JPS585919B2 - Organic phosphorus-substituted imidazolidinedione derivatives and their production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to (1) general formula [I] [wherein, , lower alkoxy group, lower alkoxyalkoxy group, unsubstituted or substituted phenoxy group with lower alkylmerkabuto group, alkylamino group kenylamino group, cyanogen-substituted lower alkylamino group, lower alkylmercapto group, or aralkylmerkabuto group .

] and (2) an organic phosphorus-substituted imidazolidinedione derivative represented by the general formula [■] [wherein 2 is a halogen atom, and Y, R1 and R2 have the same meanings as above.

] and the general formula (■) [In the formula, X has the same meaning as above.

It is represented by general formula [I], which is characterized by reacting with an imidazolidinedione derivative shown in ].

This is a method for producing an organic phosphorus-substituted imidazolidinedione derivative.

Numerous organic synthetic compounds and antibiotic substances with antibacterial properties have been discovered and developed as fungicides for agricultural and horticultural use, protecting agricultural and horticultural crops from pathogenic bacteria and greatly contributing to the stable supply of agricultural products.

In recent years, it has become possible to control most diseases, with the exception of soil-borne diseases and diseases caused by bacteria or viruses, by spraying appropriate fungicides.

However, in recent years, so-called drug resistance of plant pathogenic bacteria has come to be regarded as an important practical problem.

It is often experienced that even if chemicals are sprayed in fields where drug-resistant bacteria have appeared, little control effect is observed.
In addition, many reports have been made of the appearance of bacteria resistant to a large number of drugs.

An appropriate method for preventing the emergence of such resistant bacteria is the alternate or mixed application of agents with different antibacterial action mechanisms against pathogenic bacteria.

Therefore, there is a need to develop a fungicide for agriculture and horticulture that differs from conventional fungicides in its action mechanism and has excellent disease control effects.

From the above viewpoint, the present inventors investigated the disease control effects of a wide variety of organic synthetic compounds, and also examined their antibacterial properties against pathogenic bacteria that have already become drug-resistant.

As a result, the organic phosphorus-substituted imidazolidinedione derivative represented by the general formula [I] of the present invention, which is a compound of the present invention, exhibits excellent antibacterial properties against a wide range of plant pathogenic bacteria, and is also effective against drug-resistant bacteria (susceptible wild bacteria). It was found that it has the same antibacterial activity as against bacteria (bacteria).

Diseases to be controlled for which the compound of the present invention exhibits excellent control effects include pear black spot, apple spot leaf spot, apple scab, apple monilia, citrus black spot, citrus scab, citrus blue mold, Citrus green mold, peach botrytis, grape botrytis, grape late rot, persimmon anthracnose, vegetable sclerotia, botrytis, botrytis, cucurbit anthracnose and downy mildew, cruciferous crops These include black spot of rice, late blight of potato, ring spot of tomato, and sheath blight of rice.

On the other hand, disinfectants that can actually be used must have low toxicity to humans and livestock.

All of the compounds of the present invention had extremely low toxicity to experimental animals, and also had low toxicity to fish.

As described above, the compound of the present invention has many excellent properties as a fungicide for agricultural and horticultural purposes, shows control effects against various crop diseases, and has strong antibacterial properties against drug-resistant bacteria. Its use as an agent is extremely beneficial in agriculture.

The present invention was completed based on the above-mentioned new findings, and (
1) relates to the organic phosphorus-substituted imidazolidinedione derivative itself represented by the general formula [■], and (2) relates to its production method.

In the present invention (2), the imidazolidinedione derivative represented by the general formula [■] and an equivalent or excess amount of the halogenated organophosphorus compound represented by the general formula [■] are generally used without a solvent or in an appropriate solvent. For example, diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane,
In the presence of day glyme etc., more preferably in the presence of an alkali hydride such as sodium hydride or a suitable dehydrohalogenating agent, cooling or heating as necessary, stirring or standing, the product represented by the general formula [I] is obtained. The compound of the present invention is obtained.

The present invention will be explained in more detail with reference to Examples and Reference Examples below, but it goes without saying that the present invention is not limited to these.

Example 1 A dried tetrahydrofuran solution containing 0.05 mol of 3-(3,5-dichlorophenyl)imidazolidine-2,4-dione represented by the general formula [■] was cooled to below 10°C to form sodium hydride. Gradually add 0.06 mol and then stir at room temperature for 1 hour.

Next, 0,0-dimethylthionophosphoryl chloride 0
．． 05 mol was added dropwise under water cooling, and the mixture was stirred at room temperature for 17 hours.

After the reaction, the reaction solution is poured into ice water, extracted with ether, washed with dilute hydrochloric acid, hydrogenated sodium chloride solution, and water, and dried over magnesium sulfate.

After passing the solution through the mouth and distilling off the ether, separation was performed by column chromatography to obtain 11.0 g (yield 61%) of 1-(0.0-dimethylthionophosphoryl)-3-
(3,5-dichlorophenyl)imitazolidine-2,4
- Obtain dione.

The results obtained in the same manner are shown in Table 1.

Reference Example 1 Chinese cabbage black soot disease control effect test During the third true leaf stage of Chinese cabbage (variety: Nagaoka cross No. 2 Chinese cabbage "Kamome") grown in a flower pot with a diameter of 9 m, a test chemical in the form of an emulsion was diluted with water. , with a predetermined concentration, and ■lom per pot.
1 was sprayed on the leaves.

After 4 hours, Chinese cabbage black sooty fungus (Alternariab) obtained by culturing on vegetable juice agar medium for 10 days
rassicicola) was spray-inoculated and kept at constant temperature and humidity of 27 to 28° C. and 100% humidity for 48 hours in the dark, after which the plants were illuminated and disease onset was investigated one day later.

Incidentally, the degree of disease onset was calculated using an index of 0, 1, 2, 4, and 8 based on the following formula.

No lesions are recognized...
...Less than 10% of lesions are observed on the 0 leaf surface...
・・・・・・・・・1〃 Less than 10% to 25% of lesions are observed・・・・・・2〃 Less than 25% to 60% 〃
...4. 60% to less than 100% of lesions were observed on the leaf surface...8 As a result, as shown in Table 2, the compound of the present invention was superior to the control compound tested at the same time. It showed a pesticidal effect.

Reference Example 2 Rice blast control effect test A test drug in emulsion form was diluted with water to a predetermined concentration on rice (Kinki No. 33, 4-5 leaf stage) grown in a 9 cm flowerpot, and a spray gun was used to test the effect of controlling rice blast disease. It was sprayed at a rate of 15 ml/pot.

One day after spraying, this pathogen (Pyricularia or
yzae) and placed in a constant temperature room at 24-26° C. and 90% humidity or higher. After 4 days, the degree of disease was determined based on the lesion area ratio and the control effect was examined.

The results are shown in Table 3.

The control value was calculated using the following formula.

Reference Example 3 Rice Trigger Disease Control Efficacy Test When rice (variety: Kinnanfu) grown with four plants in a 9cm flowerpot reached a plant height of approximately 60cm, 10ml/ml of the compound of the present invention in the form of a hydrating powder was applied using a spray gun. Sprayed at a rate of 1 pot.

After 24 hours, the leaf sheath of each stem was inoculated with a section (diameter 5 mm) of the disease fungus (Pelliculariasasakii) cultured in a PS synthetic medium, and the stem was placed in a 28°C incubator.

After another 4 days, the length of the diseased lesions was measured and the control effect was examined based on the severity of the disease, and the results shown in Table 4 were obtained.

The disease severity was calculated based on the following criteria.

Disease index 0...No lesions observed on the leaf sheath 1.
... Traces and stains that appear to be lesions are observed on the leaf sheath 2 ... Lesions of 3 cm or less are observed on the leaf sheath 3 ...
...Reference example where lesions of 3 cm or more are observed on leaf sheaths 4 Cucumber Sclerotinia disease control efficacy test When cucumbers (variety: Sagami Hanshiro) grown in 9 cm flower pots have developed their first true leaves, the emulsion form The compound of the present invention was diluted with water and sprayed at a rate of 7 ml per pot.

One day later, Sclerotinia sclera
bacterium-containing agar pieces (diameter 5 mm) of C. otiorum were inoculated onto the leaves, and the disease state was observed 3 days later.

The degree of disease onset was investigated by measuring the lesion diameter, and the disease severity was calculated using the following formula.

The results of this test are shown in Table 5, and the compound of the present invention showed superior pest control effect compared to the comparative control compound.

Claims (1)

[Scope of claims] 1 General formula [wherein, , unsubstituted or substituted with a lower alkylmerkabuto group, phenoxy group, alkylamino group, lower alkenylamino group, cyanogen-substituted lower alkylamino group, lower alkylmerkabuto group, or aralkylmerkabuto group. ] An organic phosphorus-substituted imidazolidinedione derivative represented by 2 General formula [wherein, X represents a halogen atom]. 3-(3,5-dihalogenophenyl)imidazolidine-2,4-dione derivative represented by the general formula
Y is an oxygen atom or a sulfur atom, R1 and R2 are the same or different, lower alkyl group, phenyl group, lower alkoxy group, lower alkoxyalkoxy group, phenoxy group unsubstituted or substituted with lower alkylmercapto group, alkylamino group , a cyanogen-substituted lower alkylamino group, a lower alkenylamino group, a lower alkylmercapto group, or an aralkylmercapto group. [In the formula, X, Y, R1 and R2 have the same meanings as above. ] A method for producing an organic phosphorus-substituted imidazolidinedione derivative.