JPH0240384A - Substituted heterocyclic carboxylic acid derivative, production thereof and agricultural and horticultural fungicide comprising the same derivative as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R is methyl or ethyl; X is -CH2- or -S-). EXAMPLE:N-(1,1,3-Trimethyl-2-oxa-4-indanyl)-2-methyl-5,6-dihydro-4H-py ran-2- carboxylic acid amide. USE:An agricultural and horticultural fungicide showing excellent effects on plant blights caused especially by fungi belonging to Basidiomycetes. PREPARATION:A substituted heterocyclic carboxylic acid (reactive derivative) (e.g., 2-methyl-5,6-dihydro-4H-pyran-2-carboxylic acid chloride) shown by formula II is reacted with 1,1,3-trimethyl-2-oxa-4-aminoindane shown by formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a substituted heterocyclic carboxylic acid derivative, a method for producing the same, and an agricultural and horticultural fungicide containing the same as an active ingredient.

<Prior art> It has been reported by G, A@Whites;
Biochemistry and Physiolo
gy 5. no (1975), B, Janks; Pe
5tic, Sci., 2.48 (1971), etc. However, the compounds exemplified in these documents are insufficient in terms of efficacy, etc., and cannot be said to be necessarily satisfactory. In view of this situation, as a result of various studies in order to develop a compound with excellent bactericidal activity, the substituted hetero derivatives represented by the following general formula It was discovered that it has bactericidal activity, leading to the present invention.

That is, the present invention is based on the general formula [wherein R represents a methyl group or an ethyl group, and X is -
CH, - or -S-. ] (hereinafter referred to as the compound of the present invention).

), its production method, 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), Rhizoctonia or
yzae, R.

5olani x type B), wheat rust (Pucc
iniastriiformislP, gramin
is, P, recondita, P.

hordei), snow rot (Typhula 1ncar)
nata, T.

1shikariensis), naked smut (Ustil)
ago tritici.

TJ, nuda), damping-off disease of various crops (Rhizoc
toniasolanil), Cortici
um rolfsii), potato, beetroot diphtonia solani, pear Gymnosporangiumhara
eanum), apple scab (Venturia 1)
nae-quaris), leaf rot disease of grasses, lawns, etc. (Rh
izoctonia solani), white silk disease (Cort
icium rolfsii), leaf rust (Uromy
ces trifol ii), M rot (Typhul
aincarnata, T., 1shikariens
is), 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 and X have the same meanings as above]. ] A substituted heterocyclic carboxylic acid represented by the formula or a reactive derivative thereof and 1,1,8-trimethyl-2-oxa-4- represented by the formula
It can be produced by reacting with 7 main twindans.

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 ethers, acetone, methyl ethyl ketone and other ketones, esters such as ethyl acetate, acetonitrile and other nitriles, dimethyl sulfoxide, dimethylformamide, water and the like, preferably tetrahydrofuran. can be mentioned.

The base of the reagent used in the above reaction is based on 1 equivalent of 1,1,8-trimethyl-2-oxa-4-aminoindan shown in Formula 1 (Material), and a substituted hetero group shown in General formula (3). The ring 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 is generally preferably from θ°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. Depending on the substituted heterocyclic carboxylic acid represented by the general formula used or its reactive derivative, the reaction can be carried out in the presence of a suitable reaction aid. For example, when using a carboxylic acid, 1-
(8-dimethylaminopropyl)-8-ethylcarbodiimide methiodide, dicyclohexylcarbodiimide, etc. can be used, and when using a carboxylic acid ester, sodium hydride, sodium methylate, sodium ethylate, etc. can be used. can. Furthermore, when using acid halides or acid anhydrides, 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, and the solvent is distilled off to obtain the substituted heterocyclic carboxylic acid derivative represented by the general formula [11]. If necessary, it can be further purified by subjecting it to operations such as chromatography and recrystallization.

The compound represented by formula (2), which is a raw material for the compound of the present invention, is, for example, as described by Jean Vc'ne and Jea
nTirouflet, Complete, rend,
Starting from 4-acetaminophthalide described in 281 p. 911-12 (1950), it can be synthesized by the following route.

＼ ＼ ＼ ＼ If the compound of the present invention is commercially available 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 99.9%, preferably 0.2 to 80%.

Examples of solid carriers include fine powders or granules such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Examples of liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene;
Alcohol such as isopropanol, ethylene glycol, cellosolve, etc. 1. Examples include 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 layer, 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 polyoxypropylene block copolymers Sorbikun Examples include nonionic surfactants such as fatty acid esters and polyoxyethylene sorbitan fatty acid esters.

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.

More specifically, the above-mentioned preparation can be used in various forms, such as by being sprayed or powdered on plants, sprayed, powdered or granulated on the soil surface, or further mixed with soil if necessary.

In addition, when used as a seed treatment agent, it can be used after seed coating 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 100 f per are, preferably 1 to 5
0t, and when applying emulsions, wettable powders, suspensions, solutions, etc. diluted with water, the application concentration is 0.001 to 1%.
, preferably 0.005 to 0.596, granules,
Powders etc. are applied as is without any dilution.

<Effects of the Invention> The compounds of the present invention are highly effective against seed diseases caused by various plant pathogenic bacteria, especially microorganisms belonging to the Basidiomycetes, and therefore can be used in various applications as active ingredients 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 (1)) 1.1.8-4 Limethyl-2-oxa-4-aminoindan (100 ml) and 49 m2 of pyridine were dissolved in 51 TIJ of tetrahydrofuran, and stirred under water cooling at an internal temperature of 5°C or lower. However, 2-methyl-5,6-sihydro 4H-
A solution prepared by dissolving 92 mf of pyran-2-carboxylic acid chloride in 2 mJ of tetrahydrofuran was added dropwise. After dripping,
The mixture was stirred at room temperature overnight, and then extracted with water and chloroform. The organic layer was washed with 5% hydrochloric acid and water, then dried and concentrated. By purifying the residue by silica gel thin layer chromatography, N-(1,1,8-trimethyl-2-oxa-4-indanyl)-2-methyl-5
,6-sihydro-4H-bilane-2-carboxylic acid amide 145mf was obtained.

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

Table 1. General formula: Examples of formulations are shown below. The compounds of the present invention are indicated by compound numbers in Table 1. Formulation Example 1 60 parts each of the compounds (1) to (8) of the present invention, 8 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide were thoroughly ground and mixed to form an effective compound. A hydrating agent pot containing component 5096 is obtained.

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

Formulation Example 8 2 parts each of the compounds (1) to (8) of the present invention, 1 part of synthetic hydrated silicon oxide '3K, 2 parts of calcium ligninsulfonate,
80 parts of bentonite and 65 parts of kaolin clay are thoroughly ground and mixed, water is added and the mixture is thoroughly kneaded, and then granulated and dried to obtain each granule containing active ingredient 29I.

Formulation Example 4 25 parts each of the compounds (1) to (8) of the present invention, 8 parts polyoxyethylene sorbitan monooleate, 8 parts 0M0,
Each suspension of active ingredient 2596 is obtained by mixing with 69 parts of water and wet milling until the particle size is less than 5 microns.

Formulation Example 5 2 parts each of the compounds (1) to (3) of the present invention, 88 parts of kaolin clay, and 10 parts of talc are thoroughly ground and mixed to obtain a powder pot containing 29 fO of active ingredients.

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

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.

In addition, the control efficacy is determined by visually observing the disease state of the test plants at the time of investigation, that is, the degree of bacterial flora and lesions on leaves, stems, etc., and if no bacterial flora or lesions are observed, it is rated ``5'' and 1096. ``4'' if the degree is recognized, 1゛3'' if the degree is recognized as 80%, 609
If it is found to be about 6, it is given a "2," if it is about 7,096, it is given a "1," and if it is more than 7,096, it is given a "1," and if it is more than 7,096, it is given a 6 of 0 to 5.
It is evaluated in stages and indicated as 0.1.2.8.4.5.

Test Example 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 rice seedlings with 4 to 6 leaves developed so as to sufficiently adhere to the leaf surface. Four hours after the spraying, agar pieces containing the rice sheath blight fungus were pasted and inoculated. 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 Rice Sheath Blight Invasion Rapid Transition Effect Test A plastic pot was filled with sandy loam, and rice Kinki No. 88) was sown and grown in a greenhouse for 8 weeks.

A test compound prepared as a hydrating powder according to Formulation Example IIζ was applied to rice plants with 4 to 5 leaves developed, diluted with water, and a predetermined amount of the solution was sprinkled on the soil, and then grown in a greenhouse for 7 days to prevent rice sheath blight. Bacteria-containing agar pieces were pasted and inoculated. 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 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 advance in a bran medium, 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 for 10 days in a greenhouse. Spores of the wheat rust fungus were inoculated into seedlings of wheat whose second and third leaves had developed Hg. After inoculation, the test compound was grown for 1 day at 28° C. in a humid environment, made into an emulsion according to Formulation Example 2, diluted with water to a predetermined concentration, and sprayed on the foliage so that it would sufficiently adhere to the leaf surface. 28℃ after spraying
The plants were grown under lighting for 7 days and their pesticidal efficacy was investigated. The results are shown in Table 6.

Claims (3)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [I] [In the formula, R represents a methyl group or an ethyl group, and X is -
Represents CH- or -S-. ] 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 an ethyl group, and X is -
CH_2- or -S-. ] Substituted heterocyclic carboxylic acid or its reactive derivative and 1,1,8-trimethyl-2-oxa-4- shown by the formula ▲ Numerical formula, chemical formula, table, etc. are available ▼
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.