JP2000063362A - Alpha-(oxyimino)-3-phenoxypyrazine acetic acid derivative and agricultural and horticultural bactericide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound as an excellent fungicidal compound for agriculture and horticulture and useful as an active ingredient of an agricultural and horticultural bactericide. SOLUTION: This α-(oxyimino)-3-phenoxypyrazine acetic acid derivative is a compound of formula I [R1 is H or a 1-5C alkyl; Z is O-atom or S-atom; Y is a 1-5C alkoxy, amino or the like; X is H, a halogen, a 1-7C alkyl, a 1-7C alkenyl or the like; (n) is 0-5 integer], e.g. α-(methoxyimino)-3-(3- trifluoromethylphenoxy)pyrazine acetic acid methyl ester. The compound of the formula I is obtained e.g. by forming a nitroso compound of 3- phenoxypyrazine acetic acid derivative of formula II to obtain an α-(hydroxyimino)-3-phenoxy pyrazine acetic acid derivative of formula III (R2 is a 1-5C alkyl), and then converting to α-(alkoxyimino)-3-phenoxypyrazine acetic acid derivative, etc., of formula IV (R1a is a 1-5C alkyl).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an α- (oxyimino) -3-phenoxypyrazine acetic acid derivative, its use as a fungicide for agricultural and horticultural use, and its production intermediate.

[0002]

2. Description of the Related Art JP-A-53-87376 and JP-A-7-12
Japanese Patent No. 6256 describes a herbicidal compound having a pyrazine ring in its structure. However, in the pyrazine acetic acid derivative, a phenyl group is bonded to the pyrazine ring via an oxygen atom or a sulfur atom, and a hydroxyimino group and an oxyimino group such as an alkoxyimino group are bonded to the α-position. There is no report yet on the existing compounds.

[0003]

Therefore, the present inventors have made it an object to synthesize an α- (oxyimino) -3-phenoxypyrazineacetic acid derivative not described in the literature and to find its usefulness.

[0004]

The present inventors have developed a novel compound, α- (oxyimino) -3 of the formula (I) of Chemical formula 5,
-A phenoxypyrazine acetic acid derivative was synthesized and found to be an excellent agricultural and horticultural fungicidal compound. The present invention is thus completed. (In the formula, R ¹ represents a hydrogen atom or a C1 to C5 alkyl group. Z represents an oxygen atom or a sulfur atom. Y represents a C1 to C5 alkoxy group, an amino group or a C1 to C5 alkyl group. A mono- or di-substituted amino group, X is a hydrogen atom, a halogen atom, a C1-C7 alkyl group, a C1-C7 alkenyl group, a C1-C7 alkoxy group, C1
To C5 haloalkyl group, C1 to C5 haloalkoxy group, C1 to C7
Alkylcarbonyl group, C1 to C7 alkoxycarbonyl group, C1 to C6 cycloalkyl group, amino group, C1 to C7 alkyl group which may be the same or different, mono- or di-substituted amino group, nitro group, cyano group, It represents a phenyl group which may be substituted, a phenoxy group which may be substituted, or a benzyloxy group which may be substituted. n represents an integer of 0 to 5. When n is 2 or more, X may be the same or different. )

[Chemical 5]

Therefore, the present invention has the following contents.
The first invention is α- (oxyimino) -of the above formula (I).
It relates to 3-phenoxypyrazine acetic acid derivatives.

The second invention relates to a 3-halogeno-α- (oxyimino) pyrazineacetic acid derivative of the formula (II) represented by the chemical formula: (In the formula, R ¹ represents a hydrogen atom or a C ¹ to C ⁵ alkyl group. R ² represents a C ¹ to C ⁵ alkyl group. R ³ represents a halogen atom.

[Chemical 6]

A third invention relates to a 3-phenoxypyrazineacetic acid derivative of the formula (III) represented by Chemical formula 7. (In the formula, R ² is
Represents a C1-C5 alkyl group. Z represents an oxygen atom or a sulfur atom. X is a hydrogen atom, a halogen atom, a C1-C7 alkyl group,
C1-C7 alkenyl group, C1-C7 alkoxy group, C1-C5 haloalkyl group, C1-C5 haloalkoxy group, C1-C7 alkylcarbonyl group, C1-C7 alkoxycarbonyl group, C1-C6
Cycloalkyl group, amino group, mono- or di-substituted amino group substituted by C1 to C7 alkyl group which may be the same or different, nitro group, cyano group, optionally substituted phenyl group, optionally substituted It represents a phenoxy group or an optionally substituted benzyloxy group. n represents an integer of 0 to 5. When n is 2 or more, X may be the same or different. )

[Chemical 7]

A fourth aspect of the present invention relates to an agricultural and horticultural germicide containing an α- (oxyimino) -3-phenoxypyrazineacetic acid derivative of the above formula (I) as an active ingredient.

The present invention will be described in detail below. In the present specification, as described in Tables 1 to 3 below, the number on the right side of the element indicating the number of atoms constituting the substituent is not a subscript number but is a half-width character. The numbers are shown.
Similarly, the number on the right side of the substituent, which indicates the number of substituents, is not a subscripted number but is simply a half-width number. In R ¹ , Y and X of the α- (oxyimino) -3-phenoxypyrazineacetic acid derivative of the formula (I) of the present invention, the substituents represented by the general concept include the following preferable substituents. There is. In R ¹ , C1 to C5 alkyl group, a methyl group, ethyl group, propyl group, isopropyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, pentyl group, A 1-methylbutyl group, a 2-methylbutyl group and a 3-methylbutyl group are included. Preferably, a C1 to C4 alkyl group, more preferably a methyl group,
It is an ethyl group.

In Y, a C1 to C5 alkoxy group is a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, a te group.
The rt-butoxy group is included. A C1-C4 alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. The amino group substituted with a C1-C5 alkyl group includes a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group and a diisopropylamino group. It is preferably a C1-C3 alkyl group, more preferably a methylamino group, an ethylamino group, a dimethylamino group, and a diethylamino group. In X, the halogen atom includes chlorine (2, 3, 4), fluorine (3, 4),
Dichlorine (3.4, 3.5), bromine (3), iodine (3),
Difluoro (3.5) is included. The number in parentheses after the halogen atom indicates the preferred bonding position of X 2. For example, 2, 3, 4 in () behind chlorine
Indicates that chlorine is bonded to any one of positions 2, 3, and 4. Dichlorine is the case where X2 is chlorine and X is chlorine, and 3, 4, 3, and 5 in () after dichlorine are
It shows that chlorine is bound to two positions, 3 and 4, 3 and 5, respectively. This regularity is also used in the description of halogen atoms other than chlorine and other substituents. Methyl (3,
4), 1,1-dimethylethyl (3,4), ethyl (3,4), 1-methylethyl (3,4), propyl (4), dimethyl (3.5), bis (1,1-) Dimethylethyl) (3.5) is included. C1-C5 alkoxy groups include methoxy (3,4), ethoxy (3,4),
(1-methylethyl) oxy (3), dimethoxy (3.
5) is included. C1-C5 haloalkyl groups include trifluoromethyl (3), bistrifluoromethyl (3
・ 5) is included. The C1-C5 haloalkoxy groups include trifluoromethoxy (3,4). The optionally substituted phenoxy group includes unsubstituted (3) and 3-iodo (3). The benzyloxy group which may be substituted includes unsubstituted (3), 2-
Chloro (3), 3-chloro (3), 4-chloro (3),
2-methyl (3), 3-methyl (3), 4-methyl (3), 3,4-dichloro (3), 2-cyano (3),
Included are 3-cyano (3) and 4-cyano (3). n is preferably 0 to 3, more preferably 1 or 2 in 0 to 5.

In the combination of the above-mentioned preferred substituents and the integers indicating the number of substituents, α-of the above formula (I)
As the (oxyimino) -3-phenoxypyrazine acetic acid derivative, the compounds shown in Table 1 of Table 1 can be exemplified.

[0012]

[Table 1] A): 4-OCH3 in the compound (I-90) represents a methoxy group bonded to the 4-position. 3,4-Cl2 in compound (I-60)
Indicates that a chlorine atom is bonded to the 3rd and 4th positions. That is, the number before the hyphen (-) indicates the bonding position, the number after the hyphen (-) indicates the substituent, and the number when the same substituent has two or more bonding positions.

In the combinations of the above-mentioned preferred substituents and the integers indicating the number of the substituents, 3- of the above formula (II) is used.
As the halogeno-α- (oxyimino) pyrazineacetic acid derivative, compounds shown in Table 2 in Table 2 can be exemplified.

[0014]

[Table 2]

In the combination of the above-mentioned preferred substituents and the integers showing the number of the substituents, 3 of the above formula (III) is used.
As the phenoxypyrazine acetic acid derivative, the compounds shown in Table 3 of Table 3 can be exemplified.

[0016]

[Table 3] A): 4-OCH3 in the compound (III-35) represents a methoxy group bonded to the 4-position. 3,4-Cl in compound (III-23)
2 indicates that chlorine atoms are bonded to the 3rd and 4th positions. That is, the number before the hyphen (-) indicates the bonding position, the number after the hyphen (-) indicates the substituent, and the number when the same substituent has two or more bonding positions.

The reaction described in the present specification will be described.
As shown in Chemical formula 8, the α- (alkoxyimino) -3-phenoxypyrazineacetic acid amide derivative of the formula (Ic) is obtained by converting the α- (alkoxyimino) -3-phenoxypyrazineacetic acid derivative of the formula (Ib) into a solvent or The formula (X
It can be produced by reacting with I) of ammonia or an alkylamine. Methylamine for alkylamine,
Ethylamine, isopropylamine, dimethylamine,
Examples include diethylamine. The solvent to be used is not particularly limited as long as it does not participate in the reaction, but alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene and toluene, polar solvents such as dimethylformamide, dimethylsulfoxide and water are preferable. Examples thereof include solvents, ethers such as tetrahydrofuran and dioxane, nitriles, and ketones. The reaction temperature is -50
C. to 100.degree. C., preferably 0.degree. C. to 80.degree. The reaction time depends on the reaction temperature, but is usually 30 minutes to 48 minutes.
It's time. (In the formula, R ² , Z, X and n have the same definition as described above. R ⁴ and R ⁵ are hydrogen or a C1 to C5 alkyl group, and may be the same or different. R ^1a is C1 to Represents a C5 alkyl group.)

[Chemical 8]

As shown in the reaction formula (9), the α- (alkoxyimino) -3-phenoxypyrazineacetic acid derivative of the formula (Ib) is converted into the α- (hydroxyimino) -formula of the formula (Ia).
It can be prepared by alkylating a 3-phenoxypyrazine acetic acid derivative with a base in a suitable solvent using an alkylating agent of the formula (XII). The alkylating agent will be exemplified below. Examples of the alkyl halide include methyl iodide, methyl bromide, ethyl iodide, ethyl bromide, isopropyl iodide and the like. Examples of di (C1-C5 alkyl) sulfate include dimethylsulfate and diethylsulfate. C1 ~ C5
As the alkanesulfonic acid C1-C5 alkyl ester,
Examples of the methanesulfonic acid methyl ester and the substituted benzenesulfonic acid C1-C5 alkyl ester include p-toluenesulfonic acid C1-C5 alkyl ester. The solvent to be used is not particularly limited as long as it does not participate in the reaction, but preferably includes amides such as dimethylformamide and dimethylacetamide, ethers such as diethyl ether, tetrahydrofuran and dioxane, and ketones such as acetone and methyl ethyl ketone. To be
Examples of the base used include metal hydrides such as sodium hydride and inorganic bases such as potassium carbonate. The reaction temperature is −50 ° C. to 100 ° C., preferably −
20 to 80 ° C. The reaction time depends on the reaction temperature, but is usually 30 minutes to 24 hours. [In the formula, R
^1a , R ² , Z, X and n have the same definition as above. L is a halogen atom or one half of the (-OSO2) group [R ^1a L
2 times the number of di (C1-C5 alkyl) sulfuric acid ester], C1-C5 alkylsulfonyloxy group, and substituted phenylsulfonyloxy group. ]

[Chemical 9]

As shown in the reaction formula of Chemical formula 10, the formula (Ia)
The α- (hydroxyimino) -3-phenoxypyrazine acetic acid derivative of is a compound (III) of 3-phenoxypyrazine acetic acid derivative in the presence of a base or an acid, a nitrite ester of formula (XIV), nitrous acid or a salt thereof. Can be used for nitrosation. The solvent used is not particularly limited as long as it does not participate in the reaction, but is preferably amides such as dimethylformamide and dimethylacetamide, ethers such as diethyl ether, tetrahydrofuran and dioxane, ketones such as acetone and methyl ethyl ketone, and ice. Acetic acid may be mentioned. The base used is a metal hydride such as sodium hydride, an alkali metal alcoholate such as potassium tert-butoxide, an inorganic base such as potassium carbonate, and the acid used is an inorganic such as hydrochloric acid or sulfuric acid. Examples thereof include acids, organic acids such as p-toluenesulfonic acid, acetic acid and trichloroacetic acid. Examples of the nitrous acid ester include ethyl nitrite, butyl nitrite, isoamyl nitrite, and tert-butyl nitrite. Among these, nitrite C4 to C5 alkyl ester is preferable for handling. Examples of the salt of nitrous acid include sodium nitrite, and the reaction temperature is -78 ° C to 100 ° C, preferably -50 ° C.
To 80 ° C. The reaction time depends on the reaction temperature, but is usually 30 minutes to 24 hours. (Where R ² , Z,
X and n have the same definition as above. R ⁶ represents a hydrogen atom, C1 to C5 alkyl group, sodium atom, potassium atom. )

[Chemical 10]

The compound (Ib) can be produced by the steps of as shown in the reaction formula of Chemical formula 11. The pyrazine acetic acid derivative of the formula (IV) is nitrosated with an ester of nitrous acid of the formula (XIV), nitrous acid or a salt thereof in the presence of a base or an acid to give a compound of formula (II-a) A -halogeno-α- (hydroxyimino) pyrazineacetic acid derivative can be prepared. The solvent to be used is not particularly limited as long as it does not participate in the reaction, but preferably, amides such as dimethylformamide and dimethylacetamide, ethers such as diethyl ether, tetrahydrofuran and dioxane, ketones such as acetone and methyl ethyl ketone, Glacial acetic acid may be mentioned. The base used is a metal hydride such as sodium hydride, an inorganic base such as potassium carbonate, and the acid used is
Examples thereof include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as p-toluenesulfonic acid, acetic acid and trichloroacetic acid. Examples of the nitrous acid ester include ethyl nitrite, butyl nitrite, isoamyl nitrite, and tert-butyl nitrite. Examples of the nitrite salt include sodium nitrite and the like. The reaction temperature is -78 ° C to 100 ° C, preferably -50 ° C to 80 ° C. The reaction time is related to the reaction temperature,
Usually, it is 30 minutes to 24 hours. By alkylating a 3-halogeno-α- (hydroxyimino) pyrazineacetic acid derivative of the formula (II-a) with a base in a suitable solvent using an alkylating agent of the formula (XII) (II-b ) 3-halogeno-α- (oxyimino)
A pyrazine acetic acid derivative can be produced. The alkylating agent will be exemplified below. Examples of the alkyl halide include methyl iodide, methyl bromide, ethyl iodide, ethyl bromide, isopropyl iodide and the like. Examples of di (C1-C5 alkyl) sulfate include dimethylsulfate and diethylsulfate. C1 ~
Examples of the C5 alkanesulfonic acid C1 to C5 alkyl ester include methanesulfonic acid methyl ester, and examples of the substituted benzenesulfonic acid C1 to C5 alkyl ester include p-toluenesulfonic acid C1 to C5 alkyl ester. The solvent used is not particularly limited as long as it does not participate in the reaction, but is preferably amides such as dimethylformamide and dimethylacetamide, diethyl ether,
Examples thereof include ethers such as tetrahydrofuran and dioxane, and ketones such as acetone and methyl ethyl ketone. Examples of the base used include metal hydrides such as sodium hydride and inorganic bases such as potassium carbonate. The α- (alkoxyimino) -3-halogenopyrazine acetic acid derivative of the formula (II-b) and the phenol (or thiophenol) of the formula (XV) are reacted in the presence of a base to remove the remaining halogen atom. , Phenoxy anion (or thiophenoxy anion) derived from compound (XV)
It can also be produced by nucleophilic substitution with. further,
If necessary, it is carried out in the presence of a catalyst composed of copper, a copper salt, a copper compound or a transition metal, a salt of a transition metal and the like. (In the formula, R ^1a , R ² , R ³ , R ⁶ , L, Z, X, and n have the same definition as above.)

[Chemical 11]

The compound (III) can be produced by the steps of as shown in the reaction formula of Chemical formula 12. 2,3-dihalogenopyrazine of formula (VII) and formula (XVI)
Propanedioic acid dialkyl ester of formula (V) is reacted with a carboxylic anion of the compound (XVI) to react nucleophilically in the presence of a base to give a compound of formula (V
The pyrazinyl propanedioic acid dialkyl ester of I) is prepared. Compound (VI) is hydrolyzed and decarboxylated to give formula (V
) 3-halogenopyrazine acetic acid is produced. The compound (V) and the C1-C5 alkanol of the formula (XVII) are subjected to an esterification reaction in the presence of an acid catalyst to give a compound of the formula (IV)
To produce an alkyl ester of 3-halogenopyrazine acetic acid. Compound (IV) and phenol of formula (XV) (or thiophenol) are reacted in the presence of a base, and the remaining halogen atom is a phenoxy anion (or thiophenoxy anion derived from compound (XV). ) Is nucleophilically substituted to produce a 3-phenoxypyrazine acetic acid derivative of formula (III). (In the formula, R ² , Z, X and n have the same definition as above. R ³ represents a halogen atom.
R ⁷ represents a C1-C5 alkyl group)

[Chemical 12]

Further, the 3-phenoxypyrazine acetic acid derivative of the formula (III) has the following formulas:
It can also be manufactured by the process of. 2,3-dihalogenopyrazine of formula (VII) and formula (XVI)
Propanedioic acid dialkyl ester of formula (V) is reacted with a carboxylic anion of the compound (XVI) to react nucleophilically in the presence of a base to give a compound of formula (V
The pyrazinyl propanedioic acid dialkyl ester of I) is prepared. The compound (VI) and the phenol (or thiophenol) of the formula (XV) are reacted in the presence of a base, and the remaining halogen atom is a phenoxy anion (or thiophenoxy anion derived from the compound (XV). ) Is nucleophilically substituted to produce the (3-phenoxypyrazinyl) propanedioic acid dialkyl ester of formula (IX). Compound (IX) is hydrolyzed and decarboxylated to give the compound of formula (VI
II) 3-phenoxypyrazine acetic acid is produced. The compound (VIII) and the C1-C5 alkanol of the formula (XVII) are subjected to an esterification reaction in the presence of an acid catalyst to give a compound of the formula (III
(3) A 3-phenoxypyrazine acetic acid derivative is produced.
(In the formula, R ² , Z, X and n have the same definition as above. R ³ represents a halogen atom. R ⁷ represents a C1 to C5 alkyl group.)

[Chemical 13]

Further, the compound (III) can be produced also by the steps of as shown in the reaction formula of Chemical formula 14. The 2,3-dihalogenopyrazine of formula (VII) and the phenol (or thiophenol) of formula (XV) are reacted in the presence of a base to give one halogen atom to the compound (XV). Nucleophilic displacement with the phenoxy anion (or thiophenoxy anion) from which it is derived to produce 2-halogeno-3-phenoxypyrazine of formula (X). Compound (X) is reacted with a propanedioic acid dialkyl ester of formula (XVI) in the presence of a base,
The remaining halogen atoms are nucleophilically substituted with the carbanion of compound (XVI) to produce the (3-phenoxypyrazinyl) propanedioic acid dialkyl ester of formula (IX). Compound (IX) is hydrolyzed and decarboxylated to give the compound of formula (VI
II) 3-phenoxypyrazine acetic acid is produced. The compound (VIII) and the C1-C5 alkanol of the formula (XVII) are subjected to an esterification reaction in the presence of an acid catalyst to give a compound of the formula (III
(3) A 3-phenoxypyrazine acetic acid derivative is produced.
(In the formula, R ² , Z, X and n have the same definition as above. R ³ represents a halogen atom. R ⁷ represents a C1 to C5 alkyl group.)

[Chemical 14]

The halogen atom on the pyrazine ring used in [Production of Compound (VI) from Compound (VII)] and [Production of Compound (IX) from Compound (X)] in the presence of a base, The reaction for nucleophilically substituting a carbanion derived from methylene sandwiched by the carbonyl group of propanedioic acid dialkyl ester (XVI) is carried out as follows. As the base used, a strong base is generally used. Examples thereof include metal hydrides such as sodium hydride, inorganic bases such as potassium hydroxide and sodium hydroxide. The inert solvent used is not particularly limited as long as it does not participate in the reaction, but amides such as dimethylformamide and dimethylacetamide are preferred. If necessary, it is carried out in the presence of a phase transfer catalyst, and when a phase transfer catalyst is used, water, dichloromethane or the like is used. The reaction temperature is 0 to 170 ° C.
The temperature is preferably 0 to 130 ° C. The reaction time is usually 1 to 5 hours.

[Production of Compound (III) from Compound (IV)], [Production of Compound (IX) from Compound (VI)], and
One halogen atom on the pyrazine ring used in [Production of compound (X) from compound (VII)] is replaced by compound (X
The reaction for nucleophilic substitution with a phenoxy anion (or thiophenoxy anion) derived from V) is usually
It is carried out using a base, and generally a strong base is used. Examples thereof include metal hydrides such as sodium hydride, inorganic bases such as potassium hydroxide and sodium hydroxide. Further, if necessary, it is carried out in the presence of a catalyst composed of copper, a copper salt, a copper compound or a transition metal, a salt of a transition metal, or the like. The inert solvent used is not particularly limited as long as it does not participate in the reaction, but amides such as dimethylformamide and dimethylacetamide are preferably used. The reaction temperature is room temperature to 200 ° C, preferably 100 ° C to 170 ° C. The reaction time is usually 1 hour to 24 hours.

The hydrolysis / decarboxylation reaction used in [Production of Compound (V) from Compound (VI)] and [Production of Compound (VIII) from Compound (IX) is preferably carried out under basic conditions. Do it below. The base used is not particularly limited, and examples thereof include inorganic bases such as potassium hydroxide and sodium hydroxide. The solvent used is not particularly limited as long as it does not participate in the reaction, but preferably methanol,
Examples thereof include alcohols such as ethanol, tetrahydrofuran, ethers such as dioxane, acetonitrile and the like, and mixed solvents of these solvents and water. The reaction temperature is room temperature to 150 ° C, preferably room temperature to 100 ° C. The reaction time varies depending on the reaction temperature and the type of solvent used, but is usually 5 hours to 24 hours.

The esterification reaction used in [Production of compound (IV) from compound (V)] and [Production of compound (III) from compound (VIII)] is carried out from the carboxy group or carboxy group of the starting material. It can be carried out by reacting a compound (XVII) with a derivatizable reactive group such as a halogenocarbonyl group. This esterification reaction can be performed using a known method.
For example, an inorganic acid such as hydrochloric acid or sulfuric acid, an organic acid such as p-toluenesulfonic acid, or an acidic compound such as an ion exchange resin having a sulfo group bonded is used as a catalyst, and the compound (XVII) is used in excess as a solvent. Then, it can be carried out by reacting a carboxylic acid and an alcohol. The reaction temperature is 0 ° C to the reflux point, preferably 20 ° C to the reflux point. The reaction time is
It is 1 to 80 hours, preferably 5 to 50 hours. Furthermore, by deriving a carboxy group to a halogenocarbonyl group such as a chlorocarbonyl group or a bromocarbonyl group,
Preferably, in the presence of a basic compound, compound (XVII)
It can also be carried out by reacting with. Suitable bases include, for example, organic bases such as triethylamine, N, N-dimethylaniline, pyridine, 4-dimethylaminopyridine and the like. The reaction is usually performed in a solvent. The type of solvent is not particularly limited as long as it does not participate in the reaction, for example, hydrocarbons such as toluene, benzene and xylene, halogenated hydrocarbons such as chloroform and methylene chloride, ethers such as diethyl ether, tetrahydrofuran and dioxane. And esters such as methyl acetate and ethyl acetate. The reaction temperature is generally 0 ° C to 100 ° C, preferably 0 ° C to 50 ° C.
The reaction time is usually 0.5 to 3 hours.

Examples of 2,3-dihalogenopyrazine of the formula (VII) include 2,3-dichloropyrazine and 2,3-dibromopyrazine. The propanedioic acid dialkyl ester of the formula (XVI) (same as dialkylmalonic acid ester) includes propanedioic acid dimethyl ester, propanedioic acid diethyl ester, propanedioic acid di (1-methylethyl) ester, propane Examples include dipropyl acid dipropyl ester and propanedioic acid dibutyl ester. As the C1-C5 alkanol of the formula (XVII), methanol,
Ethanol, propanol, butanol, pental,
Examples thereof include 1-methylethyl alcohol, 1,1-dimethylethyl alcohol, 1-methylpropyl alcohol and 2-methylbutyl alcohol.

Among the phenols (or thiophenols) of the formula (XV), phenols include phenol,
2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 3,4-dichlorophenol, 3,5-dichlorophenol, 3-bromophenol, 3 -Iodophenol, 3,5-difluorophenol, 3-methylphenol, 4-methylphenol, 3- (1,1-dimethylethyl) phenol, 4- (1,1-dimethylethyl) phenol, 3-
Ethylphenol, 4-ethylphenol, 3- (1-
Methylethyl) phenol, 4- (1-methylethyl)
Phenol, 3-propylphenol, 4-propylphenol, 3,5-dimethylphenol, 3,5-bis (1,1-dimethylethyl) phenol, 3-methoxyphenol, 4-methoxyphenol, 3-ethoxyphenol, 4 -Ethoxyphenol, 3-[(1-methylethyl) oxy] phenol, 3,5-dimethoxyphenol, 3-trifluoromethylphenol, 3,5
-Bistrifluoromethylphenol, 3-trifluoromethoxyphenol, 4-trifluoromethoxyphenol, 3-phenoxyphenol, 3- (3-iodophenoxy) phenol, 3-benzyloxyphenol, 3-[(2-chlorobenzyl) Oxy] phenol, 3-[(3-chlorobenzyl) oxy] phenol, 3-[(4-chlorobenzyl) oxy] phenol, 3-[(2-methylbenzyl) oxy] phenol, 3-[(3-methyl Benzyl) oxy] phenol, 3-[(4-methylbenzyl) oxy] phenol, 3-[(3,4-dichlorobenzyl) oxy] phenol, 3-[(2-cyanobenzyl) oxy] phenol, 3- [ (3-Cyanobenzyl) oxy] phenol, 3-[(4-cyanobenzyl ) Can be exemplified oxy] phenol.

The thiophenols include thiophenol, 2-chlorothiophenol, 3-chlorothiophenol, 4-chlorothiophenol, 2-fluorothiophenol, 3-fluorothiophenol, 4-fluorothiophenol, 3, 4-dichlorothiophenol, 3
-Chloro-4-fluorothiophenol, 3,5-dichlorothiophenol, 2-bromothiophenol, 3-
Bromothiophenol, 4-bromothiophenol, 2
-Methylthiophenol, 3-methylthiophenol,
4-methylthiophenol, 3,4-dimethylthiophenol, 2- (1,1-dimethylethyl) thiophenol, 4- (1,1-dimethylethyl) thiophenol,
2-ethylthiophenol, 4-ethylthiophenol, 2- (1-methylethyl) thiophenol, 4-
(1-methylethyl) thiophenol, 3,5-dimethylthiophenol, 3,5-bis (1,1-dimethylethyl) thiophenol, 2-methoxythiophenol,
3-methoxythiophenol, 4-methoxythiophenol, 3,4-dimethoxythiophenol, 2-trifluoromethylthiophenol, 3-trifluoromethylthiophenol, 4-trifluoromethylthiophenol, 3,5-bistrifluoromethylthiophenol,
2-trifluoromethoxy thiophenol, 4-trifluoro methoxy thiophenol, etc. can be illustrated.

The plant diseases for which the compound of the present invention is effective include, for example, rice blast (Pyricularia oryzae),
Rice sesame leaf blight (Cochliobolus miyabeanus), rice white leaf blight (Xanthomonas oryzae), rice blight (Rhizoctoni)
a solani), a rice black rot (Helminthosporium sigmoi)
deum), rice scabbard disease (Gibberella fujikuroi), apple powdery mildew (Podosphaera leucotricha), apple scab (Venturia inaequalis), apple morinia (Monilin)
ia mali), apple leaf spot (Alternaria mali), apple rot (Valsa mali), pear black spot (Alternaria kii)
kuchiana), pear powdery mildew (Phyllactinia pyri), pear red scab (Gymnosporangium asiaticum), pear scab (Ven
turia nashicola), powdery mildew of grapes (Uncinula necat)
or), grape rust (Phakopsora ampelopsidis), grape late rot (Glomerella cingulata), barley powdery mildew
(Erysiphe graminis f. Sp. Hordei), cloud disease of barley
(Rhynchosporium secalis f. Sp.hordei), barley black rust (Puccinia graminis), and barley stripe rust (Puc
cinia striiformis), wheat leaf rust (Puccinia recon
dita), wheat leaf blight (Septoria tritici), wheat stripe rust (Puccinia striiformis), wheat powdery mildew (Er
ysiphe graminis f. sp. tritici), powdery mildew of cucumber
(Sphaerotheca fuliginea), anthracnose of the cucumber (Colletotri)
chum lagenarium), Fusarium oxyspor
um f. sp. niveum), Fusarium oxys
porum f. sp. niveum), yellow radish (Fusarium oxy)
sporum f. sp. raphani), powdery mildew of tomato (Erysiphe
cichoracearum), tomato ring spot (Alternaria solani),
Powdery mildew of eggplant (Erysiphe cichoracearum), powdery mildew of strawberry (Sphaerotheca humuli), powdery mildew of tobacco
(Erysiphe cichorcearum), tobacco scab (Alternaria
longipes), brown spot of sugar beet (Cercospora beticola), summer blight of potato (Alternaria solani), brown leaf spot of soybean
(Septoria glycines), soybean purpura (Cercospora kiku)
chii), drizzle of fruit trees (Monilinia fructicola), gray mold (Botrytis cinerea), sclerotinia sclerotiorum, etc.

When the compound of the present invention is used as an active ingredient of a plant disease controlling agent, it may be used as it is without adding any other ingredients, but it is usually a solid carrier, a liquid carrier, a surfactant,
It is mixed with other auxiliaries for formulation to prepare emulsions, wettable powders, suspensions, granules, powders, liquids and the like. In these formulations, the compound of the present invention is contained as an active ingredient in a weight ratio of 0.1 to 9
9%, preferably 1-80%. As the solid carrier, for example, kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, decomposing seat, walnut powder, urea, ammonium sulfate, fine powder or granules of synthetic hydrous silicon oxide, etc. Can be mentioned.

Examples of the liquid simple substance include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol and cellosolve,
Ketones such as acetone, cyclohexanone, and isophorone,
Soybean oil, vegetable oils such as cottonseed oil, dimethyl sulfoxide, acetonitrile, water and the like, examples of the surfactant used for emulsification, dispersion, wet extension, for example, alkyl sulfate ester salts, alkyl sulfonates, Anionic surfactants such as aryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate salts, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, Nonionic surfactants, such as sorbitan fatty acid ester polyoxyethylene sorbitan fatty acid ester, etc. are mentioned. Examples of the auxiliaries for the formulation include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, carboxymethyl cellulose (CMC
), Acidic isopropyl phosphate (PAP) and the like.

These formulations are used as they are or after being diluted with water for foliar application, or they are used in various forms such as being powdered, granulated and mixed in soil, or applied to soil. In addition, when used in combination with other plant disease controlling agents, it can be expected to enhance the controlling effect. Furthermore, it can be used by mixing with an insecticide, an acaricide, a herbicide, a plant growth regulator, a fertilizer, and a soil conditioner. When the compound of the present invention is used as an active ingredient of a plant disease control agent, its application amount is 1 hectare of agricultural and horticultural land such as fields, rice fields, orchards and greenhouses.
2 to 5000 g, more preferably 50 to 1000 g, and when an emulsion, a wettable powder, a suspending agent, a liquid agent or the like is diluted with water and applied, the application concentration is 0.001% to 1.0%. , Granules, powders, etc. are applied as they are without any dilution.

[0035]

EXAMPLES The present invention will be described in detail below with reference to production examples, formulation examples, and test examples. The present invention is not limited to the following production examples and test examples as long as the gist thereof is not exceeded. Production Example 1 α- (methoxyimino) -3- (3-trifluoromethylphenoxy) pyrazineacetic acid methyl ester [Compound (I-42)] 3- (3-trifluoromethylphenoxy) pyrazine acetic acid methyl ester [Compound (III-15)] sodium hydride 0.51 g dimethylformamide (hereinafter abbreviated as DMF) 15 ml suspension The solution was cooled and dissolved in 10 ml of DMF with stirring, 3-trifluoromethylphenol [in compound (XV), Xn = 3-CF3, Z = O 2].
2.1 g of solution was added dropwise. Then 3-chloro-2-
Pyrazine acetic acid methyl ester [in the compound (IV),
R ² = CH ³ , R ³ = Cl, the one synthesized in Reference Production Example 1 was used] 5.0 g and 0.5 g of copper chloride were added and reacted at 115 ° C. for 2 hours. The reaction solution was cooled, filtered, poured into cold water to acidify, and then extracted with ethyl acetate. The extract was washed successively with water and saturated saline and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain a dark brown oily substance. Purified using silica gel chromatography and reverse phase chromatography, 3- (3-trifluoromethylphenoxy) pyrazine acetic acid methyl ester [compound (III-15)] 1.31
g was obtained as an oil. ¹ H-NMR (60MHz, CDCl ₃ , δ ppm): 3.67 (3H, S), 3.99 (2
H, S), 7.12 ~ 7.52 (4H, m), 7.93 (1H, d, J = 2.4Hz), 8.20 (1H,
(d, J = 2.4Hz)

Α- (Hydroxyimino) -3- (3-
Preparation of trifluoromethylphenoxy) pyrazine acetic acid methyl ester [compound (I-41)] 3- (3-trifluoromethylphenoxy) pyrazine acetic acid methyl ester [compound (III-15)] 0.69 g and trichloroacetic acid 0.07 g Was dissolved in 11 ml of acetic acid, 0.42 g of tert-butyl nitrite was added, and the mixture was stirred at room temperature for 1.5
Stir for hours. The solvent was evaporated under reduced pressure, cold water was added to the obtained residue, and the mixture was extracted with ethyl acetate. The extract was washed successively with water and saturated saline and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain an oily substance. α- (Hydroxyimino) -3- (3-trifluoromethylphenoxy) pyrazine acetic acid methyl ester [Compound (I-41)]
0.69 g was obtained as an oil. This was used in the next reaction without purification.

Preparation of α- (methoxyimino) -3- (3-trifluoromethylphenoxy) pyrazineacetic acid methyl ester [compound (I-42)] α- (hydroxyimino) -3- (3-trifluoromethylphenoxy) ) 0.69 g of pyrazine acetic acid methyl ester [compound (I-41)] was dissolved in 10 ml of DMF, 0.91 g of potassium carbonate and 0.73 g of dimethylsulfate were added, and the mixture was reacted at room temperature for 1.5 hours. The reaction solution was poured into water, neutralized, and then extracted with ethyl acetate. The extract was washed successively with water and saturated saline and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 0.56 g of a dark brown oily substance. Purified using silica gel chromatography, α- (methoxyimino) -3- (3-trifluoromethylphenoxy) pyrazine acetic acid methyl ester [Compound (I-42)]
0.04g of isomer (A) and 0.06g of isomer (B)
Obtained. Isomer (A) ¹ H-NMR (60MHz, CDCl ₃ , δppm): 3.82 (3H, S), 4.07 (3H,
S), 7.10 ~ 7.60 (4H, m), 8.03 (1H, d, J = 2.4Hz), 8.32 (1H, d, J
= 2.4Hz) isomer (B) ¹ H-NMR (60MHz, CDCl ₃ , δppm): 3.84 (3H, S), 4.04 (3H,
S), 7.15-7.51 (4H, m), 8.08 (1H, d, J = 2.4Hz), 8.35 (1H, d, J
= 2.4Hz)

Production Example 2 Production of 3-chloro-α- (methoxyimino) pyrazineacetic acid methyl ester [Compound (II-5)] 3-chloro-α- (hydroxyimino) pyrazineacetic acid methyl ester [Compound (II-1 )] 3-chloro-2-pyrazine acetic acid methyl ester [in compound (IV), R ¹ = CH ³ , R ³ = Cl 2, the one synthesized in Reference Production Example 1 was used] 31.7 g in 80 ml of acetic acid. It was melted and cooled with ice water. To this solution was added dropwise 18 g of sodium nitrite dissolved in the minimum required amount of water. After 5 hours, 3.2 g of sodium nitrite dissolved in the minimum necessary amount of water was added again and the reaction was carried out for 7 hours. The reaction solution was poured into cold water and extracted with dichloromethane. The extract was washed successively with water and saturated brine. After drying over anhydrous sodium sulfate, the solvent was evaporated under reduced pressure to obtain 32.5 g of a yellow solid containing 3-chloro-α- (hydroxyimino) pyrazineacetic acid methyl ester [Compound (II-1)]. Melting point: 123-129 ° C. ¹ H-NMR (60 MHz, CDCl ₃ , δppm): 3.80 (3H, S), 8.37 (1H,
d, J = 2.4Hz), 8.54 (1H, d, J = 2.4Hz), 10.87 (1H, brs)

Preparation of 3-chloro-α- (methoxyimino) pyrazineacetic acid methyl ester [Compound (II-5)] 3-chloro-α- (hydroxyimino) pyrazineacetic acid methyl ester [Compound (II-1)] 332 Dissolve 0.0 g in 300 ml of anhydrous acetone, cool to 0 ° C., add 30.0 g of potassium carbonate and 23.0 g of dimethyl sulfate, and add 0 ° C.
And reacted for 1.5 hours. The mixture was filtered, the filtrate was evaporated under reduced pressure, ethyl acetate was added to the obtained residue, and the mixture was washed successively with water, saturated aqueous ammonium chloride solution and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 36.0 g of a dark brown oily substance. Purification using silica gel chromatography gave 14.0 g of a white solid of 3-chloro-α- (methoxyimino) pyrazineacetic acid methyl ester [compound (II-5)]. (Melting point 70 to 71.5 ° C.) ¹ H-NMR (60 MHz, CDCl ₃ , δppm): 3.81 (3H, S), 4.02 (3H,
S), 8.31 (1H, d, J = 2.4Hz), 8.43 (1H, d, J = 2.4Hz)

Production Example 3 3- (3-tert-Butylphenoxy) -α- (methoxyimino) pyrazineacetic acid methyl ester [Compound (I-
33)] is prepared. After washing 0.34 g of sodium hydride with hexane,
Suspended in 10 ml of DMF and dissolved in 10 ml of DMF 3
11.32 g of -tert-butylphenol was added dropwise. After completion of dropping, when heated to 70 ° C, copper chloride 0.3 g
And 0.93 g of 3-chloro-α- (methoxyimino) pyrazine acetic acid methyl ester [compound (II-5) used in Preparation Example 2] was added. The reaction was carried out at 110 ° C for 2 hours. After cooling, the reaction solution was poured into cold water to make it acidic and then extracted with ethyl acetate. The extract was washed with water and saturated saline and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 0.8 g of a dark brown oily substance. Purified using silica gel chromatography and reverse phase chromatography, 3- (3-tert-butylphenoxy)-
0.2 g of α- (methoxyimino) pyrazine acetic acid methyl ester [compound (I-33)] was obtained. ¹ H-NMR (60MHz, CDCl ₃ , δppm): 1.27 (9H, S), 3.80 (3H,
S), 4.02 (3H, S), 6.68 ~ 7.33 (4H, m), 8.01 (1H, d, J = 2.4Hz),
8.22 (1H, d, J = 2.4Hz)

Preparation Example 4 Preparation of 3- (3-tret-butylphenoxy) -α- (methoxyimino) -N-methylpyrazineacetic acid amide [compound (I-34)] 3- (3-tert-butylphenoxy) -Α- (Methoxyimino) pyrazine acetic acid methyl ester [Compound (I-
33). Obtained by repeating the experiment of Production Example 3] 0.4 g was dissolved in 1 ml of methanol, 1 g of 40% methylamine-methanol solution was added, and the mixture was stirred at room temperature overnight. The solvent was distilled off under reduced pressure to obtain 0.42 g of a reddish brown oily substance. This oily substance was crystallized using methanol and hexane to give white crystals, 3- (3-tret-butylphenoxy) -α-.
0.2 g of (methoxyimino) -N-methylpyrazine acetic acid amide [compound (I-34)] was obtained. Melting point: 165.5 to 166.5 ° C ¹ H-NMR (60MHz, CDCl3, δppm): 1.27 (3H, S), 2.91 (3H,
d, J = 5.2Hz), 3.92 (3H, S) 6.50 ~ 7.33 (5H, m), 8.00 (1H, d, J = 2.4Hz), 8.24 (1H, d, J = 2.
4Hz)

Reference Production Example 1 3-chloropyrazine acetic acid methyl ester [compound (IV)]
In (compound (VI), R ³ = Cl ³ , R ⁷ = CH ³ ), production of R ² = CH ³ , R ³ = Cl ^{2 in} (3-chloropyrazinyl) propanedioic acid dimethyl ester
3] Preparation of 60.4 g of sodium hydride in 900 ml of DMF was dissolved in 450 ml of DMF with cooling and stirring under nitrogen atmosphere, and propanedioic acid dimethyl ester [compound (XV
In I), optionally in dropwise R ⁷ = CH3] 199.5g. After dropping, the mixture was stirred for 1 hour and then dissolved in 210 ml of DMF.
3-dichloropyrazine [in compound (VII), R ³ = C
l] 112.5 g was added and reacted at 100 ° C. for 2 hours. After cooling, the reaction solution was poured into cold water, neutralized, and extracted with ethyl acetate. The extract is a dilute aqueous solution of sodium hydrogen carbonate,
It was washed with water and saturated saline solution in that order, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to give an orange oil 210.3
g was obtained. Ethyl acetate and hexane were added for crystallization, and (3-
150.5 g of crystals of chloropyrazinyl) propanedioic acid dimethyl ester [in compound (VI), R ³ = Cl 2, R ⁷ = CH 3] were obtained. Melting point: 97 to 98 ° C. ¹ H-NMR (60 MHz, CDCl ₃ , δ ppm): 3.77 (6H, S), 5.19 (1H,
S), 8.23 (1H, d, J = 2.4Hz), 8.46 (1H, d, J = 2.4Hz)

Preparation of 3-chloropyrazineacetic acid methyl ester [in compound (IV), R ² = CH ³ , R ³ = Cl] (3-chloropyrazinyl) propanedioic acid dimethyl ester [in compound (VI), R ³ = Cl, R ⁷ = CH3]
30.0 g was dissolved in 400 ml of ethanol and heated to 50 ° C. 180 ml of sodium hydroxide aqueous solution (NaO
H: 0.54 mol) was added to carry out hydrolysis and decarboxylation reaction for 10 hours. After cooling, the solvent was distilled off under reduced pressure, and the residue was methanol [compound (XVII), R ² = CH3]-
Treated with hydrogen chloride. After standing overnight, the solvent was distilled off under reduced pressure, the residue was poured into cold water, neutralized, and then extracted with ethyl acetate. The extract was washed successively with water and saturated saline and then dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, the obtained residue was purified by silica gel chromatography, and a yellow oily substance of 3-chloropyrazine acetic acid methyl ester [in compound (IV), R ² = CH ³ , R ³ = Cl 2] was obtained. ．
3 g was obtained. ¹ H-NMR (60MHz, CDCl ₃ , δppm): 3.70 (3H, S), 3.99 (2H,
S), 8.27 (1H, d, J = 2.4Hz), 8.41 (1H, d, J = 2.4Hz)

Reference Production Example 2 Preparation of 2-chloro-3- (3-chlorophenoxy) pyrazine [compound (X), R ³ = Cl, Xn = 3-Cl, Z = O] 2.3 g of sodium hydride Of DMF (27 ml) was dissolved in 4 ml of DMF with cooling and stirring, and 3-chlorophenol [in compound (XV), Xn = 3-Cl 2, Z = O 2].
7.4 g was added dropwise. After dropping, stir for 1 hour and then DMF
6.5 g of 2,3-dichloropyrazine [compound (VII), R ³ = Cl] dissolved in 7 ml was added,
And reacted for 2 hours. After cooling, the reaction solution was poured into cold water, neutralized, and extracted with ethyl acetate. The extract was washed with a dilute aqueous solution of sodium hydrogen carbonate, water, and saturated saline in this order, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain a dark brown oily substance. Purified using silica gel chromatography, and in 2-chloro-3- (3-chlorophenoxy) pyrazine [compound (X), R ³ = Cl, Xn = Cl
, Z = O] was obtained as an oily product (6.7 g). ¹ H-NMR (60MHz, CDCl ₃ , δppm): 6.80 ~ 7.50 (4H, m), 7.8
8 (1H, d, J = 2.4Hz), 8.00 (1H, d, J = 2.4Hz)

Reference Production Example 3 [3- (3-chlorophenoxy) pyrazinyl] propane
Diioic acid diethyl ester [Compound (IX) Odor
, R⁷= C2H5, Xn = 3-Cl, Z = O] A suspension of 0.41 g of sodium hydride in 20 ml of DMF
Propandioy dissolved in 5 ml of DMF with cooling and stirring.
Cuccinic acid diethyl ester [in compound (XIII), R⁷
= C2H5] 1.86 g was added dropwise. Stir for 1 hour after dropping
After that, 2-chloro-3- (3- dissolved in 5 ml of DMF.
Chlorophenoxy) pyrazine [in the compound (X),
R³= Cl, Xn = Cl, Z = O] 1.40g and added at 105 ℃
Reacted for 3.5 hours. After cooling, pour the reaction mixture into cold water and
After the addition, the mixture was extracted with ethyl acetate. The extract is water, saturated food
After sequentially washing with brine, it was dried over anhydrous sodium sulfate. Melting
The medium was distilled off under reduced pressure to obtain a dark brown oily substance. silica gel
Purify using chromatography, [3- (3-
Lophenoxy) pyrazinyl] propanedioic acid diet
Chill ester [in compound (IX), R⁷= C2H5, Xn = 3
-Cl, Z = O] 0.6 g was obtained. ¹ H-NMR (60MHz, CDCl₃, δppm): 1.25 (6H, t, J = 7.2Hz),
4.21 (4H, q, J = 7.2Hz), 5.07 (1H, S), 6.80 ~ 7.25 (4H, m), 7.9
4 (1H, d, J = 2.4Hz), 8.15 (1H, d, J = 2.4Hz)

Reference Production Example 4 Production of [3- (4-methoxyphenoxy) pyrazinyl] propanedioic acid diethyl ester [in compound (IX), R ⁷ = C 2 H 5, Xn = 4-OCH 3, Z = O 2] Hydrogenation A suspension of 1.3 g of DMF in 15 ml of DMF was cooled and stirred to dissolve 4-methoxyphenol in 15 ml of DMF [in compound (XV), Xn = 4-OCH3, Z = O 2].
4.0 g was added dropwise. Then dissolved in 5 ml DMF,
(3-chloropyrazinyl) propanedioic acid diethyl ester [in compound (VI), R ³ = Cl, R ⁷ = C 2 H 5
] 4.1 g and 0.1 g of copper chloride were added and the mixture was added at 110 ° C. for 4
Reacted for hours. After cooling, the reaction solution was poured into cold water to neutralize,
It was extracted with ethyl acetate. The extract was washed with a dilute aqueous solution of sodium hydrogen carbonate, water, and saturated saline in this order, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain a dark brown oily substance. Purification using silica gel chromatography [the compound ^{(IX), R 7 = C2H5} , Xn = 4-OCH3, Z = O] [3- (4- methoxyphenoxy) pyrazinyl] propane dioic acid diethyl ester 1. 7
9 g was obtained. ¹ H-NMR (60MHz, CDCl ₃ , δ ppm): 1.24 (6H, t, J = 7.2H
z), 3.72 (3H, S), 4.22 (4H, q, J = 7.2Hz), 5.10 (1H, S), 6.97 (2
H, d, J = 9.6Hz), 6.99 (2H, d, J = 9.6Hz), 7.92 (1H, d, J = 2.4H
z), 8.09 (1H, d, J = 2.4Hz)

The compounds shown in Table 1 were synthesized by the operations according to the above Production Examples 1 to 3. Properties and NMR of these compounds
The data are shown in Table 4, Table 4.

[0048]

[Table 4]

The compounds in Table 2 were synthesized by the operations according to the above Production Examples 1 to 3. Properties and NMR of these compounds
The data are shown in Table 5, Table 5.

[0050]

[Table 5]

The compounds shown in Table 3 were synthesized by the operations according to the above Production Examples 1 to 3. Properties and NMR of these compounds
The data are shown in Table 6, Table 6.

[0052]

[Table 6]

[0053]   Formulation Example 1: Dust                                                   Parts by weight     Compound (I-33) 3     Cray 40     Talc 57 Are crushed and mixed, and then used by being dusted.

[0054]   Formulation Example 2: wettable powder                                                   Parts by weight     Compound (I-34) 50     Lignin sulfonate 5     Alkyl sulfonate 3     Diatomaceous earth 42 Is pulverized and mixed to obtain a wettable powder, which is diluted with water before use.

Formulation Example 3: Granules Part by weight Compound (I-58) 5 Bentonite 43 Cle 45 Lignin sulfonate 7 is evenly mixed, water is further added and kneaded, and the mixture is processed into granules by an extrusion granulator and dried. And make granules.

[0056]   Formulation Example 4: Emulsion                                                   Parts by weight     Compound (I-27) 20     Polyoxyethylene alkyl allyl ether 10     Polyoxyethylene sorbitan monolaurate 3     Xylene 67 Are uniformly mixed and dissolved to obtain an emulsion.

Test Example 1 Wheat leaf rust control effect test Wheat (cultivar: Norin 64) at the second leaf stage cultivated in a rectangular plastic pot (6.4 cm x 6.4 cm) was treated with water as in Formulation Example 2. A water remedy in a prescribed concentration (1000 m
g / l), and the mixture was sprayed at a ratio of 100 l / 10 a. After air-drying the sprayed leaves, spores of wheat leaf rust fungus were spray-inoculated and kept under high humidity conditions at 20 to 24 ° C. for 24 hours. After that, it was managed in the greenhouse. Ten to 14 days after the inoculation, the scab severity of wheat leaf rust was investigated, and the control value was calculated by the formula 1, and the results are shown in Table 7 in Table 7. (Survey Criteria) Risk Factor Rust Disease Rate Scale of Peterson et al. A) 0 No disease 0.5 Less than 1% 1 Less than 1% less than 5% 2 More than 5% less than 10% 3 10% or more and less than 30% 4 30% or more and less than 50% 5 50% or more A): Japan Plant Protection Association, Field test method for fungicides such as rice and wheat, page 111 (1990).

[0058]

[Formula 1] Control value (%) = (1-spraying area paste disease rate / non-spraying area paste disease rate) × 100

[0059]

[Table 7]

Test Example 2 Wheat Powdery Mildew Control Effect Test A second leaf stage wheat (cultivar: Norin No. 64) cultivated in a rectangular plastic pot (6.4 cm × 6.4 cm) was prepared as in Formulation Example 2. A wettable powder in water at a specified concentration (1000 m
(g / l) and air-dried sprayed leaves sprayed at a ratio of 100 l / 10 a, sprinkled with spores of wheat powdery mildew fungus, and inoculated thereafter in a greenhouse. On the 7th day after inoculation, the degree of control of wheat powdery mildew was investigated and the control value was calculated using formula 2.
The results are shown in Table 8 in Table 8. (Survey Criteria) Disease rate 0 Disease area rate 0 No disease rate 0.5 Disease area rate less than 1% 1 Disease area rate 1% to less than 5% 2 Disease area rate 5% to less than 10% 3 Disease area rate 10% or more and less than 30% 4 Disease area rate 30% or more and less than 50% 5 Disease area rate 50% or more

[0061]

[Formula 2] Control value (%) = (1-spray area paste disease rate / non-spray area paste disease rate) x 100

[0062]

[Table 8]

Test Example 3 Cucumber gray mold control effect test Cucumber in the cotyledon stage (cultivar: Sagamihanjiro) cultivated in a rectangular plastic pot (6.4 cm x 6.4 cm) was hydrated as in Formulation Example 2. Prepare the drug formulation with water to a specified concentration (1000 m
g / l) and air-dried the sprayed leaves sprayed at a ratio of 100 l / 10 a, then place 4 paper disks (diameter 8 mm) impregnated with spore fluid of Botrytis cinerea at 20 ° C. It was kept under high humidity conditions. On the 4th day after the inoculation, the disease degree of gray mold of cucumber was investigated and the average disease rate of 4 points was obtained. The control value was calculated by the formula 3, and the results are shown in Table 9 in Table 9. (Survey Criteria) Disease rate 0 Disease-free area 0.5 Disease-free area ratio less than 10% 1 Disease-free area ratio 10% to less than 20% 2 Disease-free area ratio 20% to 40% Less than 3 Disease area ratio 40% or more and less than 60% 4 Disease area ratio 60% or more and less than 80% 5 Disease area ratio 80% or more

[0064]

[Formula 3] Control value (%) = (1-average sickness of sprayed area ÷ average sickness of non-dispersed area) x 100

[0065]

[Table 9]

Test Example 4 Cucumber downy mildew control effect test A cotyledonary cucumber (cultivar: Sagamihanjiro) cultivated in a rectangular plastic pot (6.4 cm x 6.4 cm) was hydrated as in Formulation Example 2. Prepare the drug formulation with water to a specified concentration (1000 m
(g / l) was diluted and suspended, and sprayed leaves sprayed at a ratio of 100 l / 10 a were air-dried, and then a spore suspension of cucumber downy mildew was spray-inoculated and kept under high humidity conditions at 20 ° C. 7-10 after inoculation
On the day, the degree of cucumber downy mildew disease was investigated, the control value was calculated by the formula 4, and the results are shown in Table 10 in Table 10. (Survey Criteria) Disease rate 0 Disease-free area 0.5 Disease-free area ratio less than 10% 1 Disease-free area ratio 10% to less than 20% 2 Disease-free area ratio 20% to 40% Less than 3 Disease area ratio 40% or more and less than 60% 4 Disease area ratio 60% or more and less than 80% 5 Disease area ratio 80% or more

[0067]

[Formula 4] Control value (%) = (1-average sickness of sprayed area ÷ average sickness of non-dispersed area) x 100

[0068]

[Table 10]

Test Example 5 Tomato Late Blight Control Effect Test Tomatoes of 3 to 4 leaf stage (cultivar: Fukuju No. 2) cultivated in a rectangular plastic pot (6.4 cm X 6.4 cm) were treated with water as in Formulation Example 2. Prepare a hydrated form in water at the specified concentration (125 mg
/ l) and diluted and suspended, and sprayed at a ratio of 100 l / 10 a. After air-drying the sprayed leaves, a spore suspension of Phytophthora infestans was spray-inoculated and kept under high humidity conditions at 20 ° C. On the 5th to 7th day after the inoculation, the disease severity of tomato epidemic was investigated, the control value was calculated by the formula 5, and the results are shown in Table 11 of Table 11. (Survey Criteria) Disease rate 0 Disease-free area 1 Disease area less than 10% 2 Disease area ratio 10% to less than 30% 3 Disease area ratio 30% to less than 50% No. 4 Disease area ratio 50% or more and less than 70% 5 Disease area ratio 70% or more

[0070]

[Formula 5] Control value (%) = (1-average sickness of sprayed area ÷ average sickness of non-dispersed area) x 100

[0071]

[Table 11]

[0072]

INDUSTRIAL APPLICABILITY The α- (oxyimino) -3-phenoxypyrazineacetic acid derivative of the above formula (I) of the present invention can be used as an active ingredient of an agricultural and horticultural fungicide.

Claims (4)

[Claims] 1. An α- (oxyimino) of the formula (I) of formula 1
-3-Phenoxypyrazine acetic acid derivative. (In the formula, R ¹ is
It represents a hydrogen atom or a C1-C5 alkyl group. Z is an oxygen atom,
Represents a sulfur atom. Y is a C1-C5 alkoxy group, an amino group, or a mono- or di-substituted amino group substituted by a C1-C5 alkyl group. X is a hydrogen atom, a halogen atom, C1 to C7
Alkyl group, C1-C7 alkenyl group, C1-C7 alkoxy group, C1-C5 haloalkyl group, C1-C5 haloalkoxy group,
C1-C7 alkylcarbonyl group, C1-C7 alkoxycarbonyl group, C1-C6 cycloalkyl group, amino group, mono- or di-substituted amino group substituted by the same or different C1-C7 alkyl group, nitro group, cyano Group, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted benzyloxy group.
n represents an integer of 0 to 5. When n is 2 or more, X may be the same or different. ) [Chemical 1] 2. A 3-halogeno-α-of the formula (II) of the formula 2
(Oxyimino) pyrazine acetic acid derivative. (In the formula, R ¹ is
It represents a hydrogen atom or a C1-C5 alkyl group. R ² represents a C1~C5 alkyl group. R ³ represents a halogen atom. [Chemical 2] 3. A 3-phenoxypyrazine acetic acid derivative of the formula (III) represented by Chemical formula 3. (In the formula, R ² represents a C1 to C5 alkyl group. Z represents an oxygen atom or a sulfur atom. X represents a hydrogen atom, a halogen atom, a C1 to C7 alkyl group, a C1 to C7 alkenyl group,
C1-C7 alkoxy group, C1-C5 haloalkyl group, C1-C5 haloalkoxy group, C1-C7 alkylcarbonyl group, C1-C7
Alkoxycarbonyl group, C1 to C6 cycloalkyl group, amino group, mono- or di-substituted amino group substituted by C1 to C7 alkyl groups which may be the same or different, nitro group, cyano group, optionally substituted phenyl group Represents an optionally substituted phenoxy group and an optionally substituted benzyloxy group. n represents an integer of 0 to 5. n is 2
In the above cases, X may be the same or different. ) [Chemical 3] 4. An α- (oxyimino) of the formula (I) of the chemical formula 4.
A fungicide for agricultural and horticultural use containing a 3-phenoxypyrazine acetic acid derivative as an active ingredient. (In the formula, R ¹ is a hydrogen atom, C 1
~ Represents a C5 alkyl group. Z represents an oxygen atom or a sulfur atom. Y is a C1-C5 alkoxy group, amino group or C1-C5
A mono- or di-substituted amino group substituted with an alkyl group. X is a hydrogen atom, a halogen atom, a C1-C7 alkyl group,
C1-C7 alkenyl group, C1-C7 alkoxy group, C1-C5 haloalkyl group, C1-C5 haloalkoxy group, C1-C7 alkylcarbonyl group, C1-C7 alkoxycarbonyl group, C1-C6
Cycloalkyl group, amino group, mono- or di-substituted amino group substituted by C1 to C7 alkyl group which may be the same or different, nitro group, cyano group, optionally substituted phenyl group, optionally substituted It represents a phenoxy group or an optionally substituted benzyloxy group. n represents an integer of 0 to 5. When n is 2 or more, X may be the same or different. ) [Chemical 4]