JPS6025968A - Isonicotinic acid anilide derivative and agricultural and horticultural fungicide composed of said derivative - Google Patents

Abstract

NEW MATERIAL:The isonicotinic acid anilide derivative of formula I (X is H or halogen; Y is lower alkyl or lower alkyloxy; Q is H or OH). EXAMPLE:Isonicotinic acid-2-(alpha-hydroxy-4-methylbenzyl)-anilide. USE:An agricultural and horticultural fungicide. It exhibits excellent action to the blights of useful crops, has high safety to man, animal and fish, and is absolutely harmless to crops. PREPARATION:The compound of formula I is produced by reacting the isonicotinyl halide of formula II (Z is halogen) or its hydrogen halide salt with the aniline derivative of formula III in a proper solvent. The reaction is preferably carried out in the presence of an acid acceptor such as pyridine, triethylamine, etc.

Description

Detailed Description of the Invention The present invention is based on the general formula [■] (where X represents a hydrogen atom or a halogen atom, Y represents a lower alkyl group or a lower alkyloxy group, and Q represents a hydrogen atom or a hydrogen group). This invention relates to an agricultural and horticultural fungicide consisting of an isonicotinic acid anilide derivative represented by the following formula and its compound.

Many synthetic organic compounds and antibiotics with bactericidal properties have already been discovered, and many substances have been developed as fungicides for agriculture and horticulture.

However, in recent years, the emergence of resistant bacteria and environmental pollution due to mass spraying have become problems.

In addition, in recent years, many inventions related to so-called azole compounds as agricultural and horticultural fungicides have been announced.

For example, JP-A-56-152446, JP-A-57-168
70, JP-A-57-48982, JP-A-57-1205
79, Japanese Unexamined Patent Publication No. 57-126479.

However, these compounds often have plant growth inhibitory and herbicidal effects, and have the drawback that they cannot necessarily be said to be safe to use.

In order to compensate for these shortcomings, the present inventors have
The present invention was achieved through intensive efforts to develop a drug that has a novel skeleton and is highly effective even in small amounts.

The compound of the present invention represented by the general formula [■] is a novel compound that exhibits excellent effects against diseases of useful cultivated crops, is highly safe for humans, livestock, and fish, and is effective against crops. It does not show any adverse effects on

The compound of the present invention represented by the general formula [■] is widely used as an agricultural and horticultural fungicide for both prevention and treatment of various pathogenic bacteria belonging to the fungi, ascomycetes, basidiomycetes, and deuteromycetes. It can be applied. In particular, it shows excellent efficacy against powdery mildew, rust, etc. of useful plants.

The compound of the present invention represented by the general formula [■] is novel,
It can be manufactured by the method shown below.

(1) Isonicotinic acid halide or its hydrohalide represented by the general formula [■] (in the formula, 2 represents a halogen atom) is added to the isonicotinic acid halide or its hydrohalide represented by the general formula [■] ( However, in the formula, Q represents a hydrogen atom or a hydrogen group.

X and Y have the same meanings as above. ) to produce the compound of the present invention represented by the general formula [■]. In this case, the reaction will proceed smoothly if a deoxidizing agent such as pyridine, triethylamine, N,N-dialkylaniline, soda carbonate or potassium carbonate is used. Further, suitable solvents include benzene, toluene, chloroform, dioxane, dimethylformamide, and the like.

(2) General formula [■] (However, in the formula, X and Y have the same meanings as above.)
The compound of the present invention represented by the general formula [■] can be produced by reducing the isonicotinic acid derivative represented by the following with an appropriate reducing agent.

Suitable reducing agents include, for example, sodium borate, lithium aluminum hydride, and the like.

A manufacturing example will be given and explained below.

Production Example 1, Isonicotinic acid-2-(α-hydroxy-4-methylbenzyl)-anilide (compound number 1) Dissolve 2.1 g of 2-amino-4'-methylbenzhydrol in 50 ml of pyridine, and add this solution. Cool with ice and add 1.8 g of isonicotinic acid chloride hydrochloride little by little while stirring. This will take approximately 30 minutes. After further stirring at room temperature for 3 hours, 250 ml of water was added to the reaction solution, and crystals were precipitated. When these crystals are collected and recrystallized from a mixed solvent of ethyl acetate and n-hexane, the melting point is 152 ~
2.7 g (yield: 85%) of the title substance was obtained at 153°C.

Elemental analysis value C20H13N2O2 (molecular weight 318.37
) C H N Calculated value (%) 75.45 5.70 8.80 Experimental value (
%) 75.40 5.73 8.76 Production Example 2, Isonicotinic acid-4-chloro-2-(α-hydroxy-
4-Methoxypenzyl)-anilide (Compound No. 4) Sodium borohydride was added to a solution of 3.7 g of isonicotinic acid-4-chloro-2-(4-methoxybenzoyl)-anilide in 100 ml of methanol with stirring. Add 0.5g little by little. This requires approximately 30 minutes. After further stirring at room temperature for 2 hours, 200ml of water was added.
When added, crystals precipitated. The obtained crystals were recrystallized from a mixed solvent of ethyl acetate and n-hexane to obtain 3.3 g (yield: 90%) of the title substance having a melting point of 155-156°C.

Elemental analysis value C2H17ClN2O3 (molecular weight 368.8
1) C H N Calculated value (%) 65.13 4.64 7.59 Experimental value (
%) 65.17 4.61 7.55 The compounds of the present invention thus obtained are shown in Table 1.

However, the compounds in Table 1 do not limit the compounds of the present invention.

The compound numbers in the table also apply to the following test examples and formulation examples.

In addition, the position numbers of substituents X and Y in Table 1 are as shown below.

Since the compound of the present invention thus obtained has systemic transferability to plants, any treatment method such as above-ground foliage treatment, seed treatment, water surface treatment, or soil destruction treatment is possible.

In addition, since the compounds of the present invention do not have any adverse effects on the target useful plants, the timing of use of the compounds of the present invention is as follows:
It can be used at any stage of useful plants, such as before sowing, during the sowing period, during the seedling period, during the growing period, or during the fruiting period.

When actually using the compound of the present invention, it is possible to use it as it is without adding other ingredients, but in order to make it more convenient to use, it is possible to use various solid and liquid carriers that are used in the preparation of general agricultural chemicals. It can be mixed with powder to produce wettable powders, emulsions, oils, powders, 2-grain powders, flowable preparations, etc. In addition, drugs include dispersants, diluents, emulsifiers, spreading agents, wetting agents,
adsorbent.

Auxiliary agents such as thickeners, antifoaming agents, and anti-caking agents may also be added.

The carrier referred to herein may be either solid or liquid, or a combination thereof. Listing these examples,
Talc, clay, bentonite.

Kaolin, diatomaceous earth, calcium carbonate, wood flour, starch, gum arabic, water, alcohol, kerosene.

Examples include naphtha, xylene, cyclohexanone, methylnaphthalene, benzene, acetone, dimethylformamide, glycol ether, and N-methylpyrrolidone.

Examples of the adjuvant include polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan monooleate, ethylene oxide propylene oxide copolymer, and lignin sulfonate. Sorbitan esters, soaps, sulfated oils.

Alkyl sulfate ester salts, petroleum sulfonates.

Dioctylsulfosacinate salts, alkylbenzene sulfonates, aliphatic amine salts, quaternary ammonium salts. Alkylpyridinium salts.

Examples include alkylaminoethylglycine, alkyldimethylbetaine, polyglycol sulfate, alkylamine sulfone butylene, isopropyl phosphate, carboxymethyl cellulose, polyvinyl alcohol, hydroxypropyl cellulose, ethylene glycol, xanthan gum, and the like.

It can also be used as an aerosol agent by mixing with a propellant such as fluorotrichloromethane or dichlorodifluoromethane, or as a fumigant or smoke agent by mixing with an appropriate blowing agent or combustion agent.

For formulation, the mixing specific gravity is generally 0.05 to 95%, preferably 0.1 to 80% by weight of the compound of the present invention.
%, particularly preferably 1 to 70%, and 7% as a carrier.
0-99%, optimally 0-20% as an adjuvant. In addition, other fungicides include herbicides, plant growth regulators, insecticides,
By using it in combination with pesticides such as acaricides, fertilizers, etc., a wider range of effects can be expected.

When the compound of the present invention is actually used, the timing of use,
Weather conditions, method of use, dosage form, location of use, target disease,
It goes without saying that it is selected appropriately depending on the target crop, etc., but the concentration used is generally 0.5 to 1000 mm, preferably 3 to 500 mm, and the amount used (as the compound of the present invention) is generally 10 mm. The amount is 0.5 to 500 g per are, preferably 1 to 250 g per 10 are.

Next, the usefulness of the compound of the present invention as a fungicide for agriculture and horticulture will be explained using test examples.

Test example 1, cucumber powdery mildew control test (preventive effect) diameter 1.5 cm
A clay pot was filled with granular soil for gardening, and 10 cucumbers (variety: Takasago) were sown. This was cultivated in a greenhouse for 10 days, and young seedlings with expanded cotyledons were used as samples.

The hydrating powder of the compound of the present invention obtained in Formulation Example 2 was diluted with water to a predetermined concentration and sprayed onto these seedlings in an amount of 15 ml per pot. After drying with chemical solution, cucumber powdery mildew fungus (Sph
An aqueous solution of conidia of Aerotheca fuliginea was spray inoculated onto the stems and leaves. After inoculation, 23-26℃
After cultivating for 10 days under greenhouse conditions, the disease state was investigated.

The disease severity was calculated by the following method.

That is, depending on the lesion area of the investigated leaf, 0.
The disease was classified into severity indexes of 1, 2, 3, and 4.5.

Based on the disease onset index thus obtained, the disease severity was calculated using the following formula, and the control value was further calculated from the comparison with the disease severity in the untreated area using the following formula.

The results are shown in Table 2.

Table 2 Test Example 2, Cucumber Powdery Mildew Control Test (Treatment Effect) A clay pot with a diameter of 15 cm was filled with horticultural soil, and a cucumber (variety: Takasago) 10
The grains were sown and cultivated in a greenhouse for 10 days, and young seedlings with fully expanded cotyledons were used for testing.

This young seedling is infected with cucumber powdery mildew fungus (Sphaeroth).
cafuliginea) and left in a greenhouse at 23 to 26°C for 1 day, the emulsion of the compound of the present invention obtained in Formulation Example 3 was diluted with water to a predetermined concentration, and 15 ml per needle was used. It was sprayed. After air drying, 23~
After cultivating for 10 days under greenhouse conditions at 26°C, the disease state was investigated.

The disease severity index, disease severity, and control value are in accordance with Test Example 1.

The results are shown in Table 3.

Table 3 Test Example 3, Wheat powdery mildew control test (preventive effect) A clay pot with a diameter of 12 cm was filled with Arakida soil, and wheat (variety:
Norin No. 61) 15 seeds were sown. This was cultivated in a greenhouse for 12 days, and the young seedlings whose first leaves had developed were used for testing.

The emulsion of the compound of the present invention obtained by Formulation Method 4 was diluted with water to a predetermined temperature and sprayed onto the seedlings in an amount of 15 ml per pot.

After air drying, wheat powdery mildew fungus (Erysiphe gra
A conidial aqueous solution of M. minis) was inoculated by spraying. After inoculation, the plants were cultivated for 10 days under greenhouse conditions at 20 to 24°C, and then the disease state was investigated.

The disease severity index, disease severity, and control value are in accordance with Test Example 1.

The results are shown in Table 4.

Table 4 Test Example 4, Wheat powdery mildew control test (therapeutic effect) Fill a clay pot with a diameter of 12 cm with Arakida soil, and add wheat (variety:
No. 61) 15 seeds were sown, cultivated in a greenhouse for 12 days, and the seedlings with the first leaf developed were used as a test sample.

This young seedling is infected with wheat powdery mildew fungus (Erysiphe gr.
After inoculating by spraying an aqueous solution of conidia of P. aminis) and leaving it for 1 day under greenhouse conditions at 20 to 23°C, add a hydrating powder of the compound of the present invention obtained by the method of Formulation Example 2 to a predetermined concentration with water. Dilute and spray 15ml per pot, after air drying 20~2
After cultivating at room temperature of 4°C for 10 days, the disease state was investigated.

The disease severity index, disease severity, and control value are in accordance with Test Example 1. The results are shown in Table 5.

Table 5 Formulation examples are shown below. In the examples, "parts" indicate "parts by weight."

Formulation example 1 powder Compound number 1 2 parts Clay 98 parts The above is mixed and pulverized to obtain a powder.

Formulation example 2 Hydrating agent Compound number 2 10 parts Sodium alkyl sulfonate 5 parts Clay 85 parts The above ingredients are mixed and ground to obtain a wettable powder.

Preparation example 3 Emulsion Compound number 3 5 parts Alkylbenzenesulfonic acid Calcium 4 parts polyoxyethylene alkyl Phenyl ether 11 parts Cyclohexanone 10 parts Xylene 70 parts The above is mixed to obtain an emulsion.

Formulation example 4 emulsion Compound number 4 10 parts Alkylbenzenesulfonic acid Calcium 3 parts polyoxyethylene alkyl Phenyl ether 12 parts Dimethylformamide 10 parts xylene 65 parts The above is mixed to obtain an emulsion.

Formulation Example 5 Granules Compound No. 5 2 parts calcium ligninsulfonate 2 parts bentonite 30 parts talc 66 parts or more are mixed, water is added and kneaded, then granulated and dried to obtain granules.

Formulation example 6 Flowable agent Compound number 4 10 parts Ethylene glycol 5 parts Xanthan gum 0.2 parts polyoxyethylene sorbitan Monooleate 5 parts Water 79.8 parts The above is wet-pulverized to obtain a flowable agent.

Applicant: Chugai Seidu Co., Ltd.

Claims (1)

[Scope of Claims] 1) Iso represented by the general formula (wherein X represents a hydrogen atom or a halogen atom, Y represents a lower alkyl group or a lower alkyloxy group, and Q represents a hydrogen atom or a hydroxyl group) Nicotinic acid anilide derivative. 2) Isonicotinic acid anilide derivatives represented by the general formula (wherein X represents a hydrogen atom or a halogen atom, Y represents a lower alkyl group or lower alkyloxy group, and Q represents a hydrogen atom or a hydrogen atom group) An agricultural and horticultural fungicide characterized by containing one or more of the following as active ingredients.