JPH08208611A - Imidazo(4,5-b)pyridine-based compound and pest-controlling agent containing the same - Google Patents

Abstract

PURPOSE: To obtain a new trifluoromethylpyridine-based compound useful as an intermediate for new imidazo[4,5-b]pyridine-based compounds useful as pest- controlling agents. CONSTITUTION: The objective compound, a trifluoromethylpyridine-based compound, is expressed by formula I (B1 is nitro or amino; B2 is a halogen, alkoxyl or alkylthio), e.g. 2-amino-6-chloro-3-nitro-5-trifluoromethylpyridine. The compound of formula I, for example, the illustrated compound, is obtained by the following process: fuming sulfuric acid is first added to 6-chloro-5- trifluoromethyl-2-pyridone to form 6-chloro-3-nitro-5-trifluoromethyl-2-pyridone, which is then reacted with thionyl chloride into 2,6-dichloro-3-nitro-5- trifluoromethylpyridine, which is then reacted with ammonia. The compound of formula I is useful as an intermediate for the other objective compound, an imidazo[4,5-b]pyridine-based compound, of formula II [X1 is CF3 , nitro or a halogen; X2 is H, a halogen, etc.; Y is SO2 R2 (R2 is an alkyl, etc.); Z is a halogen, alkyl, etc.].

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel imidazo [4,5-b] pyridine compound, a pesticidal agent containing them as an active ingredient, and a method for producing them.

[0002]

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)

[0003]

Embedded image

Wherein 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 —S
(O) _n -group, n is an integer of 0 to 2, and 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

[0005]

Embedded image

R ₃ is a hydrogen atom or an alkyl group, and R ₄ is an alkyl group) or

[0007]

[Chemical 4]

A group (R ₅ is an optionally substituted alkyl group,
An optionally substituted phenyl group, an optionally substituted alkoxy group, an optionally substituted phenoxy group or

[0009]

Embedded image

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, An optionally substituted pyridyl group, a cyano group, a —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 0),

[0011]

[Chemical 6]

A group (R ₉ and R ₁₀ are a hydrogen atom or an alkyl group), or

[0013]

[Chemical 7]

It is a group].

In the general formula (I), R ₁ , R ₂ , R ₅ ,
An optionally substituted alkyl group represented by Z, R ₃ , R
Examples of the alkyl group represented by ₄ , R ₆ , R ₇ , R ₈ , R ₉ , and R ₁₀ , and the alkyl portion of the optionally substituted alkoxy group represented by R ₅ include a methyl group, an ethyl group,
n-propyl group, iso-propyl group, n-butyl group,
Examples include an iso-butyl group, a sec-butyl group, and a tert-butyl group. Examples of the halogen atom represented by X ₁ , X ₂ , and Z include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Examples of 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 include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. And the like, and the number of substituents is preferably from 1 to 5. R ₁ , R ₂ ,
An optionally substituted phenyl group represented by R ₅ and Z, R
Examples of the substituent of the optionally substituted pyridyl group represented by ₁ , R ₂ and Z, the optionally substituted phenoxy group represented by R ₅ 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, a nitro group and the like.

Among the imidazo [4,5-b] pyridine compounds represented by the above general formula (I), the following compounds 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 —S (O) _n — group, n is an integer of 0 to 2, and R ₁ is a fluorine atom An alkyl group which may be substituted with a phenyl group or a pyridyl group which may be substituted with a chlorine atom). (3) Y is a —SO ₂ R ₂ — group (R ₂ is an alkyl group optionally substituted by a fluorine atom, a phenyl group or

[0017]

Embedded image

Wherein R ₃ is a hydrogen atom or an alkyl group, and R ₄ is an alkyl group) or

[0019]

[Chemical 9]

(R ₅ is a phenoxy group or

[0021]

[Chemical 10]

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 an integer of 0 to 2, and R ₈ is a hydrogen atom or an alkyl group And m is 0 when R ₈ is a hydrogen atom), or

[0023]

[Chemical 11]

It is a base.

Further, the following trifluoromethylpyridine-based compound is preferable as an intermediate of the imidazo [4,5-b] pyridine-based compound represented by the general formula (I). General formula (a) or (b):

[0026]

[Chemical 12]

[0027] wherein, A ₁ is a halogen atom or a methylthio group, A ₂ is chlorine atom or a hydroxyl group, B ₁
Is a nitro group or an amino group, B ₂ is a halogen atom,
An alkoxy group or an alkylthio group].

A novel imidazo [4,5-b] pyridine compound represented by the general formula (I)

The product can be specifically manufactured by the following method.

[0030]

[Chemical 13]

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

As the solvent, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene: chloroform, carbon tetrachloride, methylene chloride, dichloroethane,
Cyclic or acyclic aliphatic hydrocarbons such as trichloroethane, n-hexane, cyclohexane: ethers such as diethyl ether, dioxane, tetrahydrofuran: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone: acetonitrile, propionitrile, acrylonitrile, etc. Nitriles: aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and sulfolane.

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

The above 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) is
General formula:

[0037]

Embedded image

And / or

[0039]

[Chemical 15]

Wherein X ₁ , X ₂ , Y and Z are as described above. The compound represented by the general formula (II) has tautomers represented by the following general formulas (II-a) and (II-b). When (I-
a) or (Ib) or a mixture thereof can be obtained.

[0041]

Embedded image

The compound represented by the general formula (II) has the general formula:

[0043]

[Chemical 17]

And

[0045]

Embedded image

[Wherein, 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, An optionally substituted phenyl group or an optionally substituted pyridyl group, R ₁₃ is an alkyl group, and l 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.

[0047]

[Chemical 19]

[0048]

Embedded image

[0049]

[Chemical 21]

[0050]

[Chemical formula 22]

[0051]

[Chemical formula 23]

[0052]

[Chemical formula 24]

[0053]

[Chemical 25]

[Wherein X ₁ , X ₂ , R ₉ , R ₁₀ , R ₁₁ ,
R ₁₂ , R ₁₃ and l are as described above]

Examples of the substituted part of the optionally substituted alkyl group represented by R ₁₂ in formula (II-3) include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. Examples of the substituted portion of the 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. Examples of the alkyl group represented by R ₁₃ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an iso-group.
-Butyl group, sec-butyl group, tert-butyl group and the like.

The compound represented by the general formula (VI) is
General formula:

[0057]

[Chemical formula 26]

Wherein X ₁ is as described above, R ₁₄ is a hydrogen atom or a halogen atom, and r is an integer of 1 to 2. The formulas (VI-1) and (VI-
The compounds represented by 2), (VI-3) and (VI-4) can be synthesized, for example, as follows.

[0059]

[Chemical 27]

[0060]

[Chemical 28]

[0061]

[Chemical 29]

[0062]

Embedded image

[Wherein X ₁ , R ₁ , R ₁₄ and r are as described above] The production methods [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].

[0064]

[Chemical 31]

[0065]

[Table 1]

[0066]

[Table 2]

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

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

[Table 5]

Of the representative compounds described in Table 2 above, No. 16A and no. 16B; 17A and N
o. 17B is in a structural isomer relationship with each other,
No. Nos. 1 to 15 and Nos. 18 to 21 are mixtures 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) Dimethylsulfamoyl-6-trifluoromethylimidazo [4,5-b] pyridine (Compound No. 1)
[1] 55 ml of 25% fuming sulfuric acid was cooled on ice, and 48 g of 6-chloro-5-trifluoromethyl-2-pyridone as a starting compound was gradually added at 20 ° C. or lower. Then 70-75
33 ml of fuming sulfuric acid (specific gravity 1.52) was gradually added dropwise within the range of ° C., and the mixture was reacted at this temperature with stirring for 1 hour. After the reaction was completed, the reaction product was put on ice, and the precipitated crystals were filtered off,
It was 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-mentioned crystals, and as a product, 6-having a melting point of 121 to 123 ° C
36 g of chloro-3-nitro-5-trifluoromethyl-2-pyridone were obtained. The results in Table 3 were obtained by the same operation as in the step [1].

[0072]

[Table 6]

[2] 48.5 g of 6-chloro-3-nitro-5-trifluoromethyl-2-pyridone obtained in the above step [1] as a starting compound was added to 50 ml of thionyl chloride.
And dimethylformamide 1.5m
1 was added and the mixture was reacted at the reflux temperature for 3 hours. After completion of the reaction, water was added to the residue obtained by evaporating thionyl chloride, and the crystals were separated by filtration, washed with water, dried and then dried to give 2,6-
49.6 g of dichloro-3-nitro-5-trifluoromethylpyridine were obtained. The same operation as in the step [2] was performed, and the results in Table 4 were obtained.

[0074]

[Table 7]

[3] As a starting compound, 13 g of 2,6-dichloro-3-nitro-5-trifluoromethylpyridine obtained in the above step [2] is dissolved in 50 ml of acetone.
100 ml of 8% aqueous ammonia was added dropwise at room temperature, and the mixture was reacted with stirring for 30 minutes. After completion of the reaction, the precipitated crystals were separated by filtration,
After washing with water, washing with normal hexane, and drying, 2-amino-6-chloro-3-nitro-5-trifluoromethylpyridine 1 having a melting point of 181 to 183 ° C was obtained as a product.
1.9 g was obtained. The same operation as in the step [3] was performed, and the results in Table 5 were obtained.

[0076]

[Table 8]

[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, and the reaction mixture was heated to 65 to 75 ° C. 25g iron powder while holding
Was gradually added. After completion of the addition, the mixture was reacted at the same temperature for 1 hour with stirring. After the completion of the reaction, 500 ml of ethyl acetate was added to remove the precipitated iron salt, and 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 normal hexane to give a product having a melting point of 145 to 1
21.5 g of 2,3-diamino-6-chloro-5-trifluoromethylpyridine at 47 ° C. were obtained. The step [4]
The same operation as described above was performed, and the results in Table 6 were obtained.

[0078]

[Table 9]

[5] Methyl trichloroacetimidate was added to a mixture of 10.5 g of 2.3-diamino-6-chloro-5-trifluoromethylpyridine obtained in the above step [4] as a starting compound and 80 ml of acetic acid. 6 g was added at room temperature and reacted overnight with stirring. After the completion of the reaction, the reaction solution was poured into water, and the precipitated crystals were separated by filtration and dried. 8.8 g of 1H-2-trichloromethyl-5-chloro-6-trifluoromethylimidazo [4,5-b] pyridine was obtained as a product. I got By performing the same operation as in the step [5], the results in Table 7 were obtained.

[0080]

[Table 10]

[0081]

[Table 11]

[6] 0% in 60 ml of 40% ammonia water
1H- obtained at the above step [5] as a starting compound at ~ 5 ° C.
2-Trichloromethyl-5-chloro-6-trifluoromethylimidazo [4,5-b] pyridine 8.8 g was added slowly. After the addition, the mixture was allowed to stand at room temperature with stirring. After the completion of the reaction, insolubles were filtered off, and the filtrate was neutralized with dilute hydrochloric acid at a temperature of 10 ° C. or lower to pH3. The precipitated crystals and the ethyl acetate extract 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.

[0083]

[Table 12]

[0084]

[Table 13]

[7] As starting materials, 2.4 g of 1H-2-cyano-5-chloro-6-trifluoromethylimidazo [4,5-b] pyridine obtained in the above step [6], 70 ml of acetonitrile and carbonic anhydride 1.5 g of potassium was mixed and stirred for 1 hour under reflux. Next, the temperature of the reaction system was set to 3
Dimethylsulfamoyl chloride 1.7 lowered to 0 ℃
g was added, and the mixture was reacted again under reflux for 1 hour. After completion of the reaction, the inorganic salt was separated by filtration, the solvent was distilled off, and the residue was separated by silica gel column chromatography using methylene chloride as a developing solvent to give the desired product having a melting point of 179-184 ° C.
4 g was obtained. Perform the same operation as in the step [7], and
The results in the table were obtained.

[0086]

[Table 14]

[0087]

[Table 15]

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

After the completion of the reaction, the reaction product was poured into water, and the precipitated crystals were separated by filtration and dried to obtain 6- (2,4-
14.1 g of (dichlorophenoxy) -3-nitro-5-trifluoromethyl-2-pyridone were obtained. [2] to [7] 6-obtained by the step [1]
Synthesis Example 1 using (2,4-dichlorophenoxy) -3-nitro-5-trifluoromethyl-2-pyridone
The desired product was obtained in the same manner as in [2] to [7]. The results shown in Table 10 were obtained by the same operation as in [1] of Synthesis Example 2.

[0090]

[Table 16]

Synthesis Example 3 1H, (3H) -2-cyano-
Synthesis of 1, (3) -dimethylsulfamoyl-5-phenoxy-6-trifluoromethylimidazo [4,5-b] pyridine (Compound No. 4) [1] 2-amino-6-chloro as starting material -3-
24.2 g of nitro-5-trifluoromethylpyridine,
120 ml of dimethylformamide and 10.3 of phenol
7 g of potassium hydroxide was gradually added to the resulting mixture at 50 to 60 ° C., and the temperature was maintained at the same temperature for 1.5 hours after the addition. After completion of the reaction, the reaction product was put into water and extracted with ethyl acetate. After washing with water, the extract was dried over anhydrous sodium sulfate, and 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 step [1] was performed and the results shown in Table 11 were obtained.

[0092]

[Table 17]

[2] 20 g of 2-amino-3-nitro-6-phenoxy-5-trifluoromethylpyridine obtained in the above [1] as a starting compound was added to 250 ml of ethanol.
Was dissolved in, and 5% -palladium / carbon (2 g) was added thereto, and a 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 give 2,3-diamino-6-phenoxy-5-triene having a melting point of 130 to 132 ° C. as a product. 11.3 g of fluoromethylpyridine was obtained. [3] to [5] Using 2,3-diamino-6-phenoxy-5-trifluoromethylpyridine obtained in the step [2], the same as [5] to [7] in the above Synthesis 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.

[0094]

[Table 18]

Synthesis Example 4 1H, (3H) -2-cyano-
1, (3) -dimethylsulfamoyl-5-methylsulfonyl-6-trifluoromethylimidazo [4,5-
b] Synthesis of pyridine (Compound No. 2) 1H, (3H)
-2-cyano-1, (3) -dimethylsulfamoyl-
A solution of 2.7 g of m-chloroperbenzoic acid in 110 ml of methylene chloride in a solution of 2 g of 5-methylthio-6-trifluoromethylimidazo [4,5-b] pyridine in 300 ml of methanol was added dropwise at room temperature. The reaction was carried out under stirring for 1.5 hours. After completion of the reaction, the reaction mixture was put into water, extracted with methylene chloride, washed with a sodium carbonate solution, further washed with water, and then dried over anhydrous sodium sulfate. Then, the solvent was distilled off, and acetonitrile was added to n-
Recrystallization from a hexane mixed solution yielded 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
Synthesis of -bistrifluoromethylimidazo [4,5-b] pyridine (Compound No. 8) [1] 2,3-Diamino-6- (pyridin-2-ylthio) -5-trifluoromethylpyridine 2 as a starting compound A mixture of 0.8 g, 4 ml of trifluoroacetic acid and 3 ml of trifluoroacetic anhydride was reacted under reflux for 2 hours. After completion of the reaction, 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.
1H-5- (pyridin-2-ylthio) at 4-236 ° C
-2,6-bistrifluoromethylimidazo [4,5-
b] 2.3 g of pyridine was obtained. The results in Table 13 were obtained by the same operation as in the step [1].

[0096]

[Table 19]

Synthesis Example 6 1H-1-dimethylsulfamoyl-2-methylthio-6-trifluoromethylimidazo [4,5-b] pyridine and 3H-3-dimethylsulfamoyl-2-methylthio-6-tri Fluoromethylimidazo [4,5-b] pyridine (Compound No. 17
A, Compound No. Synthesis of 17B) [1] to [4] 2,3-Diamino-5-trifluoromethylpyridine was obtained in the same manner as in [1] to [4] of Synthesis Example 1. [5] 2, 3 obtained in [1] to [4] of Synthesis Example 6
-Diamino-5-trifluoromethylpyridine 3.0
g, 8.0 g of potassium ethyl xanthate, 90 ml of ethanol and 18 ml of water were mixed and reacted at reflux temperature for 16 hours. After the completion of the reaction, the solvent was distilled off, and water 30
The resulting precipitate was filtered and 1H-2-mercapto-6 having a melting point of 300 ° C. or more was added.
-Trifluoromethylimidazo [4,5-b] pyridine was obtained. [6] 3.8 g of 1H-2-mercapto-6-trifluoromethylimidazo [4,5-b] pyridine obtained in the above step [5] is dissolved in 1.0 ml of dimethyl sulfoxide. 3 g 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 poured into water, and the crystal was filtered and dried to obtain 1H-2-methylthio-6-trifluoromethylimidazo [4,5-b] pyridine (sublimated from a melting point of 210 ° C.). [7] A mixture of 2.3 g of 1H-2-methylthio-6-trifluoromethylimidazo [4,5-b] pyridine obtained in the above step [6], 30 ml of acetonitrile, and 1.5 g of anhydrous potassium carbonate for 1 hour After refluxing, the mixture was cooled to 30 ° C., and 1.44 g of dimethylsulfamoyl chloride was added.
Was added and 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. Separation and purification by silica gel column chromatography using methylene chloride as a developing solvent gave the desired compound No.
1.1 g of 17A (melting point: 102-104 ° C.) and compound N
o. 0.5 g of 17B (melting point: 154 to 156 ° C.) was obtained.

Synthesis Example 7 1H-2-chloro-1-dimethylsulfamoyl-6-trifluoromethylimidazo [4,5-b] pyridine and 3H-2-chloro-3-dimethylsulfimoyl-6-tri Fluoromethylimidazo [4,5-b] pyridine (Compound No. 16A, Compound No. 16B) [1] 1H-2-mercapto-6-trifluoromethylimidazo [4,5-b] pyridine 5 g and acetic acid 140 ml
And 30 ml of water, and chlorine gas was blown in under ice cooling for 2.5 hours. After the completion of the reaction, put into water and extract with ethyl acetate,
After washing with water and drying, the solvent was distilled off. Normal hexane was added to the residue, and 1H-2-chloro-
Crystals of 6-trifluoromethylimidazo [4,5-b] pyridine were obtained. [2] 1H-2-chloro-6-trifluoromethylimidazo [4,5-b] pyridine obtained in the above step [1]
1 g, acetonitrile 8 ml and anhydrous potassium carbonate 0.1 g.
After refluxing 5 g of the mixture for 45 minutes, it was cooled to 30 ° C. and 0.8 g of dimethylsulfamoyl chloride was added.
The reaction was carried out at reflux temperature for 3 hours. After completion of the reaction, the mixture was poured into water, extracted with ethyl acetate, dried and concentrated. Separation and purification by silica gel column chromatography using methylene chloride as a developing solvent gave the desired compound No. 16A (melting point 75
-85 ° C) and 240 mg of Compound No. 16B (melting point 12
370 mg).

The compounds of the present invention are useful as pesticides. Agricultural and horticultural fungicides include rice blast, rice sheath blight, cucumber anthracnose, cucumber powdery mildew, tomato late blight, tomato ring spot, citrus black spot, citrus green mold, pear scab, Apple spot leaf blight, grape downy mildew,
Excellent control effect against various diseases such as gray mold, sclerotium, rust and soil diseases caused by plant pathogens such as Fusarium, Picium, Rhizoctonia, Verticillium, Plasmodiophora In particular, it has excellent control effects on diseases caused by algae such as potato and tomato diseases, downy mildew of cucumber and grape, blue mold of tobacco, and various soil diseases caused by pycium. 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 harmful to agricultural and horticultural insects, mites, nematodes, for example, insects such as aphids, diamondback moths, leafhoppers, adzuki beetles,
It shows an excellent control effect against mites such as scabbard mites and spider mites, and nematodes such as sweet potato 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. In addition, the general formula (II)
The intermediate represented by is also useful as a pest control agent, as will be seen in the test examples below.

When used, various forms such as emulsions, powders, wettable powders, liquids and the like can be prepared together with auxiliary agents, as in the case of conventional pesticide preparations. 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 and used. Examples of the adjuvant include a carrier, an emulsifier, a suspending agent, a dispersing agent, a spreading agent, a penetrating agent, a wetting agent, a thickener, a stabilizer, and the like. The carrier is divided into a solid carrier and a liquid carrier. As the solid carrier, starch, activated carbon, soy flour, wheat flour, wood flour, fish flour,
Animal and plant powders such as milk powder, talc, kaolin, bentonite, calcium carbonate, zeolite, diatomaceous earth, white carbon, clay, alumina, mineral powders such as sulfur powders, etc., as liquid carriers, water, methyl alcohol, ethylene Alcohols such as glycol, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane and tetrahydrofuran, kerosene,
Aliphatic hydrocarbons such as kerosene, aromatic hydrocarbons such as xylene, trimethylbenzene, tetramethylbenzene, cyclohexane, and solvent naphtha, chloroform,
Examples thereof include halogenated hydrocarbons such as chlorobenzene, acid amides such as dimethylformamide, esters such as ethyl acetate and fatty acid glycerin ester, nitriles such as acetonitrile, and 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 and the like, and cannot be specified unconditionally, but is usually 1 to 10,000 ppm, preferably 20 to 2,000 per active ingredient.
ppm.

If necessary, other agricultural chemicals, such as insecticides, acaricides, nematicides, fungicides, antivirals, attractants, herbicides, plant growth regulators, etc., may be mixed or used in combination. 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- (3,5,6-trichloro-2-pyridyl)
Organic phosphoric ester compounds such as phosphorothioate, O, S-dimethylacetyl phosphoroamidothioate, O- (2,4-dichlorophenyl) O-ethyl S-propyl phosphorodithioate; 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 methylcarbamate, 2-dimethylamino-5,6-dimethylpyrimidin-4-yl dimethylcarbamate, S And carbamate compounds such as S'-2-dimethylaminotrimethylenebis (thiocarbamate); 2,2,2-trichloro-1,1-bis (4-chlorophenyl) ethanol, 4-chlorophenyl 2,4,5 Organic chlorine compounds such as trichlorophenyl sulfone; organometallic compounds such as tricyclohexyltin hydroxide; (RS) -α-cyano-3-phenoxybenzyl (RS) -2- (4-chlorophenyl) -3 -Methylbutyrate, 3-phenoxybenzyl (1RS) -cis , 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-dimethylcyclo Propane carboxylate, (RS) -α-cyano-3-phenoxybenzyl (1RS) -cis, trans-3- (2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate Pyrethroid compounds such as citrate; 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-
A benzoylurea compound such as difluorobenzoyl) urea; 2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazin-4-one; Compounds such as trans-5- (4-chlorophenyl) -N-cyclohexyl-4-methyl-2-oxothiazolidinone-3-carboxamide, N-methylbis (2,4-xylyliminomethyl) amine; isopropyl ( 2E, 4
E) -11-Methoxy-3,7,11-trimethyl-
Juvenile hormone-like compounds such as 2,4-dodecasinate; and dinitro compounds,
Organic sulfur compounds, urea compounds, triazine compounds and the like can be mentioned. Furthermore, it can be mixed and used in combination with a microbial pesticide such as a BT agent and an insect pathogenic virus agent.

For example, as a bactericide, S-benzyl
Organic phosphorus compounds such as O, O-diisopropylphosphorothioate, O-ethyl S, S-diphenylphosphorodithioate, aluminum ethylhydrogenphosphonate; 4,5,6,7-tetrachlorophthalide, tetrachloroisophthalonitrile Organic chlorine compounds such as: Manganese polymer of ethylenebis (dithiocarbamate), polymer of zinc ethylenebis (dithiocarbamate), complex compound of zinc and manneb, dizincbis (dimethyldithiocarbamate) ethylenebis (dithiocarbamate) , A dithiocarbamate compound such as a polymer of zinc propylene bis (dithiocarbamate); 3a, 4,7,7a-tetrahydro-N-
(Trichloromethanesulfenyl) phthalimide, 3
a, 4,7,7a-tetrahydro-N- (1,1,2,2
2-tetrachloroethanesulfenyl) phthalimide,
N-halogenothioalkyl-based compounds such as N- (trichloromethylsulfenyl) phthalimide;
5-dichlorophenyl) -N-isopropyl-2,4-
Dioxoimidazolidin-1-carboxamide, (R
S) -3- (3,5-Dichlorophenyl-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane Dicarboximide compounds such as -1,2-dicarboximide; methyl 1- (butylcarbamoyl) benzimidazol-2-yl carbamate, dimethyl 4,4 ′-(o-phenylene) bis (3
-Thioallophanate); 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) butanone; 1- (biphenyl Yl-4-yloxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) butan-2-ol, 1- [N
-(4-chloro-2-trifluoromethylphenyl)-
2-propoxyacetoimidoyl] imidazole, 1-
[2- (2,4-dichlorophenyl) -4-ethyl-
1,3-dioxolan-2-ylmethyl] -1H-1,
2,4-triazole, 1- [2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolane-2
-Ylmethyl] -1H-1,2,4-triazole, 1
-[2- (2,4-dichlorophenyl) pentyl] -1
Azole compounds such as H-1,2,4-triazole: 2,4′-dichloro-α- (pyrimidin-5-yl) benzhydryl alcohol, (±) -2,4′-difluoro-α- (1H-1,2,4-triazole-1
Carbinol compounds such as -ylmethyl) benzhydryl alcohol; benzanilide compounds such as 3'-isopropoxy-o-toluanilide and α, α, α-trifluoro-3'-isopropoxy-o-toluanilide; methyl N- (2-methoxyacetyl) -N-
Acylalanine compounds such as (2,6-xylyl) -DL-alaninate; 3-chloro-N- (3-chloro-2,6-dinitro-4-α, α, α-trifluorotolyl) -5 Pyridinamine compounds such as trifluoromethyl-2-pyridinamine; and other compounds such as piperazine compounds, morpholine compounds, anthraquinone compounds, quinoxaline compounds, crotonic acid compounds, sulfenic acid compounds, and urea. System compounds, antibiotics and the like.

Hereinafter, Test Examples and Formulation Examples according to the present invention will be described. Test Example 1 Cucumber downy mildew preventive effect test Cucumber (cultivar: four leaves) is 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 is adjusted to a predetermined concentration is sprayed. It was sprayed with a gun.
After being kept in a greenhouse at 24 to 25 ° C. for one day and night, a spore suspension of downy mildew was sprayed and inoculated. Six days after the inoculation, the lesion area ratio (%) of the first leaf was examined, and the control value was determined by the following formula.
The results shown in Table 4 were obtained.

[0104]

[Table 20]

Test Example 2 Test of therapeutic effect on cucumber downy mildew Cucumber (cultivar: four-leaf) was cultivated in a polypot having a diameter of 7.5 cm, and when the two-leaf stage was reached, a spore suspension of downy mildew was sprayed and inoculated. did. After 6 hours, 10 ml of a chemical solution in which each test compound was adjusted to a predetermined concentration was sprayed using a spray gun. Two
After being kept in a greenhouse at 4 to 25 ° C. for 6 days, the lesion area ratio (%) of the first leaf was investigated, and the control value was obtained in the same manner as in the case of 1 of the above-mentioned test example. I got

[0106]

[Table 21]

Test Example 3 Cucumber downy mildew penetration test A cucumber (cultivar: four-leaf) was cultivated in a 7.5 cm-diameter plastic pot, and when the two-leaf stage was reached, each test compound was adjusted to a predetermined concentration. 10 ml of the drug solution was irrigated on the soil surface using a pipette. 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 inoculation, the lesion area ratio (%) of the first leaf was investigated, and the control value was determined in the same manner as in Test Example 1 above, and the results in Table 16 were obtained.

[0108]

[Table 22]

Test Example 4 Test for Preventive Effect on Tomato Blight Tomato (cultivar: Ponterosa) was cultivated in a plastic pot having a diameter of 7.5 cm. When the four-leaf stage was reached, 10 ml of a drug solution in which each test compound was adjusted to a predetermined concentration was added. Sprayed using a spray gun. After keeping it in a greenhouse at 24 to 25 ° C for one day and night, it was spray-inoculated with a zoosporangium suspension of Phytophthora. Five days after the inoculation, the number of lesions was examined, and the control value was determined by the following formula, and the results in Table 17 were obtained.

[0110]

[Table 23]

Test Example 5 Cucumber Anthracnose Preventive Effect Test Cucumber (cultivar: four-leaf) was cultivated in a polypot having a diameter of 7.5 cm, and when the two-leaf stage was reached, a chemical solution in which each test compound was adjusted to a predetermined concentration. 10 ml was sprayed using a spray gun.
After keeping it in a greenhouse at 24 to 25 ° C for one day, 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 determined by the following formula, and the results in Table 18 were obtained.

[0112]

[Table 24]

Test Example 6 Rice Sheath Blight Preventive Effect Test Paddy rice (cultivar: Chukyo Asahi) was cultivated in a 7.5 cm-diameter plastic pot, and when the five-leaf stage was reached, each test compound was adjusted to a predetermined concentration. 20 ml of the drug solution was sprayed using a spray gun.
After being kept in a greenhouse at 24 to 25 ° C. for 24 hours, rice straw in which sheath blight fungus had been cultured was sandwiched between leaf sheaths and inoculated. After keeping it in an inoculation room at a temperature of 28 ° C and a humidity of 100% for 5 days,
The lesion length of 5 stalks per pot was investigated, and the control value was calculated by the following formula, and the results shown in Table 19 were obtained.

[0114]

[Table 25]

Test Example 7 Antibacterial test (phytopathogenic bacteria) Potato-glucose agar medium (P) containing 100 ppm of streptomycin and 100 ppm of each active ingredient compound
Cucumber cotton rot fungus ( Pyth ) pre-cultured on DA medium)
ium aphanidermatum ) (a cold punch) was transplanted. After culturing at 22 ° C. for 48 hours, the flora diameter was investigated,
The mycelial growth inhibition rate (%) was determined by the following formula, and the results in Table 20 were obtained.

[0116]

[Table 26]

Test Example 8 Antibacterial Test (Bacteria) To 10 ml of bouillon agar medium, 0.5 ml of each chemical solution of the compound adjusted to a concentration of 200 ppm was added. Bacillus subtilis ( Bacill)
us subtilis) , Staphylococcus aureus ( St
aphylococcusaureus ), and cultured at 37 ° C. for 16 hours. After observing the growth state of the test bacteria, Compound No. 5 and No. 16-B. Test Example 9 Antibacterial test (fungus) To each medium of 10 ml of Sabouraud agar medium added with 1% of a 1,000 ppm aqueous solution of kanamycin, 0.5 ml of each chemical solution of the compound adjusted to a concentration of 200 ppm was added. Trichophyton rubrum ( Trichophyton
rubrum ) and cultured at 28-30 ° C for 5 days.
As a result of observing the growth state of the test bacterium, the most effective compound was Compound No. It was 1. Test Example 10 Acaricidal mite killing test Kidney bean (variety: Edogawa green beans) was cultivated in a plastic pot with a diameter of 7.5 cm, and when the initial leaf stage was reached, one primary leaf was left and other leaves were cut off. After inoculating about 30 larvae of the spider mite (Dicofol and organophosphate resistance), the seedlings were added to about 20 ml of a drug solution adjusted to a predetermined concentration of each test compound.
It was immersed for 0 seconds. After air-drying, it was left to stand in a 26 ° C. illuminated incubator, and two days after release, it was determined whether it was alive or dead. The mortality (%) was obtained by the following formula, and the results shown in Table 21 were obtained.

[0118]

[Table 27]

Test Example 11 Oxidation test of spider mite The leaves of only one primary leaf of kidney bean were transplanted into a polypot , inoculated with an adult of the spider mite, and spawned for 24 hours to remove the adult. Next, about 20 ml of the drug solution adjusted to a predetermined concentration of each test compound was added with about 1 of the kidney bean.
It was immersed for 0 second, air-dried, and then kept in a 26 ° C. illuminated thermostat. Five days after the treatment, the hatching status of the eggs was investigated, and the ovicidal rate (%) was determined by the following equation, and the results shown in Table 22 were obtained. In addition, the death immediately after hatching was also regarded as egg killing.

[0120]

[Table 28]

Test Example 12 Insecticidal test of peach peach aphid A piece of cabbage leaf was immersed in 20 ml of a chemical solution adjusted to a predetermined concentration of each test compound for about 10 seconds and air-dried to a diameter of 9 cm.
Wet filter paper was placed in a Petri dish of 3 and air-dried leaf pieces were placed thereon. The peach aphid wingless viviparous female worm was released there, and the lid was kept in an incubator with lighting 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.

[0122]

[Table 29]

Test Example 13 Sweet potato root-knot nematode
Nematicidal test Sweet potato root-knot nematode-contaminated soil was packed in a 1 / 14,000a pot, and 20 ml of a chemical solution in which each test compound was adjusted to 200 g / a with the active ingredient was irrigated onto the soil surface using a pipette. 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, the degree of cat vegetation was examined according to the following criteria, and the results shown in Table 24 were obtained. Evaluation criteria for degree of ginkgo growth 0; ginkgo growth-none 1; ginkgo growth-low 2; 〃-medium 3; 〃-high 4; 〃

[0124]

[Table 30]

Test Example 14 Novier herbicidal 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 the Nobies germinated, they were immersed in 3 cm of water, and a predetermined amount of a drug solution in which each test compound was adjusted to 50 g / a with an active ingredient was dropped with a pipette. Twenty days after the chemical treatment, the growth was visually observed, and the degree of growth inhibition was evaluated according to the following criteria. The results shown in Table 25 were obtained.

[0126]

[Table 31]

Test Example 15 Firefly and Urikawa herbicide test
Test 1 / 10,000a pots were filled with paddy field soil, firefly seeds and urikawa tubers were sown, and kept in shallow water. When the firefly was grown at the first leaf stage, it was flooded to 3 cm, and a predetermined amount of a chemical solution in which each test compound was adjusted to 50 g / a with an active ingredient was dropped by a pipette. 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 14 above. The results shown in Table 26 were obtained.

[0128]

[Table 32]

Test Example 16 Field Weed Soil Surface Treatment Test Field soil was packed into 1 / 3,000a pots, and barley, radish and soybean were sown. On the next day after seeding, a predetermined amount (3) of each test compound was adjusted to 50 g / a with the active ingredient.
0 l / a of spray water) was applied to the soil surface. 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.

[0130]

[Table 33]

Test Example 17 Field Weed Stem Treatment Test A 1 / 3,000a pot was filled with field soil, and barley, radish and soybean were sown. Thereafter, when the millet, radish, and soybean reached the three-leaf stage, the second-leaf stage, and the first true-leaf stage, respectively, a chemical solution in which each test compound was adjusted to 2,000 ppm was subjected to 10 ml / pot foliage treatment. Twenty days after 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, and the results shown in Table 28 were obtained.

[0132]

[Table 34]

As in the compound of the present invention, the compound represented by the above general formula (II)
The intermediate represented by (Table 1) is also useful as a pest control agent. The test examples and formulation examples are described below. Test Example 18 Test for preventive effect of cucumber downy mildew The results in Table 29 were obtained in the same manner as in Test Example 1 described above.

[0134]

[Table 35]

Test Example 19 Test for preventive effect of rice sheath blight In the same manner as in Test Example 6, the results shown in Table 30 were obtained.

[0136]

[Table 36]

Test Example 20 Antibacterial Test (Plant Pathogenic Bacteria) In the same manner as in Test Example 7, the results shown in Table 31 were obtained.

[0138]

[Table 37]

Test Example 21 Antibacterial Test (Bacteria) A test similar to that of Test Example 8 was performed.
o. 10 and No. 11 also showed similar activity. Test Example 22 Nobies Herbicidal Test In the same manner as in Test Example 14, the results shown in Table 32 were obtained.

[0140]

[Table 38]

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

[0142]

[Table 39]

Test Example 24 Field Weed Soil Surface Treatment Test In the same manner as in Test Example 16, the results shown in Table 34 were obtained.

[0144]

[Table 40]

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.

[0146]

[Table 41]

Formulation Example 1 (A) Compound No. 150 parts by weight (b) Sieglite 40 〃 (c) Sodium lignin sulfonate 7 〃 (d) Dialkyl sulfosuccinate 3 〃 The above ingredients were uniformly mixed to obtain a wettable powder. Formulation Example 2 (A) Compound No. 3 20 parts by weight (b) 72 g of siegrite (c) 8 g of sodium ligninsulfonate More than one were uniformly mixed to obtain a wettable powder.

Formulation Example 3 (a) Compound No. 45 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) xylene 60% (c) polyoxyethylene alkyl allyl ether 20% The above components were mixed and dissolved to form an emulsion. Formulation Example 5 (a) Sigrite 78 parts by weight (b) β-sodium naphthalene sulfonate formalin condensate 2 〃 (c) Polyoxyethylene alkylallyl sulphate 5 〃 (d) White carbon 15 〃 A mixture of the above components and , Compound No. And 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) Bentonite 61 (c) Siegrite 33 (d) Sodium ligninsulfonate 5) An appropriate amount of required granulation water is added to each of the above components, mixed and granulated to obtain a granulating agent. Was. Formulation Example 7 (a) No. 1 in Table 1 850 parts by weight (b) Sieglite 40 〃 (c) Sodium lignin sulfonate 7 〃 (d) Dialkyl sulfosuccinate 3 〃 The above ingredients were uniformly mixed to obtain a wettable powder. Formulation Example 8 (a) No. 1 in Table 1 10 20 parts by weight (b) Sieglite 72 〃 (c) Sodium lignin sulfonate 8 〃 The above ingredients were uniformly mixed to obtain a wettable powder. Formulation Example 9 (a) No. 1 in Table 1 115 parts by weight (b) Talc 95% or more were uniformly mixed to obtain a wettable powder.

Formulation Example 10 (a) No. 1 in Table 1 12 20 parts by weight (b) xylene 60 〃 (c) polyoxyethylene alkyl allyl ether 20 〃 The above components were mixed and dissolved to prepare an emulsion. Formulation Example 11 (A) 78 parts by weight of ziglite (B) β-naphthalenesulfonic acid sodium formalin condensate 2 (C) Polyoxyethylene alkyl allyl sulfate 5 (D) White carbon 15 The mixture of the above components and , No. 1 in Table 1. 15 and 4:
The mixture was mixed at a weight ratio of 1 to obtain a wettable powder. Formulation Example 12 (a) No. 1 in Table 1 12 1 parts by weight (b) Bentonite 61 〃 (c) Sikhlite 33 〃 (d) Sodium lignin sulfonate 5 〃 Add appropriate amount of required water to the above components, mix and granulate to granulate Got

 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Kazumi Suzuki, 3-3-1 Nishishibukawa, Kusatsu City, Shiga Ishihara Sangyo Co., Ltd. Central Research Laboratory (72) Inventor Shigeyuki Nishimura 2-3, Nishishibukawa, Kusatsu City, Shiga Prefecture No. 1 Ishihara Sangyo Co., Ltd. Central Research Institute (72) Inventor Shuji Yoshimura 2-3-1, Nishi-Shibukawa, Kusatsu City, Shiga Prefecture Ishihara Sangyo Co., Ltd. Central Research Institute

Claims (1)

[Claims] 1. A compound of the general formula (b): Wherein B ₁ is a nitro group or an amino group, and B ₂ is a halogen atom, an alkoxy group or an alkylthio group.
A trifluoromethylpyridine compound represented by: