JPH03161476A - Imidazole derivative, production and fungicide - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R1 is 1-4C alkyl; R2 is 4-10C alkenyl or phenylalkyl). EXAMPLE:N-1-(1-p-n-Amyloxybenzyloxycarbonyl)propyliden-1-yl-N-(1- imidazolylcarbonyl) methylamine. USE:A fungicide effective for preventing and treating blights of crops caused by plant pathogenic fungi of powdery mildew, rust, GANMONBYO, leaf blight, blast, sheath blight, gray mold and black spot. PREPARATION:A compound shown by formula II (X is eliminable group) is reacted with imidazole in a solvent such as dimethylformamide in the presence of a base (e.g. potassium carbonate) at 20-150 deg.C to give a compound shown by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to imidazole derivatives, methods for producing the same, and fungicides using the same as an effective component.

[Conventional technology]

Examples of dazole derivatives include:
Compounds shown in Japanese Patent Application Laid-open No. 150590 and Japanese Patent Application Laid-Open No. 60-260572 are known.

However, in (2), in the following formula C, R represents a hydrogen atom, a methyl group or an ethyl group; R4 represents a lower alkyl group; and X and C each represent a carbon atom or a nitrogen atom. ) has been disclosed to have bactericidal activity, but these compounds have complex chemical structures1 and are difficult to produce on an industrial scale and have insufficient efficacy. It is difficult to say that it has.

In the following formula (wherein, R represents a hydrogen atom or a lower alkyl group; R represents a lower alkyl group; R represents an alkenyl group, a cycloalkyl group, an alkoxyalkyl group, or a higher alkyl group; Re represents a hydrogen atom or a lower alkyl group; Z represents an oxygen atom or a sulfur atom) is disclosed to have bactericidal activity, but these compounds also have no industrial use. [Problems to be Solved by the Invention] The purpose of the present invention is to provide a novel imidazole derivative, a method for producing the same, and a method for producing the same. An object of the present invention is to provide a bactericidal agent which is effective to a certain extent.

Means for Solving Problem C] As a result of intensive research to solve the above problems, the present inventors discovered that a new ξidazole derivative has strong bactericidal activity, and completed the present invention. I ended up dying.

That is, the present invention provides (1) the following formula R, (wherein R represents an alkyl group having 1 to 4 carbon atoms;
R2 represents an alganyl group having 4 to 10 carbon atoms or a haphenylalkyl group, and the phenyl ring thereof may be substituted. ) Compound (2) represented by the following formula R (wherein R and R2 have the same meanings as above; X represents a leaving group) is characterized by reacting a compound represented by the following formula with imidazole The method for producing the compound (2) (1) above (3) relates to a bactericide containing the compound of formula (I) as an effective component.

The present invention will be explained in detail below.

The above-mentioned target compound, a novel iguodazole derivative (■
), in the compound (n) which is the raw material for its production, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, proyl group, butyl group, etc.). However, a methyl group is preferable.

R! As, straight chain or branched alkyl group having 4 to 10 carbon atoms, straight chain or branched alganyl group having 4 to 1 o carbon atoms, straight chain or branched chain having 1 to 12 carbon atoms Examples include phenylalkyl groups substituted with alkyl groups, preferably linear or branched alkenyl groups having 4 to 10 carbon atoms, and 1 to 12 carbon atoms.
A phenyl alkyl group substituted with a linear or branched alkyl group is preferable, and more preferably a linear alkenyl group having 4 to 6 carbon atoms or a linear alkyl group having 1 to 4 carbon atoms. A phenyl alkyl group substituted with is preferable. This phenyl ring may be substituted with a halogen atom, an alkyl group, an alkoxy group, an alkenyloxy group, a substituted or unsubstituted phenoxy group, or the like.

X is not particularly limited, and for example, a halogen atom (
chlorine atom, bromine atom, iodine atom, etc.), alkylthio groups (methylthio group, ethylthio group, propylthio group, butylthio group, etc.), alkanesulfonyloxy groups optionally substituted with halogen atoms (methanesulfonyloxy group, ethanesulfonyloxy group) (eg, trifluoromethanesulfonyloxy group), arylsulfonyloxy group (benzenesulfonyloxy Lp-}luenesulfonyloxy group, etc.), and hydroxyl group, but preferably a halogen atom.

The raw material compound (II) used in the present invention can be easily produced by reacting a secondary amine and phosgene by a conventional method.

The target compound (I) is usually preferably produced by reacting the starting compound (II) with imidazole in a solvent in the presence of a base, but the reaction can also be carried out without adding a base, and () of the raw material compound without solvent
I[) and imidazole can also be heated and dissolved to react.

Solvents that can be used in the production method are not particularly limited as long as they are not directly involved in this reaction, and examples include benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, and dichloromethane. Chlorinated or non-chlorinated aromatic, aliphatic, cycloaliphatic hydrocarbons such as benzene, methylene chloride, chloroform, dichloroethane, trichlorethylene, cyclohexane: diethyl ether, dimethyl ether tetrahydrofuran, dioxane Ethers such as acetone, methyl ethyl ketone, etc.; Alcohols or their hydrates such as mechnol, ethanol, ethylene glycol, etc.; N,N-dimethylformamide, N,N-
Amides such as dimethylacetamide; organic bases such as pyridine, N,N-diethylaniline, etc.; 1
, 3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; mixtures of the above solvents; examples of the base include triethylamine, vinylodine,
Organic bases such as NN-diethylaniline etc.; alkali metal alkoxide bases such as sodium methoxide, sodium ethoxide etc.; inorganic bases such as sodium amide, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydride etc. Examples include bases.

In the production method, the ratio of the raw material compound (I[) and imidazole is 0.1 mole of the raw material compound (■) to 1 mole of the raw material compound (■). It can be added at a ratio of 5 to 5.0 moles, but preferably 1. 0 to 2.0 mol is preferable.

The reaction temperature is not particularly limited as long as it is below the boiling point of the solvent used, but it is preferable to shorten the reaction time by heating, for example, 20 to 150°C, preferably 50°C.
~100°C is good.

The reaction temperature can be generally 10 minutes to 8 hours, preferably 1 to 3 hours.

The target compound (1) can be easily obtained by appropriately purifying it by known means such as recrystallization and various chromatography methods.

The object compound (1) of the present invention is, for example, powdery mildew, rust, eye spot disease, leaf blight, rice blast, sesame leaf blight, sheath blight, gray mold, sclerotinia, and seedling damping-off. It is highly effective in the prevention and treatment of crop diseases caused by plant pathogenic fungi such as P. nigra, brown spot, black spot, bakanae blight, and scab. prevention·
It is also highly effective in treatment.

The fungicide of the present invention contains one or more types of compound (1) as an effective ingredient.

Compound (1) can be used alone, but can be used in combination with other fungicides, herbicides, plant growth regulators, etc. in order to save labor and enhance pest control effects. Then, carriers, surfactants, dispersants, adjuvants, etc. are usually added by conventional methods (e.g., powders, emulsions, fine granules, granules, permanent agents, oily suspensions, aerosols, etc.) Preferably, it is used after preparation).

Examples of carriers include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea; hydrocarbons (kerosene, mineral oil, etc.), aromatic hydrocarbons (
Hensen, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene glycol acetate, etc.) , dibutyl maleate, etc.), alcohols (methanol, n-
hexanol, ethylene glycol, etc.), polar solvents (
dimethylformamide, dimethyl sulfoxide, etc.),
Examples include liquid carriers such as water; gas carriers such as air, nitrogen, carbon dioxide, and freon (in this case, they can be mixed and injected).

Examples of surfactants and dispersants that can be used to improve properties such as adhesion to animals and plants, absorption, dispersion, emulsification, and spreading of drugs include alcohol sulfate esters, alkyl sulfonates, lignin sulfonate,
Examples include boroxyethylene glycol ether.

In order to improve the properties of the preparation, carboxymethyl cellulose, polyethylene glycol, gum arabic, etc. can be used as adjuvants.

In the standard production, the carrier, surfactant, dispersant, and auxiliary agent described above may be used alone or in appropriate combinations depending on the purpose.

When the compound (.1) of the present invention is formulated, the effective concentration is usually 1 to 50% by weight in an emulsion, and usually 0.5% in a powder.
3 to 25% by weight, usually 1 to 90% by weight for permanent agents, and usually 0.0% for granules. 5-5% by weight, usually 0.5-5% for oil agents
5% by weight, and for aerosols it is usually 0.1 to 5% by weight.

Depending on the purpose, these preparations can be diluted to an appropriate concentration and applied to the transplanted stems, soil, or water surface of paddy fields.
Alternatively, it can be applied directly for various purposes.

(Example〕 Hereinafter, the present invention will be illustrated by reference examples and examples.

Note that these Examples do not limit the scope of the present invention.

Reference Example 1 [Synthesis of N-1-(1-p-n-amyloxybenzyloxycarbonyl)propyliden-1-yl-N-chlorocarbonyl-methylamine]N-1-(1-p-
n-Amyloxybenzyloxycarbonyl)propylidene methylamine (5.8 g, 20 mmoffi) was dissolved in toluene (Loom2), and trichloromethyl formate (3.0 g, 15 mmol) was dissolved in this solution.
1! ) was added. Next, triethylamine (4.0 g, 60 mmof) was added dropwise to this solution while stirring at room temperature.

After stirring at room temperature for 30 minutes, the mixture was poured into water, and the toluene layer was concentrated and dried to obtain the desired product in the form of a slurry.

This was used in the following combinations without purification.

Example 1 [N-1-(1-p-n-amyloxybenzyloxycarbonyl)propyliden-1-yl-N-(1
-Imidazolylcarbonyl)monomethylamine] Unpurified raw material compound (II) of Reference Example 1 (3.5 g, 1
0 mmof), imidazole (1.0 g, 15 mmof), imidazole (1.0 g, 15 mmof)
l) and potassium carbonate (2.1 g, 15 mm
of) was dissolved in dimethylformagode (30mj2) as a solvent, and the mixture was heated and stirred at 45°C for 2 hours. After the reaction was completed, water was added, and then toluene was added and the extracted toluene layer was washed with water, dried over anhydrous sodium sulfate, and then the toluene was distilled off under reduced pressure.

The resulting residue was subjected to silica gel column chromatography (
Wakogel C-200, l-luene: ethyl acetate = 8:
1 elution) to obtain 3.0 g of the target compound as a pale yellow crystalline solid.

Examples 2 to 4 The target compounds (1
) was obtained.

(Hereinafter, blank space) Table 1 Example 5 [Preparation of permanent agent] Compound 1 of Example 1 0. 0 0 parts, kaolin 69.
75 parts, white carbon i s. 0 parts, 1.80 parts of Neoperex, and 0.45 parts of Demol EP (trade name; manufactured by Kao Atlas) were uniformly mixed and ground to obtain a fine powder permanent agent.

When using this product as a leaf-destroying agent, add 20
Dilute it 0 to 2000 times and spray it on plants. When used as a seed disinfectant, it is diluted 20 to 1000 times and the rice seeds are soaked for 10 minutes to 48 hours.

Example 6 [Preparation of emulsion] 60 parts of the compound of Example 1, 23 parts of methyl ethyl ketone and 17 parts of polyoxyethylene nonylphenyl ether were mixed and dissolved to obtain an emulsion.

When using this product as a foliar spray, add 50% water to
Dilute it 0 to 4000 times and spray it on plants. When used as a seed disinfectant, the rice seeds may be diluted 10 to 400 times and immersed for 10 minutes to 48 hours, or they may be used as is to reduce the weight of the seeds to 0. 5-1% is coated.

Example 7 [Preparation of powder] 2 parts of the compound of Example 2 and 98 parts of clay were uniformly mixed and ground to obtain a powder.

Example 8 [Preparation of granules] 15 parts of water was added to 5 parts of the compound of Example 2, 25 parts of bentonite, and 67 parts of white carbon, granulated after kneading, and dried in a fluidized fluid dryer to obtain granules. Ta.

Example 9 [Efficacy test against rice Bakanae disease] Rice (variety: Nipponbare) was spray-inoculated with a concentrated spore suspension of Bakanae disease during the flowering stage. And so.

For seed disinfection, a diluted solution with a predetermined concentration was prepared using a permanent agent prepared according to Example 5, and the ratio of the amount of the chemical solution (V
/V) at 1:l and immersed at 20'C for 24 hours.

The sample paddy after disinfection was soaked in water at 20°C for 3 days, then germinated at 30°C for 24 hours, and when it became dove-breast shaped, it was sown in the soil according to the seedling box raising method. ,
Cultivation was managed in a glass greenhouse.

To investigate disease onset, 25 days after sowing (four-leaf stage), all seedlings from each treatment area were sampled, and the number of diseased rice seedlings was investigated to determine the diseased seedling rate (%).
From this, the seed disinfection rate (%) was calculated (1 ward 5
We went in tandem. ).

In addition, the chemical damage to rice was investigated using the same criteria as in the above test example, and evaluated on a 6-level scale (o: none, 1: slight, 2: a little, 3: a lot, 4: severe, 5: severe).

The results are shown in Table 2 [compounds used 'Jjy
J(I) is shown by the example number in the compound column in the table. ).

× 1 O0 Table 2 Comparative drug Benol (commercially available) Co-NHC4 I H9 Compound A (compound disclosed in JP-A No. 150590/1983) Example 10 [Control efficacy test against rice blast disease (preventive effect) )] A solution prepared by diluting a permanant agent prepared according to Example 5 to a predetermined concentration was applied to rice (variety: Nipponbare) grown in soil in a greenhouse using a plastic pot with a diameter of 5 cm at the 1.5 leaf stage. was sprayed at a rate of 10 mf, and one day later, a spore suspension of rice blast fungus was inoculated by spraying. Five days after inoculation, the number of rice blast lesions per leaf was investigated.

The drug effect is evaluated on a 6-point scale from 5 to O, with 5 being no lesions and 4 being less than 10% of the lesion area compared to the untreated area.
Approximately 20% of cases were given a 3, 40% were given a 2, 60% were given a 1, and cases where the entire population was affected were given a 0.

Further, chemical damage to rice was investigated using the same criteria as in the above test example, and evaluated using the 6-step method described in Example 9.

The results are shown in Table 3 [Compound used (1)
are indicated by the example number in the compound column in the table.

[Effects of the Invention] The present invention provides imidazole derivatives with excellent bactericidal effects. can do.

Claims (3)

[Claims] (1) The following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R_1 represents an alkyl group having 1 to 4 carbon atoms; R_2 is an alkenyl group having 4 to 10 carbon atoms, or phenyl (represents an alkyl group, the phenyl ring thereof may be substituted). (2) Compound represented by the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (In the formula, R_1 and R_2 have the same meanings as described in claim 1; X represents a leaving group.) and imidazole The formula according to claim 1, characterized in that the formula (
I) Method for producing the compound. (3) A fungicide containing the compound of formula (I) according to claim 1 as an active ingredient.