JPS5848560B2 - Methyl N-acylanthranilate derivatives, their production methods, and agricultural and horticultural fungicides containing these as active ingredients - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel methyl N-acylanthranilate derivative, a method for producing the same, and an agricultural and horticultural fungicide containing the compound as an active ingredient.

For further details, the present invention is (1) General formula CI) [In the formula, R represents a furyl group.

] Methyl N-acylanthranilate derivative.

(2) General formula (II) RCOOH (II) [In the formula, R has the same meaning as above.

] and (3) a method for producing a methyl N-acylanthranilate derivative represented by the general formula [■], which is characterized by reacting a carboxylic acid represented by the formula [2] or a reactive derivative thereof with methyl anthranilate; This is an agricultural and horticultural fungicide characterized by containing a methyl N-acylanthranilate derivative represented by (2) as an effective ingredient.

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

In recent years, it has become possible to control most diseases, excluding 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 been established, 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 agricultural fungicides that differ from conventional fungicides in terms of antibacterial action mechanism and have excellent disease control effects.

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

As a result, the methyl N-acylanthranilate derivative of the present invention represented by the above-mentioned general formula (I) showed excellent control effects on powdery mildew in agricultural and horticultural crops, and was also effective against drug-resistant bacteria in the wild. It was found that it has the same antibacterial activity against (drug-susceptible bacteria).

Diseases to be controlled that the compound of the present invention exhibits excellent control effects include powdery mildew on fruit trees such as apples, pears, persimmons, and grapes, and on vegetables such as cucumbers, tomatoes, eggplants, melons, pumpkins, and green peppers. Examples include powdery mildew on cereals such as barley and wheat.

Furthermore, the compounds of the present invention can be used to treat diseases such as rice blast, pear black spot, apple spot leaf spot, apple scab, citrus black spot, botrytis gray mold, grape late rot, peach gray spot, and potato late blight. It has also been shown that it has a control effect against.

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

The compound of the present invention has extremely low toxicity to experimental animals such as mice and rats, and also has low toxicity to fish.

As described above, the compound of the present invention has many excellent properties as an agricultural and horticultural fungicide, exhibits excellent control effects on powdery mildew on fruit trees, vegetables, and grains, and has strong antibacterial properties against drug-resistant bacteria. Therefore, the use of the compound of the present invention as a fungicide is extremely useful in agriculture.

The present invention was completed based on the above-mentioned new findings, and (
1) is the methyl N-acylanthranilate derivative itself represented by the general formula CI), (2) is related to its production method, and (3) is the methyl N-acylanthranilate derivative represented by the general formula CI). This is an agricultural and horticultural fungicide characterized by containing a derivative as an active ingredient.

In the present invention (2), methyl anthranilate is generally dissolved in a suitable solvent such as tetrahydrofuran, thioxane, benzene, toluene, xylene, chlorobenzene, methylene chloride, chloroform, etc., preferably benzene, and an equivalent amount of Add the carboxylic acid represented by the formula [■], add a suitable dehydrating agent such as dicyclohexylluposiimide at room temperature or while heating or cooling if necessary, and react with stirring to precipitate N-N-zinchlorohexyl. After removing urea, the solvent is distilled off to obtain a methyl N-acylanthranilate derivative represented by the general formula CI) with good purity and high yield.

Alternatively, methyl anthranilate is dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, tetrahydrofuran, dioxane, benzene, toluene, xylene, chlorobenzene, methyl isobutyl ketone, acetone, methylene chloride, chloroform, etc., preferably benzene, and in the presence or absence of a dehydrohalogenating agent such as triethylamine, pyridine, quinoline, N-N-dimethylaniline, N-N-diethylaniline, N-methylmorpholine, sodium methylate, etc., preferably in the presence of triethylamine. Below is the general formula (I
Add the acid halide of the carboxylic acid represented by I) under stirring at room temperature or while heating or cooling if necessary, and continue stirring for a while.

After the reaction is complete, the hydrogen halide salt is removed by filtration or washing with water, and the solvent is distilled off to obtain the methyl N-acylanthranilate derivative represented by the general formula [I] with good purity and high yield. It will be done.

This product can be further purified by recrystallization with benzene, hexane, methyl alcohol, ethyl alcohol, etc.

When actually applying the compound of the present invention obtained in this way, it can be used in pure form without adding other ingredients, or it can be mixed with a carrier to make it easier to use as a fungicide. and commonly used forms, such as powders,
It can also be used as a liquid powder, such as wettable powders, oil solutions, emulsions, tablets, granules, fine granules, and aerosols.

The active compounds (including mixed compounds) are generally present in said preparations.
0.1 to 95.0% by weight, preferably 0.2 to 95.0%
Contains 90.0%, usually 1.0% per 10 ares. 0? ~
An application rate of 1000f is suitable.

Furthermore, the concentration used is preferably in the range of 0.001% to 1.0%, but since the amount and concentration used vary depending on the dosage form, application time, method, location, target disease, target crop, etc. There is no problem in increasing or decreasing the amount without regard to the above.

Furthermore, it can be used in combination with other fungicides, such as N-(3,5-dichlorophenyl), 2-dimethylsicpropane-1,2-dicarboximide, S-
Normal-butyl S'-paratertiary butyl benzyl dithiocarbonimidate, O-O-dimethyl 0
-2,6-dichloride/L/-4-methylphenylphosphorothioate, methyl N-penzimidazol-2-yl-N(butylcarbamoyl)carbamate, N-4lichloromethylthio-4-cyclohexene-1,2- Dicarboximide, cis-N-(1,1,2,2-tetracroethylthio)-4-cyclohexene-1,2-dicarboximide, polyoxin, streftomycin, zinc ethylene bisdithiocarbamate, zinc dimethylthiocarbamate, Manganis ethylene bisdithiocainomate, bis(dimethylthiorubamoyl) disulfide, tetrachlorinated nitrile, 8-
Hydroxyquinoline, dodecylguanidine acetate-1.
, 5,6-dihydro-2-methyl-14-oxathiin-3-carpoxanilide, N'dichlorofluoromethylthio N-N-dimethyl N-phenylsulfamito, 1
-(4-k00phenoxy)-3,3-dimethyl-1-
(] ・2.4-1.Riazol-1-yl)-2-butanone, 1.2-bis(3-methoxycarbonyl-2-
It can be used in combination with benzene (thioureido), etc., and neither of these will reduce the control effect of each agent alone.

It can also be used in combination with insecticides.

For example, 0.0-dimethyl 〇1 (4-nitrometh-
}Ryl) phosphorothioate, O-balacyanophenyl O-O-dimethylphosphorothioate, O-paracyanophenyl 〇1ethylphenylphosphonothioate 1.
, O-O-dimethyl S-(N~methyl-rubamoylmethyl) phosphorodithioate, 2-methyl-xy-4H-1
・3.2 benzodioxaphosphorine-2-sulfide,
O-O-dimethyl S-(]monoethoxycarbonyl-■
-phenylmethyl)phosphorodithioate, α-cyano 3-phenoxybenzyl 2-(4chlorophenyl)
-invalerate, 3-phenoxybenzyl 2,2-
It can be used in combination with dimethyl-3-(2,2-)chlorovinyl)cyclopropane lupoxylate, 3-phenoxybenzyl chrysansemate, etc.
Even if there is a difference, the control effect of each single agent will not be lost.

Therefore, it is possible to control two or more types of pests at the same time, and a synergistic effect by mixing them is also expected.

The present invention will be explained in more detail with reference to examples and formulation examples below, but the types and mixing ratios of additives to the compounds of the present invention are not limited to these, and can be varied within a wide range. The examples are only a part of typical tests, and it goes without saying that the compounds of the present invention have a wide range of applications as agricultural and horticultural fungicides.

Example 1 Production method Methyl N-furoylanthranilate 300rnl4
13. Charge 200 mg of benzene, 15.1 g of methyl anthranilate, and 11 g of triethylamine into a flask and stir at room temperature. 0.1 J of IP Froilk was added dropwise.

After the dropwise addition was completed, the reaction solution was heated under reflux for 2 hours.

After cooling, the precipitated triethylamine hydrochloride was removed by filtration, the solvent was distilled off under reduced pressure, and the residue was recrystallized from n-hexane to obtain the desired methyl N-furoylanthranilate 2.
0.89 was obtained.

Melting point 114.5-1155℃ *Elemental analysis value C (%) H (%) N (%) Calculated value 63,68 4.52 5.7
1 (as C, 3H,, NO4) Actual value 63,70 4.61 5.6
Examples of compounds obtained as above are listed in Table 1.

Example 2 Kyu'J 5 powdery mildew control effect test When a cucumber (variety: Sagami Hanshiro) grown in a flower pot with a diameter of 9crrL began to develop its first leaves, the leaves were pinched and the test drug in the form of an emulsion was applied to the cotyledons. Dilute with water and add 10 per pot.
It was sprayed at a rate of TIll.

After 1 day, powdery mildew (Sphaerotheca)
fuliginea) was inoculated by spraying, and 14 days later, the disease state was observed.

The disease severity was calculated by the following method. In other words, calculate the percentage of lesion area on the investigated leaf and set it as 0, ■, or 2 depending on the degree.
, 3, 4, and 50 indices, the number of leaves corresponding to each disease index was investigated, and the disease severity was calculated using the following formula.

Disease index disease state 0 No bacterial flora observed on the leaf surface disease state Less than 10% bacterial flora is observed on the leaf surface. ,, 30%! / 〃 60% 〃 〃 95% 〃 〃 95% or more bacterial flora is observed ? Disease severity = Σ (sickness index 8 number of leaves) x.

. The results of the 5× number of leaves test are shown in Table 2, and as is clear from the results, the compound of the present invention showed a superior pesticidal effect compared to the control compound.

Example 3 Control effect test against drug-resistant bacteria - Cucumber powdery mildew (S phaerothecafuli) showing drug resistance to methyl N-penzimidazol-2-yl N-(butylcarbamoyl) carbamate
ginea), a cucumber powdery mildew control effect test was conducted in the same manner as in Example 2.

The method for investigating the onset of the disease and the method for calculating the degree of onset of the disease are also the same as in Example 1.
It is similar to

*5 The results of this test are shown in Table 3.

As is clear from the comparison between the present results and the results of Example 2, the comparative compound methyl N-penzimidazole-
Although 2-il-N-(butylcarbamoyl) carbamate exhibits a control effect against wild bacteria (drug-susceptible bacteria), it exhibits almost no control effect against drug-resistant bacteria.

On the other hand, the compounds of the present invention showed high control effects against drug-resistant bacteria as well as against susceptible bacteria.

Example 4 Barley powdery mildew control effect test 1 Barley (variety: Akashinriki) was grown in a flower pot with a diameter of 9 cr I'L. When the first true leaf developed, the test chemical in emulsion form was diluted with water and 1 The leaves were sprayed at a rate of 10 ml per pot.

After air-drying the chemical solution, powdery mildew fungus (Erysi phegra)
minis) was inoculated and cultivated under fluorescent lamp illumination at 18°C for 10 days, and then the disease state was observed.

The method of investigating the onset of the disease and the method of calculating the degree of onset of the disease are the same as in Example 2.

The results of this test are shown in Table 4, and as is clear from the results, the compound of the present invention exhibited a superior pesticidal effect compared to the comparison compound.

Formulation Example 1 Emulsion By mixing 10 parts of the compound of the present invention (2), 50 parts of xylene, 30 parts of dimethyl sulfoxide, and 10 parts of an emulsifier (phoryoxyethylene phenylphenol ether),
An emulsion with a base concentration of 10% is obtained.

Formulation Example 2 Wettable Dispersible Agent 50 parts of the compound of the present invention (1), 5 parts of a wetting agent (alkylbenzenesulfonic acid calcium salt) and 45 parts of diatomaceous earth are ground and mixed to obtain a permanent powder with a base ingredient content of 50%.

Claims (1)

[Claims] 1. General formula [wherein R represents a furyl group]. ] A methyl N-acylanthranilate derivative. 2 General Formula [In the formula, R represents a furyl group. ] Characterized by reacting a carboxylic acid represented by the above formula or a reactive derivative thereof with methyl anthranilate [wherein R has the same meaning as described above]. ] A method for producing a methyl N-acylanthranilate derivative. 3 General Formula [In the formula, R represents a furyl group. ] An agricultural and horticultural fungicide characterized by containing a methyl N-acylanthranilate derivative as an active ingredient.