JPH0256467A - Amide derivative, production thereof and agricultural and horticultural germicide containing same derivative as active ingredient - 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 relates to a novel amide derivative, a method for producing the same, and an agricultural and horticultural fungicide containing the same as an active ingredient.

<Prior Art> Cabtan, cabtafor, and dithiocarbamate agents are known as agricultural and horticultural fungicides that are currently widely used, particularly in the fields of late blight and pests. However, all of these drugs have only preventive effects and do not show therapeutic effects. Considering the practical application situation for plant disease control, in some cases spraying may be performed after the onset of the disease.In particular, the drug used to control algae and fungi, which is rapidly developing, has high preventive efficacy, excellent systemic transferability, and therapeutic properties. A great deal of effectiveness is required. Under these circumstances, metalaxyl (N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)alanine, which has excellent permeability and therapeutic activity,
However, due to the emergence of resistant bacteria in a short period of time, its excellent therapeutic activity has not been realized in some areas. Currently, particularly in the field of grapes, there is a desire for the emergence of therapeutic agents that have new effects and excellent penetration properties.

Many amide compounds having fungicidal or herbicidal activity have been known. Among them, 2-(1,8-dimethylpyrazole-6-carboxyamino)-4-methyl-8-pentenenitrile is described in GB-2190875 as a derivative similar to the 7-sylaminonitrile derivative of the present invention. ing.

<Problem to be solved by the invention> However, although this compound is excellent in terms of efficacy and systemic transferability, it is not practical due to strong phytotoxicity to the plants to be controlled, which is thought to be due to its suppressive effect. It is difficult to say that it is necessarily satisfactory as a control agent for algae and fungi.

Means for Solving the Problems> In view of the above circumstances, the present inventors conducted various studies to develop a compound that has excellent efficacy against plant diseases and has less phytotoxicity, and as a result, the following formula (1) The present inventors have discovered that the amide derivative represented by has excellent preventive and therapeutic efficacy against plant diseases, has excellent permeability, and has the excellent properties of reducing chemical damage that could not be solved using conventional techniques. Ta.

That is, the present invention provides a novel 7[do derivative] represented by the formula (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.

Next, the method for producing the compound of the present invention will be explained in detail. [In the formula, X represents a halogen atom] The compound can be obtained by reacting an acid halide represented by the following formula with an aminonitrile derivative represented by the formula.

The reaction temperature and reaction time of the reaction are usually -80 to 50
℃, preferably from about 0'C to room temperature, and from about 80 minutes to about 24 hours, preferably from about 1 to about 8 hours, to achieve the purpose.

The reaction is usually carried out in the presence of a base, examples of which include pyridine, 4-dimethylaminopyridine, triethylane, N,N-dimethylaniline, tributylamine,
B-class amines such as N-methylmorpholine, sodium hydroxide, calcium carbonate, C, H.

For each equivalent of acid halide ζ, the aminoacetonitrile derivative and base represented by formula (1) are each
It is equivalent. It is also possible to use an a[noacetonitrile derivative] represented by the above formula (III) as a reaction base.

In the above reaction, a solvent is not necessarily required, but preferably a solvent is used. Examples of solvents that can be used in the reaction include aliphatic hydrocarbons such as hexane, heptane, ligroin, petroleum ether, benzene, toluene, xylene, etc. aromatic hydrocarbons, halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloromethane, and chlorobenzene,
Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate, Nitro compounds such as nitromethane and nitrobenzene, nitriles such as acetonitrile and isobutylnitrile, formamide, N, N
Examples include amides such as -dimethylformamide and N,N-dimethylacetamide, and sulfur compounds such as dimethyl sulfoxide and sulfolane. In addition, when a spring water base such as sodium hydride is not used, water can also be used as a solvent. Also, the above solvents can be used in combination. After the reaction is completed, the desired compound can be obtained by carrying out usual post-treatments such as water washing and concentration, and purifying by operations such as chromatography and recrystallization, if necessary.

The compound of the present invention can also be obtained by reacting a carboxylic acid represented by the formula with N,N-thionyldiimidazole to obtain an acylimidazole derivative represented by the formula, and then using this and an aminonitrile derivative represented by the formula (Iff). or a salt thereof.

In the above reaction, the reaction temperature and reaction time are usually about -
80°C to about 50°C, preferably about 10°C to room temperature, about 8°C
The purpose can be sufficiently achieved within the range of 0 minutes to about 24 hours, preferably about 1 to about 8 hours.

The amount of reagents used in the reaction is usually about 1 equivalent of N,N'-thionyldiimidazole per equivalent of the carboxylic acid represented by formula (W), and about 1 equivalent of the amino acid represented by formula (III). The acetonitrile derivative is approximately 1 equivalent.

In the above reaction, a solvent is not necessarily required, but among the solvents used in the reaction with the nonitrile derivative, a solvent other than water can be used.

After the reaction is completed, the desired compound can be obtained by carrying out usual post-treatments such as water washing and concentration, and purifying by operations such as chromatography and recrystallization, if necessary.

Further, in the above reaction, since the acylimidazole derivative represented by formula ff) is unstable, it is usually subjected to the next reaction without being isolated.

is Au5t, J. Chem., 86, 185-18.
7 (198B). Also, N,N'-thionyldiimidazole is described by Angew, Chem.

78.26 (1961).

The aminonitrile derivative represented by the above formula C11) is
It is obtained by reacting the corresponding aldehyde compound with ammonia and sodium leanide by Schdrecker reaction. The compound of the present invention has optical isomers derived from one asymmetric carbon, and these optical isomers are also included in the present invention.

The compound of the present invention can be used as an active ingredient in agricultural and horticultural fungicides without adding any other ingredients.

However, the compounds of the present invention are usually mixed with solid carriers, liquid carriers, surfactants, and other formulation auxiliaries to formulate emulsions, wettable powders, suspensions, powders, granules, etc. It will be done.

In this case, the active ingredient content of the compound of the present invention as an active ingredient in the preparation is 0.1 to 99.9%, preferably 1 to 9%.
It is 0%.

The solid carriers mentioned above include fine particles 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 include powders or granules, and liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone, and soybean. Examples include oil, vegetable oil such as cottonseed oil, dimethyl sulfoxide, acetonitrile, water, and the like.

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 alkyl polyoxypropylene block copolymers, sorbitan Examples include nonionic surfactants such as fatty acid esters.

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

Application methods for the compound of the present invention include foliage spraying, soil treatment,
Examples include seed disinfection, but any application method commonly used by those skilled in the art can be used.

When the compound of the present invention is used as an active ingredient of an agricultural and horticultural fungicide, the amount of the active ingredient applied should be determined based on the target crop, target disease,
Although it varies depending on the degree of disease occurrence, formulation form, application method, application period, weather conditions, etc., ・# - Usually 0 per 1 are.
．． 01-50g, preferably 0.05-lOf,
When applying emulsions, wettable powders, suspensions, etc. diluted with water,
The application concentration is o,ooot to 0.5%, preferably 0,0005 to 0.2%, and powders, granules, etc. are applied as they are without any dilution.

Examples of plant diseases that can be controlled with the compounds of the present invention include the following diseases.

Downy mildew of canola and radish (Peronospora)
brassicae), spinach downy mildew (Pe
ronosporaspinaciae), tobacco downy mildew (Peronospora tabacina)
), downy mildew of cucumber (Pseudoperono
sporacubensis), grape downy mildew (
Plasmopara gray blight of cucumber (Phyto
Phytophthora capsici), Pineapple blight (Phytophthora cinnamo)
mi).

Late blight of potatoes, tomatoes, and eggplants (Phytophth)
orainfestans), tobacco, field beans,
Phytophthora n1co
tianae var, n1cotianae),
Spinach damping-off (Pythium Sp, )
Cucumber 6 seedling damping-off disease (Pythium aphan)
idermatum), wheat brown snow rot (Pyth
ium sp, ) tobacco seedling damping-off (Pyth
ium debaryanum), soybean Py
thiumRot (Pythium aphani
dermatum, P, debar-yan
um, P, irregulare, P, my
iotylum, P, ultimate).

Furthermore, the compound of the present invention can be used in fields, paddy fields, orchards, tea plantations,
It can be used as an agricultural and horticultural fungicide for pastures, lawns, etc., and can be expected to increase its bactericidal efficacy by mixing it with other agricultural and horticultural fungicides. Furthermore, it can also be used in combination with fungicides, acaricides, nematicides, herbicides, plant growth regulators, and fertilizers.

<Effects of the Invention> The compound of the present invention has no phytotoxicity to plants and has excellent effects against plant diseases caused by various plant pathogenic bacteria, especially algal fungi such as downy mildew and late blight, so it can be used as a sterilizer for agricultural and horticultural purposes. It can be used for various purposes as an active ingredient in preparations.

<Example> Hereinafter, the present invention will be explained in more detail with reference to production examples, formulation examples, and test examples.

First, a production example of the compound of the present invention will be shown.

Production example 2-amino-4-methyl-8-pentynitrile 1.8
2 P (12 mmol) and triethylamine 1.20
9 (12 mmol) in anhydrous tetrahydrofuran solution (80 mj) while cooling with water and stirring.
-Methylpyrazole-5-carbonyl chloride 1.72
A solution of Y (10 mmol) in anhydrous tetrahydrofuran was added dropwise. After dropping, the temperature was raised to room temperature and stirred for 8 hours. Tetrahydrofuran was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted with ethyl acetate.

The ethyl acetate layer was washed twice with water, dried over anhydrous magnesium sulfate, and then ethyl acetate was distilled off under reduced pressure to obtain an oil.

This was subjected to silica gel column chromatography (eluent:
By purifying with n-hexane/ethyl acetate (2/1), colorless crystals of 2-(1-ethyl-2-methylpyrazole-5-carboxyamino)-4-methyl-8-pentinenitrile 1.97F were obtained. Obtained. (yield 80%) mp99
-100°C Next, formulation examples are shown. In addition, parts represent parts by weight.

Formulation Example 1 A wettable powder of the compound of the present invention can be obtained by thoroughly pulverizing and mixing 50 parts of the compound of the present invention, 8 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide.

Formulation Example 2 The suspension of the compound of the present invention is prepared by mixing 25 parts of the compound of the present invention, 8 parts of polyoxyethylene sorbitan monooleate, 8 parts of CMC, and 69 parts of water, and wet-pulverizing the mixture until the particle size of the active ingredient becomes 6 microns or less. A clouding agent can be obtained.

Formulation Example 8 A powder of the compound of the present invention can be obtained by thoroughly pulverizing and mixing 2 parts of the compound of the present invention, 88 parts of kaolin clay, and 10 parts of talc.

Formulation Example 4 An emulsion of the compound of the present invention can be obtained by thoroughly mixing 20 parts of the compound of the present invention, 14 parts of polyoxy, diethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 60 parts of xylene.

Formulation Example 5 2 parts of each of the compounds 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, water was added and the mixture was thoroughly kneaded, followed by granulation and drying. By doing so, granules of the compound of the present invention can be obtained.

Next, test examples will show that the compounds of the present invention are useful as agricultural and horticultural fungicides. The compounds used for comparison are shown in Table 1.

In addition, the control efficacy (control value) was calculated by the following method by visually observing the disease state of the test plants at the time of the survey, that is, the bacterial flora on leaves, stems, etc., and the extent of lesions.

a: Plants (or leaves) with bacterial flora and lesions of 50% or more
Number b: Number of plants (or leaves) with 25-50% bacterial flora and lesions C: Number of plants (or leaves) with 10-25% bacterial flora and lesions d: 10 bacterial flora and lesions Plants (or leaves) that can be recognized at some level
Number e: Number of plants (or leaves) with no bacterial flora or lesions observed Test Example 1 Potato Phytophthora control test (preventive effect) Fill plastic pots with sandy loam, sow potatoes (Danshaku), and grow in a greenhouse for 40 days. It was grown for days. Thereafter, the test drug prepared as a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration of 1, and the solution was sprayed on the leaves so that it would sufficiently adhere to the leaf surface. After spraying, spray a spore suspension of potato late blight fungus,
It was warm.

After inoculation, the plants were left at 20°C under high humidity for 18 days, and then grown under lighting for 5 days to investigate the pesticidal efficacy. The result is the second
Shown in the table.

Test Example 2 Potato Phytophthora control test (therapeutic effect) A plastic pot was filled with sandy loam, and potatoes (Danshaku) were sown and grown in a greenhouse for 40 days. Thereafter, a spore suspension of Potato Phytophthora was sprayed and inoculated. After vaccination,
A test drug made into a hydrating powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the solution was sprayed on foliage so as to sufficiently adhere to the leaf surface.

After spraying, the plants were allowed to grow for 7 days under illumination, and the pesticidal efficacy was investigated. The results are shown in Table 2.

Test Example 8 Tomato Phytophthora control test (preventive effect) A plastic pot was filled with sandy loam, tomatoes (ponchirosa) were sown, and grown in a greenhouse for 20 days. To tomato seedlings that have developed their 2nd to 8th true leaves, dilute the test chemical prepared as a hydrating powder with water to a specified concentration according to Formulation Example 1, and spray it on the foliage so that it fully adheres to the leaf surface. did. After spraying, a spore suspension of Phytophthora tomato was sprayed and inoculated. After inoculation, the plants were left at 20°C under high humidity for 18 days, and then grown under lighting for 5 days to investigate the pesticidal efficacy. The results are shown in Table 2.

Test Example 4 Phytophthora late blight control test (therapeutic effect) A plastic pot was filled with sandy loam, tomatoes (ponchirosa) were sown, and grown in a greenhouse for 20 days. A spore suspension of Phytophthora tomato was sprayed and inoculated to young tomato seedlings in which the 2nd to 8th true leaves had developed. After inoculation, leave at 20℃ and high humidity for 18 days,
A test drug made into a hydrating powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the solution was sprayed on foliage so as to sufficiently adhere to the leaf surface. After covering, the plants were allowed to grow for 5 days under illumination, and their pesticidal efficacy was investigated. The results are shown in Table 2.

Test Example 5 Grape Vine Disease Control Test (Preventive Effect) A plastic pot was filled with sandy loam, and grapes (Beri-A) were sown and grown in a greenhouse for 60 days. Thereafter, a hydrating powder was applied according to Formulation Example 1. The test chemical was diluted with water to a predetermined concentration, and then sprayed on the foliage of grape seedlings that had developed their 8th to 4th true leaves so that it would adhere sufficiently to the leaf surface.After spraying, the grapevine and disease bacteria were The spore suspension was sprayed and inoculated.After inoculation, 20
After being left at 18°C under high humidity, the plants were grown for another 7 days under lighting, and the pesticidal efficacy was investigated. The results are shown in Table 2.

Test Example 6 Grapevine disease control test (therapeutic effect) A plastic pot was filled with sandy loam, grapes (Beri-A) were sown, and grown in a greenhouse for 50 days. A spore suspension of grapevine and disease fungi was sprayed and inoculated onto young grape seedlings in which the 8th to 4th true leaves had developed. After inoculation, leave at 20℃ and high humidity for 18 days,
Formulation Example 1] A test drug made into a wettable powder according to ζ was diluted with water to a predetermined concentration, and sprayed on foliage so as to sufficiently adhere to the leaf surface. After spraying, the plants were allowed to grow for 7 days under illumination, and the pesticidal efficacy was investigated. The results are shown in Table 2.

Test Example 6 Cucumber and disease control test (preventive effect) A plastic pot was filled with sandy loam, and cucumbers (Sumo Hanshiro) were sown and grown in a greenhouse for 14 days21). Thereafter, the test drug prepared as a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the solution was sprayed on the leaves so that it was sufficiently attached to the leaves. After spraying, a spore suspension of cucumber and disease bacteria was sprayed and inoculated.

After inoculation, the plants were left at 20° C. and high humidity for 18 days, and then grown for another 6 days under lighting, and the pesticidal efficacy was investigated. The result is the second
Shown in the table.

Test Example 8 Cucumber and disease control test (therapeutic effect) A plastic pot was filled with sandy loam, and cucumbers (Sumo Hanshiro) were sown and grown in a greenhouse for 14 days. Young cucumbers were sprayed and inoculated with a spore suspension of cucumber and disease bacteria. After inoculation, the test drug was left in a humid environment of 20'C1 for 18 days, and then the test drug made into a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and sprayed on the foliage so that it adhered sufficiently to the leaf surface. did. After spraying, the plants were allowed to grow for another 6 days under illumination, and their control efficacy was investigated. The results are shown in Table 2.

Test Example 9 Chemical damage test A test drug prepared as a wettable powder according to Formulation Example 1 was diluted with water to a specified concentration on young cucumber (Sumo Hanpaku) seedlings, and then
Sprayed on foliage to ensure sufficient adhesion to the leaf surface. After spraying, the seeds were grown in a greenhouse for one week, and the degree of chemical damage was investigated. The results are shown in Table 8.

Plant damage was evaluated by visual observation of the growth level of the test plants from the time of spraying to the time of the survey, using a six-level scale of 0.1.2.8.4.5.

"5": Severe chemical damage, no growth observed.

"0": No drug damage observed.

Table-1

Claims (4)

[Claims] (1) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ An amide derivative represented by (2) An acid halide represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X represents a halogen atom] and an amino compound represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The method for producing an amide derivative according to claim 1, which comprises reacting. (3) A carboxylic acid represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is reacted with N,N-thionyldiimidazole to form an acylimidazole compound represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 2. The method for producing an amide derivative according to claim 1, characterized in that the amino compound represented by the formula ▲ has a numerical formula, a chemical formula, a table, etc. ▼. (4) A fungicide for agriculture and horticulture, which contains the amide derivative according to claim 1 as an active ingredient.