JP2009149598A - Azine derivative, and agricultural and horticultural fungicide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an agricultural and horticultural fungicide containing a new azine derivative and its salt, which can be produced industrially advantageously and become the agricultural and horticultural fungicide having a sure effect and can be used safely. <P>SOLUTION: This azine derivative is expressed by formula (I) [wherein, X is an alkyl or the like; R<SP>1</SP>, R<SP>2</SP>are each an alkyl, phenyl, a heterocyclic group or the like; R<SP>3</SP>, R<SP>4</SP>are each an alkyl or the like; R<SP>5</SP>is H or the like; Y and Z are each O or the like; and (n) is an integer] or its salt. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a novel azine derivative and a salt thereof, and an agricultural and horticultural fungicide containing at least one of these compounds as an active ingredient.

  In the cultivation of agricultural and horticultural crops, many control agents are used against crop diseases, but their control efficacy is insufficient, their use is restricted by the emergence of drug-resistant pathogens, and From the viewpoints of causing phytotoxicity and pollution to plants, or toxicity to human and livestock fish and impact on the environment, there are many things that are not necessarily satisfactory control agents. Accordingly, there is a strong demand for the emergence of such a drug that can be safely used with few defects.

  In relation to the present invention, Patent Document 1 discloses an iminooxymethylpyridine compound (A) having a chemical structure similar to that of the compound of the present invention shown below and an agricultural and horticultural fungicide containing it as an active ingredient. It is disclosed.

(In the formula, X ′ represents an oxygen atom or a direct bond, and Y ′ and Z ′ are each independently one or two or more selected from the group consisting of a phenyl group, an oxygen atom, a sulfur atom or a nitrogen atom. A heterocycle containing an atom is shown.)
JP 2007-137852 A

  The present invention has been made in view of such circumstances, a novel azine derivative and a salt thereof, which can be produced industrially advantageously and can be used as an agricultural and horticultural fungicide that is reliable and can be used safely. An object of the present invention is to provide an agricultural and horticultural fungicide containing at least one of these compounds as an active ingredient.

  In order to solve the above problems, the present invention first provides an azine derivative represented by the following formula (I) or a salt thereof.

[Wherein, X represents a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C1-20 haloalkyl group, or a C1-20 haloalkoxy group,
R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C2-20 alkenyl group, a C2-20 alkynyl group, a C1-20 haloalkyl group, a C2-20 haloalkenyl group, a C2— 20 haloalkynyl group, C1-20 alkoxy group, C2-20 alkenyloxy group, C2-20 alkynyloxy group, C1-20 haloalkoxy group, C2-20 haloalkenyloxy group, C2-20 haloalkynyloxy group, unsubstituted Alternatively, it represents a C3-10 cycloalkyl group having a substituent, a phenyl group having no substituent or a substituent, a cyano group, a nitro group, a C1-20 alkylthio group, or a heterocyclic group having no substituent or a substituent. However, R ¹ and R ² are not both hydrogen atoms. R ¹ and R ² may be bonded together to form a ring.
R ³ is a hydrogen atom, a C1-20 alkyl group, a C2-20 alkenyl group, a C2-20 alkynyl group, a C1-20 haloalkyl group, a C2-20 haloalkenyl group, a C2-20 haloalkynyl group, or unsubstituted or substituted. Represents a C3-10 cycloalkyl group having a group,
R ⁴ is a hydrogen atom, C1-20 alkyl group, C2-20 alkenyl group, C2-20 alkynyl group, C1-20 haloalkyl group, C2-20 haloalkenyl group, C2-20 haloalkynyl group, cyano group, nitro group. Or represents a C1-20 alkylthio group,
R ⁵ represents a hydrogen atom, a C1-20 alkyl group, an acyl group, a formyl group, a C1-20 alkoxy C1-20 alkyl group, a C1-20 alkylsulfonyl group, or an unsubstituted or substituted phenylsulfonyl group,
Y represents an oxygen atom or a sulfur atom,
Z represents a single bond, an oxygen atom, a sulfur atom, or a group represented by NR ⁶ (R ⁶ represents a hydrogen atom or a C1-30 alkyl group);
n represents an integer of 0 to 4. ]

  The present invention secondly provides a compound represented by the following formula (II).

[Wherein, X represents a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C1-20 haloalkyl group, or a C1-20 haloalkoxy group,
R ³ is a hydrogen atom, a C1-20 alkyl group, a C2-20 alkenyl group, a C2-20 alkynyl group, a C1-20 haloalkyl group, a C2-20 haloalkenyl group, a C2-20 haloalkynyl group, or unsubstituted or substituted. Represents a C3-10 cycloalkyl group having a group,
R ⁴ is a hydrogen atom, C1-20 alkyl group, C2-20 alkenyl group, C2-20 alkynyl group, C1-20 haloalkyl group, C2-20 haloalkenyl group, C2-20 haloalkynyl group, cyano group, nitro group. Or a C1-20 alkylthio group,
R ⁵ represents a hydrogen atom, a C1-20 alkyl group, an acyl group, a formyl group, a C1-20 alkoxy C1-20 alkyl group, a C1-20 alkylsulfonyl group, or an unsubstituted or substituted phenylsulfonyl group.
Y represents an oxygen atom or a sulfur atom,
Z represents a single bond, an oxygen atom, a sulfur atom, or a group represented by NR ⁶ (R ⁶ represents a hydrogen atom or a C1-30 alkyl group);
n represents an integer of 0 to 4. ]
Thirdly, the present invention provides an agricultural and horticultural fungicide containing as an active ingredient at least one of the azine derivative represented by the formula (I) or a salt thereof.

The azine derivatives and salts thereof of the present invention are novel compounds, have excellent bactericidal activity, and are useful as active ingredients for agricultural and horticultural fungicides.
The agricultural and horticultural fungicide of the present invention is an agent that has an excellent control effect, does not cause phytotoxicity or contamination on the plant body, and has little toxicity to human fish and environmental impact.

Hereinafter, the present invention will be described in detail.
The present invention is an agricultural and horticultural fungicide containing an azine derivative represented by the formula (I) or a salt thereof, and at least one of these compounds as an active ingredient.

1) An azine derivative represented by formula (I) or a salt thereof The first aspect of the present invention is an azine derivative represented by formula (1) or a salt thereof.
In formula (1), X represents a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C1-20 haloalkyl group, or a C1-20 haloalkoxy group, and is a halogen atom or a C1-20 alkyl group. Is preferred.

Examples of the halogen atom for X include a fluorine atom, a chlorine atom, and a bromine atom.
As C1-20 alkyl group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, n -Hexyl group, n-heptyl group, n-octyl group, n-decyl group and the like.

  As the C1-20 alkoxy group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, An n-hexyloxy group etc. are mentioned.

  C1-20 haloalkyl groups include fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, 2,2,2 -A trifluoroethyl group, a 2,2,2-trichloroethyl group, a pentafluoroethyl group, etc. are mentioned.

  As C1-20 haloalkoxy group, chloromethoxy group, dichloromethoxy group, trichloromethoxy group, trifluoromethoxy group, 1-fluoroethoxy group, 1,1-difluoroethoxy group, 2,2,2-trifluoroethoxy group And pentafluoroethoxy group.

R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C2-20 alkenyl group, a C2-20 alkynyl group, a C1-20 haloalkyl group, a C2-20 haloalkenyl group, a C2— 20 haloalkynyl group, C1-20 alkoxy group, C2-20 alkenyloxy group, C2-20 alkynyloxy group, C1-20 haloalkoxy group, C2-20 haloalkenyloxy group, C2-20 haloalkynyloxy group, unsubstituted Alternatively, it represents a C3-10 cycloalkyl group having a substituent, a phenyl group having no substituent or a substituent, a cyano group, a nitro group, a C1-20 alkylthio group, or a heterocyclic group having no substituent or a substituent. However, R ¹ and R ² are not both hydrogen atoms.

Specific examples of the halogen atom, C1-20 alkyl group, C1-20 haloalkyl group, C1-20 alkoxy group, C1-20 haloalkoxy group of R ¹ and R ² include the halogen atom of C, C1-20 The same thing as what was listed as a specific example of 20 alkyl group, C1-20 haloalkyl group, C1-20 alkoxy group, C1-20 haloalkoxy group is mentioned.

Examples of the C2-20 alkenyl group for R ¹ and R ² include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, and 1-methyl-2-propenyl. Group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1 -Hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like can be mentioned.

  C2-20 alkynyl groups include ethynyl, 1-propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-methyl-3-butynyl Group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-2-butynyl group, 2-methyl-3-pentynyl group, 1-hexynyl group, 1,1-dimethyl -2-butynyl group and the like.

  Examples of the C2-20 haloalkenyl group include 3-chloro-2-propenyl group, 4-chloro-2-butenyl group, 4,4-dichloro-3-butenyl group, 4,4-difluoro-3-butenyl group, 3 , 3-dichloro-2-propenyl group and the like.

  Examples of the C2-20 haloalkynyl group include 3-chloro-1-propynyl group, 3-chloro-1-butynyl group, 3-bromo-1-butynyl group, 3-bromo-2-propynyl group, and 3-iodo-2. -A propynyl group etc. are mentioned.

  Examples of the C2-20 alkenyloxy group include an allyloxy group, a 2-propenyloxy group, a 2-butenyloxy group, and a 2-methyl-3-propenyloxy group.

  Examples of the C2-20 alkynyloxy group include a 2-propynyloxy group, a 2-butynyloxy group, and a 1-methyl-2-propynyloxy group.

  Examples of the C2-20 haloalkenyloxy group include 3-chloro-2-propenyloxy group, 3,3-dichloro-2-propenyloxy group, 4-chloro-2-butenyloxy group, and 4,4-dichloro-3-butenyloxy. Group, 4,4-difluoro-3-butenyloxy group and the like.

  Examples of the C2-20 haloalkynyloxy group include 2-chloroethynyloxy group, 3-chloro-2-propynyloxy group, and 3-fluoro-2-propynyloxy group.

  Examples of the C3-10 cycloalkyl group of an unsubstituted or substituted C3-10 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

  Examples of the substituent for the C3-10 cycloalkyl group include a C1-6 alkyl group such as a methyl group and an ethyl group; a C1-6 alkoxy group such as a methoxy group and an ethoxy group; a nitro group; a cyano group;

  Examples of the C1-20 alkylthio group include methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group and the like.

  The heterocyclic group of the unsubstituted or substituted heterocyclic group is not particularly limited as long as it has a hetero atom in the ring, but is saturated or contains 1 to 4 N, O, or S atoms. Unsaturated 5-6 membered heterocyclic groups are preferred.

  Specific examples of the heterocyclic group include 2-furyl group, 3-furyl group, oxazol-2-yl group, oxazol-4-yl group, oxazol-5-yl group, isoxazol-3-yl group, and isoxazole. -4-yl group, isoxazol-5-yl group, 1,2,4-oxadiazol-3-yl group, 1,2,4-oxadiazol-5-yl group, 1,3,4- Oxadiazol-2-yl group, thiazol-2-yl group, thiazol-4-yl group, thiazol-5-yl group, isothiazol-3-yl group, isothiazol-4-yl group, isothiazol-5 -Yl group, 1,2,4-thiadiazol-3-yl group, 1,2,4-thiadiazol-5-yl group, 1,3,4-thiadiazol-2-yl group, imidazol-2-yl Group, imidazole-4 Yl group, 2-thienyl group, 3-thienyl group, pyrazol-3-yl group, pyrazol-4-yl group, 1,2,4-triazol-3-yl group, tetrazol-5-yl group, 4,5 -Dihydroisoxazol-3-yl group, 4,5-dihydroisoxazol-4-yl group, 4,5-dihydroisoxazol-5-yl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group Etc.

Examples of the substituent for the phenyl group and heterocyclic group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom;
Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, 2-cyclopropylethyl group, 3,3-dimethylpropyl group A C1-6 alkyl group such as
A C3-7 cycloalkyl group such as a cyclopropyl group;

Vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, A C2-10 alkenyl group such as a 3-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 4-hexenyl group;
Ethynyl group, 1-propynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 1-methyl-2-propynyl group, 2-methyl-3-butynyl group, 1-pentynyl group, 3-pentynyl group, 2 -C2 such as cyclopropylethynyl group, 2-t-butylethynyl group, 1-methyl-2-butynyl group, 2-methyl-3-pentynyl group, 1-hexynyl group, 1,1-dimethyl-2-butynyl group -10 alkynyl groups;

C1-6 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group;
Fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 1-fluoroethyl group, 1,1-difluoroethyl group A C1-6 haloalkyl group such as 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, pentafluoroethyl group;
A C1-6 haloalkoxy group such as a chloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group;
A C2-7 alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group;

C1-6 alkylthio groups such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group;
A C1-6 alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an n-butylsulfonyl group;
A C1-6 alkylsulfonyloxy group such as a methylsulfonyloxy group, an ethylsulfonyloxy group, an n-propylsulfonyloxy group, a t-butylsulfonyloxy group;
A cyano group; an unsubstituted or substituted amino group such as a dimethylamino group;
A phenyl group, an unsubstituted or substituted phenyl group such as 4-fluorophenyl;
Examples thereof include unsubstituted or substituted heterocyclic groups such as pyrrolidin-1-yl group, piperidin-1-yl group, and 3-fluoro-azetidin-1-yl group.

A plurality of these substituents may be the same or different and may be substituted at any position, and two adjacent substituents are bonded together to form a 2,3-methylenedioxy group, 2 A ring such as a 3-difluoromethylenedioxy group may be formed.
Among these, as a substituent of the said phenyl group and heterocyclic group, a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, a C1-6 haloalkyl group, or a C1-6 haloalkoxy group is preferable.

R ¹ and R ² may be bonded together to form a ring. Examples of such rings include monocyclic rings such as cyclopropane ring, cyclopentane ring and cyclohexane ring; condensed rings such as indane and tetrahydronaphthalene. These rings may have a substituent.

Among ^these, R 1, ^{R 2,} or a C1~20 alkyl or C1~20 haloalkyl ^group, or a R 1, ^{R 2} are combined to form a ring together, it is one It is preferably a C1-20 alkyl group, and the other is an unsubstituted or substituted phenyl group or an unsubstituted or substituted heterocyclic group.

R ³ is a hydrogen atom, C1-20 alkyl group, C2-20 alkenyl group, C2-20 alkynyl group, C1-20 haloalkyl group, C2-20 haloalkenyl group, C2-20 haloalkynyl group, unsubstituted or substituted Represents a C3-10 cycloalkyl group having

Specific examples of the C1-20 alkyl group and C1-20 haloalkyl group of R ³ include the same as those listed as specific examples of the C1-20 alkyl group and C1-20 haloalkyl group of X. .

Said ^{R 3,} C2-20 alkenyl, C2-20 alkynyl, C2-20 haloalkenyl group, C2-20 haloalkynyl group, specific examples of C3~10 cycloalkyl group having unsubstituted or substituted group, Specific examples of C 2-20 alkenyl group, C 2-20 alkynyl group, C 2-20 haloalkenyl group, C 2-20 haloalkynyl group, unsubstituted or substituted C 3-10 cycloalkyl group of R ¹ and R ² Are similar to those listed.

R ⁴ is a hydrogen atom, C1-20 alkyl group, C2-20 alkenyl group, C2-20 alkynyl group, C1-20 haloalkyl group, C2-20 haloalkenyl group, C2-20 haloalkynyl group, cyano group, nitro group. Represents a C1-20 alkylthio group, preferably a C1-20 alkyl group.

Specific examples of R ⁴ , C1-20 alkyl group, C2-20 alkenyl group, C2-20 alkynyl group, C1-20 haloalkyl group, C2-20 haloalkenyl group, C2-20 haloalkynyl group, C1-20 alkylthio group Specific examples of C 2-20 alkenyl group, C 2-20 alkynyl group, C 1-20 haloalkyl group, C 2-20 haloalkenyl group, C 2-20 haloalkynyl group, C 1-20 alkylthio group of the above R ¹ and R ² Examples are the same as those listed.

R ⁵ represents a hydrogen atom, a C1-20 alkyl group, an acyl group, a formyl group, a C1-20 alkoxy C1-20 alkyl group, a C1-20 alkylsulfonyl group, an unsubstituted or substituted phenylsulfonyl group, hydrogen An atom is preferred.

Specific examples of the C1-20 alkyl group of R ⁵ include the same as those listed as specific examples of the C1-20 alkyl group of X.

As the acyl group, an acetyl group, a propionyl group, a pivaloyl group, a trifluoroacetyl group, a trichloroacetyl group, a benzoyl group, a 4-methylbenzoyl group, a 2-chlorobenzoyl group, or the like: —C (═O) R ^{7 (R 7} are, C1-20 alkyl group, C1-20 haloalkyl group, a phenyl group or an unsubstituted or substituted group.) can be mentioned.

Examples of the C1-20 alkoxy C1-20 alkyl group of R ⁵ include methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, 2-ethoxy. Examples include an ethyl group, a 1-methoxy-n-propyl group, a 2-methoxy-n-propyl group, and a 3-methoxy-n-propyl group.

Examples of the C1-20 alkylsulfonyl group for R ⁵ include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an i-propylsulfonyl group, and the like.

Examples of the unsubstituted or substituted phenylsulfonyl group for R ⁵ include a phenylsulfonyl group, a 4-methylphenylsulfonyl group, a 2-chlorophenylsulfonyl group, and a 2,4-dimethylphenylsulfonyl group.
Y represents an oxygen atom or a sulfur atom.

Z represents a single bond, an oxygen atom, a sulfur atom, or a group represented by NR ⁶ .
R ⁶ represents a hydrogen atom or a C1-30 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, or a t-butyl group.
n represents an integer of 0 to 4.

  In the present invention, among these, the azine derivative represented by the formula (I) is represented by the following formula (Ia):

(Wherein R ^{1 to} R ⁵ , X, Y, Z and n represent the same meanings as described above) are preferred, and the compound represented by formula (Ib)

(Wherein R ^{1 to} R ⁵ , X, Z and n represent the same meaning as described above) are more preferable, and the compound represented by formula (Ic)

(Wherein R ^{2 to} R ⁵ , X, Z and n represent the same meaning as described above, and R ¹¹ represents a C 1-20 alkyl group or an unsubstituted or substituted phenyl group). Particularly preferred is a compound.
Specific examples of the C ¹¹ -C 20 alkyl group of R ¹¹ , unsubstituted or substituted phenyl group include the C ¹ -C 20 alkyl group of X, R ¹ and R ² , an unsubstituted or substituted phenyl group as The thing similar to what was illustrated is mentioned.

  In the azine derivative represented by the above formula (I) of the present invention, there may exist cis-trans geometric isomers based on a carbon-nitrogen double bond. included.

(Production method)
The compound of the present invention can be produced, for example, as follows.

  That is, the desired compound represented by the formula (I) can be obtained by condensing the hydrazine compound represented by the formula (1) and the compound represented by the formula (II).

  The amount of the ketone compound represented by formula (2) is usually 0.5 to 2 times mol, preferably 0.7 to 1.5 times mol, of the hydrazine compound represented by formula (1). is there.

This reaction is preferably performed in the presence of an acid catalyst or a base catalyst, and more preferably in the presence of an acid catalyst. Examples of the acid catalyst to be used include benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, pyridinium p-toluenesulfonate, hydrochloric acid, sulfuric acid and the like. Examples of the base catalyst include pyridine, triethylamine, potassium hydroxide and the like.
Further, a dehydrating agent such as anhydrous sodium sulfate may be added to the reaction system.
The usage-amount of a catalyst is 0.0001-1 times mole normally with respect to the hydrazine compound represented by Formula (1).

This reaction can be carried out in a suitable solvent. The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran; aromatic hydrocarbon solvents such as toluene, benzene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane Solvent; Halogenated hydrocarbon solvent such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane; Amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; Examples thereof include nitrile solvents such as acetonitrile and benzonitrile; alcohol solvents such as methanol, ethanol and n-propanol; and mixed solvents composed of two or more of these.
Although the usage-amount of a solvent is not specifically limited, It is 1-100 ml normally with respect to 1g of hydrazine compounds represented by Formula (1).

  The reaction temperature is a temperature range from room temperature to the boiling point of the solvent used. The reaction time is usually several minutes to several tens of hours.

  The hydrazine compound represented by the formula (1) is, for example, a hydrazine represented by the formula (3) (or hydrazine monohydrate), as shown below, in the ketone compound represented by the formula (2). Can be obtained by reacting.

  Formula (II), which is an intermediate for producing the derivative represented by Formula (I)

(In the formula, X, n, R ^{3 to} R ⁵ , Y and Z have the same meaning as described above.)
A compound represented by the formula (hereinafter sometimes referred to as “compound (II)”) is a novel compound.
As the compound (II), the following formula (II-1)

(Wherein, X, n, R ^{3 to} R ⁵ , Y and Z have the same meaning as described above) are preferred, and the following formula (II-2)

(In the formula, X, n, R ^{3 to} R ⁵ , and Z represent the same meaning as described above.)
The compound represented by these is more preferable.
Compound (II) can be produced, for example, as follows.

(In the formula, X, n, R ^{3 to} R ⁵ , Y and Z have the same meaning as described above.)
That is, first, an oxyamine compound represented by the formula (5) (hereinafter referred to as “the compound (4)”) in the presence of a base is added to the fluoride compound represented by the formula (4) (hereinafter sometimes referred to as “compound (4)”). A compound represented by the formula (6) (hereinafter, sometimes referred to as “compound (6)”) is obtained by reacting the compound (sometimes referred to as “compound (5)”). Next, the compound (6) is reacted with an amide compound represented by the formula (7) (hereinafter sometimes referred to as “compound (7)”) and a base to obtain the desired ketone compound (II). Obtainable.

  In the reaction for obtaining the compound (6), the amount of the compound (5) to be used is generally 0.8 to 5 times mol, preferably 1 to 3 times mol for 1 mol of the compound (4).

Examples of the base used for the reaction for obtaining the compound (6) include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide. Metal alkoxides such as potassium ethoxide and potassium t-butoxide; metal hydrides such as sodium hydride, potassium hydride and calcium hydride; triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo [5.4.0] And organic bases such as undec-7-ene (DBU) and 1,4-diazabicyclo [2.2.2] octane.
The usage-amount of a base is 1-20 times mole normally with respect to 1 mol of compounds (4).

This reaction can be carried out in a suitable organic solvent. The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, sulfur-containing solvents such as dimethyl sulfoxide and diethyl sulfoxide; ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran; aromatic hydrocarbon solvents such as toluene, benzene and xylene; n-pentane and n- Aliphatic hydrocarbon solvents such as hexane and n-heptane; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; nitrile solvents such as acetonitrile and benzonitrile; And a mixed solvent composed of two or more of these; and the like.
Although the usage-amount of a solvent is not specifically limited, It is 1-100 ml normally with respect to 1 g of compounds (4).

The reaction for obtaining the compound (6) proceeds smoothly in a temperature range from 0 ° C. to the boiling point of the solvent used.
After completion of the reaction, the desired product can be obtained by subjecting it to normal post-treatment operations in organic synthetic chemistry, and if desired, separation and purification means such as column chromatography.

  Specific examples of the compound (7) used for the reaction for obtaining the compound (II) include N, N-dimethylacetamide, N, N-dimethylpropionamide and the like.

  The amount of compound (7) to be used is generally 0.8 to 5 times mol, preferably 1 to 3 times mol, per 1 mol of compound (6).

Examples of the base used in the reaction for obtaining the compound (II) include organic lithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium and lithium diisopropylamide; alkali metals such as metallic sodium and metallic potassium; sodium hydride Metal hydrides such as potassium hydride and calcium hydride;
The usage-amount of a base is 1-20 times mole normally with respect to 1 mol of compounds (6).

  This reaction can be carried out in a suitable organic solvent. The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran; aromatic hydrocarbon solvents such as toluene, benzene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane Solvent; and the like.

The reaction to obtain compound (II) proceeds smoothly in a temperature range from −100 ° C. to the boiling point of the solvent used.
After completion of the reaction, the desired product can be obtained by subjecting it to normal post-treatment operations in organic synthetic chemistry, and if desired, separation and purification means such as column chromatography.

In addition, among the compounds (II) obtained as described above, the compound (II-a) in which Y and Z are oxygen atoms is obtained by converting the substituent R ³ to another substituent R by a known transesterification method. It can be converted to ³ '(the following reaction formula).

(In the formula, X, n and R ^{3 to} R ⁵ represent the same meaning as described above.)
The salt of the compound of the present invention is not particularly limited as long as it is an agricultural and horticulturally acceptable salt. For example, salts of inorganic acids such as hydrochloric acid and sulfuric acid; salts of organic acids such as acetic acid and lactic acid; These salts can be produced by a conventionally known method using an acid corresponding to the azine derivative represented by the formula (I).

In any reaction, after completion of the reaction, the desired product can be isolated by purifying by a conventional post-treatment operation and, if desired, known and conventional purification means such as distillation, recrystallization and column chromatography.
The structure of the target product can be identified and confirmed by known analytical means such as IR spectrum, NMR spectrum, mass spectrum, and elemental analysis.

  The compounds of the present invention (azine derivatives represented by the formula (I) or salts thereof) are used in a wide variety of filamentous fungi, such as algae (Omycetes), Ascomycetes, incomplete fungi ( It has an excellent bactericidal power against bacteria belonging to Deuteromycetes) and Basidiomycetes. Therefore, as described later, the compound of the present invention is useful as an active ingredient of agricultural and horticultural fungicides.

2) Agricultural and horticultural fungicide The second aspect of the present invention is an agricultural and horticultural fungicide (hereinafter referred to as "this") containing at least one of the azine derivative represented by the formula (I) of the present invention or a salt thereof as an active ingredient. Inventive fungicide ").

  The fungicide of the present invention contains the compound of the present invention as an active ingredient, and a wide variety of filamentous fungi such as algae (Omycetes), Ascomycetes, Deuteromycetes, basidiomycetes It has excellent bactericidal power against bacteria belonging to (Basidiomycetes).

  The fungicide of the present invention can be used by seed treatment, foliage spraying, soil application, water application, etc., for controlling various diseases that occur during cultivation of agricultural and horticultural crops including flower buds, turf, and grass.

For example,
Sugar beet brown spot (Cercospora beticola)
Peanut brown spot (Mycosphaerella arachidis)
Black astringent disease (Mycosphaerella berkeleyi)
Cucumber powdery mildew (Sphaerotheca furiginea)
Vine Blight (Mycosphaella melonis)
Sclerotinia sclerotiorum
Gray mold disease (Botrytis cinerea)
Black star disease (Cladosporium cucumerinum)
Brown spot disease (Corynespora casiccola)
Seedling Blight (Phythium debaryanam, Rhizoctonia solani Kuhn)
Spotted bacterial disease (Pseudomonas syringae pv. Lecrymans)
Tomato gray mold (Botrytis cinerea)
Leaf mold (Cladosporium fulvum)
Eggplant gray mold (Botrytis cinerea)
Black blight (Corynespora melogenae)
Powdery mildew (Erysiphe cichoracerarum)
Susmolder disease (Mycovellosi natrassii)
Strawberry Gray mold disease (Botrytis cinerea)
Powdery mildew (Sohaerotheca humuli)
Anthracnose (Colletotrichum acutatum, Colletotrichum fragariae)
Onion gray rot (Botrytis allii)
Gray mold disease (Botrytis cinerea)
White spotted leaf blight (Botrytis squamosa)
Cabbage root-knot disease (Plasmodiophora brassicae)
Soft rot (Erwinia carotovora)
Kidney bean sclerotia (Sclerotinia sclerotiorum)
Gray mold disease (Botrytis cinerea)
Apple powdery mildew (Podosphaera leukotrica)
Venturia inaequalis
Moniria disease
Rot rot (Valsa mali)
Spotted leaf fall (Alternaria mary)
Red Star Disease (Gymnosporium yamadae)
Ring-shaped disease (Botryosphaeria berengeriana)
Anthracnose (Colletotrichum gloeosprioides)
Brown spot disease (Diplocarpon mary)
Oyster powdery mildew (Phyllactinia kakicola)
Anthracnose (Gloeosporium kaki)
Spotted leaf disease (Cercospora kaki)

Peach out ash scab (Monilinia fracticola)
Grapes Gray mold (Botrytis cinerea)
Powdery mildew (Uncinula necator)
Late rot (Glomerella cingulata)
Pear black scab (Venturia nashicola)
Red Star Disease (Gymnosporium asiaticum)
Black spot disease (Alternaria kikuchiana)
Cha ring spot disease (Pestaloti theae)
Anthracnose (Colletotrichum theae-sinensis)
Citrus common scab (Elsinoe fawceti)
Blue mold disease (Penicillium italicum)
Green mold (Penicillium digitatum)
Gray mold disease (Botrytis cinerea)
Black spot disease (Diaporthe citri)
Sickness disease (Xanthomonas campestris pv. Citri)
Wheat powdery mildew (Erysiphe graminis f. Sp. Tritici)
Red mold disease (Gibberella zeae)
Red rust (Puccinia recondita)
Brown snow rot (Pythium iwayamai)
Scarlet Snow Rot (Monographella nivalis)
Eye disease (Pseudocercosporella herpotriochoides)
Leaf blight (Septoria tritici)
Blight disease (Leptosphaeria nodorum)
Typhula incarnata (Typhula incarnata)
Snow rot large mycobacterial disease (Myriosclerotinia borealis)
Blight (Gaeumanomyces graminis)

Barley leaf spot (Pyrenophora graminea)
Rhynchosporium secalis
Bare Scab (Ustilago tritici, U. nuda)
Rice blast disease (Pyricularia oryzae)
Rhizoctonia solani
Idiot Seedling (Gibberella fujikuroi)
Sesame leaf blight (Cochliobolus niyabeanus)
Tobacco sclerotia (Sclerotinia sclerotiorum)
Powdery mildew (Erysiphe cichoracerarum)
Tulip Gray mold disease (Botrytis cinerea)
Bentgrass (Sclerotinia borealis)
Orchardgrass powdery mildew (Erysiphe graminis)
Soybean Purpura (Cercospora kikuchii)
Potato tomato plague (Phytophthora infestans)
Cucumber downy mildew (Pseudoperonospora cubensis)
Grape downy mildew (Plasmopara viticola)
It can be used for the control of etc.

  In recent years, resistance to benzimidazole fungicides, dicarboximide fungicides, and the like has developed in various pathogenic bacteria, resulting in insufficient efficacy of these drugs, and drugs effective against resistant bacteria are desired. The bactericidal agent of the present invention has an excellent bactericidal effect not only for pathogenic bacteria sensitive to these drugs but also for resistant bacteria.

  For example, gray mold fungus (Botrytis cinerea), sugar beet brown fungus (Cercospora beticola), Venturia inaequalis, Venturia ina ol (Venturia inaequilis), Venturia in ol The fungicides of the present invention are also effective against).

  Furthermore, the fungicides of the present invention are also effective against gray mold fungi (Botrytis cinerea) that are resistant to dicarboximide fungicides (for example, vinclozoline, procymidone, iprodione).

  More preferable diseases to be applied include brown spot of sugar beet, powdery mildew of wheat, rice blast, rice black spot, gray mold of cucumber, brown spot of peanut and the like.

The fungicide of the present invention is a highly safe drug with little phytotoxicity, low toxicity to fish and warm-blooded animals.
When the fungicide of the present invention is actually applied, even if the compound of the present invention is used in a pure form without adding other components, a form that can be taken by a general pesticide for the purpose of use as an agrochemical, , Wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, granular wettable powders and the like.

  Additives and carriers that can be added to the agrochemical formulation include vegetable powders such as soybean flour and wheat flour, diatomaceous earth, apatite, gypsum, talc, bentonite, and pyrophyllite for solid dosage forms. Organic and inorganic compounds such as mineral fine powders such as clay, sodium benzoate, urea, and sodium sulfate are used.

  For liquid dosage forms, kerosene, xylene and petroleum aromatic hydrocarbons, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, Water or the like can be used as a solvent.

Furthermore, in order to take a uniform and stable form in these preparations, a surfactant may be added as necessary.
The surfactant that can be added is not particularly limited. For example, alkylphenyl ether added with polyoxyethylene, alkyl ether added with polyoxyethylene, higher fatty acid ester added with polyoxyethylene, polyoxyethylene Sorbitan higher fatty acid ester added with polyoxyethylene, nonionic surfactant such as tristyryl phenyl ether added with polyoxyethylene, sulfate ester salt of alkylphenyl ether added with polyoxyethylene, alkylbenzene sulfonate, sulfuric acid of higher alcohol Examples include ester salts, alkyl naphthalene sulfonates, polycarboxylates, lignin sulfonates, formaldehyde condensates of alkyl naphthalene sulfonates, and isobutylene-maleic anhydride copolymers.

  The wettable powder, emulsion, flowable powder, aqueous solvent, and granular wettable powder thus obtained are diluted with water to a predetermined concentration to obtain a powder, granule as a solution, suspension or emulsion. Is used as it is by spraying on plants.

  The amount of the active ingredient in the fungicide of the present invention is usually preferably 0.01 to 90% by weight, more preferably 0.05 to 85% by weight, based on the entire composition (formulation).

  The application amount of the fungicide of the present invention varies depending on weather conditions, formulation form, application magnetism, application method, application place, disease to be controlled, target crop, etc., but usually 1 to 1,000 g as an active ingredient compound amount per hectare. , Preferably 10 to 100 g.

  When a wettable powder, emulsion, suspension, aqueous solvent, granular wettable powder or the like is diluted with water and applied, the applied concentration is 1-1000 ppm, preferably 10-250 ppm.

  In addition to the compound of the present invention, one or two or more of various fungicides, insecticides / acaricides, and synergists can be mixed in the present fungicide.

  Typical examples of fungicides, insecticides, acaricides, and plant growth regulators that can be used in combination with the compounds of the present invention are shown below.

Fungicide:
Captan, phorpet, thiuram, ziram, dineb, manneb, mancozeb, propineb, polycarbamate, chlorothalonil, quintosen, captaphor, iprodione, prosaimidin, vinclozolin, fluoroimide, thymoxanyl, mepronil, flutolanil, pencyclon, oxycarboxyl, fosetyl aluminum, Propamocurve, triadimephone, triadimenol, propiconazole, diclobutrazole, viteltanol, hexaconazole, microbutanyl, flusilazole, metconazole, etaconazole, fluotrimazole, cyproconazole, epoxyconazole, flutriaphene, beconazole , Diniconazole, cyproconazole, phenalimol, triflumizole, prochlor , Imazalyl, pefrazoate, tridemorph, fenpropimorph, triphorin, butiobate, pyrifenox, anilazine, polyoxin, metalaxyl, oxadixyl, furaxyl, isoprothiolane, probenazole, pyrrolnitrin, blasticidin S, kasugamycin, validamycin, dihydrostreptomycin sulfate , Benomyl, carbendazim, thiophanate methyl, hymexazole, basic copper chloride, basic copper sulfate, fentin acetate, triphenyltin hydroxide, dietofencarb, metasulfocarb, quinomethionate, binapacryl, lecithin, baking soda, dithianon, dinocup, phenaminosulfur, Dichromemedin, Guazatine, Dodin, IBP, Edifenphos, Mepanipyrim, Fermzo , Trichlamide, methasulfocarb, fluazinam, Etokinorakku, dimethomorph, pyroquilon, tecloftalam, fthalide, phenazine oxide, thiabendazole, tricyclazole, vinclozolin, cymoxanil, cyclobutanyl, guazatine, propamocarb hydrochloride, oxolinic acid, hydroxy isoxazole, iminoctadine acetate, and the like.

Insecticides and acaricides:
Organophosphorus and carbamate insecticides:
Fenthion, fenitrothion, diazinon, chlorpyrifos, ESP, bamidthione, phentoate, dimethoate, formothione, marathon, trichlorfone, thiometone, phosmet, dichlorvos, acephate, EPBP, methyl parathion, oxydimethone methyl, ethion, salicione, cyanophos, isoxathione, cyanophos, isoxathione Methidathione, Sulprophos, Chlorfenvinphos, Tetrachlorvinphos, Dimethylvinphos, Propafos, Isophenphos, Ethylthiomethone, Profenofos, Piracrofos, Monocrotophos, Adinfosmethyl, Aldicarb, Mesomil, Thiodicarb, Carbofuran, Carbosulfan, Benhracarb, Furatiocarb Propoxur, BPMC, M MC, MIPC, carbaryl, pirimicarb, ethiofencarb, fenoxycarb, EDDP, and the like.
Pyrethroid insecticides:
Permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatoline, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propraslin, phenothrin, protorin, fulvalinate, cyfluthrin, cyhalothrin, flucitrinate, etofenprox, cycloprotorin, thoramethrin , Silafluophene, brofenprox, aclinasrin, etc.
Benzoylurea and other insecticides:
Diflubenzuron, Chlorfluazuron, Hexaflumuron, Triflumuron, Tetrabenzuron, Flufenoxuron, Flucycloxuron, Buprofezin, Pyriproxyfen, Metoprene, Benzoepine, Diafenthiuron, Acetamiprid, Imidacloprid, Nitenpyram, Fipronil, Cartap Thiocyclam, bensultap, nicotine sulfate, rotenone, metaldehyde, machine oil, microbial pesticides such as BT and entomopathogenic viruses.

Nematicides:
Phenamifos, phostiazates, etc.
Acaricide:
Chlorbenzilate, phenisobromolate, dicofol, amitraz, BPPS, benzomate, hexithiazox, fenbutazin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentedin, cihexatin, pyridaben, fenpyroximate, tebufenpyrad, thiomidibene Dienochlor etc.
Plant growth regulator:
Gibberellins (eg, gibberellin A3, gibberellin A4, gibberellin A7), IAA, NAA and the like.

EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited at all by the following example.

Example 1
(1) Production of t-butyl N- (5-bromo-2-chlorophenoxy) carbamate

  To a solution prepared by dissolving 5.00 g of 4-bromo-1-chloro-2-fluorobenzene and 4.14 g of N-Boc-hydroxylamine in 50 ml of dimethyl sulfoxide, 12.34 g of potassium hydroxide was added at room temperature, and 60 ° C. For 2 hours. After cooling to room temperature, the reaction solution was poured into ice water and extracted with ethyl acetate. The obtained organic layer was washed 3 times with water, dried over magnesium sulfate and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 5: 1) to obtain 7.39 g of the target t-butyl N- (5-bromo-2-chlorophenoxy) carbamate. (Yield 96%) was obtained.

¹ H-NMR (CDCl _{3 /} TMS, δ ppm): 7.60 (bs, 1H), 7.47 (d, 1H), 7.20 (d, 1H), 7.10 (dd, 1H), ¹ .52 (s, 9H)

(2) Production of t-butyl N- (5-acetyl-2-chlorophenoxy) carbamate

  Under nitrogen atmosphere, 500 ml of tetrahydrofuran (THF) is cooled to −78 ° C., 198 ml of n-butyllithium (2.77 mol / L) is added, and N- (5-bromo-2-chlorophenoxy) carbamic acid dissolved in 170 ml of THF 67.43 g of t-butyl was added dropwise. After stirring at −78 ° C. for 10 minutes, 54.63 g of dimethylacetamide was added dropwise, and the mixture was stirred at −78 ° C. for 1 hour. After completion of the reaction, an aqueous ammonium chloride solution was added at −78 ° C., and the mixture was extracted with ethyl acetate. Magnesium sulfate was added to the obtained organic layer, dried and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; n-hexane: ethyl acetate = 3: 1) to obtain the target t-butyl 29-N- (5-acetyl-2-chlorophenoxy) carbamate. .18 g (yield 49%, melting point: 120-123 ° C.) was obtained.

(3) Production of methyl N- (5-acetyl-2-chlorophenoxy) carbamate

  28.93 g of t-butyl N- (5-acetyl-2-chlorophenoxy) carbamate was dissolved in 380 ml of methylene chloride, 15.37 g of triethylamine was added under ice cooling, and 12.44 g of methyl chloroformate was added dropwise. After stirring at room temperature for 1 hour, water was added under ice-cooling to separate the methylene chloride layer, and anhydrous magnesium sulfate was added thereto for drying and filtration, and then the solvent was distilled off under reduced pressure. To the obtained residue, 250 ml of methylene chloride was added, 64 ml of trifluoroacetic acid was added dropwise under ice cooling, and the mixture was stirred at room temperature for 1.5 hours. After completion of the reaction, the reaction solution was poured into saturated aqueous sodium hydrogen carbonate and extracted by adding methylene chloride. Magnesium sulfate was added to the resulting methylene chloride layer, dried and filtered, and then the solvent was distilled off under reduced pressure. The obtained crystal was washed with n-hexane to obtain 23.28 g (yield 94%, melting point: 154-155 ° C.) of the target methyl N- (5-acetyl-2-chlorophenoxy) carbamate.

(4) Production of [1- (2,4-difluorophenyl) ethylidene] hydrazine

  1.88 g of 2,4-difluoroacetophenone was dissolved in 20 ml of ethanol, 0.75 g of hydrazine monohydrate was added, and the mixture was refluxed for 1 hour. After cooling to room temperature, methylene chloride and water were added, the organic layer was separated, magnesium sulfate was added to this, dried and filtered, and then the solvent was distilled off under reduced pressure to obtain the desired [1- (2,4-difluorophenyl) Ethylidene] hydrazine (1.64 g, yield 96%) was obtained.

¹ H-NMR (CDCl _{3 /} TMS, δ ppm): 7.53 to 7.45 (m, 1H), 6.88 to 6.75 (m, 2H), 5.40 (bs, 2H), 2. 13 (d, 3H)

(5) Methyl N- [2-chloro-5- (1-{[1- (2,4-difluorophenyl) ethylidene] hydrazono} ethyl) phenoxy] carbamate

  0.30 g of methyl N- (5-acetyl-2-chlorophenoxy) carbamate was dissolved in 15 ml of dioxane, 0.27 g of [1- (2,4-difluorophenyl) ethylidene] hydrazine, 3 g of sodium sulfate, 23 mg of p-toluenesulfonic acid monohydrate was added and refluxed for 3 hours. After cooling to room temperature, ethyl acetate and water were added, and the organic layer was separated. Magnesium sulfate was added to this, dried and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by NH gel column chromatography (developing solvent; hexane: ethyl acetate = 2: 1), and the desired N- [2-chloro-5- (1-{[1- (2, 0.20 g of methyl 4-difluorophenyl) ethylidene] hydrazono} ethyl) phenoxy] carbamate (yield 41%, mp 133-135 ° C.) was obtained.

Examples of the azine derivatives of the present invention obtained as described above are shown in Tables 1 to 15 below including the compounds of Examples. In the following table, Me represents a methyl group, Et represents an ethyl group, c-Pr represents a cyclopropyl group, c-Pen represents a cyclopentyl group, c-Hex represents a cyclohexyl group, and i-Am represents an isoamyl group. , [] Indicates the melting point (° C.).
In addition, a compound with * in front of the compound number is an isomer.
In Table 1, in the column of R ^1, R ^2, "*" is in the compound, indicating the position of the nitrogen atom bonded to the carbon atom to which R ^1, R ² are attached. In this column, the carbon atoms to which R ¹ and R ² are bonded are displayed. In the table, the substitution position of (X) n corresponds to the number described in the formula (I-1) in Table 1.

  Next, although some examples of the composition of the present invention are shown, the additive and the addition ratio are not limited to these examples, and can be varied in a wide range. Moreover, the part in a formulation Example shows a weight part.

Formulation Example 1 Wetting agent Compound of the present invention 40 parts Clay 48 parts Dioctylsulfosuccinate sodium salt 4 parts Lignin sulfonic acid sodium salt 8 parts or more are uniformly mixed and finely pulverized, and 40% active ingredient wettable powder Get.

Formulation Example 2 Emulsion Compound of the present invention 10 parts Solvesso 200 53 parts Cyclohexanone 26 parts Calcium dodecylbenzenesulfonate 1 part Polyoxyethylene alkylallyl ether 10 parts The above components are mixed and dissolved to obtain an emulsion containing 10% active ingredient.

Formulation Example 3 Powder The present compound 10 parts Clay 90 parts The above is uniformly mixed and finely pulverized to obtain a powder of 10% active ingredient.

Formulation Example 4 Granules Compound of the present invention 5 parts Clay 73 parts Bentonite 20 parts Dioctylsulfosuccinate sodium salt 1 part Potassium phosphate 1 part After pulverizing and mixing well, adding water and kneading well, granulation drying As a result, granules containing 5% active ingredient are obtained.

Formulation Example 5 Suspension Compound of the present invention 10 parts Polyoxyethylene alkyl allyl ether 4 parts Polycarboxylic acid sodium salt 2 parts Glycerin 10 parts Xanthan gum 0.2 parts Water 73.8 parts The above is mixed and the particle size is 3 microns or less The suspension is wet-pulverized until a suspension of 10% active ingredient is obtained.

Formulation Example 6 Granule wettable powder Compound of the present invention 40 parts Clay 36 parts Potassium chloride 10 parts Alkylbenzenesulfonic acid sodium salt 1 part Ligninsulfonic acid sodium salt 8 parts Formaldehyde condensate of alkylbenzenesulfonic acid sodium salt
Mix 5 parts or more uniformly and pulverize finely, add an appropriate amount of water and knead to make clay. The clay-like product is granulated and then dried to obtain a wettable powder containing 40% of the active ingredient.

Test examples of the pest control agent of the present invention obtained as described above are shown below.
(Test Example 1) Apple scab control test An emulsion of the compound of the present invention was sprayed at a concentration of 100 ppm of the active ingredient on apple seedlings (variety “Kunimitsu”, 3-4 leaf stage) cultivated in an unglazed pot. After natural drying at room temperature, conidia spores of Venturia inaequalis were inoculated, and the light and darkness was repeated every 12 hours, and kept in a room at 20 ° C. and high humidity for 2 weeks. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.

As a result, the following compounds showed an excellent control value of 75% or more.
Compound number (compound number corresponds to the compound number in Table 1 to Table 15 above. The same applies hereinafter):
1-13, 1-24 to 1-26, 2-1 to 2-7, 2-15, 2-26 to 2-52, 2-54 to 2-63, 2-241 to 2-248, 3- 1-3-3, 3-8, 3-10-3-16, 3-18-3-20, 3-30, 3-78, 7-1, 9-3, 9-4, 9-13 9-14, 11-5, 11-7 to 11-14, 11-16, 11-17, 11-52, 11-56, 11-71, 11-81 to 11-93, 11-95 to 11- 98, 11-100 to 11-109, 14-1, 15-1

(Test Example 2) Wheat powdery mildew control test Wheat seedlings (variety “Chihoku”, 1.0-1.2 leaf stage) cultivated in an unglazed pot were sprayed with a wettable powder of the compound of the present invention at a concentration of 100 ppm. . After air-drying the leaves, conidia of wheat powdery mildew (Erysiphe graminis f. Sp. Tritici) were sprinkled off and inoculated in a 22-25 ° C. greenhouse for 7 days. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.

As a result, the following compounds showed an excellent control value of 75% or more.
Compound number:
1-24 to 1-26, 2-1 to 2-7, 2-15, 2-26, 2-27, 2-31 to 2-40, 2-44 to 2-52, 2-54, 2- 55, 2-57 to 2-63, 2-241 to 2-243, 2-246 to 2-248, 3-1 to 3-3, 3-8, 3-10 to 3-16, 3-18 to 3-20, 3-30, 3-78, 9-13, 9-14, 11-5, 11-7, 11-8, 11-10 to 11-14, 11-16, 11-17, 11- 52, 11-56, 11-71, 11-81 to 11-93, 11-95 to 11-98, 11-100 to 11-104, 11-106 to 11-109, 14-1

(Test Example 3) Wheat red rust control test A wheat seedling (cultivar “Noribayashi No. 61”, 1.0-1.2 leaves) cultivated in an unglazed pot was sprayed with a wettable powder of the compound of the present invention at a concentration of 100 ppm. . After air-drying the leaves, summer spores of wheat red rust fungus (Puccinia recondita) were shaken off and inoculated in a greenhouse at 22-25 ° C. for 10 days. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.

As a result, the following compounds showed an excellent control value of 75% or more.
Compound number:
1-13, 1-24 to 1-26, 2-1 to 2-7, 2-26, 2-27, 2-29, 2-31, 2-32, 2-34 to 2-38, 2- 40, 2-42, 2-44, 2-45, 2-49, 2-51, 2-54, 2-55, 2-57 to 2-63, 2-241 to 2-243, 2-246 to 2-248, 3-1 to 3-3, 3-8, 3-10 to 3-16, 3-18 to 3-20, 3-30, 3-78, 11-5, 11-7, 11- 8, 11-10 to 11-14, 3-16, 3-17, 3-52, 3-56, 11-71, 11-81 to 11-86, 11-88 to 11-93, 11-95 to 11-98, 11-100 to 11-102, 11-104 to 11-109, 14-1

Claims (3)

An azine derivative represented by the following formula (I) or a salt thereof.

[Wherein, X represents a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C1-20 haloalkyl group, or a C1-20 haloalkoxy group,
R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a C1-20 alkyl group, a C2-20 alkenyl group, a C2-20 alkynyl group, a C1-20 haloalkyl group, a C2-20 haloalkenyl group, a C2— 20 haloalkynyl group, C1-20 alkoxy group, C2-20 alkenyloxy group, C2-20 alkynyloxy group, C1-20 haloalkoxy group, C2-20 haloalkenyloxy group, C2-20 haloalkynyloxy group, unsubstituted Alternatively, it represents a C3-10 cycloalkyl group having a substituent, a phenyl group having no substituent or a substituent, a cyano group, a nitro group, a C1-20 alkylthio group, or a heterocyclic group having no substituent or a substituent. However, R ¹ and R ² are not both hydrogen atoms. R ¹ and R ² may be bonded together to form a ring.
R ³ is a hydrogen atom, a C1-20 alkyl group, a C2-20 alkenyl group, a C2-20 alkynyl group, a C1-20 haloalkyl group, a C2-20 haloalkenyl group, a C2-20 haloalkynyl group, or unsubstituted or substituted. Represents a C3-10 cycloalkyl group having a group,
R ⁴ is a hydrogen atom, C1-20 alkyl group, C2-20 alkenyl group, C2-20 alkynyl group, C1-20 haloalkyl group, C2-20 haloalkenyl group, C2-20 haloalkynyl group, cyano group, nitro group. Or a C1-20 alkylthio group,
R ⁵ represents a hydrogen atom, a C1-20 alkyl group, an acyl group, a formyl group, a C1-20 alkoxy C1-20 alkyl group, a C1-20 alkylsulfonyl group, or an unsubstituted or substituted phenylsulfonyl group.
Y represents an oxygen atom or a sulfur atom,
Z represents a single bond, an oxygen atom, a sulfur atom, or a group represented by NR ⁶ (R ⁶ represents a hydrogen atom or a C1-30 alkyl group);
n represents an integer of 0 to 4. ] A compound represented by the following formula (II).

[Wherein, X represents a halogen atom, a C1-20 alkyl group, a C1-20 alkoxy group, a C1-20 haloalkyl group, or a C1-20 haloalkoxy group,
R ³ is a hydrogen atom, a C1-20 alkyl group, a C2-20 alkenyl group, a C2-20 alkynyl group, a C1-20 haloalkyl group, a C2-20 haloalkenyl group, a C2-20 haloalkynyl group, or unsubstituted or substituted. Represents a C3-10 cycloalkyl group having a group,
R ⁴ is a hydrogen atom, C1-20 alkyl group, C2-20 alkenyl group, C2-20 alkynyl group, C1-20 haloalkyl group, C2-20 haloalkenyl group, C2-20 haloalkynyl group, cyano group, nitro group. Or a C1-20 alkylthio group,
R ⁵ represents a hydrogen atom, a C1-20 alkyl group, an acyl group, a formyl group, a C1-20 alkoxy C1-20 alkyl group, a C1-20 alkylsulfonyl group, or an unsubstituted or substituted phenylsulfonyl group.
Y represents an oxygen atom or a sulfur atom,
Z represents a single bond, an oxygen atom, a sulfur atom, or a group represented by NR ⁶ (R ⁶ represents a hydrogen atom or a C1-30 alkyl group);
n represents an integer of 0 to 4. ]   An agricultural and horticultural fungicide containing, as an active ingredient, at least one of the azine derivative represented by the formula (I) according to claim 1 or a salt thereof.