JPH0240374A - Substituted heterocyclic carboxylic acid derivatives, their production methods, and agricultural and horticultural fungicides containing them as active ingredients - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention provides a substituted heterocyclic carboxylic acid derivative, a method for producing the same, and an active ingredient thereof! % related to horticultural fungicides.

<Prior art> It is known that some carboxylic acid anilide derivatives have bactericidal activity.
ioch emistry and physsiol
ogy 14m26 (1980), 5,880 (1980)
75), 25, 188 (1986), J.L.Hup.
patz; Au5t, J, Chem.

86.185 (1988), E, H, Pommer; P
roceed-ings of the 2nd In
international IUPACCongres
s of Pe5ticide Chemistry
5.897 (1971), etc.

<Problems to be solved by the invention> However, the compounds exemplified in these documents are insufficient in terms of efficacy, etc., and cannot be said to be necessarily satisfactory, and it is desirable to develop drugs with fewer such drawbacks. It is rare.

Means for Solving the Problems In view of the above circumstances, the present inventors conducted various studies to develop a compound with excellent bactericidal activity. It was discovered that the derivative has an aggressive bactericidal activity with few of the above-mentioned drawbacks, and the present invention was achieved.

That is, the present invention is based on the general formula [wherein R represents a methyl group or a halogen atom,
represents an oxygen atom or a sulfur atom, and n represents an integer of 1 to 8. The present invention provides a substituted heterocyclic carboxylic acid derivative represented by (hereinafter referred to as the compound of the present invention), a method for producing the same, and an agricultural and horticultural fungicide containing the same as an active ingredient.

Plant diseases for which the compound of the present invention has excellent efficacy include:
For example, rice sheath blight (Rhizoctoniasol)
ani), pseudosheath blight (Rhizoctonia o
ryzae.

R, 5olani type IB), wheat rust (Puc
ciniastriiformis, P. grami
nis, P. recondita, P.

hordei), snow rot (Typhula 1n)
carnata, T.

i sh 1kar 1ens is), naked smut (Ustilago triticf.

TJ, nuda), damping-off disease (Rhizoc) of various rice crops.
toniasolanil), Cortici
um rolfsii), potato and beetroot diphtonia disease (Rhizoctonia solani),
Gymnosporang iumha
raeanum), apple scab (Venture
iainaequaris), leaf rot disease of grasses, lawns, etc. (
Rhiz o -ctonia aolani)
, Corticium rolfsii, leaf rust (Uromycea trifolii), snow rot (Typhula 1ncarnata, T.
1shikarienais), etc.

Next, the method for producing the compound of the present invention will be explained in detail.

The compound of the present invention can be expressed, for example, by the general formula [wherein R, X and n represent the same meanings as above]. ] It can be produced by reacting with a substituted heterocyclic carboxylic acid represented by the following formula or 1,1,8-" trimethyl-2-oxa-4-a[twindan].

In the above reaction, a solvent is not necessarily required, but examples of solvents that can be used include hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as chlorobenzene, methylene chloride, chloroform, and carbon tetrachloride. , diisopropyl ether, tetrahydrofuran, dioxane, and other ketones; acetone, methyl ethyl ketone, and other ketones; ethyl acetate, and other esters; acetonitrile and other nitrites; dimethyl sulfoxide, dimethyl formamide, water, etc., with preference given to tetrahydrofuran. It will be done.

The amount of the reagent used in the above reaction is 1 equivalent of 1,1.8-)dimethyl-2-oxa-4-aminoindan represented by formula (2) (for ζ, the substituted amount represented by general formula (4)) The heterocyclic carboxylic acid or its reactive derivative is 0.4 to
1.5 equivalents, preferably in the range of 0.5 to 1.1 equivalents.

The above reaction temperature can be set arbitrarily, but it is usually preferably from 0°C to the reflux temperature of the reaction solution.

The substituted heterocyclic carboxylic acid represented by the general formula (3) or its reactive derivative used may include the corresponding carboxylic acid, acid anhydride, acid chloride, acid bromide, carboxylic acid ester, etc. The reaction can be carried out in the presence of a suitable reaction aid depending on the substituted heterocyclic carboxylic acid represented by the general formula (4) or its reactive derivative used. For example, when using carboxylic acid, 1
-(8-Dimethylaminopropyl)-8-ethylcarbodiimide metodide, dicyclohexylcarbodiimide, etc. are used, and when using carboxylic acid esters, sodium hydride, sodium methylate, sodium ethylate, etc. can be used. Furthermore, when using an acid decogenide or an acid anhydride, sodium hydroxide, potassium hydroxide, triethylamine, N-methylmorpholine, pyridine, etc. can be used.

These reaction aids are usually used in an amount ranging from a catalytic amount to 2 equivalents, but preferably 0.95 to 1.1 equivalents.

After the reaction is completed, the reaction aid or its reaction product is removed by filtration or washing with water, etc., and the solvent is distilled off to obtain the substituted heterocyclic carboxylic acid derivative represented by the general formula CI]. If necessary, it can be further purified by chromatography, recrystallization, etc.

Incidentally, the compound represented by the formula Wataru, which is a raw material for the compound of the present invention, e.g., Jean Ve'ne and Jean
Tirouflet, Compt, rend, 2
81, 911-12 (1950) 4-
Starting from acetaminophthalide, it can be synthesized by the following route.

When using the compound of the present invention as an active ingredient of a fungicide,
Although it may be used as is without adding any other ingredients, it is usually mixed with solid carriers, liquid carriers, surfactants, and other formulation auxiliaries to form emulsions, wettable powders, suspensions, and granules. , powder,
It is used by formulating it into a liquid formulation, etc.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 99.996%, preferably 0.2 to 80%.
contains.

As solid carriers, fine powders such as kaolin clay, attabulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, kuru electric shell powder, urea, ammonium sulfate, synthetic hydrous silicon oxide, etc. Examples of liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene;
Examples include alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, acetonitrile, and water.

Surfactants used for emulsification, dispersion, wet spreading, etc. include alkyl sulfate salts, alkyl (aryl)
Anionic surfactants such as sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl ethers, polyoxyethylene polyoxybrobylene block copolymers Examples include nonionic surfactants such as sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester.

As formulation adjuvants, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC
(carboxymethylcellulose), PAP (isopropyl acid phosphate), etc.

These preparations are applied undiluted or, for example, diluted with water, directly to plants or to soil.

It can be used in a mild form, such as by scattering it or, if necessary, subsequently mixing it with the soil.

In addition, when used as a seed treatment agent, kernels can be prepared by applying seed dressing treatment, seed soaking treatment, etc. Furthermore, by mixing it with other fungicides, it can be expected to increase the bactericidal efficacy. In addition, insecticides, acaricides, nematicides,
It can also be used in combination with herbicides, plant growth regulators, fertilizers, and soil conditioners.

The compound of the present invention can be used in rice fields, fields, orchards, pastures,
It can be used as an active ingredient in fungicides for lawns, etc.

When the compound of the present invention is used as an active ingredient of a fungicide, the application amount varies depending on weather conditions, formulation form, application timing, method, location, target disease, target crop, etc., but usually 1.
0.5 to 1oof per are, preferably 1 to 50
F, and when applying emulsions, wettable powders, suspensions, solutions, etc. diluted with water, the application concentration is 0.001 to 1%,
Preferably, it is 0.005 to 0.596, and granules, powders, etc. are applied as they are without any dilution.

<Effects of the Invention> The compound of the present invention is highly effective against plant diseases caused by many plant pathogenic bacteria, especially microorganisms belonging to Basidiomycetes, and therefore can be used in many applications as an active ingredient of fungicides. .

<Examples> The present invention will be explained in more detail below using production examples, formulation examples, and test examples.

First, a manufacturing example will be shown.

Production Example 1 (Synthesis of compound (8)) 1 s 1 * 8- )'Linter-2-oxer 4
-Aminoindan aomr and pyridine 89mF were dissolved in 5mj of tetrahydrofuran, and the internal temperature was 6°C under water cooling.
While stirring, add 79 mf of 2,4-dimethylfuran-8-carboxylic acid chloride to 2 m of tetrahydrofuran.
Drop the solution dissolved in j, t, f=.

After one hour, the mixture was stirred at room temperature overnight, and then extracted with water and chloroform. The organic layer was washed with 6% hydrochloric acid and water, then dried and concentrated. By purifying the residue with silica gel thin layer chromatography, N-(1,1,8-
trimethyl-2-oxa-4-indanyl) -214
116 my of -dimethylfuran-8-carboxylic acid amide was obtained.

Table 1 shows some of the compounds of the present invention that can be produced by the above production method.

Formulation examples are shown in Table fs1. The compounds of the present invention are indicated by compound numbers in Table 1. Parts are parts by weight.

Formulation Example 1 50 parts each of the compounds (1) to (8) of the present invention, 8 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide were thoroughly ground and mixed to obtain 50% hydration of the active ingredient. Obtain each agent.

Formulation Example 2 10 parts each of the compounds (1) to (8) of the present invention, 14 parts of polyoxyethylene steryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 70 parts of xylene were thoroughly mixed to form an emulsion containing 10% active ingredient. Get a pot.

Formulation Example 8 2 parts each of the compounds (1) to (8) of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 80 parts of bentonite and 65 parts of kaolin clay were thoroughly ground and mixed, and water was added. After thorough kneading, the mixture is granulated and dried to obtain granules containing active ingredient 296.

Formulation Example 4 26 parts each of the compounds (1) to (8) of the present invention, 8 parts polyoxyethylene sorbitan monooleate, 3 parts CMC,
69 parts of water are mixed and wet milled until the particle size is less than 5 microns to obtain each suspension of 25% active ingredient.

Formulation Example 5 Two parts of each of the compounds (1) to (8) of the present invention, 88 parts of kaolin clay, and 10 parts of talc are thoroughly ground and mixed to obtain powders containing 296 active ingredients.

Formulation Example 6 10 parts of each of the compounds (1) to (8) of the present invention, 1 part of polyoxyethylene styrylphenyl ether, and 89 parts of water are mixed to obtain each liquid preparation of active ingredient 1096.

Next, test examples will show that the compounds of the present invention are useful as active ingredients of fungicides. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 2. Observe with the naked eye the degree of bacterial flora and lesions on the stems, etc. If no bacterial flora or lesions are observed, rate it as ``6'', if approximately 10% is observed, rate it as ``4'', if approximately 8096 is observed, rate it as ``8'', and 50. ``2'' if approximately % is recognized, ``1'' if approximately 70% is recognized
If there is no difference from the disease onset state when no compound is tested, it is evaluated as "0" and evaluated on a scale of 0 to 5, and indicated as 0.1.2.8.4.5.

Test row 1 Rice sheath blight preventive effect test A plastic pot was filled with sandy loam, and rice (Kinki No. 88) was sown and grown in a greenhouse for 20 days. A test compound prepared as an emulsion according to Formulation Example 2 was diluted with water to a predetermined concentration and sprayed on the foliage of a rice seedling with 4 to 5 leaves developed so as to sufficiently adhere to the leaf surface. Four hours after the spraying, a edible agar piece of the rice sheath blight fungus was applied and the solution was warmed. After inoculation, the plants were grown for 4 days at 28°C under humid conditions, and their pesticidal efficacy was investigated. The results are shown in Table 8.

Table 2 Test Example 2 Penetration and transfer effect test for rice sheath blight A plastic pot was filled with sandy loam, and rice plants (Goki No. 88) were sown and grown in a greenhouse for 8 weeks.

A test compound prepared as a hydrating agent according to Formulation Example 1 was diluted with water to rice plants with 4 to 5 leaves developed, and a predetermined amount of the compound was sprinkled on the soil, and the rice was grown in a greenhouse for 7 days. Inoculation was carried out by attaching a piece of agar containing pathogenic bacteria. After inoculation, the seeds were grown for 4 days at 28°C under high humidity.
The pesticidal efficacy was investigated.

The results are shown in Table 4.

@Table 4 Table 5 Test Example 8 Preventive effect test on French bean white silk disease White silk pathogenic bacteria, which had been cultured in Musuma medium in advance, was thoroughly mixed with sandy loam and packed in a plastic pot. On top of that, green beans (Taisho Kintoki) were sown. A test compound made into a wettable powder according to Formulation Example 1 was diluted with water, and a predetermined amount of the solution was sprinkled onto the soil.

After irrigation, the plants were grown in a greenhouse for 8 weeks, and the control efficacy was investigated based on the degree of disease onset on the stems at the ground level. The results are shown in Table 5.

Test Example 4 Treatment effect test for wheat rust
It was grown in a greenhouse for 10 days. Spores of the wheat rust fungus were inoculated into wheat seedlings in which the 2nd to 8th M had developed. After inoculation, the plants were grown for one day at 23° C. under humid conditions, and the test compound made into an emulsion according to Formulation Example 2 was diluted with water to a predetermined concentration and sprayed on the leaves so that it would adhere sufficiently to the leaf surface. After spraying, the plants were grown for 7 days under lighting at 28°C, and their pesticidal efficacy was investigated. The results are shown in Table 6.

Table 6

Claims (3)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R represents a methyl group or a halogen atom,
represents an oxygen atom or a sulfur atom, and n represents an integer of 1 to 3. ] A substituted heterocyclic carboxylic acid derivative represented by (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R represents a methyl group or a halogen atom, and
represents an oxygen atom or a sulfur atom, and n represents an integer of 1 to 3. ] Substituted heterocyclic carboxylic acid shown by or its reactive derivative and 1,1,3-trimethyl-2-oxa-4- shown by the formula ▲ Numerical formula, chemical formula, table, etc. ▼
2. The method for producing a substituted heterocyclic carboxylic acid derivative according to claim 1, which comprises reacting the substituted heterocyclic carboxylic acid derivative with aminoindan. (3) A fungicide for agriculture and horticulture, which contains the substituted heterocyclic carboxylic acid derivative according to claim 1 as an active ingredient.