JP2526037B2 - Intermediate of imidazo [4,5-b] pyridine compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to novel imidazo [4,5-b] pyridine compounds, pest control agents containing them as active ingredients, and methods for producing them.

(Disclosure of the Invention) The compound of the present invention is a novel imidazo [4,5-b] pyridine compound represented by the following general formula (I).

General formula (I) [In the formula, X ₁ is a trifluoromethyl group, a nitro group or a halogen atom, and X ₂ is a hydrogen atom, a halogen atom or -A.
A —R ₁ group (A is an oxygen atom or a —S (O) _n — group, and n is 0
To an integer of 2, R ₁ is an optionally substituted alkyl group, an optionally substituted phenyl group or an optionally substituted pyridyl group), and Y is a —SO ₂ R ₂ group (R ₂ Is an optionally substituted alkyl group, an optionally substituted phenyl group, an optionally substituted pyridyl group, an optionally substituted thienyl group or R ₃ is a hydrogen atom or an alkyl group, and R ₄ is an alkyl group) or (R ₅ is an optionally substituted alkyl group, an optionally substituted phenyl group, an optionally substituted alkoxy group, an optionally substituted phenoxy group or And R ₆ is a hydrogen atom or an alkyl group, and R ₇ is an alkyl group), and Z is a halogen atom, an optionally substituted alkyl group, an optionally substituted phenyl group, or an optionally substituted phenyl group. Good pyridyl group, cyano group, -S (O) _m R ₈ group (m is an integer of 0 to 2, R ₈ is a hydrogen atom or an alkyl group, and when R ₈ is a hydrogen atom, m is O ), (R ₉ and R ₁₀ are a hydrogen atom or an alkyl group), or Is).

An optionally substituted alkyl group represented by R ₁ , R ₂ , R ₅ and Z in the above general formula (I), R ₃ , R ₄ , R ₆ , R ₇ , R ₈ and R ₉ ,
The alkyl group represented by R ₁₀ and the alkyl moiety of the optionally substituted alkoxy group represented by R ₅ include
Methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, te
Examples of the halogen atom represented by X ₁ , X ₂ , and Z include a chlorine atom, a fluorine atom, a bromine atom, and a rt-butyl group.
Examples include iodine atoms. The substituent of the optionally substituted alkyl group represented by R ₁ , R ₂ , R ₅ and Z and the optionally substituted alkoxy group represented by R ₅ includes a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. Etc., and the number of substituents is preferably 1 to 5. Also, an optionally substituted phenyl group represented by R ₁ , R ₂ , R ₅ and Z, an optionally substituted pyridyl group represented by R ₁ , R ₂ and Z, and an optionally substituted represented by R _5. Examples of the substituent of the phenoxy group and the optionally substituted thienyl group represented by R ₂ include a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a trifluoromethyl group, a cyano group and a nitro group. The number is preferably 1 to 5.

Further, the imidazo compound represented by the general formula (I) [4,5-
b] Among the pyridine compounds, the following are particularly desirable.

(1) X ₁ is a trifluoromethyl group.

(2) X ₂ is a hydrogen atom, a halogen atom or a -A-R ₁ group (A
Is an oxygen atom or a —S (O) _n — group, n is an integer from O to 2, R ₁ is an alkyl group optionally substituted with a fluorine atom, a phenyl group optionally substituted with a chlorine atom, or Pyridyl group).

(3) Y is a —SO ₂ R ₂ — group (R ₂ is an alkyl group which may be substituted with a fluorine atom, a phenyl group or R ₃ is a hydrogen atom or an alkyl group, and R ₄ is an alkyl group) or (R ₅ is a phenoxy group or And R ₆ is a hydrogen atom or an alkyl group, and R ₇ is an alkyl group).

(4) Z is a halogen atom, an alkyl group which may be substituted with a fluorine atom, a cyano group, a —S (O) _m R ₈ group (m is 0 to 2
R ₈ is a hydrogen atom or an alkyl group, R ₈
Is a hydrogen atom, m is 0), or Is.

Furthermore, the following trifluoromethylpyridine-based compound is an imidazo [4,5-
b] Desirable as an intermediate of a pyridine compound.

General formula (a) or (b): [In the formula, A ₁ is a halogen atom or a methylthio group, and A ₂
Is a chlorine atom or a hydroxyl group, B ₁ is a nitro group or an amino group, and B ₂ is a halogen atom, an alkoxy group or an alkylthio group].

The novel imidazo [4,5 represented by the general formula (I)
-B] The pyridine compound can be specifically produced by the following method.

(In the formula, X ₁ , X ₂ , Y and Z are as described above, and hal is a halogen atom.) The above reaction is carried out in the presence of a solvent and an acid acceptor, if necessary.

As the solvent, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene: cyclic or non-cyclic aliphatic hydrocarbons such as chloroform, carbon tetrachloride, methylene chloride, dichloroethane, trichloroethane, n-hexane, and cyclohexane: diethyl Ethers such as ether, dioxane and tetrahydrofuran: acetone,
Ketones such as methyl ethyl ketone and methyl isobutyl ketone: nitriles such as acetonitrile, propionitrile and acrylonitrile; dimethylformamide, N
-Aprotic polar solvents such as methylpyrrolidone, dimethyl sulfoxide, sulfolane and the like can be mentioned.

Examples of the acid acceptor include inorganic bases such as sodium hydroxide, potassium hydroxide, alkali metal or alkaline earth metal carbonates, and organic bases such as triethylamine.

The reaction can be carried out in the presence of a suitable catalyst. Examples of the catalyst include a phase transfer catalyst such as a quaternary ammonium salt derivative.

Examples of the halogen atom represented by hal in the general formula (III) include chlorine atom, fluorine atom, bromine atom and iodine atom.

The compound represented by the general formula (I) has the general formula: [Wherein X ₁ , X ₂ , Y and Z are as described above].

Since the compound represented by the general formula (II) has tautomers represented by the following general formulas (II-a) and (II-b), the compound of the present invention is used as a starting material. When manufactured, (I-a) or (I-b),
Or a mixture thereof can be obtained.

The compound represented by the general formula (II) has the general formula: [In the formula, X ₁ , X ₂ , R ₉ and R ₁₀ are as described above, R ₁₁ is a chlorine atom, a bromine atom or an iodine atom, and R ₁₂ is an optionally substituted alkyl group, Is a phenyl group or an optionally substituted pyridyl group, R ₁₃ is an alkyl group, and 1 is an integer of 1 to 2].
The compounds represented by II-1 to II-9 can be synthesized, for example, by the following method.

[Wherein X ₁ , X ₂ , R ₉ cost, R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and l are as described above] Substituted by R ₁₂ in the general formula (II-3) The substituted portion of the alkyl group which may be present includes a chlorine atom, a fluorine atom, a bromine atom, an iodine atom, and the like,
Examples of the substituted portion of the optionally substituted phenyl group and the optionally substituted pyridyl group include a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a trifluoromethyl group, a cyano group and a nitro group. The alkyl group represented by R ₁₃ includes a methyl group, an ethyl group, an n-propyl group,
iso-propyl group, n-butyl group, iso-butyl group, sec
-Butyl group, tert-butyl group and the like can be mentioned.

The compound represented by the general formula (VI) has the general formula: [Wherein, X ₁ is as described above, R ₁₄ is a halogen atom, and r is an integer of 1 to 2]. The general formulas (VI-1), (VI-2), (VI-3) and (VI-
The compound represented by 4) can be synthesized, for example, as follows.

[In the formula, X ₁ , R ₁ , R ₁₄ and r are as described above] The manufacturing method [A], [B], [C], [D],
Table 1 shows typical examples of the intermediates of the compound of the present invention represented by the general formula (II) synthesized by [E], [F] or [G].

Representative examples of the compounds of the present invention are shown in Table 2.

No. 1 of the representative compounds listed in Table 2 above
6A and No. 16B; No. 17A and No. 17B are structural isomers of each other, and Nos. 1 to 15 and Nos. 18 to 21 are a mixture of structural isomers.

 Next, specific synthesis examples of the compound of the present invention will be described.

Synthesis Example 1 1H (3H) -5-chloro-2-cyano-1
(3) Synthesis of dimethylsulfamoyl-6-trifluoromethylimidazo [4,5-b] pyridine (Compound No.1) [1] 25 ml of 25% fuming sulfuric acid was ice-cooled and used as a starting compound at 20 ° C or lower. 48 g of 6-chloro-trifluoromethyl-2-pyridone was gradually added. Next, 33 ml of fuming sulfuric acid (specific gravity 1.52) was gradually added dropwise in the range of 70 to 75 ° C, and then 1
The reaction was carried out with stirring for a time.

After completion of the reaction, the reaction product was put on ice, and the precipitated crystals were separated by filtration, washed with water and dried. The aqueous layer was extracted with methylene chloride, washed with water and dried, and the solvent was distilled off under reduced pressure to obtain crystals. This was combined with the above crystals, and as a product, a 6-mp having a melting point of 121 to 123 ° C.
36 g of chloro-3-nitro-5-trifluoromethyl-2-pyridone was obtained.

The results in Table 3 were obtained by the same operation as in the step [1].

[2] As a raw material compound, 48.5 g of 6-chloro-3-nitro-5-trifluoromethyl-2-pyridone obtained in the above step [I] was mixed with thionyl chloride (50 ml) at room temperature, and dimethylformamide (1.5 ml) was added. The reaction was carried out at the transition temperature for 3 hours.

After completion of the reaction, water was added to the residue obtained by evaporating thionyl chloride, the crystals were separated by filtration, washed with water and dried to obtain 49.6 g of 2,6-dichloro-3-nitro-trifluoromethylpyridine as a product. .

The same operation as in the step [2] was performed, and the results in Table 4 were obtained.

[3] 2,6-dichloro-3-nitro-5-trifluoromethylpyridine obtained in the above step [2] as a raw material compound
13 g was dissolved in 50 ml of acetone, 100 ml of 28% aqueous ammonia was added dropwise at room temperature, and the mixture was reacted for 30 minutes with stirring.

After the reaction was completed, the precipitated crystals were separated by filtration, washed with water, washed with normal hexane and dried to give a product having a melting point of 18
2-amino-6-chloro-3-nitro-5 at 1 to 183 ° C
11.9 g of trifluoromethylpyridine was obtained.

The same operation as in the step [3] was performed, and the results in Table 5 were obtained.

[4] As a raw material compound, 30 g of 2-amino-6-chloro-3-nitro-5-trifluoromethylpyridine obtained in the above step [3] was mixed with 300 ml of acetic acid to prepare a reaction mixture at 65 to 75 ° C.
25 g of iron powder was gradually added while maintaining the temperature. After completion of the addition, the mixture was reacted at the same temperature for 1 hour with stirring.

After completion of the reaction, 500 ml of ethyl acetate was added, the precipitated iron salt was removed, the ethyl acetate layer was washed with water, and dried over anhydrous sodium sulfate. Then, the solvent was distilled off, and the residue was washed with normanhexane to give 2,3-diamino-6-chloro-5-trifluoromethylpyridine (21.5 g) having a melting point of 145 to 147 ° C as a product.
I got

The same operation as in the step [4] was performed and the results shown in Table 6 were obtained.

[5] 2.3-Diamino-6-chloro-5-trifluoromethylpyridine obtained in the above step [4] as a raw material compound
To a mixed solution of 10.5 g and 80 ml of acetic acid, 9.6 g of methyltrichloroacetimidate was added at room temperature, and the mixture was reacted overnight with stirring.

After completion of the reaction, the mixture was poured into water and the precipitated crystals were separated by filtration and dried to obtain 8.8 g of 1H-2-trichloromethyl-5-chloro-6-trifluoromethylimidazo [4,5-b] pyridine as a product. Obtained.

The same operation as in the step [5] was performed and the results shown in Table 7 were obtained.

[6] 1H-2-trichloromethyl-5-chloro-6-trifluoromethylimidazo [4,5] obtained as a starting compound in 60 ml of 40% aqueous ammonia at 0-5 ° C.
-B] 8.8 g of pyridine was gradually added. After the addition, the mixture was allowed to stand at room temperature with stirring.

After completion of the reaction, insoluble matter is filtered off and the filtrate is adjusted to pH below 10 ° C.
It was neutralized with diluted hydrochloric acid up to 3. The precipitated crystals and the ethyl acetate extracts of the aqueous layer were collected and dried to obtain 2.4 g of 1H-2-cyano-5-chloro-6-trifluoromethylimidazo [4,5-b] pyridine as a product.

The same operation as in the above step [6] was performed and the results in Table 8 were obtained.

[7] 1H-2-obtained as the starting compound in the above step [6]
2.4 g of cyano-5-chloro-6-trifluoromethylimidazo [4,5-b] pyridine, 70 ml of acetonitrile and 1.5 g of anhydrous potassium carbonate were mixed and stirred under reflux for 1 hour.
Next, the temperature of the reaction system was lowered to 30 ° C., 1.7 g of dimethylsulfamoyl chloride was added, and the mixture was reacted again under reflux for 1 hour.

After the reaction was completed, the inorganic salt was filtered off, the solvent was distilled off, and the product was separated with silica gel column chromatography using methylene chloride as a developing solvent to give the desired product having a melting point of 179 to 184 ° C.
Obtained 1.4 g.

The same operation as in the step [7] was performed and the results shown in Table 9 were obtained.

Synthesis Example 2 1H, (3H) -2-cyano-1, (3) -dimethylsulfamoyl-5- (2,4-dichlorophenoxy)
Synthesis of 6-trifluoromethylimidazo [4,5-b] pyridine (Compound No. 3) [1] 6-chloro-3-nitro-5-as a starting compound
Trifluoromethyl-2-pyridone 10g, dioxane 70m
5.3 g of potassium hydroxide was added at 50-60 ° C. to a mixed solution of 7.4 g of 2,4-dichlorophenol as a nucleophile and then heated to the boiling point of dioxane and reacted for 4 hours.

After completion of the reaction, the reaction product was put into water, and the precipitated crystal was separated by filtration and dried to obtain 6- (2,4-dichlorophenoxy) -3-nitro-5-trifluoromethyl-2- as a product.
14.1 g of pyridone was obtained.

[2] to [7] 6- (2, obtained by the above step [1],
4-dichlorophenoxy) 3-nitro-5-trifluoromethyl-2-pyridone is used, and the synthesis agent 1 [2]
The desired product was obtained in the same manner as in [7]-[7].

The same operation as in [1] of Synthesis Example 2 was performed to obtain the results shown in Table 10.

Synthesis Example 3 Synthesis of 1H, (3H) -2-cyano-1, (3) -dimethylsulfamoyl-5-phenoxy-6-trifluoromethylimidazo [4,5-b] pyridine (Compound No. 4) [1] 2-amino-6-chloro-3-as a raw material compound
To a mixture of 24.2 g of nitro-5-trifluoromethylpyridine, 120 ml of dimethylformamide and 10.3 g of phenol,
Gradually add 7 g of potassium hydroxide at 50-60 ° C and after the addition 1.
It was kept at the same temperature for 5 hours.

After completion of the reaction, the reaction product was put into water and extracted with ethyl acetate. After washing with water and drying over anhydrous sodium sulfate, the solvent was distilled off to obtain 21.8 g of 2-amino-3-nitro-6-phenoxy-5-trifluoromethylpyridine as a product.

The same operation as in the above step [1] was performed and the results shown in Table 11 were obtained.

[2] 2-amino-obtained in [1] above as a raw material compound
20 g of 3-nitro-6-phenoxy-5-trifluoromethylpyridine was dissolved in 250 ml of ethanol, and 5% of this was dissolved.
-Palladium / carbon (2 g) was added, and the reduction reaction was carried out with stirring under hydrogen pressure overnight.

After completion of the reaction, 5% -palladium / carbon was filtered off,
The solvent was distilled off and the residue was washed with normal hexane to obtain 11.3 g of 2,3-diamino-6-phenoxy-5-trifluoromethylpyridine having a melting point of 130 to 132 ° C as a product.

[3] to [5] Using 2,3-diamino-6-phenoxy-5-trifluoromethylpyridine obtained in the above step [2], the same as in [5] to [7] of the above formulation example 1 The desired product was obtained by the method.

The results shown in Table 12 were obtained by the same operation as in [2] of Synthesis Example 3 above.

Synthesis Example 4 1H, (3H) -2-cyano-1, (3) -dimethylsulfamoyl-5-methylsulfonyl-6-tolufluoromethylimidazo [4,5-b] pyridine (Compound No.
Synthesis of 2) 1H, (3H) -2-cyano-1, (3) -dimethylsulfamoyl-5-methylthio-6-tolufluoromethylimidazo [4,5-b] pyridine 2 g was dissolved in 300 ml of methanol. To the solution was added 2.7 g of m-chloroperbenzoic acid and 110 m of methylene chloride.
The solution dissolved in 1 was added dropwise at room temperature and then reacted for 1.5 hours with stirring.

After the reaction was completed, the reaction mixture was put into water, extracted with methylene chloride, washed with a sodium carbide solution, further washed with water, and then dried over anhydrous sodium sulfate. Then, the solvent was distilled off, and acetonitrile was recrystallized from a mixed solution of n-hexane to obtain 0.8 g of the desired product having a melting point of 209 to 211 ° C.

Synthesis Example 5 1H, (3H) -1, (3) -dimethylsulfamoyl-5- (pyridin-2-ylthio) -2,6-bistrifluoromethylimidazo [4,5-b] pyridine (Compound No. 8)
Synthesis of [1] 2,3-diamino-6- (pyridin-2-ylthio) -5-trifluoromethylpyridine as a raw material compound
2.8g, trifluoroacetic acid 4ml and trifluoroacetic anhydride 3
The mixture of ml was reacted under reflux for 2 hours.

After the reaction was completed, the remaining trifluoroacetic acid and trifluoroacetic anhydride were distilled off, and the mixture was separated by silica gel column chromatography using a mixed solvent of ethyl acetate and normal hexane (1: 1) as a developing solvent. 1
1H-5- (pyridin-2-ylthio) -2,6-bistrifluoromethylimidazo [4,5-b] pyridine 2.3 at 36 ° C
got g.

 The results shown in Table 13 were obtained by the same operation as in the step [1].

Synthesis Example 6 1H-1-dimethylsulfamoyl-2-methylthio-6-trifluoromethylimidazo [4,5-b]
Pyridine and 3H-3-dimethylsulfamoyl-2-methylthio-6-trifluoromethylimidazo [4,5-
b] Synthesis of pyridine (Compound No. 17A, Compound No. 17B) [1] to [4] 2,3-diamino-5-trifluoro by the same method as in [1] to [4] of Synthesis Example 1 above. Methylpyridine was obtained.

[5] 2,3-obtained in [1] to [4] of Synthesis Example 6 above
Diamino-5-trifluoromethylpyridine 3.0 g, potassium ethyl xanthate 8.0 g, ethanol 90 ml, water 18
ml was mixed and reacted at reflux temperature for 16 hours.

After completion of the reaction, the solvent was distilled off, 30 ml of water was added to the residue, the pH was adjusted to 5.5 with acetic acid, and the formed precipitate was filtered and 1H-2-mercapto-6-trifluoromethylimidazo [having a melting point of 300 ° C. or higher [ 4,5-b] pyridine was obtained.

[6] 1H-2-mercapto-obtained in the above step [5]
6-trifluoromethylimidazo [4,5-b] pyridine
3.8 g was dissolved in 1.0 ml of dimethyl sulfoxide, 1.3 g of anhydrous potassium carbonate was added, and the mixture was stirred at room temperature. Next, 3.7 g of methyl iodide was added, and the mixture was stirred at room temperature for 24 hours.

After completion of the reaction, the mixture was put into water, the crystallized product was filtered and dried,
1H-2-methylthio-6-trifluoromethylimidazo [4,5-b] pyridine (sublimation from melting point 210 ° C.) was obtained.

[7] 1H-2-methylthio-obtained in the above step [6]
6-trifluoromethylimidazo [4,5-b] pyridine
A mixture of 2.3 g, 30 ml of acetonitrile and 1.5 g of anhydrous potassium carbonate was refluxed for 1 hour, cooled to 30 ° C., 1.44 g of dimethylsulfamoyl chloride was added, and the mixture was reacted at reflux temperature for 2.5 hours.

After completion of the reaction, the mixture was poured into water, extracted with ethyl acetate, dried and concentrated. Separated and purified by silica gel column chromatography as methylene chloride developing solvent, 1.1 g of target compound No. 17A (melting point 102-104 ° C) and compound No. 17B (melting point)
(154-156 ° C) 0.5 g was obtained.

Synthesis Example 7 1H-2-chloro-1-dimethylsulfamoyl-6-trifluoromethylimidazo [4,5-b] pyridine and 3H-2-chloro-3-dimethylsulfofimoyl-6-trifluoromethylimidazo [4,5-b] Pyridine (Compound No. 16A, Compound No. 16B) [1] 1H-2-mercapto-6-trifluoromethylimidazo [4,5-b] pyridine 5 g in acetic acid 140 ml and water 30 ml In addition, chlorine gas was blown in under ice cooling for 2.5 hours.

After completion of the reaction, the mixture was poured into water, extracted with ethyl acetate, washed with water,
It was dried and the solvent was distilled off. Normal hexane was added to the residue to obtain crystals of 1H-2-chloro-6-trifluoromethylimidazo [4,5-b] pyridine having a melting point of 150 to 153 ° C.

[2] A mixture of 1.1 g of 1H-2-chloro-6-trifluoromethylimidazo [4,5-b] pyridine obtained in the above step [1], 8 ml of acetonitrile and 0.5 g of anhydrous potassium carbonate was added to 4
After refluxing for 5 minutes, the mixture was cooled to 30 ° C., 0.8 g of dimethylsulfamoyl chloride was added, and the mixture was reacted at reflux temperature for 3 hours. After completion of the reaction, the mixture was poured into water, extracted with ethyl acetate, dried and concentrated. Separated and purified by silica gel column chromatography using methylene chloride as a developing solvent, 240 mg of target compound No. 16A (melting point 75-85 ° C) and compound No. 16B
370 mg was obtained (melting point 120-125 ° C.).

The compound of the present invention is useful as a pest control agent.
Examples of fungicides for agricultural and horticultural use include rice blast, rice blight, cucumber anthracnose, cucumber powdery mildew, tomato blight, tomato ring spot, citrus black spot, citrus green mold, pear scab, Diseases such as apple leaf spot disease, grape downy mildew, various types of gray mold, sclerotium, rust and Fusarium bacterium,
Pythium, Rhizoctonia, Verticillium, shows excellent control effect against soil diseases caused by plant pathogens such as Plasmodiophora, especially diseases of potatoes and tomatoes, downy mildew of cucumber and grapes,
It has excellent control effect against diseases caused by algae such as blue mold of tobacco and various soil diseases caused by Pythium. Since the compound of the present invention has not only a preventive effect but also a therapeutic effect, and furthermore has excellent systemic transfer properties, it is possible to control the disease of the foliage by treating the soil. Further, the compound of the present invention is an agricultural and horticulturally harmful insect,
Mites, nematodes, for example, aphids, diamondback moth, leafhopper leafhoppers, insects such as adzuki bean weevils, spider mites,
It shows an excellent control effect against mites such as spider mites and nematodes such as sweet potato nematode nematodes. The compound of the present invention also has a herbicidal activity, and is useful as a herbicide for paddy fields, fields, orchards, and non-cultivated lands. Furthermore, the compound of the present invention is also useful as a pharmaceutical antifungal agent as shown in the test examples described later. Further, the intermediate represented by the general formula (II) is also useful as a pest control agent, as will be seen in the test examples below.

At the time of use, it can be formulated into various forms such as emulsions, powders, wettable powders, liquids and the like together with auxiliary agents, as in the case of conventional pesticide formulations. In the actual use of these preparations, they can be used as they are or diluted with a diluent such as water to a predetermined concentration before use. Examples of the auxiliary agent include a carrier, an emulsifying agent, a suspending agent, a dispersing agent, a spreading agent, a penetrating agent, a wetting agent, a thickener, a stabilizer, and the like,
It may be added as needed. The carrier is divided into a solid carrier and a liquid carrier, and as the solid carrier, starch, activated carbon, soybean flour, wheat flour, wood flour, fish meal, powdered animal or vegetable powder such as milk powder, talc, kaolin, bentonite, calcium carbonate, zeolite, Mineral powders such as diatomaceous earth, white carbon, clay, alumina, and sulfur powder can be used. As liquid carriers, water, alcohols such as methyl alcohol and ethylene glycol, ketones such as acetone and methyl ethyl ketone, dioxane, tetrahydrofuran, etc. Ethers, kerosene, aliphatic hydrocarbons such as kerosene, aromatic hydrocarbons such as xylene, trimethylbenzene, tetramethylbenzene, cyclohexane and solvent naphtha, halogenated hydrogencarbonates such as chloroform and chlorobenzene, dimethylformamide, etc. Acid amides, ethyl acetate, esters such as glycerin esters of fatty acids, nitriles such as acetonitrile, sulfur-containing compounds such as dimethyl sulfoxide.

The application concentration of the compound of the present invention varies depending on the target crop, application method, formulation form, application amount, etc. and cannot be specified unconditionally, but is usually 1 to 10,000 ppm, preferably 20 to 2,000 ppm per active ingredient. .

Further, if necessary, other pesticides, such as insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides, plant growth regulators, etc., can be mixed and used in combination. However, in this case, a more excellent effect may be exhibited.

For example, insecticides, acaricides, or nematicides include O- (4-bromo-2-chlorophenyl) O-ethyl S-propyl phosphorothioate, 2,2-dichlorovinyl dimethyl phosphate, ethyl 3-methyl- 4- (methylthio) phenyl isopropyl phosphoramidate, O, O-dimethyl O-4-nitro-m
-Tolyl phosphorothioate, O-ethyl O-4-nitrophenyl phenylphosphonothioate, O, O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate, O, O-dimethyl O
Such as-(3,5,6-trichloro-2-pyridyl) phosphorothioate, O, S-dimethyl acetylphosphoramidothioate, O- (2,4-dichlorophenyl) O-ethyl S-propyl phosphorodithioate Organic phosphate compound; 1-naphthylmethyl carbamate, 2-isopropoxyphenyl methyl carbamate, 2-methyl-2- (methylthio) propionaldehyde O-methylcarbamoyl oxime, 2,3-dihydro-2,2- Dimethylbenzofuran-7-yl methyl carbamate, dimethyl N, N '-[thiobis [(methylimino) carbonyloxy]] bisethaneimidothioate, S-methyl N- (methylcarbamoyloxy)
Thioacetimidate, N, N-dimethyl-2-methylcarbamoyloxyimino-2- (methylthio) acetamide, 2- (ethylthiomethyl) phenyl methylcar
Bamate, 2-dimethylamino-5,6-dimethylpyrimidin-4-yl dimethylcarbamate, S, S'-2
Carbamate compounds such as dimethylaminotrimethylene bis (thiocarbamate); 2,2,2-trichloro-1,1-bis (4-chlorophenyl) ethanol, 4-
Organochlorine compounds such as chlorophenyl 2,4,5-trichlorophenyl sulfol; Organometallic compounds such as tricyclohexyltin hydroxide; (RS) -α
-Cyano-3-phenoxybenzyl (RS) -2- (4-
Chlorophenyl) -3-methylbutyrate, 3-phenoxybenzyl (1RS) -si, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate, (RS) -α-cyano- 3-phenoxybenzyl (1RS) -cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate, (RS) -α-cyano-3-phenoxybenzyl
(1RS) -cis-3- (2,2-dibromovinyl) -2,2-
Dimethylcyclopropanecarboxylate, (RS) -α
-Cyano-3-phenoxybenzyl (1RS) -cis,
Pyrethroid compounds such as trans-3- (2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate; 1- (4-chlorophenyl) -3- (2,6 -Difluorobenzoyl) urea, 1- [3,5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl]-
3- (2,6-difluorobenzoyl) urea, 1- (3,5
-Dichloro-2,4-difluorophenyl) -3- (2,6-
Benzoylurea-based compounds such as difluorobenzoyl) urea; 2-ter't-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,
3,5-thiadiazin-4-one, trans-5- (4-
Chlorophenyl) -N-cyclohexyl-4-methyl-
2-oxothiazolidinone-3-carboxamide, N-
Compounds such as methylbis (2,4-xylyliminomethyl) amine; isopropyl (2E, 4E) -11-methoxy-
Juvenile hormone-like compounds such as 3,7,11-trimethyl-2,4-dodecasinoate; and, as other compounds,
Examples thereof include dinitro compounds, organic sulfur compounds, urea compounds and triazine compounds. In addition, microbial agents such as BT agents and insect pathogenic virus agents can be mixed and used together.

For example, as a bactericide, an organophosphorus compound such as S-benzyl O, O-diisopropylphosphorothioate, O-ethyl S, S-diphenylphosphorodithioate, and aluminum ethylhydrogenphosphoinate;
Organochlorine compounds such as 4,5,6,7-tetrachlorophthalide and tetrachloroisophthalonitrile; Manganese ethylene bis (dithiocarbamate) polymer, zinc, ethylene bis (dithiocarbamate) polymer, Dithiocarbamate compounds such as zinc and manneb complex compounds, polymers of dizinc bis (dimethyldithiocarbamate) ethylene bis (dithiocarbamate), zinc propylene bis (dithiocarbamate); 3a, 4,7,7a
-Tetrahydro-N- (trichloromethanesulfenyl) phthalimide, 3a, 4,7,7a-tetrahydro-N-
N-halogenothioalkyl compounds such as (1,1,2,2-tetrachloroethanesulfenyl) phthalimide and N- (trichloromethylsulfenyl) phthalimide;
(3,5-Dicrylorophenyl) -N-isopropyl-2,4
-Dioxoimidazolidine-1-carboxamide, (R
S) -3- (3,5-Dichlorophenyl-5-methyl-5
-Vinyl-1,3-oxazolidine-2,4-dione, N-
Carboximide compounds such as (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide; methyl 1- (butylcarbamoyl) benzimidazol-2-ylcarbamate, dimethyl 4,
Benzimidazole compounds such as 4 '-(o-phenylene) bis (3-thioallophanate); 1- (chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazole-1) -Yl) butanone, 1- (biphenylyl-4-yloxy) -3,3-dimethyl-1- (1H-1,2,4
-Triazol-1-yl) butan-2-ol, 1-
[N- (4-chloro-2-trifluoromethylphenyl) -2-propoxyacetimidoyl] imidazole, 1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolane-2- Ilmethyl] -1H-1,2,4
-Triazole, 1- [2 (2,4-dichlorophenyl)
-4-Propyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole Azole compounds such as: 2,4'-dichloro-α-
(Pyrimidin-5-yl) benzhydryl alcohol,
Carbinol compounds such as (±) -2,4'-difluoro-α- (1H-1,2,4-triazol-1-ylmethyl) benzhydryl alcohol; 3'-isopropoxy-o
-Benzanilide compounds such as toluanilide and α, α, α-tolufluoro-3'-isopropoxy-o-toluanilide; methyl N- (2-methoxyacetyl)-
Acyl alanine compounds such as N- (2,6-xylyl) -DL-alaninate; 3-chloro-N- (3-chloro-
Pyridinamine-based compounds such as 2,6-dinitro-4-α, α, α-trifluorotolyl) -5-trifluoromethyl-2-pyridinamine; as other compounds, piperazine-based compounds, morpholine-based compounds , Anthraquinone compounds, quinoxaline compounds, crotonic acid compounds, sulfenic acid compounds, urea compounds, antibiotics and the like.

The test examples and formulation examples according to the present invention will be described below.

Test Example 1 Cucumber downy mildew preventive effect test Cucumber (variety: four leaves) is cultivated in a plastic pot with a diameter of 7.5 cm, and when reaching the two-leaf stage, 10 ml of leaf liquid in which each test compound is adjusted to a predetermined concentration is sprayed. It was sprayed with a gun. twenty four~
After keeping it in a greenhouse at 25 ° C for one day, it was spray-inoculated with a spore suspension of downy mildew. Six days after the inoculation, the lesion area ratio (%) of the first leaf was investigated, and the control value was calculated by the following formula, and the results shown in Table 14 were obtained.

Test Example 2 Cucumber downy mildew disease therapeutic effect test Cucumber (cultivar: four leaves) was cultivated in a plastic pot with a diameter of 7.5 cm, and when reaching the 2-leaf stage, a spore suspension of downy mildew was spray-inoculated. Six hours later, 10 ml of a drug solution in which each test compound was adjusted to a predetermined concentration was sprayed using a spray gun. 24-24 ° C
After 1 day storage in the greenhouse, the area ratio of lesions on the first leaf (%)
The control value was also determined in the same manner as in the case of Test Example 1 above, and the results shown in Table 15 were obtained.

Test Example 3 Cucumber downy mildew penetration migration test Cucumber (variety: four leaves) was cultivated in a plastic bowl with a diameter of 7.5 cm, and when the two-leaf stage was reached, 10 ml of a drug solution containing each test compound adjusted to a predetermined concentration was pipetted. Was used to irrigate the soil surface. After keeping in a greenhouse at 24 to 25 ° C for 2 days, a spore suspension of downy mildew was spray-inoculated. Six days after the inoculation, the lesion area ratio (%) of the first leaf was investigated, and the control value was determined in the same manner as in the case of Test Example 1 above, and the results shown in Table 16 were obtained.

Test Example 4 Tomato epidemic prevention effect test Tomato (cultivar: Ponteroza) in a plastic bowl with a diameter of 7.5 cm
Was cultivated, and when the 4 leaf stage was reached, 10 ml of a drug solution in which each test compound was adjusted to a predetermined concentration was sprayed using a spray gun. After keeping it in a greenhouse at 24 to 25 ° C for one day and night, it was sprayed and inoculated with a suspension of zoospores of Phytophthora infestans. The number of lesions was examined 5 days after the inoculation, and the control value was determined by the following formula, and the results shown in Table 17 were obtained.

Test Example 5 Cucumber Anthracnose Preventive Effect Test Cucumber (variety: four leaves) was cultivated in a plastic bowl with a diameter of 7.5 cm, and when reaching the two-leaf stage, 10 ml of a chemical solution in which each test compound was adjusted to a predetermined concentration was spray gun. Was sprayed. twenty four~
After keeping it in a greenhouse at 25 ° C for one day and night, it was spray-inoculated with a spore suspension of anthracnose. Seven days after the inoculation, the number of lesions on the first leaf was examined, and the control value was calculated by the following formula, and the results shown in Table 18 were obtained.

Test Example 6 Rice Blight Disease Prevention Effect Test Paddy rice (cultivar: Nakakyo Asahi) was cultivated in a plastic pot with a diameter of 7.5 cm, and when reaching the 5 leaf stage, 20 ml of a chemical solution in which each test compound was adjusted to a predetermined concentration was sprayed. It was sprayed with a gun. twenty four~
After keeping it in a greenhouse at 25 ° C for one day and night, rice straw in which the bacterial blight fungus had been cultivated in advance was sandwiched between leaf sheaths and inoculated. After keeping in an inoculation room at a temperature of 28 ° C. and a humidity of 100% for 5 days, the lengths of lesions on 5 stalks per pot were investigated, and the control value was obtained by the following formula, and the results shown in Table 19 were obtained.

Test Example 7 Antibacterial test (plant pathogen) Cucumber cotton rot fungus ( Pythium aph ) precultured on potato-glucose agar medium (PAD medium) containing 100 ppm of streptomycin and 100 ppm of each active ingredient compound.
Anidermatum ) disk (cold punch ) was transplanted. twenty two
After culturing at 48 ° C. for 48 hours, the diameter of the flora was examined, and the mycelial growth inhibition rate (%) was determined by the following formula, and the results shown in Table 20 were obtained.

Test Example 8 Antibacterial Test (Bacteria) 0.5 ml of each chemical solution of the compound adjusted to a concentration of 200 ppm was added to each medium of 10 ml of broth agar medium. Bacillus subtilus ( Bacillus subtilus) as a test bacterium on the agar
is ), Staphylococc
us aureus ), and after culturing at 37 ℃ for 16 hours, the growth state of the test bacteria was observed. As a result, Compound No. 5 was found to be effective.
And No. 16-B.

Test Example 9 Antibacterial test (fungus) 0.5 ml of each chemical solution of the compound adjusted to a concentration of 200 ppm was added to each medium of 10 ml of Sabouraud agar medium containing 1,000 ppm of 1% kanamycin aqueous solution. The agar was inoculated with Trichophyton rubrum as a test bacterium, and after culturing at 28 to 30 ° C for 5 days, the growth state of the test bacterium was observed. As a result, Compound No. 1 was found to be effective. It was

Test Example 10 Acaricidal mite killing test Kidney beans (variety: Edogawa green beans) were cultivated in a plastic pot with a diameter of 7.5 cm, and when the initial leaf stage was reached, one leaf was left and the other leaf was cut off. After inoculating about 30 larvae of Dioscorea japonicus (Dicofol and organophosphorus drug resistant), this seedling was immersed in 20 ml of a chemical solution adjusted to a predetermined concentration of each test compound for about 10 seconds. After air-drying, leave it in a 26 ° C illuminated incubator and release 2 insects.
After a day, life and death is judged and the mortality rate (%) is calculated by the following formula,
The results shown in Table 21 were obtained.

Test Example 11 Nymphalid mite ovicidal test A plant in which only one primary leaf of common bean was left was transplanted into a plastic pot, and adults of Namidani mite were inoculated for 24 hours to lay eggs to remove the adults. Then, the kidney bean was soaked in 20 ml of a chemical solution adjusted to a predetermined concentration of each test compound for about 10 seconds, air-dried, and then kept in a 26 ° C. lighted incubator. Five days after the treatment, the hatching condition of the eggs was examined, and the ovicidal rate (%) was calculated by the following formula, and the results shown in Table 22 were obtained. Note that death immediately after hatching was also considered as killing eggs.

Test Example 12 Green peach aphid insecticidal test Cabbage leaf pieces were immersed in 20 ml of a chemical solution adjusted to a predetermined concentration of each test compound for about 10 seconds, and a damp filter paper was placed on an air-dried Petri dish with a diameter of 9 cm, and air-dried on it. I put the leaf pieces. There, the wingless peach aphid wingless female worms were released, covered and kept in a lighted incubator at 26 ° C. After 2 days from the release of the insects, life and death were determined, and the mortality rate (%) was determined in the same manner as in Test Example 10 above, and the results shown in Table 23 were obtained.

Test Example 13 Sweetpotato nematode nematicidal test Sweetpotato nematode contaminated soil was packed in a 1 / 14,000a pot, and each test compound was adjusted to 200 g / a with 20 g / a of the active ingredient, and 20 ml of the drug solution was applied to the soil surface using a pipette. Irrigated. Two days after the treatment, the soil was mixed with all layers, and tomato seedlings (variety: Ponterosa) at the 3-4 leaf stage were transplanted. Twenty days after the treatment with the chemical solution, the degree of fecundity of the cats was investigated according to the following criteria, and the results shown in Figure 24 were obtained.

Evaluation criteria for degree of growth of cats 0; growth of cats-no 1; growth of cats-small 2; 〃-medium 3; 〃-large 4; 〃-long Test Example 14 Novier herbicide test 1 / 10,000a pots were filled with paddy soil, impregnated with water to a saturated state, seeds of Novier were sown, and the soil was lightly covered with soil. When Nobie was germinated, it was flooded to 3 cm, and each test compound was adjusted to 50 g / a with the active ingredient, and a predetermined amount of the drug solution was added dropwise with a pipette. Visually observe the growth state after 20 days of chemical treatment, evaluate the degree of growth inhibition according to the following criteria,
The results shown in Table 25 were obtained.

Evaluation criteria for the degree of growth inhibition 5; Complete withering | 1; Growth similar to untreated plot Test Example 15 Firefly and Urikawa herbicide test 1 / 10,000a pots were filled with paddy soil, and seeds of Firefly and Urikawa tubers were sown and kept in a shallow water state. When the firefly grew in the 1-leaf stage, it was flooded to 3 cm, and each test compound was adjusted to 50 g / a with the active ingredient, and a predetermined amount of the drug solution was added dropwise with a pipette. After 20 days from the treatment, the growth state was visually observed, and in the case of Test Example 14, the degree of growth inhibition was determined in the same manner, and the results in Table 26 were obtained.

Evaluation criteria for the degree of growth inhibition 5; Complete withering | 1; Growth similar to untreated plot Test Example 16 Upland weed soil surface treatment test 1 / 3,000a pot was filled with upland soil, and seeds of millet, Japanese radish and soybean were sown. On the day after seeding, the surface of the soil was treated with a predetermined amount (30 l / a of sprayed water) of a chemical solution in which each test compound was adjusted to have an active ingredient content of 50 g / a. After 24 days from the treatment, the growth state was visually observed, and the degree of growth inhibition was investigated based on the following criteria, and the results shown in Table 27 were obtained.

Evaluation criteria for the degree of growth inhibition 10; Complete withering | 1; Growth similar to untreated plot Test Example 17 Field Weed Stem / Leaf Treatment Test A 1 / 3,000a pot was filled with field soil and seeded with millet, radish and soybean. Thereafter, when the millet, radish, and soybean reached the 3-leaf stage, the 2-leaf stage, and the first true leaf stage, respectively, 10 ml / pot foliar treatment of a chemical solution in which each test compound was adjusted to 2,000 ppm was performed. After 20 days from the treatment, the growth state was visually observed and the degree of growth inhibition was determined in the same manner as in Test Example 16 above, and the results in Table 28 were obtained.

Similar to the compound of the present invention, the intermediate represented by the general formula (II) (Table 1) is also useful as a pest control agent. The test examples and formulation examples are described below.

Test Example 18 Cucumber downy mildew preventive effect test In the same manner as in Test Example 1 above, the results shown in Table 29 were obtained.

Test Example 19 Rice blight prevention effect test In the same manner as in Test Example 6, the results shown in Table 30 were obtained.

Test Example 20 Antibacterial test (plant pathogen) In the same manner as in Test Example 7, the results shown in Table 31 were obtained.

Test Example 21 Antibacterial test (bacteria) A test similar to Test Example 8 above was carried out, and an intermediate was obtained.
No. 10 and No. 11 also showed similar activity.

Test Example 22 Novier herbicide test The results shown in Table 32 were obtained in the same manner as in Test Example 14 above.

Test Example 23 Firefly and Urikawa herbicide test In the same manner as in Test Example 15 above, the results shown in Table 33 were obtained.

Test Example 24 Field weed soil surface treatment test In the same manner as in Test Example 16 above, the results in Table 34 were obtained.

Test Example 25 Field weed foliage treatment test In the same manner as in Test Example 17, the results shown in Table 35 were obtained.

Formulation Example 1 (a) Compound No. 1 50 parts by weight (b) Dichrite 40 〃 (c) Sodium lignin sulfonate 7 〃 (d) Dialkyl sulfosuccinate 3 〃 did.

Formulation Example 2 (a) Compound No. 3 20 parts by weight (b) Sikhlite 72 〃 (c) Sodium lignin sulfonate 8 〃 The above ingredients were uniformly mixed to obtain a wettable powder.

Formulation Example 3 (a) Compound No. 4 5 parts by weight (b) Talc 95 〃 The above ingredients were uniformly mixed to obtain a wettable powder.

Formulation Example 4 (a) Compound No. 2 20 parts by weight (b) Xylent 60 〃 (c) Polyoxyethylene alkylallyl ether 20 〃 The above components were mixed and dissolved to give an emulsion.

Formulation Example 5 (a) Sigrite 78 parts by weight (b) β-naphthalene sulfonic acid soda formalin condensate 2 〃 (c) Polyoxyethylene alkylallyl sulphate 5 〃 (d) White carbon 15 〃 A mixture of the above components and And Compound No. 7 were mixed at a weight ratio of 4: 1 to obtain a wettable powder.

Formulation Example 6 (a) Compound No. 13 1 part by weight (b) Bentonate 61 〃 (c) Sikhlite 33 〃 (d) Sodium lignin sulfonate 5 〃 Add the required granulation water to the above components and mix , Granulation was performed to obtain increased grain size.

Formulation Example 7 (a) No. 8 50 parts by weight in Table 1 (b) Sikhlite 40 〃 (c) Sodium lignin sulfonate 7 〃 (d) Dialkyl sulfosuccinate 3 〃 Made into a Japanese medicine.

Formulation Example 8 (a) No. 10 20 parts by weight in Table 1 (b) Sikhlite 72 〃 (c) Sodium lignin sulfonate 8 〃 The above ingredients were uniformly mixed to obtain a wettable powder.

Formulation Example 9 (b) No. 11 5 parts by weight in Table 1 (b) Talc 95 〃 The above ingredients were uniformly mixed to obtain a wettable powder.

Formulation Example 10 (b) No. 12 in Table 1 20 parts by weight (b) xylene 60 〃 (c) polyoxyethylene alkylallyl ether 20 〃 The above components were mixed and dissolved to give an emulsion.

Formulation Example 11 (a) Sikrite 78 parts by weight (b) β-naphthalene sulfonic acid soda formalin condensate 2 〃 (c) Polyoxyethylene alkylallyl sulphate 5 〃 (d) White carbon 15 〃 A mixture of the above components and , No. 15 in Table 1 were mixed in a weight ratio of 4: 1 to obtain a wettable powder.

Formulation Example 12 (a) 1 part by weight of No. 12 in Table 1 (b) Bentonite 61 〃 (c) Sieglite 33 〃 (d) Sodium lignin sulfonate 5 〃 Add appropriate amount of water for granulation to the above components The mixture was added and granulated to obtain granules.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Shigeyuki Nishimura Inventor Shigeyuki Nishi Shibukawa 2-3-1 Ishihara Sangyo Co., Ltd. Central Research Institute (72) Inventor Shuji Yoshimura 2-3-1 Nishishibukawa Kusatsu Ishihara Sangyo Central Research Institute Co., Ltd. Examiner Shoei Hoshino

Claims (1)

(57) [Claims] 1. General formula (a): [In the formula, A ₁ is a halogen atom or a methylthio group, and A ₂
Is a chlorine atom or a hydroxyl group].