KR20050059321A - Fungicidal compositions for the control of paddy rice diseases - Google Patents

Abstract

Fungicidal compositions effective in the control of paddy rice diseases, containing as the active ingredients both a compound represented by the general formula (1) or an acid addition salt thereof and at least one member selected from among strobilurin insecticides: (1) wherein R is hydrogen, -COR1, -COOR1 (wherein R1 is alkyl having 1 to 4 carbon atoms), -COCH2 OCH3, or -COCH2OCOCH3.

Description

Fungicidal composition for rice pest control {FUNGICIDAL COMPOSITIONS FOR THE CONTROL OF PADDY RICE DISEASES}

The present invention relates to a bactericidal composition having an excellent control effect against rice disease, and more particularly to a bactericidal composition having an excellent control effect against fungal diseases of rice, including rice fever.

WO 01/92231 filed by the Applicant (International Application Date: December 6, 2001) describes a compound of formula (1) or an acid addition salt thereof having excellent bactericidal activity:

Wherein R is a hydrogen atom; -COR ¹ or -COOR ¹ wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms; -COCH ₂ OCH ₃ ; Or -COCH ₂ OCOCH ₃ . In this publication, the physicochemical properties of the compound and the control effect of the compound against rice fever are also described. Furthermore, the publication describes that the compound is excellent in the therapeutic effect against rice febrile disease, as well as the residual activity and the preventive effect, and these effects are different from the therapeutic effect of conventional rice febrile control agents.

The mechanism of action of the compound of formula (1) has not been described in detail yet. However, these compounds have, for example, a rice plant because the control effect can also be obtained against resistant bacteria against sugamicin, organophosphate and strobilucin compounds and in addition bactericidal activity is manifested without inhibition of melamine biosynthesis in the medium. It is expected to have a mechanism of action different from conventional control agents for febrile diseases.

Strobiliur bactericidal compounds have excellent control effects against many fungal diseases of rice, including rice fever, or pathogens as a causative agent of various fungal diseases or diseases causing the cultivation problems of barley, wheat, vegetables, and fruit trees. Or has a high bactericidal activity. Excellent control effects of strobiliurine compounds and their mechanisms of action are described, for example, in the 2001 edition of the Agricultural Chemistry Handbook (issued by the Japan Plant Control Association) and the General Contract Test Report (issued by the Japan Plant Control Association). .

Rice fever is the most serious disease associated with rice cultivation. Rice fever is a type of filamentous fungus that is caused by an infection of the genus Pyricularia, which belongs to an incomplete fungus. To date, excellent control and control methods for rice fever have been reported.

In some cases, however, rice fever occurs even after the application of these remedies in unusual climates, such as abnormal low temperatures in summer and in the rainy season, and due to undesirable cultivation conditions such as unsatisfactory management of seedlings and fertilizer cycles. For this reason, there has been a demand for the development of a control agent having a better control effect against rice fever. In addition, the increase in the number of farmers with side jobs and the increase in the elderly population in agriculture require the development of technologies that can extend the period of control of pests and reduce the frequency and amount of labor applied. . Moreover, in view of the reduction of labor and the amount of pesticides to be applied, there is a need for the development of a medicament capable of simultaneously controlling a number of diseases.

As a result of evaluating the overall effects such as the plural activities and the duration of these activities, the present inventors found that the compound represented by the formula (1) (2,3-dimethyl-6-t-butyl-8-fluoro-4-qui Mixed composition comprising at least one compound selected from the group consisting of a nolinol derivative) and a strobiliurin insecticide, without sacrificing the activity of each component, at the same time develops a synergistic effect and shows an excellent control effect against rice fever. I found that. In this regard, the composition exhibits excellent control effects at low doses for long periods of time against rice fever, which is a representative disease of rice, not only when the composition is applied at a suitable time but also when the application time is delayed after a suitable time. Found. The present invention has been made based on this invention.

Accordingly, it is an object of the present invention to provide a medicament having an excellent control effect against rice disease and having an excellent control effect at a low dose for a long time even when the application time is delayed from a suitable application time.

According to aspects of the present invention there is provided a bactericidal composition comprising as an active ingredient at least one compound selected from the group consisting of a compound of formula (1) or an acid addition salt thereof and a strobiliurin fungicide:

Wherein R is a hydrogen atom; -CHR ¹ or -COOR ¹ wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms; -COCH ₂ OCH ₃ ; Or -COCH ₂ OCH ₃ .

According to another aspect of the present invention, there is provided a rice fever control method comprising applying an effective amount of the bactericidal composition to the area to be treated.

According to another aspect of the present invention, there is provided the use of the bactericidal composition for producing a control against rice blight.

The bactericidal composition according to the present invention comprises a mixture of two compounds having different mechanisms of action and bactericidal spectra. The bactericidal composition according to the present invention can be used for rice fever and other rice paddies such as, for example, crustal fever, ear blight caused by Helminthosporium leaf spots, Cercospora leaf spots, for example rice discoloration caused by the genus Curvularia and Alternaria, and scab disease. It has an excellent control against fungal diseases. According to the bactericidal composition of the present invention, the components of the bactericidal composition act together in a synergistic role to provide unexpected and significant control effects. Therefore, according to the bactericidal composition of the present invention, the required agent per unit area can be reduced. In addition, according to the bactericidal composition of the present invention, an excellent control effect can be obtained at a low dosage compared with the use of each individual composition component. In this case, the control effect is sustainable for a long time. Therefore, according to the bactericidal composition according to the present invention, the required number of treatments of the plant can be reduced. In addition, the total amount of the medicament used in the target plant may be reduced during the growing period. The bactericidal composition according to the present invention exhibits excellent control effects when applied for control treatment at a suitable time and even when the application time is delayed after the suitable time. The bactericidal composition according to the present invention is capable of simultaneous control of a number of diseases and at the same time can reduce the risk of resistance to bacteria. The bactericidal composition according to the present invention can greatly contribute to labor-saving, environmental conservation, and safe food production in agriculture.

Bactericidal compositions

As described above, the bactericidal composition according to the present invention contains at least one compound belonging to the compound of formula (1) or an acid addition salt thereof and a strobilurine fungicide thereof as an active ingredient.

The bactericidal composition can be used for controlling the disease of plants, preferably for controlling rice, and more preferably for controlling rice. Examples of such diseases include rice fever; Ear blight due to Helminthosporium leaf spot or Cercospora leaf spot; Rice discoloration caused by, for example, the genus Curvularia and Alternaria; Embers and; Contains cortical plaques. More preferably, the bactericidal composition according to the present invention is used for the control of rice fever.

In the present invention, "contained as an active ingredient" means that a carrier suitable for the desired composition can of course be incorporated, in addition to other agents that can be used in combination with the compounds of the present invention.

Here, "rice" means rice that grows in rice fields and dry files. The term "rice" means rice grown in rice fields.

Compound of formula (1)

The bactericidal composition according to the present invention comprises a compound of formula (1) or an acid addition salt thereof.

In formula (1), R represents a hydrogen atom, -COR ¹ , -COOR ¹ , -COCH ₂ OCH ₃ , or -COCH ₂ OCOCH ₃ . In the present invention, R ¹ represents an alkyl group having 1 to 4 carbons. In the present invention, the alkyl group is in any of linear, branched, and cyclic forms. Furthermore, one or more hydrogen atoms in the alkyl group may be optionally substituted by one or more same or different substituents. Specific examples of R ¹ include methyl, ethyl, n-propyl, isopropyl, and n-butyl.

In formula (1), when R is a hydrogen atom, the compound of formula (1) may have a structure of formula (2) which is a tautomer of the compound of formula (1). Those skilled in the art will understand that a compound of formula (1) means a compound of formula (2).

In the present invention, the term "acid adduct" generally means an acid that can be used in agriculture and horticulture, for example hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and acetic acid.

Note that the compound of formula (1) may have the form of a hydrate or solvate.

Specific examples of the compound of formula (1) include compound 1 to compound 11 of the examples to be described later.

Process for preparing compound of formula (1)

Compounds of formula (10) may be synthesized by any suitable method for the formation of bonds or introduction of substituents.

For example, the compound of formula (1) can be prepared from 4-t-butyl-2-fluoroaniline, which can be synthesized by conventional methods, according to the following diagram.

here

R represents a hydrogen atom, -COR ¹ , -COOR ¹ , -COCH ₂ OCH ₃ or -COCH ₂ OCOCH ₃ ;

R ¹ represents an alkyl group having 1 to 4 carbon atoms; And

R ² represents —R ¹ , —OR ¹ , —CH ₂ OCH ₃ , or —CH ₂ OCOCH ₃ .

According to this illustration, the compound of formula (2) is first provided (step (a)), and if necessary, the compound of formula (2) is prepared by the formula (3) or (4) in the presence or absence of a base. Reaction with the compound produces the compound of formula (1).

The illustration will be explained in more detail.

Step (a):

The compound of formula (2) is, for example, J. Am. Chem. Soc. 70, 2402 (1984) and Tetrahedron Lett. 27, 5323 (1086), firstly prepared from 4-t-butyl-2-fluoroaniline and ethyl 2-methyl-acetoacetate. The compound of formula (2) corresponds to the compound of formula (1) wherein R is a hydrogen atom. 4-t-butyl-2-fluoroaniline used herein is described, for example, in Chem. Abs. 42, 2239 or J. Chem. Soc., Chem. It may be prepared by the conventional method described in Commun., 1992, 595.

Step (b):

If a compound of formula (1) is then required, wherein R represents a group other than a hydrogen atom, the compound is prepared by the reaction of a compound of formula (2) with a compound of formula (3) with or without a base Can be.

Bases that can be used here include, for example, organic amines such as triethylamine and pyridine, inorganic salts such as sodium carbonate, potassium carbonate and sodium hydride. The compound of formula (3) or the compound of formula (4) is preferably used in an amount of 1 to 50 equivalents, more preferably 1 to 20 equivalents, based on the compound of formula (2). The reaction of step (b) may be carried out in the absence of solvent or at a temperature of, for example, 0 to 140 ° C., for example in the presence of an organic solvent which is inert to the reaction, for example dimethylformamide or tetrahydrofuran.

Strobulin-based fungicide

In the present invention, strobiliurine fungicides may be any known in the art as strobiliurine fungicides. Strobilirin fungicides are, for example, pesticides in pesticide handbook 2001 (issued in 2001 by the Japan Plant Control Association) and pesticide cradles (issued in 2001 by the Japan Plant Control Association, 2001). It is described. One of ordinary skill in the art, with reference to these documents, can appropriately select strobiliurine fungicides.

Specific examples of strobiliurin fungicides that can be used in the present invention include azoxystrobin, metominostrobin, kresoxim-methyl, trifloxystrobin, orosastrobin (orysastrobin), fluoxastrobin, pyraclostrobin and picoxystrobin.

In a preferred embodiment of the invention, the strobilurin-based fungicide is selected from azoxystrobin, metominostrobin and orissastrobin.

In a more preferred embodiment of the invention, the strobilurine fungicide is selected from azoxystrobin and metominostrobin.

Other ingredients

When the bactericidal composition according to the present invention is substantially applied, the composition constituting the active ingredient can only be used by it. Optionally, the composition is mixed with a carrier or adjuvant suitable for the formulation to prepare any stable formulation, such as, for example, powders, granules, packs, hydrates, granulocytes, flocs, liquids, microcapsules or emulsifier concentrates. Can be. This allows the bactericidal composition according to the invention to be suitably used for various suitable applications.

The formulations may be prepared by methods known in the general pesticide art. In particular, for example, the preparation can be prepared if necessary, for example by mixing the active ingredient with a solid carrier, a solvent, a surfactant and other auxiliaries. The carrier and the like may be selected depending on the purpose of use, for example, for improving the properties of the preparation, stabilizing the active ingredient and enhancing the effect.

Solid carriers which can be used here are, for example, clay, talc, calcium carbonate, diatomaceous earth, zeolite, bentonite, acidic clay, activated clay, attapulgus clay, vermiculite, pearlite, pumice, white carbon, titanium dioxide, water soluble salts, Wood flour, corncob, walnut wet, cellulosic powder, starch, dextrin, and saccharides.

Examples of solvents that can be used here include aromatic solvents such as xylene, C ₉ alkylbenzenes, C ₁₀ alkylbenzenes, alkylnaphthalenes, and high boiling aromatic hydrocarbons; aliphatic solvents such as n-paraffins, iso-paraffins, and naphthenes; Mixed solvents such as kerosene or coal oil; Mechanical oils such as high boiling aliphatic hydrocarbons; Alcohols such as ethanol, isopropanol, and cyclohexanol; Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, and polypropylene glycol; Polyhydric alcohol derivatives such as propylene glycol ethers; Ketones such as cyclohexane and gamma-butyrolactone; Esters such as fatty acid methyl esters (eg coconut oil fatty acid methyl esters) and dibasic acid methyl esters (eg succinic dimethyl esters, glutamic acid dimethyl esters); Nitrogen-containing solvents such as N-alkylpyrrolidone; Fats and oils such as coconut oil, soybean oil, and rapeseed oil; And water.

Examples of surfactants that can be used in the present invention include sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid diesters, polyoxy Ethylene castor oil, polyoxyethylene hardened castor oil, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene dialkylphenyl ether, polyoxyethylene alkylphenyl ether / formalin condensate, polyoxyethylene / polyoxypropylene Block polymers, alkylpolyoxyethylene / polyoxypropylene block polymer ethers, alkylphenyl polyoxyethylene / polyoxypropylene block polymer ethers, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene bisphenyl ethers, polyoxyethyl Benzylphenyl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene ether-type silicone, ester-type silicone, fluorosurfactant or other nonionic surfactants, alkyl sulfates, polyoxeethyl alkyl ether sulfates, polyoxy Ethylene alkylphenyl ether sulfate, polyoxyethylene benzylphenyl ether sulfate, polyoxyethylene / polyoxypropylene block polymer sulfate, paraffin sulfonate, AOS, dialkylsulfosuccinate, alkylbenzene sulfonate, naphthalene sulfonate, naphthalene sulfonate Formalin condensates, alkyldiphenyl ether disulfonates, lignin sulfonates, polyethylene alkylphenyl ether sulfonates, polyoxyethylene alkyl ether sulfosuccinate acid halfesters, fatty acid salts, N-methyl-fatty acid sarcosinates, resins Acid, Polyoxyethylene Alkyl Ether Force Pate, polyoxyethylene alkylphenyl ether phosphate, polyoxyethylene benzylated phenyl ether phosphate, polyoxyethylene / polyoxypropylene block polymer phosphate, lecithin, alkylphosphate, alkyltrimethylammonium chloride, methyl / polyoxyethylene alkylammonium chloride, Alkyl N-methyl-pyridinium bromide, alkylmethylate ammonium chloride, alkylpentamethylenepropylenediamine dichloride, alkyldimethylbenzalconium dichloride, benzethonium chloride, dialkyldiaminoethylbetaine, and alkyldimethylbenzyl Contains betaine.

Adjuvants usable in the present invention include, for example, isopropyl phosphate, carboxymethylcellulose, PVA, sodium tripolyphosphate, sodium hexametaphosphate, xan gum, guar gum, carboxymethylcellulose, sodium benzoate, potassium sorbate, p-hydroxybenzoester, 1,2-thiazolin-3-one, ethylene glycol, diethylene glycol, propylene glycol, polyvinyl pyrrolidone, urea, hexamethylenetetramine, antioxidant, UV absorber, zeolite, quicklime , Magnesium oxide, hydrophobic high boiling point solvent, sodium polyacrylate, alginic acid, kraft lignin, methacrylic acid / vinyl pyrrolidone copolymer, glycerin, sorbitol and water-swellable polymerizable compounds.

The carriers, surfactants, dispersants and adjuvants may be used alone or in combination of two or more selected from the same or different groups.

In the bactericidal composition according to the present invention, at least one mixing property selected from the group consisting of the compound of formula (1) or an acid addition salt thereof and a strobiliurin fungicide is such that the total amount (the total amount of the active ingredients) of these compounds is a bactericidal composition. 0.1 to 90 parts by weight, preferably 1 to 70 parts by weight, based on 100 parts by weight.

The total amount of the active ingredient may be selected in consideration of the preparation form of the bactericidal composition, the method of application, the environment of use and other conditions. For example, if the bactericidal composition is in the form of a hydrate, the total amount of active ingredient is 5-50% by weight, preferably 10-30% by weight. On the other hand, if the fungicide composition is a powder, the total amount of the active ingredient is 0.5 to 5.0% by weight, preferably 1.0 to 2.0% by weight.

In the bactericidal composition according to the present invention, the mixing ratio between the compound of formula (1) or an acid addition salt thereof and at least one compound selected from the group consisting of strobiliurin fungicides is in the range of 2:50 to 50: 2, preferably Is in the range 1:10 to 10: 1.

When a bactericidal composition according to the invention is used, such a bactericidal composition can be used directly. If desired, the bactericidal composition may be diluted with a diluent liquid such as water and then treated, for example, applied to the area to be treated, mixed with the area to be treated, or immersed in the area to be treated. Specific examples of treatments include the application of the plant itself (applied to stems and leaves), to the nursery box, to the soil (mixed with soil or to the side stripe), to paddy fields (on the surface of the water). Or application to rice fields) and to seed (seed treatment).

According to another aspect of the present invention, there is provided a method of controlling pests of rice, the method comprising applying an effective amount of the bactericidal composition according to the invention to the area to be treated. The term "region to be treated" refers to the region to be treated with the bactericidal composition according to the invention for rice pest control purposes. Examples of such areas include rice plants, nurseries, soil, rice fields and seeds. Preferably, the area to be treated is a rice plant, soil or paddy field.

The amount of the bactericidal composition according to the present invention to be used may preferably be varied depending on the environment of use, the state of growth of the target plant, the mixing ratio of the active ingredients, the form of the preparation, the time of application, the method of application, and the purpose of the pest to be controlled. Generally, the amount of bactericidal composition used is 1 to 1500 g, preferably 10 to 150 g per 10 acres in terms of the total amount of active ingredient. For example, when the bactericidal composition is applied to a rice plant, the amount of the bactericidal composition to be used is 5 to 500 g, preferably 10 to 100 g in terms of the total amount of the active ingredient.

The bactericidal composition according to the invention can be used, for example, as a mixture with other fungicides, insecticides, tick insecticides, herbicides, plant growth regulators, or fertilizers.

In general, the bactericidal composition according to the invention is already formed with the desired formulation in this manner. Optionally, the method comprises an active ingredient in the composition, i.e., a formulation comprising one of at least one compound selected from the group consisting of a compound of formula (1) or an acid addition salt thereof and a strobiliurin fungicide thereof, and other active ingredients It can be modified to prepare the preparations comprising the in advance, and to mix these preparations in situ together in use.

Therefore, in another aspect according to the invention, there is provided a combination comprising at least one compound selected from the group consisting of a compound of formula (1) or an acid addition salt thereof and a strobiliurin fungicide.

In a preferred embodiment, the compound of formula (1) or acid addition salt thereof in the combination is provided as the first composition comprising the compound of formula (1) or acid addition salt thereof as the active ingredient, and is provided with a strobiliurin fungicide At least one compound selected from the group consisting of is provided as a second composition comprising at least one compound as an active ingredient. In this case, as with the bactericidal composition, the first composition and the second composition may be in the form of any formulation prepared using further suitable carriers or auxiliaries. This combination may be provided in the form of a medicament set.

According to another aspect of the present invention, there is directed to the use of said combination for the production of a rice pest control agent. "Rice pest control agents" include bactericidal compositions according to the invention.

According to yet another aspect of the present invention, there is provided a method for controlling disease of rice, the method simultaneously comprising at least one compound selected from the group consisting of a compound of formula (1) or an acid addition salt thereof and a strobiliurin fungicide thereof Or applying to areas to be treated separately.

In this method, the "simultaneous" application is wherein the compound of formula (1) or at least one compound thereof selected from the group consisting of acid addition salts and strobiliurin fungicides is premixed together to form a mixture and then to the target area. Means the same implementation as applied. "Individual" application means that the compound of formula (1) or acid addition salt thereof without pre-mixing the compound of formula (1) or acid addition salt thereof with at least one compound selected from the group consisting of strobiliurin fungicides By an embodiment, such as applying before or after other components.

In another preferred embodiment of the present invention, there is provided a method for controlling rice pests, the method

(A) a first composition comprising as an active ingredient a compound of formula (1) or an acid addition salt thereof, and

(B) applying to the area to be treated a second composition comprising, as an active ingredient, at least one compound selected from the group consisting of strobiliurin fungicides.

Example

The following examples further illustrate the invention but are not intended to be limiting thereof.

Preparation of Compound of Formula (1)

The compound (compound 1-11) of Formula (1) which has a substituent shown in following Table 1 was prepared.

Table 1

Compounds 1-11 were prepared according to the following steps.

Preparation of 4-t-butyl-2-fluoroaniline

SELECTFLUOR (manufactured by Aldrich Chemical Comapny Inc.) (1-chloro-methyl-4-fluoro-1,4-diazoniabicyclo [2,2,2] octane-bis-tetrafluoroborate) (15 g) It was added to acetonitrile (200 mL) and the mixture was heated at 70 ° C. for 30 minutes to dissolve SELECTFLUOR in acetonitrile. The reaction solution thus obtained was cooled to 60 ° C. and 4-t-butyl-acetonitrile (5.7 g) was added to the cooled reaction solution. The mixture was stirred at 100 ° C. for 1 hour and left to cool the reaction solution. The cooled reaction solution was then added to water (200 mL) and extracted with ethyl acetate (100 mL, twice). The ethyl acetate layer was washed with saturated brine and dried over anhydrous sulfate, and then the solvent was removed by distillation under reduced pressure. The crude product thus obtained was purified by chromatography on salica gel (Wako Gel C-200 from Wako Pure Chemical Industries, Ltd., elution solvent: n-hexane-ethyl acetate (10: 1)) to 4-t-butyl 2-Fluoro-acetonitrile (3.06 g) was obtained. This 4-t-butyl-2-fluoro-acetonitrile (3.67 g) was added to a mixed solution containing ethanol (30 mL) and concentrated hydrochloric acid (15 mL), and the mixture was stirred at 95 ° C for 2 hours. It was. The reaction solution was left to cool, the cooled reaction solution was poured into water, neutralized with saturated aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine and dried over anhydrous sodium sulfate. The solvent was then distilled off under reduced pressure to afford 4-t-butyl-2-fluoroaniline (3.49 g). ¹ H-NMR data in deuterium-chloroform for this compound is shown below.

Compound 1: 2,3-dimethyl-6-t-butyl-8-fluoro-4-hydroxyquinoline

The reaction solution was prepared by refluxing 4-butyl-2-fluoroaniline (4.79 g) prepared according to the above method in toluene (60 mL) for 3 hours in the presence of fluoroborane etherite (0.3 mL). The reaction solution thus obtained was washed with saturated aqueous sodium hydrocarbon solution and saturated brine and dried over anhydrous sodium sulfate. The reaction product was refluxed in diphenyl ether (80 mL) for 1 hour and left to cool. The precipitated product was collected by filtration under reduced pressure to give 2,3-dimethyl-6-t-butyl-8-fluoro-4-hydroxyquinoline (Compound 1, 1.66 g). ¹ H-NMR data in deuterium-chloroform for this compound is shown below.

Compound 2: 2,3-dimethyl-6-t-butyl-8-fluoro-4-acetyl-quinoline

Compound 1 (50 mg) was stirred in acetic anhydride (3 mL) at 120 ° C. for 3 hours to prepare a reaction solution. Acetic anhydride was distilled off under reduced pressure to remove the reaction solution. The residue was dissolved in ethyl acetate. The solution was washed with saturated aqueous sodium hydrocarbon solution and saturated brine and then dried over anhydrous sodium sulfate and distilled under reduced pressure to remove the solvent. The crude product was purified by chromatography on silica gel (Wako Gel C-200, elution solvent: n-hexane-ethyl acetate (5: 1)) to give 2,3-dimethyl-6-t-butyl-8-fluoro-4 Acetylquinoline (Compound 2, 35.7 mg) was obtained. ¹ H-NMR data in deuterium-chloroform for this compound is shown below.

Compound 3: 2,3-dimethyl-6-t-butyl-8-fluoro-4-propionylquinoline

60% sodium hydride (20 mg) was suspended in tetrahydrofuran (3 mL). Compound 1 (124 mg) was added to the suspension under ice cooling and the mixture was stirred for 30 minutes. In addition, propionyl chloride (200 μl) was added thereto and the mixture was stirred for 3 hours. The reaction solution thus obtained was poured into iced water, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was then removed by filtration under reduced pressure. The crude product was purified by chromatography on silica gel (Wako Gel C-200, elution solvent: n-hexane-ethyl acetate (3: 1)) to give 2,3-dimethyl-6-t-butyl-8-fluoro-4 Propionylquinoline (Compound 3, 21 mg) was obtained. ¹ H-NMR data in deuterium-chloroform for this compound is shown below.

Compound 4: 2,3-dimethyl-6-t-butyl-8-fluoro-4-butyrylquinoline

60% sodium hydride (20 mg) was suspended in tetrahydrofuran (3 mL). Compound 1 (124 mg) was added to the suspension under ice cooling and the mixture was stirred for 30 minutes. In addition, butyl chloride (200 μl) was added thereto and the mixture was stirred for 3 hours. The reaction solution thus obtained was poured into iced water, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was then removed by filtration under reduced pressure. The crude product was purified by chromatography on silica gel (Wako Gel C-200, elution solvent: n-hexane-ethyl acetate (3: 1)) to give 2,3-dimethyl-6-t-butyl-8-fluoro-4 Butyrylquinoline (Compound 4, 64 mg) was obtained. ¹ H-NMR data in deuterium-chloroform for this compound is shown below.

Compound 5: 2,3-dimethyl-6-t-butyl-8-fluoro-4-valerylquinoline

60% sodium hydride (20 mg) was suspended in tetrahydrofuran (3 mL). Compound 1 (124 mg) was added to the suspension under ice cooling and the mixture was stirred for 30 minutes. In addition, valeryl chloride (200 μl) was added thereto and the mixture was stirred for 3 hours. The reaction solution thus obtained was poured into iced water, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was then removed by filtration under reduced pressure. The crude product was purified by chromatography on silica gel (Wako Gel C-200, elution solvent: n-hexane-ethyl acetate (3: 1)) to give 2,3-dimethyl-6-t-butyl-8-fluoro-4 Valerylquinoline (Compound 5, 120 mg) was obtained. ¹ H-NMR data in deuterium-chloroform for this compound is shown below.

Compound 6: 2,3-dimethyl-6-t-butyl-8-fluoro-4-methoxycarbonylquinoline

60% sodium hydride (20 mg) was suspended in tetrahydrofuran (3 mL). Compound 1 (124 mg) was added to the suspension under ice cooling and the mixture was stirred for 30 minutes. In addition, methylchloroformate (200 μl) was added thereto and the mixture was stirred for 3 hours. The reaction solution thus obtained was poured into iced water, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was then removed by filtration under reduced pressure. The crude product was purified by chromatography on silica gel (Wako Gel C-200, elution solvent: n-hexane-ethyl acetate (3: 1)) to give 2,3-dimethyl-6-t-butyl-8-fluoro-4 -Methoxycarbonylquinoline (Compound 6, 100 mg) was obtained. ¹ H-NMR data in deuterium-chloroform for this compound is shown below.

Compound 7: 2,3-dimethyl-6-t-butyl-8-fluoro-4-ethoxycarbonylquinoline

60% sodium hydride (60 mg) was suspended in tetrahydrofuran (10 mL). Compound 1 (200 mg) was added to the suspension under ice cooling and the mixture was stirred for 30 minutes. In addition, ethylchloroformate (200 μl) was added thereto and the mixture was stirred for 3 hours. The reaction solution thus obtained was poured into iced water, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was then removed by filtration under reduced pressure. The crude product was purified by chromatography on silica gel (Wako Gel C-200, elution solvent: n-hexane-ethyl acetate (3: 1)) to give 2,3-dimethyl-6-t-butyl-8-fluoro-4 -Ethoxycarbonylquinoline (Compound 7, 220 mg) was obtained. ¹ H-NMR data in deuterium-chloroform for this compound is shown below.

Compound 8: 2,3-dimethyl-6-t-butyl-8-fluoro-4-n-propoxycarbonylquinoline

60% sodium hydride (20 mg) was suspended in tetrahydrofuran (3 mL). Compound 1 (124 mg) was added to the suspension under ice cooling and the mixture was stirred for 30 minutes. In addition, n-propyl chloroformate (200 μl) was added thereto and the mixture was stirred for 3 hours. The reaction solution thus obtained was poured into iced water, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was then removed by filtration under reduced pressure. The crude product was purified by chromatography on silica gel (Wako Gel C-200, elution solvent: n-hexane-ethyl acetate (3: 1)) to give 2,3-dimethyl-6-t-butyl-8-fluoro-4 -n-propoxycarbonylquinoline (Compound 8, 96 mg) was obtained. ¹ H-NMR data in deuterium-chloroform for this compound is shown below.

Compound 9: 2,3-dimethyl-6-t-butyl-8-fluoro-4-n-butoxycarbonylquinoline

60% sodium hydride (60 mg) was suspended in tetrahydrofuran (10 mL). Compound 1 (200 mg) was added to the suspension under ice cooling and the mixture was stirred for 30 minutes. In addition, n-butyl chloroformate (200 μl) was added thereto and the mixture was stirred for 3 hours. The reaction solution thus obtained was poured into iced water, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was then removed by filtration under reduced pressure. The crude product was purified by chromatography on silica gel (Wako Gel C-200, elution solvent: n-hexane-ethyl acetate (3: 1)) to give 2,3-dimethyl-6-t-butyl-8-fluoro-4 -n-butoxycarbonylquinoline (Compound 9, 142 mg) was obtained. ¹ H-NMR data in deuterium-chloroform for this compound is shown below.

Compound 10: 2,3-dimethyl-6-t-butyl-8-fluoro-4-methoxyacetylquinoline

60% sodium hydride (165 mg) was suspended in tetrahydrofuran (10 mL). Compound 1 (680 mg) was added to the suspension under ice cooling and the mixture was stirred for 30 minutes. In addition, methoxyacetyl chloride (200 μl) was added thereto and the mixture was stirred for 3 hours. The reaction solution thus obtained was poured into iced water, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was then removed by filtration under reduced pressure. The crude product was purified by chromatography on silica gel (Wako Gel C-200, elution solvent: n-hexane-ethyl acetate (3: 1)) to give 2,3-dimethyl-6-t-butyl-8-fluoro-4 -Methoxyacetylquinoline (Compound 10, 390 mg) was obtained. ¹ H-NMR data in deuterium-chloroform for this compound is shown below.

Compound 11: 2,3-dimethyl-6-t-butyl-8-fluoro-4-acetoxyacetylquinoline

60% sodium hydride (44 mg) was suspended in tetrahydrofuran (10 mL). Compound 1 (200 mg) was added to the suspension under ice cooling and the mixture was stirred for 30 minutes. In addition, acetoxyacetyl chloride (100 μl) was added thereto and the mixture was stirred for 3 hours. The reaction solution thus obtained was poured into iced water, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was then removed by filtration under reduced pressure. The crude product was purified by chromatography on silica gel (Wako Gel C-200, elution solvent: n-hexane-ethyl acetate (3: 1)) to give 2,3-dimethyl-6-t-butyl-8-fluoro-4 Acetoxyacetylquinoline (Compound 11, 140 mg) was obtained. ¹ H-NMR data in deuterium-chloroform for this compound is shown below.

Formulation example

Formulation Example 1: Hydrating Agent

The following components were ground homogeneously to prepare a hydrating agent.

20 parts by weight of compound 2

20 parts by weight of azooxystrobin

Diatomite 28 parts by weight

White Carbon (trade name: manufactured by Shionogi & Co., LTD.) 13 parts by weight

12 parts by weight of polyoxyethylene lauryl ether

Calcium lignin sulfonate 7 parts by weight

Formulation Example 2: Hydration

The following components were ground homogeneously to prepare a hydrating agent.

15 parts by weight of compound 2

5 parts by weight of azooxystrobin

Diatomite 47 parts by weight

10 parts by weight of clay

White Carbon (trade name: manufactured by Shionogi & Co., LTD.) 10 parts by weight

8 parts by weight of polyoxyethylene lauryl ether

Calcium lignin sulfonate 5 parts by weight

Formulation Example 3: Hydration

The following components were ground homogeneously to prepare a hydrating agent.

20 parts by weight of compound 2

10 parts by weight of azooxystrobin

Diatomite 42 parts by weight

5 parts by weight of clay

White Carbon (trade name: manufactured by Shionogi & Co., LTD.) 10 parts by weight

8 parts by weight of polyoxyethylene lauryl ether

Calcium lignin sulfonate 5 parts by weight

Formulation Example 4: Hydration

The following components were ground homogeneously to prepare a hydrating agent.

20 parts by weight of compound 2

Metominostrobin 20 parts by weight

Diatomite 37 parts by weight

White Carbon (trade name: manufactured by Shionogi & Co., LTD.) 10 parts by weight

8 parts by weight of polyoxyethylene lauryl ether

Calcium lignin sulfonate 5 parts by weight

Formulation Example 5: Hydration

The following components were ground homogeneously to prepare a hydrating agent.

15 parts by weight of compound 2

Methinostrobin 5 parts by weight

Diatomite 47 parts by weight

10 parts by weight of clay

White Carbon (trade name: manufactured by Shionogi & Co., LTD.) 10 parts by weight

8 parts by weight of polyoxyethylene lauryl ether

Calcium lignin sulfonate 5 parts by weight

Formulation Example 6: Hydration

The following components were ground homogeneously to prepare a hydrating agent.

20 parts by weight of compound 2

Metominostrobin 10 parts by weight

Diatomite 42 parts by weight

5 parts by weight of clay

White Carbon (trade name: manufactured by Shionogi & Co., LTD.) 10 parts by weight

8 parts by weight of polyoxyethylene lauryl ether

Calcium lignin sulfonate 5 parts by weight

Formulation Example 7: Powder

1.2 parts by weight of compound 2

0.5 parts by weight of azooxystrobin

97.1 parts by weight of clay

0.5 parts by weight of calcium carbonate

White Carbon (trade name: manufactured by Shionogi & Co., LTD.) 0.2 parts by weight

Driless A (trade name; product of SANKYO CO., LTD) 0.5 parts by weight

Formulation Example 8: Powder

Compound 2 1 part by weight

0.5 parts by weight of azooxystrobin

97.1 parts by weight of clay

0.5 parts by weight of calcium carbonate

White Carbon (trade name: Shionogi & Co., LTD.) 0.4 parts by weight

Driless A (trade name; product of SANKYO CO., LTD) 0.5 parts by weight

Formulation Example 9: Powder

1.2 parts by weight of compound 2

Metominostrobin 0.5 parts by weight

97.1 parts by weight of clay

0.5 parts by weight of calcium carbonate

White Carbon (trade name: manufactured by Shionogi & Co., LTD.) 0.2 parts by weight

Driless A (trade name; product of SANKYO CO., LTD) 0.5 parts by weight

Formulation Example 10 Powder

Compound 2 1 part by weight

Metominostrobin 0.5 parts by weight

97.1 parts by weight of clay

0.5 parts by weight of calcium carbonate

White Carbon (trade name: Shionogi & Co., LTD.) 0.4 parts by weight

Driless A (trade name; product of SANKYO CO., LTD) 0.5 parts by weight

Evaluation

Test A: Effect of rice fever control according to application before rice fever spread (control timely test)

The culture soil was placed in a plastic container (about 30 cm × 50 cm), and after forced germination, rice seed (variety: Koshihikari) was inoculated into the container and used for cultivating dense plants.

Rice was grown in a greenhouse for about two weeks at 25 ° C. during the day and 20 ° C. at night. When rice is grown to 3 or 4 leaf stages, the rice fever bacteria (race 037) have been inoculated beforehand, and the leaves of the rice fever disease are placed in densely planted rice and left under humid conditions for 24 hours of inoculation. It was. Then, the rice plants were returned to the greenhouse. After 7 or 8 days, the presence of lesions was observed and a first drug spread was performed. In this case, the test chemical was diluted to a predetermined concentration with 10% aqueous acetone solution (5000 times diluted neoesterin (trade name: KUMIAI CHEMICAL INDUSTRY CO., LTD) added as an electrodeposition agent). Each test chemical thus prepared was applied in an amount of 15 ml per container using a spray gun. When the second drug spread was performed 6 or 7 days after the first spread, the second drug spread was performed in the same manner as the first drug application.

After drug application, rice was managed in a greenhouse. During this period, at one to two day intervals, rice was placed under humid conditions for 24 hours to promote the development and spread of rice fever.

After 10 days of application of the final medicament, for 40 plants per container, the lesion area of the surface of the blade located on one leaf below the highest leaf was observed and the lesion area rate at the treated plot was measured. The lesion area ratio at the untreated site was also measured in the same manner as at the treated site. For each test drug, the control value was calculated according to the following equation from the results obtained at the treated site and at the untreated site.

Control value = [1- (lesion area ratio at treatment site / lesion area ratio at untreated site)] × 100

The prophylactic and residual effects of the test agent can be measured by observing whether the lesion area rate has increased after a predetermined day after drug treatment. Therefore, the preventive effect and residual effect were judged based on whether the final control price increased.

The test was carried out for each group consisting of the drugs described in Tables A1 to A3 below. Drug application was performed once or twice.

The results are shown in Tables A1 to A3.

Table A1: Two Application Tests

drugs Concentration (ppm) Lesion area ratio Control Untreated Compound 2 Azooxystrobin Compound 2+ Azooxystrobin 808040 + 40 35.95.03.00.4 869299

Table A2: One Application Test

drugs Concentration (ppm) Lesion area ratio Control Untreated Compound 2 Azooxystrobin Compound 2+ Azooxystrobin 808040 + 40 35.817.920.010.6 504470

Table A3: One-Time Application Test

drugs Concentration (ppm) Lesion area ratio Control Untreated Compound 2 Compound 3 Compound 11 Azooxystrobin Methominostrobin Compound 2 + Azooxystrobin Compound 3 + Azooxystrobin Compound 11 + Azooxystrobin Compound 2 + Methominostrobin Compound 3 + Methominost Robin Compound 11+ Methominostrobin 808080808040 + 4040 + 4040 + 4040 + 4040 + 4040 + 40 40.615.121.418.314.120.94.16.95.410.913.614.5 6347556549908387736664

Test B: Effect of control of rice fever by application after the spread of rice fever (application delay test)

The culture soil was placed in a plastic container (about 30 cm × 50 cm), and after forced germination, rice seed (variety: Koshihikari) was inoculated into the container and used for cultivating dense plants.

Rice was grown in a greenhouse for about two weeks at 25 ° C. during the day and 20 ° C. at night. When rice is grown to 3 or 4 leaf stages, the rice fever bacteria (race 037) have been inoculated beforehand, and the leaves of the rice fever disease are placed in densely planted rice and left under humid conditions for 24 hours of inoculation. It was. Then, the rice plants were returned to the greenhouse. After 7 or 8 days, the presence of lesions was observed. The rice was then left to stand for 24 hours under humid conditions to promote secondary infection and to spread rice fever in the container. After about 3 or 4 days after the promotion of the spread of rice fever, a very small secondary lesion was identified and the first drug application was performed.

Other tests such as test drug conditions, application method, application interval, application of rice fever development and control after initiation, and control value were the same as test A. When the second drug application was conducted, the drug interval was the same as in test A.

The test is shown in the following B1 to B4.

Table B1: Two Application Tests

drugs Concentration (ppm) Lesion area ratio Control Untreated Compound 2 Azooxystrobin Compound 2+ Azooxystrobin 808040 + 40 81.527.621.412.2 667485

Table B2: One Application Test

drugs Concentration (ppm) Lesion area ratio Control Untreated Compound 2 Azooxystrobin Compound 2+ Azooxystrobin 808040 + 40 74.527.954.119.8 632773

Table B3: Single Application Test

drugs Concentration (ppm) Lesion area ratio Control Untreated Compound 2 Azooxystrobin Compound 2+ Azooxystrobin 808040 + 40 30.016.610.94.5 456485

Table B4: One-Time Application Test

drugs Concentration (ppm) Lesion area ratio Control Untreated Compound 2 Compound 3 Compound 11 Azooxystrobin Methominostrobin Compound 2 + Azooxystrobin Compound 3 + Azooxystrobin Compound 11 + Azooxystrobin Compound 2 + Methominostrobin Compound 3 + Methominost Robin Compound 11+ Methominostrobin 808080808040 + 4040 + 4040 + 4040 + 4040 + 4040 + 40 73.319.031.327.819.027.414.413.112.511.515.315.5 7457627463808283847979

Claims (16)

As an active ingredient, Compound of formula (1) or acid addition salt thereof: Wherein R is a hydrogen atom; -COR ¹ or -COOR ¹ (wherein R ¹ represents an alkyl group having 1 to 4 carbons); -COCH ₂ OCH ₃ ; Or -COCH ₂ OCOCH ₃ And A bactericidal composition comprising one or more compounds selected from the group consisting of strobiliurin fungicides. The bactericidal composition according to claim 1, wherein the compound belonging to the strobiliurin fungicide is selected from azooxystrobin and metominostrobin. The bactericidal composition according to claim 1 or 2 for use in controlling pests of rice. The bactericidal composition according to claim 1 or 2 for use in controlling diseases of rice fields. The bactericidal composition according to claim 3, wherein the disease is rice fever. Compound of formula (1) or acid addition salt thereof: Wherein R is a hydrogen atom; -COR ¹ or -COOR ¹ (wherein R ¹ represents an alkyl group having 1 to 4 carbons); -COCH ₂ OCH ₃ ; Or -COCH ₂ OCOCH ₃ And Combination comprising at least one compound selected from the group consisting of strobiliurin fungicides. Use of the bactericidal composition according to claim 1 or 2 for the production of control agents against rice pest diseases. Use of a combination according to claim 6 for the production of control agents against rice pest diseases. Use according to claim 7 or 8, wherein the disease is rice fever. A method for controlling rice pests, comprising applying an effective amount of the bactericidal composition according to claim 1 to the area to be treated. Compound of formula (1) or acid addition salt thereof: Wherein R is a hydrogen atom; -COR ¹ or -COOR ¹ , wherein R ¹ represents an alkyl group having 1 to 4 carbons; -COCH ₂ OCH ₃ , or -COCH ₂ OCOCH ₃ And A method of controlling rice disease comprising applying at least one compound selected from the group consisting of strobiliurin fungicides simultaneously or separately to a region to be treated. The method of claim 11 wherein all components are applied to the area to be treated simultaneously. The method according to any one of claims 10 to 12, wherein the compound belonging to the strobiliurin fungicide is selected from azooxystrobin and metominostrobin. The method according to any one of claims 10 to 13, wherein the pest is a pest of rice. The method according to any one of claims 10 to 14, wherein the disease is rice fever. The method according to any one of claims 10 to 15, wherein the area to be treated is rice plant itself, soil or paddy field.