powder.

When used, the above-mentioned powder is sprayed as is in an amount of active ingredient of 10 to 1000 g per hectare.

Formulation Example 9 Granule Compound of the present invention 5 parts Bentonite 25 parts Tart 7
After uniformly mixing and pulverizing 0 parts or more, a small amount of water is added, the mixture is stirred and mixed, and the mixture is granulated using an extrusion type granulator and dried to form granules.

When used, the above-mentioned granules are directly dispersed in an amount of 10 to 1000 g of active ingredient per hectare.

4 Next, the effects of the compounds of the present invention in biological tests will be specifically described.

Test Example 1 Cucumber and Disease Preventive Effect Test When cucumbers (cultivar Sagami Hanshiro) grown in pots with a diameter of 7 cm reached the 1st to 2nd leaf stage, a test sample was prepared in the form of an emulsion prepared according to Formulation Examples 4 and 5 above. Dilute the compound with water to adjust to the desired concentration,
A spray gun was used to spray 20ml per pot. The day after spraying, cucumbers and diseased bacteria (Pseudoperonosp)
spore suspension (2x105
cells/ml) and placed in an inoculation box at a temperature of 25°C and a humidity of 95% or higher overnight. Thereafter, the plants were placed in a greenhouse, and the ratio of the area of lesions formed 7 days after inoculation to the inoculated leaves was measured, and the control value was calculated according to the following formula.

The results of this test are shown in Table 5.

Table 5 (Treatment concentration: 10100pp Compound Nα
Control value Pseudope 6 Test Example 2 Cucumber and disease-curing effect test When cucumbers (variety: Sumo Hanshiro) grown in pots with a diameter of 7 cm reached the 1st to 2nd leaf stage, cucumbers and Pseudope
ronospora cubensis) was sprayed and placed in an inoculation box at a temperature of 25° C. and a humidity of 95% or higher overnight for inoculation.The next day, according to Formulation Examples 4 to 5 above. The prepared test compound in the form of an emulsion was diluted with water, adjusted to a predetermined concentration, and sprayed at 20 ml per pot using a spray gun.Then, the inoculated leaves were placed in a greenhouse and covered with the area of lesions formed 7 days after inoculation. The percentage of the total number of insects was measured, and the control value was calculated according to the formula below.

Test Example 3 Preventive effect test on tomato late blight When tomatoes (cultivar: Fukuju) grown in a pot with a diameter of 8 cm reached the 3-leaf stage, a wettable powder prepared according to Formulation Examples 1 to 3 above was diluted with water. to obtain a predetermined concentration of the active ingredient;
It was sprayed at 20ml per pot using a spray gun. The day after spraying, tomato late blight fungus (Phytophthora
1nfestans) spore suspension (2x105 spores/
ml') was sprayed and kept in an inoculation box at a temperature of 20°C and a humidity of 95% or more for 5 days, the ratio of the area of lesions formed to the inoculated leaves was measured, and the control value was calculated according to the formula below. .

The test results are shown in Table 6.

Table 6 (Treatment concentration: 10100pp Compound Nα
Control value Table 7 shows the results of this chemical damage test.

Table 7 (Treatment concentration: 10,100pp Compound Nα Control value Phytotoxicity 7 8 Test example 4 Tomato late blight treatment effect test When tomatoes (variety: Fukuju) grown in 8 cm diameter pots reached the 3-leaf stage, tomato late blight fungus (Phytophth
spore suspension (2x
105 pieces/ml) at a temperature of 20°C and a humidity of 95%.
It was kept in the above inoculation box for one day and night. After that, the above formulation examples 1 to
The wettable powder prepared according to 3 was diluted with water to give a predetermined concentration of the active ingredient, and 20 rnl of it was sprayed per pot using a spray gun.

After air-drying, the pot was placed in the inoculation box described above, and the proportion of the area of lesions formed after 5 days to the inoculated leaves was measured, and the control value was calculated according to the following formula.

The results of this test are shown in Table 8.

Claims (3)

[Claims] (1) General formula [1]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] [In the formula, R^1 and R^2 represent an alkyl group that may be the same or different, and R ^3 represents a hydrogen atom or a halogen atom, and R^4 represents an unsubstituted or optionally substituted phenyl group. ] An imidazole amidoxime derivative represented by (2) The agricultural and horticultural fungicide according to claim (1), which contains an imidazole amidoxime derivative represented by the general formula [1] as an active ingredient. (3) General formula [2]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [2] [In the formula, R^3 represents a hydrogen atom or a halogen atom,
R^4 represents a phenyl group which may be unsubstituted or substituted. ] An imidazole amidoxime derivative represented by