JPS6115867A - N-benzyl-cyclopropanecarboxamide derivative, its preparation and agricultural and horticultural fungicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X is halogen; n is 1 or 2; R<1>- R<3> are H or lower alkyl). EXAMPLE:N-( 4-chloro-alpha-methylbenzyl )2,2-dichloro-1-methyl-(trans)-3-methylcyclopropanecarboxamide. USE:An agricultural and horticultural insecticide. It exhibits excellent activity especially for the control of rice blast. PREPARATION:The compound of formula I can be prepared by reacting the compound of formula II with the compound of formula III (A is OH or halogen) in a solvent at a temperature between -20 deg.C and the boiling point of the reaction mixture, preferably at 0-100 deg.C, optionally in the presence of an acid acceptor (e.g. alkali metal hydroxide, triethylamine, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel N-benzyl-cyclopropane carboxamide derivative, its production method, and a fungicide for agricultural and horticultural use.

More specifically, the present invention provides N- represented by the following formula (1).
This invention relates to benzyl-cyclopropane carboxamide derivatives.

General formula: In the formula, X represents a halogen atom, n represents 1 or 2, and R1, RN and Ra each represent a hydrogen atom or a lower alkyl group.

The compound of general formula (1) above can be produced by the following method, and the present invention also relates to this production method.

Production method 1) Ni General formula 2 In the formula, A method for producing the N-benzyl-cyclopropane carboxamide derivative of the general formula (1), which comprises reacting a compound represented by the formula (1).

The present invention also relates to an agricultural and horticultural fungicide containing the N-benzyl-cyclopropane carboxamide derivative of the general formula (1) as an active ingredient.

In the specification of JP-A-55-66555, which was known before the filing date of the present application, the general formula;
1 represents an alkyl group or a cyclo6-alkyl group, and R1 and R may form a ring. It is stated that the N-benzyl-acetamide derivative represented by the following formula has herbicidal activity. The specification describes, for example, a compound represented by the formula.

However, the above general formula (4) does not include the compound of the above general formula (1) specified in the present invention, and furthermore, there is no mention of its use as a fungicide.

Furthermore, in the specification of JP-A No. 58-26847, which was known before the filing date of the present application, the general formula: or a lower alkenyl group, or R1 and R3 together represent an alkylene group; It is stated that the N-benzyl-acetamide derivative shown in ) has bactericidal activity for agricultural and horticultural purposes. The specification describes, for example, a compound represented by the formula.

However, from the table, the above general formula (B) does not include the compound of the above general formula (1) specified in the present invention.

The present inventors have carried out synthesis and biological activity screening in order to create novel compounds with biological activity.

As a result, they succeeded in synthesizing a novel N-benzyl-cyclopropane carboxamide derivative of the general formula (1), and discovered that the compound of formula (1) has excellent bactericidal activity for, for example, agricultural and horticultural purposes. .

According to the research of the present inventors, the general formula (1) of the present invention
The N-benzyl-cyclopropane carboxamide derivative is a new compound that has not been described in any publications known before the filing date of the present application.

It has also been found that the compound of the present invention exhibits excellent control efficacy that is particularly suitable for the purpose of controlling plant diseases, and in particular, exhibits optimal and outstanding efficacy for controlling rice blast disease. Such a control effect can be obtained from compounds having similar chemical structures, such as formula (, (-1) and formula (B-
It brings about a much superior effect compared to the efficacy shown by the compound 1).

The superior biological activity of the compounds of the present invention is due to
This is due to the correlation with the chemical structure of the compound. That is,
The structural characteristics of the compounds of the present invention are that a halogen-substituted -α-methylbenzyl group is bonded to the nitrogen atom in the acid amide bond, and a substituted cyclopropyl group is bonded to the carbon atom of the carbonyl group, as shown in the above general formula (1). At the point where it connects.

The plant disease control activity of the compound of the present invention also exhibits a more significant effect in terms of its residual efficacy. For example, especially when controlling rice blast, the residual effect of the control agent is determined by the relationship between the appropriate treatment period and the onset of rice blast, in relation to the most important disease in rice cultivation. The property is the most important factor, and the practical value of the compound is determined by its residual effect. The compounds of the present invention are excellent biologically active compounds that are completely satisfactory in this respect.

Accordingly, an object of the present invention is to provide an N-pendylcyclop-pancarboxamide derivative of the general formula (1), a method for producing the same, and its use as an agricultural and horticultural fungicide.

The above objects and many other objects and advantages of the present invention will become more apparent from the following description.

The compound of the present invention does not cause phytotoxicity to plants,
It is safe to use, exhibits excellent control efficacy against a wide range of plant diseases in addition to rice blast, and has excellent residual efficacy, making it advantageous for controlling a wide range of plant diseases. It can be applied conveniently and conveniently.

The bactericidal spectrum of the compound of the present invention is, for example, against archaeal bacteria [Archimycetes], algae [Phycomycetes], etc.
, Ascomycete x, (Ascornyc
etetes) :], Basidiomycetes [Pasidiomycetes/1.
(Baaidiomycetes)], Deuteromycetes [
Fungi Impgrf
ecti)), and various other plant diseases caused by fungi.

As a representative example of the fungicidal spectrum of the compound of the present invention, for example, rice blast disease (pyrtcwlaria oryzae
), cucurbit anthracnose (CCo11etotrtchu
laganartum), etc.
The bactericidal spectrum should not be limited to these.

The N-benzyl-cyclopropane carboxamide derivative of general formula (1) of the present invention can be prepared, for example, by the following method:
It can be easily manufactured.

Manufacturing method 1) Knee 1 R2 (II) (11) (wherein, X
, n, R', R2,R'' and A are the same as above.

) In the above reaction formula, X represents a halogen atom such as fluoro, chloro, bromo, or iodo, and n
represents 1 or 2, R'lR2 and R1 each independently represent a hydrogen atom or a lower alkyl group, where specific examples of the lower alkyl group include methyl, ethyl, propyl, isopropyl, n- (1so-, 5ec- or t
trrt-)butyl and the like l3- can be exemplified.

A represents a hydroxyl group or a norogen atom as exemplified above.

In the method for producing the compound of the general formula (RI) of the present invention shown in the above reaction formula, specific examples of the compound of the general formula (1) as a raw material include 4-chloro-α-methylbenzylamine, 4-promo α -Methylbenzylamine, 2-chloro-α-methylbenzylamine, 3,4-dichloro-α
-Methylbenzylamine and the like can be exemplified.

Similarly, specific examples of the compound of general formula (1) which is a raw material include 2,2-dichloro-1-methylcyclopropanecarboxylic acid, 2,2-dichloroo-1-xylcyclopropanecarboxylic acid, 2゜2-dichloro-(trans)-3-methylcyclopropanecarboxylic acid, 212-dichloro-1-methyl-(trans)-3-methylcyclopropane=14-carboxylic acid, 2,2-dichloro-1-ethyl -(trans)-3-ethylcyclopropanecarboxylic acid, 2.2-
Examples include dichloro-3,3-dimethylcyclopropanecarboxylic acid, 2,2-dichloro-3°3-diethylcyclopropanecarboxylic acid, 2,2-dichloro-1,3,3-trimethylcyclopropanecarboxylic acid, etc. is possible,
In addition, in place of the above carboxylic acids, those acid halides,
For example, acid chloride and acid bromide can also be exemplified.

Next, the above manufacturing method will be specifically explained using representative examples.

The above manufacturing method can be carried out desirably using a solvent or a diluent. All inert solvents and diluents can be used for this purpose.

Examples of such solvents or diluents include water and aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated) such as hexane, -/chlorohexane,
Petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride and hydrichloroethylene, chlorobenzene; other ethers such as diethyl ether, methyl ethyl ether, di-180-propyl ether, Butyl ether, propion oxide, dioxane, tetrahydrone, ketones such as acetone, methyl ethyl ketone, methyl is.

-propyl ketone, methyl-1so-butyl ketone; nitriles such as acetonitrile, propionitrile,
Acrylonitrile; alcohols such as methanol,
Ethanol, 180-propanol, phthanol, ethylene glycol; Esters such as ethyl acetate, amyl acetate; Acid amides such as dimethylformamide, dimethylacetamide; Sulfones, sulfoxides such as dimethylsulfoxide, sulfolane; and bases such as pyridine. can be given.

In the above method, a dehydration condensation agent can be used,
An example thereof is N,N'-dicyclohexylcarbodiimide.

Further, in the above method, when an acid halide is used as a raw material of general formula (II), the reaction of the present invention can also be carried out in the presence of an acid binder.

Examples of such acid binders include commonly used alkali metal hydroxides, carbonates, bicarbonates, alcoholades, etc., and tertiary amines such as triethylamine, diethylaniline, pyridine, etc. I can do it.

The method of the invention can be carried out within a wide temperature range. For example, it can be carried out between about -20°C and the boiling point of the mixture, preferably between about θ and about 100°C. Further, although it is preferable to carry out the reaction under normal pressure, it is also possible to operate under increased pressure or reduced pressure.

When the compound of formula (1) of the present invention is used as a fungicide for agriculture and horticulture, it can be used directly after being diluted with water, or! It can be used in various formulations using methods commonly used in the agricultural chemical manufacturing field using drug adjuvants. In actual use, these various formulations can be used directly or diluted with water to a desired concentration. Examples of pesticide adjuvants mentioned here include diluents (solvents, fillers, carriers)
, surfactants (solubilizers, emulsifiers, dispersants, wetting agents),
Stabilizers, adhesion agents, propellants for aerosols, synergists may be mentioned.

Examples of the solvent include organic solvents in addition to water, such as hydrocarbons [e.g., n-hexane, petroleum ether,
Naphtha, petroleum distillates (paraffin wax, kerosene, light oil, medium oil,
heavy oil), benzene, toluene, xylenes], halogenated hydrocarbons (e.g. chloromethylene, carbon tetrachloride,
trichloroethylene, ethylene chloride, ethylene dibromide, chlorobenzene, chloroform]; alcohols [for example, methyl alcohol, ethyl alcohol, furoyl alcohol, ethylene glycol] oligoethers [
For example, ethyl ether, ethylene oxide, dioxane]; alcohol ethers [e.g. ethylene glycol monomethyl ether]; ketones [e.g. acetone, isophorone]; esters [e.g. ethyl acetate, acetic alkylamines [e.g. dimethylformamide,
dimethylacetamide] and oligosulfoxides [for example, dimethyl sulfoxide].

Extending agents or carriers include, for example, slaked lime, magnesium lime, gypsum, calcium carbonate, silica, perlite, pumice, calcite, diatomaceous earth, amorphous silicon oxide, alumina, zeolite, clay minerals (e.g. pyrophyllite,
Inorganic powder particles such as talc, montmorillonite, beidellite, vermiculite, kaolinite, mica);
For example, rich in plant powders such as grain flour, starch, modified starch, sugar, glucose, crushed plant stems, etc.
Examples include powders of synthetic resins such as phenol resins, urea resins, vinyl chloride resins, and the like.

Examples of the surfactant include anionic surfactants such as alkyl sulfate esters (e.g., sodium lauryl sulfate), aryl sulfonic acids (e.g., alkylaryl sulfonate, sodium alkylnaphthalene sulfonate), succinates, Polyethylene glycol alkyl aryl ether sulfate salts cationic surfactants, such as alkylamines [e.g., laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride], polyoxyethylene alkylamines; nonionic Surfactants, such as polyoxyethylene glycol ethers [such as polyoxyethylene alkylaryl ethers and condensates thereof]
, polyoxyethylene glycol esters [e.g.
polyoxyethylene fatty acid ester], polyhydric alcohol esters [for example, polyoxyethylene sorbitan monolaurate]; amphoteric surfactants; and the like.

Other stabilizers, fixing agents [e.g., agricultural soap, casein lime, sodium alginate, polyvinyl alcohol (
PVA), vinyl acetate adhesive, acrylic adhesive],
Propellants for aerosols [e.g. trichlorofluoromethane, dichlorofluoromethane, 1,2,2-)dichloro-1,1,2-toIJ fluoroethane, chlorobenzene, LNG.

Lower ether] Rich (for smoking agents) Combustion regulators [e.g. nitrite, zinc dust, dicyandiamide]: Oxygen supply agent [e.g. chlorate]: Efficacy extender 2 Dispersion stabilizer, e.g.
casein, tragacanth, carboxymethyl cellulose (
CMC), polyvinyl alcohol (PVA)): synergists can be mentioned.

The compound of the present invention can be manufactured into various formulations by methods generally practiced in the field of pharmaceutical manufacturing.

Forms of preparations include emulsions, oils, wettable powders, aqueous solutions, suspensions, powders, granules, powders, smoking agents, tablets, aerosols, pastes, capsules, etc. can.

The agricultural and horticultural fungicide of the present invention contains, for example, about 0% of the active ingredient.
．． It can contain from 1 to about 95% by weight, preferably from about 0.5 to about 90% by weight.

In actual use, the various formulations and spray preparations described above (ready-1o-use-prepara.
The active compound content in -tton) is, for example, approximately 0.0
001 to about 20% by weight, preferably about 0.005 to about 1
A range of 0 weight - is suitable.

The content of these active ingredients can be appropriately changed depending on the form of the preparation, the method of application, purpose, timing, location, and disease occurrence situation.

The compounds of the present invention may also be used, if necessary, with other agricultural chemicals, such as insecticides, fungicides, acaricides, nematicides, antiviral agents, herbicides, plant growth regulators, attractants [e.g. Phosphoric ester compounds, carbamate compounds, ditheo (or thiol) carbamate compounds, organochlorine compounds, dinitro compounds, organic sulfur or metal compounds,
Antibiotics, substituted diphenyl ether compounds, urea compounds, triazine compounds] or/and fertilizers can also be present.

Various formulations or spray preparations containing the active ingredients of the invention (raQdy-tO-u8e-praparG
Application methods, spraying, spraying, misting (minting), atomizing (atomizing), etc.
tomizing), dusting, powdering, water surface application, boring (pourtng): l: smoking: soil application,
[For example, contamination, sprinkle
ng), fumigation (vaporsnrt), irrigation:]
: For surface m [: For example, coating, wrapping (bandi)
ng), powder coating, coating]: Can be applied by dipping, etc. Also, the so-called ultra-high concentration small amount spraying method (ULTR
A-1ow-volume) can also be applied. In this way it is possible to contain 100 grams of active ingredient.

The application amount per unit area can be selected as appropriate, but for example, about 0.03 to about 10 kg of active compound per hectare.
p, preferably about 0.3 to 6 kg. However, in special cases, exceeding these ranges may be
or lower is possible, and sometimes even necessary.

According to the present invention, the compound of the general formula (1) is included as an active ingredient, and a diluent (solvent and/or filler and/or carrier) and/or surfactant, and if necessary, for example, a stabilizer. , a fixing agent, and a synergist can be provided.

Furthermore, according to the present invention, the compound of the general formula (1) is applied alone or to the site of pathogenic bacteria and/or their outbreaks and crop diseases, or by adding a diluent (solvent and/or filler and/or carrier) and/or Alternatively, a method for controlling crop diseases can be provided in which a surfactant and, if necessary, a stabilizer, a fixing agent, and a synergist are mixed and applied.

Next, the content of the present invention will be specifically explained using examples.
The present invention should not be limited to this only.

Example 1 4-chloro-α-methylbenzylamine (15,6II
), triethylamine (10,1p) to toluene (1p)
2.2-50mg) at 0-10℃ without stirring.
Dichloro-1-methyl-(trans)-3-methylcyclopropanecarboxylic acid chloride (20,2N))
Le! (30 m/) solution was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. The reaction solution is poured into ice water, the aqueous layer is washed with toluene, the toluene layers are combined, washed in this order with a 1-III aqueous hydrochloric acid solution, a 1-III sodium hydroxide aqueous solution, and water, and dried over anhydrous sodium sulfate. When toluene is distilled off under reduced pressure, the desired colorless crystal N-(4
-chloro-α-methylbenzyl)2,2-dichloro-1
-Methyl-(trans)-3-methylcyclopropanecarboxamide (29,9) is obtained. mp, 132~
134°C (Compound Al) The compounds of the present invention synthesized according to the same method as above are shown in Table 1 below.

Example 2 (Irrigation agent) Compound A of the present invention 1.15 parts, mixture of powdered diatomaceous earth and powdered clay (1:5), 80 parts, sodium alkylbenzenesulfonate, 2 parts, sodium alkylnaphthalenesulfonate formalin condensate , 3 parts are ground and mixed to form a wettable powder. This is diluted with water and sprayed onto locations where pathogenic bacteria and/or their outbreaks and crop diseases occur.

Example 3 (Emulsion) 61.30 parts of the compound of the present invention, 55 parts of xylene, 8 parts of polyoxyethylene alkylphenyl ether, and 7 parts of calcium alkylbenzenesulfonate were mixed and stirred to prepare an emulsion. This is diluted with water and sprayed onto pathogenic bacteria and/or locations where pathogens and/or crop diseases occur.

Example 4 (Powder) 3.2 parts of the compound A of the present invention and 98 parts of powdered clay were pulverized and mixed to prepare a powder. This is sprinkled on areas where pathogens and/or their outbreaks and crop diseases occur.

Example 5 (Powder) 1.1.5 parts of the compound of the present invention, isopropyl hydrogen phosphate (PAP), 0.5 parts, powdered clay, 9
Pulverize and mix 8 parts to make a powder, and remove pathogens and/or germs.
Sprinkle dust on the outbreak and areas where crop diseases occur.

Example 6 (granules) To a mixture of 63.10 parts of the compound of the present invention, 30 parts of bentonite (montmorillonite), 58 parts of talc, and 2 parts of lignin sulfonate, 25 parts of water was added,
The mixture is thoroughly kneaded and made into 10 to 40 mesh granules by extrusion granulation, and dried at 40 to 50°C to form granules. This is sprinkled on areas where pathogens and/or their outbreaks and crop diseases occur.

Example 7 (granules) 95 parts of clay mineral particles having a particle size distribution of 0.2 to 2 degrees were placed in a rotary mixer, and while rotating, 5.5 parts of the compound of the present invention dissolved in an organic solvent was sprayed. After soaking evenly, 40~5
Dry at 0°C to form granules.

This is sprinkled on areas where pathogens and/or their outbreaks and crop diseases occur.

Example 8 Preparation of test compound for foliar spray efficacy test against rice blast disease Active compound; 50 parts by weight Carrier; Mixture of diatomaceous earth and kaolin (1:5): 45 parts by weight Emulsifier; Polyoxyethylene alkylphenyl ether: 5 parts by weight A wettable powder is prepared by grinding and mixing the above-mentioned amounts of the active compound, carrier and emulsifier, and diluting the predetermined dosage with water.

Test method Paddy rice (variety: Asahi) was grown in clay pots with a diameter of 12α, and during the third to fourth seasons, a diluted solution of the test compound prepared as described above at a predetermined concentration was sprayed at 50 μl per three pots. The next day, a suspension of artificially cultured rice blast fungus spores was spray inoculated (twice), and
The plants were kept in a greenhouse at a relative humidity of 100 °C and infected. Seven days after inoculation, the degree of morbidity of the potted beetles was graded and evaluated according to the following criteria, and the control value (%) was determined.

Morbidity: Lesion area ratio 0.5 2 or less 1 3-52
6-103
11-204 21-40 5 41 or more This test is the result of 3 pots in 1 section.

The results are shown in Table 2.

Note to Table 2) Comparison A-1: [Compound described in JP-A-55-66555] B-1= [Compound described in JP-A-58-26847] Compound of the present invention other than those exemplified in Example 8 above It was also confirmed through similar tests that the same effects as those shown in Table 2 were exhibited.

Example 9 Aftereffect test test method for rice blast Paddy rice (variety: Asahi) was grown in clay pots with a diameter of 12 cIL, and at the 3rd to 4th leaf stage, a test compound prepared in the same manner as in Example 8 was applied. A diluted solution of a predetermined concentration was sprayed at 50 doses per 3 pots. Five days after the spraying, a suspension of rice blast fungus spores cultured was spray inoculated (twice) and kept in a greenhouse at 25° C. and 100% relative humidity to allow infection. Seven days after inoculation, the disease severity of the potted plants was graded and evaluated in the same manner as in Example 8, and the control value (chi) was determined. The results are shown in Table 3.

Table 3 Note) Comparisons A-1 and B-1 are the same as in Table 2.

By the same test as in Example 9 above, for example, compound A10
．． Similarly, it was confirmed that Mu 11 also exhibited excellent residual effectiveness.

Example 10 Control test against anthracnose of cucumber Test method 9α Three pots of a diluted solution of a given concentration of the test compound in the form of an emulsion prepared according to Example 3 were added to cucumbers (variety Niyoyoha) grown in clay pots. This year, 25-sprayed. One day after the spraying, the spore liquid of this pathogen was inoculated by spraying and kept in a constant temperature room at 23° C. and humidity of 90° C. or higher for one day.

After 6 days of standing, the degree of disease was graded and evaluated based on the percentage of lesion area, and the control value (%) was determined according to the following criteria.

Morbidity: Lesion area ratio (chi) 0.5 2 or less 1 3-5 2　　　　　　6～15 3 16-30 4 31-50 5 51 or more The results are shown in Table 4.

Note to Table 4) TpN: Tetrachloroisophthalonitrile 75
Irrigation agent By the same test as in Example 10 above, for example, Compound A
It was confirmed that IO and All thereof also have excellent control power against anthracnose of cucumber.

The present invention described above in the detailed description section can be summarized as follows.

(1) General formula: In the formula, -pendyl-cycloprono(carboxamide derivative).

(2) General formula: In the formula, X and n are the same as above, and a compound represented by the general formula: In the formula, R', R2 and R3 are the same as above, and A represents a hydroxyl group or a norogen atom. The compound represented by the general formula (1) is reacted with a compound represented by
) A method for producing an N-benzyl-cyclopropane carboxamide derivative.

(3) An agricultural and horticultural fungicide containing the N-benzyl-cyclopropane carboxamide derivative of the general formula (1) as an active ingredient.

(4) The above general formula (1) ON-benzyl-cyclopropane carboxamide derivative alone, or a diluent (solvent and/or filler and/or carrier) and/or surfactant, and if necessary, a stabilizer. A crop disease control method that involves applying a mixture of , a fixing agent, and a synergist.

Claims (1)

[Claims] 1) General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X represents a halogen atom, n represents 1 or 2, and R^1, R^2, and R^ 3 each represents a hydrogen atom or a lower alkyl group, an N-benzyl-cyclopropane carboxamide derivative represented by: 2) Formula: N-(4-chloro-α-methylbenzyl)2,2-dichloro-1-methyl-(trans )-3-methylcyclopropanecarboxamide. 3) General formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, X is a halogen atom, and n represents 1 or 2. General formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R^1, R^2 and R^3 each represent a hydrogen atom or a lower alkyl group, and A represents a hydroxyl group or a halogen atom. General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X, n, R^1, R^2 and R^3 are the same as above. Production method. 4) General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X represents a halogen atom, n represents 1 or 2, and R^1, R^2, and R^3 each represent a hydrogen atom or An agricultural and horticultural fungicide containing as an active ingredient an N-benzyl-cyclopropane carboxamide derivative represented by the following formula, which represents a lower alkyl group.