JP2002193956A - Isothiazolecarboxamides and blight eliminating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide isothiazolecarboxamides having a resistance inducing effect on a phytopathogen and a good activity as a plant blight eliminating agent. SOLUTION: The isothiazolecarboxamides are represented by the formula (wherein, R1 is hydrogen or cyanomethyl, R2 is hydrogen or methyl, R3 is hydrogen, a 7-10C alkyl or methoxycarbonylphenoxymethyl, but R1, R2, and R3 are not simultaneously hydrogen atom).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to novel isothiazolecarboxamides, a method for producing the same, and use as a plant disease controlling agent.

[0002]

2. Description of the Related Art It has already been known that certain isothiazolecarboxamides have an action as a disease controlling agent (JP-A-63-119463, JP-A-1-119643).
No. 21263, JP-A-1-199963 and JP-A-2-149572), and methods for producing certain isothiazolecarboxamides useful as agricultural chemicals or intermediates thereof are already known. (See JP-A-60-139672).

[0003]

However, the known isothiazolecarboxamides are not sufficiently satisfactory in the effect and / or safety as a plant disease controlling agent.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to create a novel compound which exhibits an excellent effect as a plant disease controlling agent and has high safety.
This time, the inventors have found isothiazolecarboxamides represented by the following formula (I) having excellent biological activity.

[0005]

Embedded image

In the formula, R ¹ represents a hydrogen atom or cyanomethyl, R ² represents a hydrogen atom or methyl, and R ³ represents a hydrogen atom, C _7-10 alkyl or methoxycarbonylphenoxymethyl, provided that R ¹ , R ² and R ³ do not both represent a hydrogen atom.

The compound of the above formula (I) of the present invention can be synthesized, for example, by the following method (a). Production method (a) : 3,4-dichloro-5-isothiazolecarbonyl chloride has the formula

[0008]

Embedded image

Wherein R ¹ , R ² and R ³ have the same meanings as defined above.

The isothiazolecarboxamides of the formula (I) provided by the present invention surprisingly exhibit an action of inducing the plant itself to resist phytopathogenic fungi, and consequently have a protective effect against plant diseases. Express.

Accordingly, the compounds of the present invention are useful as plant disease controlling agents (prophylactic agents).

In the present specification, "alkyl" is preferably straight-chain, and includes, for example, n-heptyl, n-octyl, n-nonyl, n-decyl and the like.

In the compound of formula (I), preferably, R ¹ represents a hydrogen atom or cyanomethyl, R ² represents a hydrogen atom or methyl, and R ³ represents a hydrogen atom, n-heptyl, n-octyl, n-nonyl, n-decyl or 4
-Methoxycarbonylphenoxymethyl, provided that
If R ¹ represents a cyanomethyl, R ² and R ³ represents a hydrogen atom, when R ² represents methyl, R ¹ represents and R ³ represents a 4-methoxycarbonyl phenoxymethyl a hydrogen atom, and R ¹ , R ² and R ³ do not both represent a hydrogen atom.

In the compound of the formula (I), R ¹ is preferably a hydrogen atom or cyanomethyl, R ² is a hydrogen atom, and R ³ is a hydrogen atom, n-heptyl, n-octyl, n -Nonyl, n-decyl or 4-methoxycarbonylphenoxymethyl, provided that R ¹
When R represents cyanomethyl, R ² and R ³ represent a hydrogen atom, and R ¹ , R ² and R ³ do not represent a hydrogen atom.

In the production method (a), when, for example, 3,4-dichloro-5-isothiazolecarbonyl chloride and 2-aminononanenitrile are used as starting materials, it can be represented by the following reaction formula.

[0016]

Embedded image

3,4-Dichloro-5-isothiazolecarbonyl chloride used as a starting material in the above-mentioned production method (a) is a known compound, and can be produced, for example, according to the method described in JP-A-5-59024. Can be.

The compound of the formula (II) used as a starting material in the above-mentioned production method (a) is also a known compound, for example, the fourth edition of Experimental Chemistry Lecture, Vol. 22, 193-1.
95 pages (Maruzen Co., Ltd., issued on November 30, 1992)
And can be easily synthesized by a Strecker reaction.

Representative examples of the compound of the formula (II) in the above-mentioned production method (a) include the following. 2-aminobutanedinitrile, 2-aminononanenitrile, 2-aminodecanenitrile, 2-aminoundecanenitrile, 2-aminododecanenitrile, 2-amino-3- (4-methoxycarbonylphenoxy) propiononitrile, 2- Amino-3- (4-methoxycarbonylphenoxy) -2-methylpropiononitrile and the like.

The reaction of the above-mentioned production method (a) can be carried out in a suitable diluent, and the diluent used in this case can be a solvent inert to the reaction.
Water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated) such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, Carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene and the like; ethers such as ethyl ether, methyl ethyl ether,
Isopropyl ether, butyl ether, dioxane,
Dimethoxyethane (DME), tetrahydrofuran (T
HF), diethylene glycol dimethyl ether (DG
M) and the like; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl-isopropyl ketone, methyl isobutyl ketone (MIBK), and the like; nitriles, for example, acetonitrile, propionitrile, acrylonitrile, and the like; alcohols, for example, methanol, Ethanol, isopropanol, butanol, ethylene glycol and the like; esters such as ethyl acetate, amyl acetate and the like; acid amides such as dimethylformamide (DM
F), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone,
Hexamethylphosphoric triamide (HMPA)
Sulfones, sulfoxides, for example, dimethyl sulfoxide (DMSO), sulfolane and the like; bases, for example,
Pyridine and the like can be mentioned.

The production method (a) can be carried out in the presence of an acid binder. Examples of the acid binder usable here include, for example,
As inorganic bases, hydrides, hydroxides, carbonates, bicarbonates, etc. of alkali metals and alkaline earth metals, such as sodium hydride, lithium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate , Lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, etc .;
Secondary amines, dialkylaminoanilines and pyridines such as triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N, N-dimethylaniline, N, N-diethylaniline, pyridine,
4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo [2,2,2] octane (DABCO),
1,8-diazabicyclo [5,4,0] undec-7-ene (DBU) and the like.

The above-mentioned preparation method (a) can also be carried out by a method using a phase transfer catalyst in a diluent, and examples of the diluent used include water; aliphatic, cycloaliphatic and Aromatic hydrocarbons (optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chlorobenzene, dichlorobenzene and the like; ethers, for example Ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DM
E), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM) and the like; nitriles such as acetonitrile, propionitrile, acrylonitrile and the like.

Examples of the phase transfer catalyst include quaternary ions such as tetramethylammonium bromide,
Tetrapropylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, tetrabutylammonium iodide, trioctylmethylammonium chloride, benzyltriethylammonium bromide, butylpyridinium bromide, heptylpyridinium bromide, benzyltriethylammonium chloride, etc .; crown ethers For example, dibenzo-18-crown-6, dicyclohexyl-18-
Crown-6, 18-crown-6, etc .; cryptands, for example, [2.2.2] -cryptate, [2.1.
1] -cryptate, [2.2.1] -cryptate,
[2.2.B] -cryptate, [3.2.2] -cryptate and the like can be mentioned.

Process (a) can be carried out within a substantially wide temperature range, but generally from about -30 to about 1
It is preferred to work at a temperature of 50C, preferably between about 0 and about 80C. The reaction is desirably performed under normal pressure, but may be operated under increased or reduced pressure in some cases.

In carrying out the process (a), for example, 1 to 1.2 mol of the compound of the formula (II) is used per 1 mol of 3,4-dichloro-5-isothiazolecarbonyl chloride in a diluent, for example, dichloromethane. Of the compound
By reacting at the above temperature in the presence of ~ 2 mol of triethylamine, the target compound of formula (I) can be obtained in good yield.

The active compounds of the formula (I) according to the invention exhibit an action of controlling phytopathogenic fungi and indeed protect plants from unwanted phytopathogenic fungi or control unwanted phytopathogenic fungi. Can be used for
The active compounds of the formula (I) according to the invention can thus be used as agents for controlling the following phytopathogenic fungi: Plasmodiophoromycetes, Oomycete
s), zygomycetes (Zygomycetes), ascomycete (Ascomycete)
s), Basidiomycetes and incomplete fungi (Deu
teromycetes).

The compound of the formula (I) of the present invention can be used for preventing plant diseases caused by various bacteria belonging to Proteobacteria and Gram-positive groups.

The active compounds of the formula (I) according to the invention include, in particular,
It exhibits an effect of inducing host resistance to infection with plant pathogens such as rice blast (Pyricularia oryzae), and as a result, can exhibit an effect of controlling plant diseases.

The active compound of the formula (I) of the present invention exhibits a good affinity for plants at the concentration of the active compound necessary for preventing the infection of plant pathogens. Above ground treatment, rootstock and seed treatment, and soil treatment are possible.

The compounds of the present invention have low toxicity to warm-blooded animals and can be used safely as pesticides.

When the active compound of the formula (I) of the present invention is used as an agricultural chemical, it can be formulated into a usual preparation. Examples of the formulation include liquids, wettable powders, emulsions, suspensions, powders, foams, pastes,
Tablets, granules, aerosols, active compound infiltration-natural and synthetic, microcapsules, seed coatings, ULV [cold mist, warm mist
t)] and the like.

These preparations can be manufactured by a method known per se. For example, the active compound can be combined with a developing agent, ie, a liquid or solid diluent or carrier, and optionally a surfactant, ie, an emulsifier and / or dispersant and / or
Alternatively, it can be prepared by mixing with a foam former.

As the liquid diluent or carrier, generally, aromatic hydrocarbons (eg, xylene, toluene,
Alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (eg, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons [eg, cyclohexane, etc., paraffins (eg, mineral oil fractions) )], Alcohols (eg, butanol, glycol, etc.) and their ethers, esters, etc., ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strong polar solvents (eg, dimethylformamide, dimethyl sulfoxide) Etc.), water and the like. When water is used as the developing agent, for example, an organic solvent can be used as an auxiliary solvent.

As the solid diluent or carrier, for example,
Examples include ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapull guide, montmorillonite, diatomaceous earth, etc.) and ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicate, and the like).

Examples of solid carriers for granules include:
Crushed and sorted rocks (eg, calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic grains of inorganic and organic powders,
Fine particles of organic substances (eg, sawdust, coconut, corn cob, tobacco stem, etc.) can be mentioned.

Examples of the emulsifier and / or foaming agent include nonionic and anionic emulsifiers [eg, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (eg, alkylaryl polyglycol ether, alkyl sulfonate, alkyl sulfonate, Sulfates, arylsulfonates, etc.)] and albumin hydrolysis products.

As the dispersant, for example, lignin sulfite waste liquor, methyl cellulose and the like are included.

A fixing agent can also be used in the preparation (powder, granule, emulsion).
For example, carboxymethylcellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol, polyvinyl acetate, etc.) can be mentioned.

Coloring agents can also be used, such as inorganic pigments (for example, iron oxide, titanium oxide, Prussian blue, etc.), organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes. Furthermore,
Mention may be made of trace elements such as iron, manganese, boron, copper, cobalt, molybdenum, zinc and salts of these metals.

The formulations generally comprise 0.1 to 95% by weight, preferably 0.5 to 9% by weight of the active compound of the formula (I) according to the invention.
It can be contained at a concentration in the range of 0% by weight.

The active compounds of the formula (I) according to the invention include, in the abovementioned formulations or various forms of use, other known active compounds such as fungicides (fungicides, bactericides, antivirals, plants) Resistance inducer), insecticide, acaricide, nematocide, herbicide, bird repellent, growth regulator, fertilizer, and / or soil conditioner.

The active compounds of the formula (I) according to the invention can be used directly as they are, or as preparations for dispersion, emulsions, suspensions,
It can be used in the form of powders, tablets, pastes, microcapsules, granules and the like, or can be applied in the form of a further diluted preparation. The active compounds are then prepared in the customary manner, for example, by watering, dipping, spraying, atomizing, misting, irrigation, suspension formation,
Coating, dusting, dusting, dressing, wet coating, wet coating, pasty coating,
It can be applied by a method such as coating a feather.

The concentration of the active compound of the formula (I) in the actual use form in treating the parts of the plant can vary within a substantial range, but is generally 0.000.
It can be in the range of 1 to 1% by weight, preferably 0.001 to 0.5% by weight.

In the treatment of seed, the active compound of the formula (I) can be used in a proportion of generally 0.001 to 50 g, preferably 0.01 to 10 g, per kg of seed.

In the soil treatment, it is generally 0.0001 to 0.1% by weight, especially 0.0001 to 0.1% by weight, based on the point of action.
A concentration of the active compound of the formula (I) in the range of 02% by weight can be used.

Next, the present invention will be described in more detail with reference to examples, but the present invention should not be limited to these examples.

[0047]

EXAMPLES Synthesis Example 1

[0048]

Embedded image

2-amino-3-nonanenitrile (0.7
A solution of 3,4-dichloro-5-isothiazolecarbonyl chloride (1.0 g) in dichloromethane (5 ml) was added dropwise to a solution of 8 g) and triethylamine (0.56 g) in dichloromethane (10 ml) under ice-cooling. After completion of the dropwise addition, the temperature was returned to room temperature, and the mixture was further stirred for 3 hours. The reaction solution was washed with water and dried over anhydrous magnesium sulfate, the solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (elution solvent: hexane: ethyl acetate = 9: 1) to give N- (1- Cyanooctyl) -3,4-dichloro-
5-isothiazolecarboxamide (0.46 g) was obtained. n _D ²⁰ 1.5190 A compound obtained in the same manner as in Synthesis Example 1 was synthesized in Synthesis Example 1.
Table 1 below shows the compounds synthesized in the above.

[0050]

[Table 1]

Test Example 1: Test of seed treatment efficacy against rice blast Preparation of test compound Active compound: 30 to 40 parts by weight Carrier: mixture of diatomaceous earth and kaolin (1: 5) 55 to 65 parts by weight Emulsifier: 5 parts by weight of polyoxyethylene alkylphenyl ether The above-mentioned amounts of the active compound, the carrier and the emulsifier are pulverized and mixed to prepare each wettable powder, and a predetermined amount thereof is diluted with water and subjected to a test. Test Method Seeds of paddy rice (variety: Kusabue) were added to a predetermined concentration diluted solution (5 ml per 150 grains) of the active compound prepared in advance.
C. for 5 days. After immersion, air-dried seeds with a diameter of 9c
seeded into 2 m plastic pots and heated seedlings (3
(2 ° C.) for 3 days for germination. For another two weeks,
A suspension of spores of rice blast (Pyricularia Oryzae), which had been artificially cultured, was spray-inoculated (one time) onto the cultivated rice until the 2 to 2.5 leaf stage, and infected at 25 ° C. and 100% relative humidity. Was. Seven days after the inoculation, the morbidity per pot was categorized and the control value (%) was determined. At the same time, phytotoxicity was investigated. This test is the average of the results of two pots per section. Evaluation of morbidity, control value calculation methods morbidity lesion area percentage (%) 0 0 0.5 less than 2 less than 1 2-5 than 2 5-10 3 10-20 below 4 20-40 than 5 over 40 control Value (%) = (1- {morbidity of the treated group / {morbidity of the untreated group}) × 100 Test Results Compound Nos. 1, 2, 3, 4, 5 and 7 showed the drug concentration (5
(00 ppm) showed a control value of 90% or more. No phytotoxicity was seen.

Formulation Example 1 (Granules) Compound No. 1 of the present invention (10 parts), bentonite (montmorillonite) (30 parts), talc (talc) (58 parts)
And a mixture of lignin sulfonate (2 parts) and water (2
5 parts), kneaded well, and extruded granulator,
Granules of 10 to 40 mesh are formed and dried at 40 to 50 ° C. to obtain granules.

Formulation Example 2 (Granules) Clay mineral particles having a particle size distribution of 0.2 to 2 mm (95
Part) in a rotary mixer, and under rotation, spray the present compound No. 2 (5 parts) together with a liquid diluent, wet it evenly, and then dry at 40-50 ° C to obtain granules.

Formulation Example 3 (Emulsion) Compound No. 3 (30 parts) of the present invention, xylene (55
Parts), polyoxyethylene alkylphenyl ether (8 parts) and calcium alkylbenzene sulfonate (7 parts) are mixed and stirred to form an emulsion.

Formulation Example 4 (Wettable powder) Compound No. 5 (15 parts) of the present invention, a mixture of white carbon (hydrous amorphous silicon oxide fine powder) and powdered clay (1: 5) (80 parts), alkylbenzene Powdered sodium sulfonate (2 parts) and sodium alkylnaphthalene sulfonate formalin polymer (3 parts) are mixed to obtain a wettable powder.

Formulation Example 5 (Hydrated Granules) Compound No. 7 of the present invention (20 parts), sodium ligninsulfonate (30 parts), bentonite (15 parts) and calcined diatomaceous earth powder (35 parts) were thoroughly mixed. , Water and extruded and dried with a 0.3 mm screen to obtain hydrated granules.

[0057]

The novel isothiazolecarboxamides of the present invention have excellent properties as agricultural and horticultural disease control agents (preventive agents), as is clear from the above biological test examples.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C033 AA08 4H011 BA01 BB10 BC01 BC07 BC18 BC19 BC20 DA02 DA13 DA15 DC06 DC08 DH02 DH03 DH10

Claims (4)

[Claims] (1) Formula (1) In the formula, R ¹ represents a hydrogen atom or cyanomethyl, R ² represents a hydrogen atom or methyl, and R ³ represents a hydrogen atom, C _7-10 alkyl or methoxycarbonylphenoxymethyl, provided that R ¹ , R ² and R ³ is never represents a hydrogen atom together in isothiazolecarboxamides represented. 2. R ¹ represents a hydrogen atom or cyanomethyl, R ² represents a hydrogen atom or methyl, and R ³ represents a hydrogen atom, n-heptyl, n-octyl, n-nonyl, n-decyl or 4-methyl. Methoxycarbonylphenoxymethyl, provided that when R ¹ represents cyanomethyl, R ² and R ³ represent a hydrogen atom; when R ² represents methyl, R ¹ represents a hydrogen atom and R ³
4-methoxycarbonylphenoxy represents methyl, and R ^1, R ² and R ³ are never represents a hydrogen atom together a compound according to claim 1. R ¹ represents a hydrogen atom or cyanomethyl, R ² represents a hydrogen atom, and R ³ represents a hydrogen atom, n-heptyl, n-octyl, n-nonyl, n-decyl or 4-
A methoxycarbonylphenoxymethyl group, provided that when R ¹ represents cyanomethyl, R ² and R ³ represent a hydrogen atom, and R ¹ , R ² and R ³ do not represent a hydrogen atom. A compound as described. 4. An agrochemical comprising the compound according to claim 1 as an active ingredient.