JP2007137852A - Azine derivative and agricultural/horticultural fungicide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new azine derivative compound stably exerting in low concentrations high controlling effect on plant disease injuries of broad spectrum, and to provide a fungicide, especially an agricultural/horticultural fungicide, using the compound as active ingredient. <P>SOLUTION: The new azine derivative of the general formula(I)( wherein, X is an oxygen atom or indicates direct bonding; and Y and Z are each a phenyl group or heterocyclic ring containing one or more atoms selected from oxygen atom, sulfur atom and nitrogen atom ) or salts thereof is(are) provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fungicide containing an azine derivative, and particularly to an agricultural and horticultural fungicide.

  So far, several azine compounds having biological activity have been reported. For example, the compound represented by the following general formula (IV), the compound represented by the following general formula (V), and the compound represented by the following general formula (VI) may have insecticidal and / or bactericidal activity. Known (see Patent Documents 1, 2, and 3).

［式中、一般式（IV）におけるＲ_１〜Ｒ_３、Ｒ_５、Ｒ_６およびＡは特許文献１によって定義され、一般式（Ｖ）におけるＲ、Ａ、Ｂ、Ｘ、ＹおよびＺは特許文献２によって定義され、一般式（VI）におけるＲ_１〜Ｒ_３、ＡおよびＢは特許文献３によって定義される。］
国際公開第０１／４２２０１号パンフレット 欧州特許出願公開第０６２７４１１号明細書 特開２０００−２８１６４８号公報 Among these compounds, the compound represented by the general formula (IV) has a certain bactericidal activity, especially rice blast, powdery mildew such as wheat and cucumber, and red rust of wheat. High control effect against various plant diseases. However, these compounds have the disadvantage that the activity is particularly weak against gray mold disease and the control effect is reduced against the plant disease.

[Wherein R _{1 to} R ₃ , R ₅ , R ₆ and A in the general formula (IV) are defined by Patent Document 1, and R, A, B, X, Y and Z in the general formula (V) are patents. R _{1 to} R ₃ , A and B in the general formula (VI) are defined by Patent Document 3 and defined by Patent Document 3. ]
International Publication No. 01/42201 Pamphlet European Patent Application No. 0627411 JP 2000-281648 A

  The present invention provides a novel azine derivative compound that stably exhibits a high control effect at a lower concentration with respect to a broad spectrum of plant diseases without the above-mentioned drawbacks, and effectively uses these compounds. It is to provide a fungicide used as an ingredient, particularly an agricultural and horticultural fungicide.

  In order to solve the above-mentioned problems, the present inventors have intensively studied and completed the present invention. That is, the present inventors have found that an azine compound having a certain structure exhibits a preferable bactericidal activity, and can effectively control diseases, particularly plant diseases, with a composition containing the compound as an active ingredient. The present invention has been made based on such findings.

［式中、Ｘは、酸素原子あるいは直結を示し、ＹおよびＺは、それぞれ独立にフェニル基あるいは酸素原子、硫黄原子または窒素原子からなる群から選ばれた１個または２個以上の原子を含有する複素５員環または複素６員環を示し、これらのフェニル基、複素５員環あるいは複素６員環は、無置換であるかあるいはハロゲン原子、アルキル基またはハロアルキル基で置換されていてもよい。］ That is, the present invention is as follows.
(1) An azine derivative represented by the following general formula (I) or a salt thereof.

[Wherein X represents an oxygen atom or a direct bond, and Y and Z each independently contains one or two or more atoms selected from the group consisting of a phenyl group, an oxygen atom, a sulfur atom or a nitrogen atom. And a phenyl group, a hetero 5-membered ring or a hetero 6-membered ring may be unsubstituted or substituted with a halogen atom, an alkyl group or a haloalkyl group. . ]

(2) In general formula (I), Y is unsubstituted or a phenyl group which may be substituted with a halogen atom, an alkyl group or a haloalkyl group, and Z is unsubstituted or halogenated The azine derivative or a salt thereof according to (1), which is a thiazole ring optionally substituted with an atom, an alkyl group or a haloalkyl group.

(3) An agricultural and horticultural fungicide containing the azine derivative and / or salt thereof according to any one of (1) and (2).

  Y and Z in the general formula (I) are a hetero 5-membered ring or a hetero 6-membered ring containing a phenyl group or a hetero element (oxygen atom, sulfur atom or nitrogen atom). Specifically, examples of the heterocyclic 5-membered ring include thiazole, isothiazole, oxazole, isoxazole, thiophene, imidazole, pyrazole, pyrrole, triazole, thiadiazole, oxadiazole and the like. More preferred is thiazole. Examples of the hetero 6-membered ring include pyridine, pyrazine, pyrimidine and the like. More preferably, although pyridine is mentioned, it is not limited to these.

Y and Z in the above general formula (I) may be substituted with any alkyl group, and are preferably a linear or branched or cyclized C ₁ -C ₆ alkyl group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, 2-methylbutyl group 2,2-dimethylpropyl group, 3-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-ethylbutyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like. More preferably, a methyl group is mentioned, but it is not limited to these.

Y and Z in the above general formula (I) may be substituted with any haloalkyl group, and are preferably a linear or branched C ₁ -C ₆ alkyl group. Specific examples include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a pentafluoropropyl group, a pentafluorobutyl group, a pentafluoropentyl group, and a pentafluorohexyl group. In addition, a trifluoromethyl group is preferable, but it is not limited thereto.

  Y and Z in the general formula (I) may be substituted with any halogen atom, and specific examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. More preferably, a chlorine atom is mentioned.

  The compound represented by the general formula (I) according to the present invention includes its E / Z isomer. For example, the E / Z isomer at the azine moiety {-C (Me) = NN-C (Me)-} is conceivable. The compounds represented by (I) according to the present invention include all possible E / Z isomers thereof, including pure or substantially pure E or Z isomers, as well as E / Z isomer mixtures. Including.

  The compound represented by the general formula (I) according to the present invention includes a salt thereof. For example, the N portion of the azine moiety can be an anionic salt. Such salts are well known to those skilled in the art, and the compounds of the general formula (I) according to the present invention include all these possible salts.

Specific examples of the compound represented by the general formula (I) include compounds shown in Tables 1 and 2 below.
In Tables 1 and 2, “-” in column X represents direct connection.

  Among the compounds (I) according to the present invention, preferred compounds have bactericidal activity, and the agricultural and horticultural fungicides containing the compounds are cucumber gray mold, rice blast, cucumber, which are important diseases of agricultural crops. It exhibits a wide range of control effects against various diseases such as powdery mildew of barley and barley and red rust of wheat. Furthermore, it has both preventive and therapeutic effects and is useful as an agricultural and horticultural fungicide. Therefore, an excellent method for controlling plant diseases is provided by the present invention.

（式中、Ｘ、ＹおよびＺは、それぞれ前記と同じ意味を表す。） The compound represented by the general formula (I) according to the present invention can be synthesized by any method, and a particularly preferred general production method is shown below.

(In the formula, X, Y and Z each have the same meaning as described above.)

  The compound of the present invention represented by the general formula (I) can be produced by reacting the compound represented by the general formula (II) with the compound represented by the general formula (III) in an inert solvent. .

In addition, the compound represented by the general formula (III) used in this production method may form a salt with an inorganic acid such as hydrochloric acid or sulfuric acid, and is available as a commercial product or by a known method. Can be manufactured.
Inert solvents that can be used in this production method include all inert solvents that can be considered by those skilled in the art, but preferably alcohols such as methanol, ethanol, n-propanol, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, etc. Ethers, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, and water. These inert solvents can be used alone or in combination.

  The amount of the reagent used for this reaction is 1 to 10 moles, preferably 1 to 2 moles of the compound represented by the general formula (III) per 1 mole of the compound represented by the general formula (II). It is a ratio.

  In this production method, acids such as hydrochloric acid, sulfuric acid and acetic acid, or bases such as sodium acetate and sodium carbonate can be used together, and the amount used is compound 1 represented by the general formula (II). The ratio is 0.001 to 10 moles, preferably 0.01 to 2 moles per mole.

  Although this reaction can be performed under arbitrary temperature conditions, it is from -20 ° C to the boiling point of the inert solvent used, and preferably from 0 ° C to the boiling point of the inert solvent used.

  The reaction time of this reaction may be any time at which the reaction ends. The completion of the reaction means, for example, that one or both of the raw materials in the solvent are consumed, and can be confirmed by, for example, thin layer chromatography. Generally, it is in the range of 1 hour to 24 hours.

  After completion of the reaction, the compound represented by the general formula (I), which is the target product, can be obtained by a usual work-up method and using ordinary purification and isolation methods. Specifically, after completion of the reaction, after distilling off the inert solvent used in the reaction from the reaction mixture, or without distilling off the inert solvent, the reaction mixture is directly mixed with water, benzene, toluene, The target product is extracted by adding an organic solvent such as chloroform or ethyl acetate and separated, and the solvent is distilled off from the obtained organic solvent layer by distillation, and if necessary, by purification means such as chromatography and recrystallization. The target product (I) can be isolated.

（式中、ＹおよびＸは前記と同じ意味を表す。また、「ＮＢＳ」は，Ｎ−ブロモスクシイミドを表す。） Next, a typical production method of the compound represented by the general formula (II), which is a production intermediate of the compound of the present invention, is shown below.

(Wherein Y and X represent the same meaning as described above, and “NBS” represents N-bromosuccinimide.)

<Step 1-1>
When X is a direct bond, the compound represented by the general formula (IX) is obtained by combining a compound represented by the general formula (VII) and a boronic acid derivative with 1,1′-bisdiphenylphosphinoferrocenedichloropalladium (II). And it can manufacture by making it react in presence of potassium phosphate.
This reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include ethers such as ethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether. These solvents can be used alone or in combination.
The amount of the reagent used in the reaction is such that the boronic acid derivative is usually 0.8 to 1.2 moles per mole of the compound represented by the general formula (VII), and 1,1′-bisdiphenylphosphino Ferrocene dichloropalladium (II) is usually in a proportion of 0.01 to 0.1 mol, and potassium phosphate is usually in a proportion of 1 to 10 mol.
The reaction temperature of this reaction is usually in the range of −20 ° C. to 100 ° C., and the reaction time is usually in the range of 30 minutes to 24 hours.
After completion of the reaction, for example, the organic solvent layer containing the target product obtained by adding the reaction mixture to water and extracting with an organic solvent is washed with saturated brine, and the solvent is distilled off from the obtained organic solvent layer by distillation. If necessary, the target compound represented by the general formula (IX) (X is a direct bond) can be isolated by purification means such as chromatography and recrystallization.

<Step 1-2>
When X is an oxygen atom, the compound represented by the general formula (IX) can be produced by reacting the compound represented by the general formula (VIII) with a halogen-substituted compound of Y in the presence of a base. This reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, and ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane, amides such as dimethylacetamide and dimethylformamide, and dimethyl Examples thereof include sulfoxides such as sulfoxide. These solvents can be used alone or in combination.
Examples of the base used in the reaction include inorganic salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and acetate salts such as sodium acetate and potassium acetate.
The amount of the reagent used in the reaction is such that the halogen-substituted compound of Y is usually 0.8 to 1.2 mol and the base is usually 1 to 2 mol with respect to 1 mol of the compound represented by formula (VIII). Is the ratio.
The reaction temperature of this reaction is usually in the range from 0 ° C. to the boiling point of the solvent used, and the reaction time is usually in the range of 30 minutes to 24 hours.
After completion of the reaction, for example, the reaction mixture is added to an acidic aqueous solution such as dilute hydrochloric acid aqueous solution or dilute sulfuric acid aqueous solution, and the organic solvent layer containing the target product obtained by extraction with an organic solvent is converted into a basic aqueous solution such as sodium hydrogen carbonate aqueous solution. Subsequently, it is washed with a saturated saline solution, and the solvent is distilled off from the obtained organic solvent layer by distillation, and if necessary, the target compound represented by the general formula (IX) by purification means such as chromatography, recrystallization and the like ( X is an oxygen atom).

<Step 2>
The compound represented by the general formula (X) can be produced by reacting the compound represented by the general formula (IX) with N-bromosuccinimide.
This reaction is usually performed in the presence of a solvent. Examples of the solvent used for the reaction include aliphatic halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, and aromatic hydrocarbons such as benzene, chlorobenzene and dichlorobenzene. These solvents can be used alone or in combination.
The amount of the reagent used for the reaction is usually 1 to 1.5 mol of N-bromosuccinimide with respect to 1 mol of the compound represented by the general formula (IX).
The reaction temperature of this reaction is usually in the range from 0 ° C. to the boiling point of the solvent used, and the reaction time is usually in the range of 0.5 to 12 hours.
After completion of the reaction, for example, the reaction mixture is cooled to room temperature, and unnecessary substances are filtered off. The solvent is distilled off from the obtained organic solvent layer by distillation, and if necessary, it is generally purified by purification means such as chromatography and recrystallization. The target compound represented by the formula (X) can be isolated.

<Step 3>
The compound represented by the general formula (II) can be produced by reacting the compound represented by the general formula (X) with a cyanate derivative in the presence of an alcohol.
This reaction is usually performed in the presence of a solvent. Examples of the solvent used in the reaction include aliphatic halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, and diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane. And amides such as acetamide and formamide. These solvents can be used alone or in combination.
Examples of the alcohol used in the reaction include primary alcohols such as methanol, ethanol, and propanol, and an ester of compound (II) corresponding to each can be obtained.
The amount of the reagent used in the reaction is usually 0.8 to 2 mol of the cyanate derivative and 1 to 10 mol of the alcohol with respect to 1 mol of the compound represented by the general formula (X). is there.
The reaction temperature of this reaction is usually in the range of 0 ° C to 100 ° C, and the reaction time is usually in the range of 1 to 24 hours.
After completion of the reaction, for example, the reaction mixture is added to an acidic aqueous solution such as dilute hydrochloric acid aqueous solution or dilute sulfuric acid aqueous solution, and the organic solvent layer containing the target product obtained by extraction with an organic solvent is converted into a basic aqueous solution such as sodium hydrogen carbonate aqueous solution. Subsequently, the organic solvent layer is washed with saturated saline, and the solvent is distilled off from the resulting organic solvent layer. If necessary, the target compound represented by the general formula (II) is purified by purification means such as chromatography and recrystallization. It can be isolated.

  The compound represented by the general formula (I) should be analyzed, confirmed and identified by melting point, infrared absorption spectrum, 1H-NMR spectrum, 13C-NMR spectrum, mass spectrometry, X-ray structural analysis, etc., if necessary. Can do.

  The more specific synthesis method of the compound represented by the general formula (I) according to the present invention is described in Examples 1 and 2 in Examples of the present specification.

  The azine derivative represented by the general formula (I) according to the present invention exhibits bactericidal activity. Therefore, the composition containing the compound represented by general formula (I) can be used as a bactericidal agent. In particular, a composition containing the compound represented by formula (I) as an active ingredient can be used as an agricultural and horticultural fungicide.

  The composition of the agricultural and horticultural fungicide containing the compound represented by the general formula (I) according to the present invention as an active ingredient is ordinary agricultural and horticultural except that the active ingredient contains the compound represented by the general formula (I). It is good also as a composition of an antibacterial agent. The normal composition is described, for example, in an agrochemical formulation guide (1997, edited by: Japanese Society for Agricultural Chemicals Application Law, published by Japan Plant Protection Association). That is, a compound represented by the general formula (I), a suitable carrier, an auxiliary agent, a surfactant, a binder or a stabilizer may be blended.

  The composition of the agricultural and horticultural fungicide containing the compound represented by the general formula (I) according to the present invention can be formulated into any dosage form generally used as an agrochemical dosage form. For example, it is formulated into powders, coarse powders, DL (driftless) powders, flow dusts, fine granules, fine granules, granules, wettable powders, liquids, sols (flowables), emulsions or oils. Can be, but is not limited to.

  The content of the compound represented by the general formula (I) according to the present invention can be appropriately selected depending on the dosage form of the preparation and the method of use. In general, the preferable content is in the range of 0.1 to 90% by weight based on the total amount of the preparation.

  The agricultural and horticultural fungicide containing the compound represented by the general formula (I) according to the present invention as an active ingredient can be used in the same manner as a method in which a general agricultural and horticultural fungicide is used. Specifically, in the case of a wettable powder, liquid, emulsion, sol (flowable), granular wettable powder, or oil, it is diluted 50 to 2000 times with water and generally contains 1 to 10,000 ppm of the active ingredient. The solution can be prepared to have a concentration, and this diluted solution can be sprayed on the foliage at the site of disease occurrence of the plant in the range of 50 to 300 liters, usually 100 to 200 liters per 10 ares of farmland.

  Also, in the case of liquids, emulsions or sols (flowables), it is not diluted with water or diluted within 50 times, and the amount of 50 to 5000 ml per 10 are as a microdispersing agent, mainly in the air It can also be sprayed (including LV spraying, ULV spraying, S spraying, etc.). Air spraying is performed using a helicopter.

  In addition, in the case of powder, coarse powder, DL powder, flow dust, fine granule, fine granule or granule, 2-5 kg of agent (active ingredient content is about 5 to 500 g) per 10 ares, It may be applied to the foliage, soil surface, soil or water surface at the site of disease occurrence.

  The specific example of the method of formulating the compound represented with general formula (I) based on this invention as an agricultural and horticultural fungicide was described in Examples 3-7 in the Example of this specification.

  The usefulness of the agricultural and horticultural fungicide containing the compound represented by the general formula (I) according to the present invention, that is, the fungicidal activity, is described in Test Examples 1 to 3 in the Examples of the present specification.

EXAMPLES Hereinafter, although an Example and a test example demonstrate this invention concretely, the scope of the present invention is not limited by these.
In the following Examples 1-2, the manufacture example of the compound represented with general formula (I) based on this invention was described concretely.

｛ステップ１： １−（２−メチル−１，１’−ビフェニル−４−イル）エタノンの合成｝
還流冷却器、撹拌器および温度計をつけた５０ｍｌ容量の４つ口フラスコ中に、エチレングリコールジメチルエーテル（１５ｍｌ）に溶解した１−（３−メチル−４−ブロモフェニル）エタノン（１．４ｇ，６．４ｍｍｏｌ）と、１，１’−ビスジフェニルホスフィノフェロセンジクロロパラジウム（ＩＩ）（０．２ｇ，０．３２ｍｍｏｌ）およびリン酸三カリウム水和物（６．８ｇ，３２ｍｍｏｌ）とを加え、７０℃まで加温し３時間撹拌した。反応終了後、酢酸エチル（４０ｍｌ）を加え、飽和塩化ナトリウム水溶液で２回洗浄後、有機層を分離し、これを無水硫酸ナトリウムで乾燥した。減圧下にて溶媒を留去し、粗標記化合物１．８ｇ（粗収率１００％）を黄色油状物として得た。これは精製することなく次のステップで使用した。 Process for producing methyl [4- (1- {1- (4-methyl-1,3-thiazol-2-yl) ethylidenehydrazone} ethyl) -1,1′-biphenyl-2-yl] methylcarbamate (Compound No. 1)

{Step 1: Synthesis of 1- (2-methyl-1,1'-biphenyl-4-yl) ethanone}
1- (3-Methyl-4-bromophenyl) ethanone (1.4 g, 6) dissolved in ethylene glycol dimethyl ether (15 ml) in a 50 ml four-necked flask equipped with a reflux condenser, stirrer and thermometer. .4 mmol), 1,1′-bisdiphenylphosphinoferrocenedichloropalladium (II) (0.2 g, 0.32 mmol) and tripotassium phosphate hydrate (6.8 g, 32 mmol), And stirred for 3 hours. After completion of the reaction, ethyl acetate (40 ml) was added, and after washing twice with a saturated aqueous sodium chloride solution, the organic layer was separated and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 1.8 g (crude yield 100%) of the crude title compound as a yellow oil. This was used in the next step without purification.

{Step 2: Synthesis of 1- [2- (bromomethyl) -1,1'-biphenyl-4-yl] ethanone}
1- (2-Methyl-1,1′-biphenyl-4-yl) ethanone dissolved in carbon tetrachloride (15 ml) in a 30 ml four-necked flask equipped with a reflux condenser, stirrer and thermometer (1.3 g, 6.1 mmol), N-bromosuccinimide (1.1 g, 6.1 mmol) and a catalytic amount of α, α′-azobisisobutyronitrile were added and heated under reflux for 2 hours. Stir. After completion of the reaction, the insoluble matter precipitated by cooling with ice was removed by filtration, the solvent was distilled off from the filtrate under reduced pressure, and the resulting residue was subjected to silica gel column chromatography (silica gel; Silica gel 60H (manufactured by Merck). Product name), developing solvent; hexane: ethyl acetate = 25: 1) to obtain 1.5 g (yield 75%) of the title compound as a colorless oil.

{Step 3: Synthesis of methyl (4-acetyl-1,1'-biphenyl-2-yl) methylcarbamate}
1- [2- (Bromomethyl) -1,1′-biphenyl-4-yl] dissolved in dimethylformamide (5 ml) in a 30 ml four-necked flask equipped with a reflux condenser, stirrer and thermometer Ethanone (0.4 g, 1.5 mmol), potassium isocyanate (0.13 g, 1.5 mmol) and methanol (0.7 ml) were added and stirred at room temperature for 4 hours. After completion of the reaction, ethyl acetate (20 ml) was added, and after washing twice with a saturated aqueous sodium chloride solution, the organic layer was separated and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 0.5 g of the crude title compound (crude yield 100%) as a colorless oil. This was used in the next step without purification.

{Step 4: Methyl [4- (1- {1- (4-methyl-1,3-thiazol-2-yl) ethylidenehydrazone} ethyl) -1,1'-biphenyl-2-yl] methylcarbamate (Compound Synthesis of number 1)}
1- (4-Methyl-1,3-thiazol-2-yl) ethylidenehydrazine (0) dissolved in toluene (8 ml) in a 30 ml four-necked flask equipped with a reflux condenser, stirrer and thermometer. .15 g, 0.9 mmol) and methyl (4-acetyl-1,1′-biphenyl-2-yl) methylcarbamate (0.25 g, 0.9 mmol) were added and stirred at room temperature for 1 day. After completion of the reaction, toluene (12 ml) was added, and after washing twice with a saturated aqueous sodium chloride solution, the organic layer was separated and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (silica gel; Silica gel 60H (trade name, manufactured by Merck), developing solvent; hexane: ethyl acetate = 5: 1), The title compound (0.29 g, yield 76%) was obtained as yellow crystals (melting point: mp 115-120 ° C.).

｛ステップ１： １−（３−メチル−４−｛３−クロロ−５−トリフルオロメチルピリジン−２−イルオキシ｝フェニル）エタノンの合成｝
還流冷却器、撹拌器および温度計をつけた５０ｍｌ容量の４つ口フラスコ中に、ジメチルホルムアミド（２５ｍｌ）に溶解した１−（４−ヒドロキシ−３−メチルフェニル）エタノン（１．７ｇ，１１ｍｍｏｌ）と、２，３−ジクロロ−５−トリフルオロメチルピリジン（２．４ｇ，１１ｍｍｏｌ）および炭酸カリウム（１．８ｇ，１３ｍｍｏｌ）とを加え、７０℃まで加温し３時間撹拌した。反応終了後、酢酸エチル（５０ｍｌ）を加え、飽和塩化ナトリウム水溶液で２回洗浄後、有機層を分離し、これを無水硫酸ナトリウムで乾燥した。減圧下にて溶媒を留去し、粗標記化合物３．８ｇ（粗収率１００％）を黄色油状物として得た。これは精製することなく次のステップで使用した。 Process for producing methyl 5- {1- [4-methyl-1,3-thiazol-2-ylethylidenehydrazino] ethyl} -2- (3-chloro-5-trifluoromethylpyridin-2-yloxy) benzylcarbamate (Compound No. 29)

{Step 1: Synthesis of 1- (3-methyl-4- {3-chloro-5-trifluoromethylpyridin-2-yloxy} phenyl) ethanone}
1- (4-hydroxy-3-methylphenyl) ethanone (1.7 g, 11 mmol) dissolved in dimethylformamide (25 ml) in a 50 ml four-necked flask equipped with a reflux condenser, stirrer and thermometer 2,3-dichloro-5-trifluoromethylpyridine (2.4 g, 11 mmol) and potassium carbonate (1.8 g, 13 mmol) were added, and the mixture was heated to 70 ° C. and stirred for 3 hours. After completion of the reaction, ethyl acetate (50 ml) was added, and after washing twice with a saturated aqueous sodium chloride solution, the organic layer was separated and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 3.8 g (crude yield 100%) of the crude title compound as a yellow oil. This was used in the next step without purification.

{Step 2: Synthesis of 1- (3-bromomethyl-4- {3-chloro-5-trifluoromethylpyridin-2-yloxy} phenyl) ethanone}
1- (3-Methyl-4- {3-chloro-5-trifluoromethyl) dissolved in carbon tetrachloride (15 ml) in a 30 ml four-necked flask equipped with a reflux condenser, stirrer and thermometer. Pyridin-2-yloxy} phenyl) ethanone (3.6 g, 11 mmol), N-bromosuccinimide (2 g, 11 mmol) and a catalytic amount of α, α′-azobisisobutyronitrile were added and heated to reflux. Stirred for 2 hours. After completion of the reaction, the reaction mixture was cooled on ice and the precipitated insoluble matter was removed by filtration. The solvent was removed from the filtrate under reduced pressure, and the resulting residue was purified by silica gel column chromatography (silica gel; Silica gel 60H (trade name, manufactured by Merck & Co., Inc.). ), Developing solvent; hexane: ethyl acetate = 12: 1) to obtain 2.8 g (yield 62%) of the title compound as a colorless oil.

{Step 3: Synthesis of methyl 5-acetyl-2- {3-chloro-5-trifluoromethylpyridin-2-yloxy} benzyl carbamate}
1- (3-Bromomethyl-4- {3-chloro-5-trifluoromethylpyridine) dissolved in dimethylformamide (30 ml) in a 30 ml four-necked flask equipped with a reflux condenser, stirrer and thermometer. 2-yloxy} phenyl) ethanone (2.8 g, 7 mmol), potassium isocyanate (0.6 g, 7 mmol) and methanol (5 ml) were added, and the mixture was stirred at room temperature for 4 hours. After completion of the reaction, toluene (50 ml) was added, and after washing twice with a saturated aqueous sodium chloride solution, the organic layer was separated and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (silica gel; Silica gel 60H (trade name, manufactured by Merck), developing solvent; hexane: ethyl acetate = 7: 1). The title compound (1.5 g, yield 57%) was obtained as white crystals.

{Step 4: Methyl 5- {1- [4-methyl-1,3-thiazol-2-ylethylidenehydrazino] ethyl} -2- (3-chloro-5-trifluoromethylpyridin-2-yloxy) benzyl Synthesis of carbamate (Compound No. 29)}
1- (4-Methyl-1,3-thiazol-2-yl) ethylidenehydrazine (0) dissolved in methanol (15 ml) in a 30 ml four-necked flask equipped with a reflux condenser, stirrer and thermometer. 2 g, 1.3 mmol) and methyl 5-acetyl-2- {3-chloro-5-trifluoromethylpyridin-2-yloxy} benzylcarbamate (0.5 g, 1.3 mmol) were added and stirred at room temperature for 1 day did. After completion of the reaction, the solvent was distilled off under reduced pressure, and the resulting residue was subjected to silica gel column chromatography (silica gel; Silica gel 60H (trade name, manufactured by Merck), developing solvent; hexane: ethyl acetate = 12: 1). The title compound (0.5 g, yield 70%) was obtained as yellow crystals (melting point: mp 130-131 ° C.).

  The analytical data by NMR of some of the compounds of the present invention are shown in Table 3 below. The NMR data described was data measured with a JNM-LA300 spectrometer (manufactured by JEOL Datum Co., Ltd.), and all δ values were shown in ppm.

  Powdered Example: A mixture of compound No. 1 (2 parts by weight), PAP (isopropyl phosphate ester; physical property improver) (1 part by weight) and clay (97 parts by weight) was uniformly ground and mixed. A powder containing 2% by weight of the active ingredient can be obtained. Furthermore, each powder agent can be obtained by the same method except using the compounds shown in Tables 1 and 2 instead of the compound of Compound No. 1.

  Example of wettable powder: uniform mixture of compound No. 22 (20 parts by weight), potassium alkylbenzenesulfonate (3 parts by weight), polyoxyethylene nonylphenyl ether (5 parts by weight) and clay (72 parts by weight) And then pulverized to obtain a wettable powder containing 20% by weight of the active ingredient. Furthermore, each wettable powder can be obtained by the same method except that the compounds shown in Tables 1 and 2 are used instead of the compound of Compound No. 22.

  Emulsifying Example: Compound No. 25 (30 parts by weight), methyl ethyl ketone (40 parts by weight) and polyoxyethylene nonylphenyl ether (30 parts by weight) were mixed and dissolved to contain 30% by weight of the active ingredient Can be obtained. Furthermore, each emulsion can be obtained by the same method except that the compounds shown in Tables 1 and 2 are used in place of the compound of Compound No. 25.

  Example of Sol Preparation: Compound No. 27 (40 parts by weight), lauryl sulfate (2 parts by weight), sodium alkylnaphthalene sulfonate (2 parts by weight), acetoxypropyl cellulose (1 part by weight) and water (55 parts by weight) Part) is uniformly mixed to obtain a sol containing 40% by weight of the active ingredient. Furthermore, each sol agent can be obtained by the same method except using each compound shown in Tables 1 and 2 instead of the compound of Compound No. 27.

  Example of granulation: Compound No. 29 (10 parts by weight), lauryl sulfate (1 part by weight), calcium lignin sulfonate (5 parts by weight), bentonite (30 parts by weight), and clay (54 parts by weight) After adding water (15 parts by weight) to this mixture and kneading with a kneader, the mixture is granulated with a granulator and dried with a fluid dryer to obtain a granule containing 10% by weight of the active ingredient. Can do. Furthermore, each granule can be obtained by the same method except that the compounds shown in Tables 1 and 2 are used instead of the compound of Compound No. 29.

(Test example)
Hereinafter, the usefulness of the azine derivative represented by the general formula (I) according to the present invention and the agricultural and horticultural fungicide containing the azine derivative as an active ingredient will be clarified with reference to Test Examples 1 to 3 below. To do. However, the utility of the present invention is not limited to the utility revealed by these test examples. Moreover, a test compound number represents the same number as the compound number represented by Tables 1-2.

(Test Example 1)
Barley powdery mildew control effect test A dilute solution of a wettable powder prepared according to Example 4 was used on a 1-leaf seedling of barley (variety: Azuma Golden) grown in a plastic pot with a diameter of 6 cm in a greenhouse ( 100 ppm) was sprayed (sprinkles of leaves and leaves) per pot. The day after the drug treatment, a spore suspension of spores (spore concentration 5 × 10 ⁵ cells / ml) of barley powdery mildew (Erysiphe graminis) formed on another barley leaf was sprayed in advance. The pot was inoculated with 5 ml of spray per pot, and the disease was controlled in an artificial weather chamber at 20 ° C. Seven days after the inoculation, the lesion area ratio (%) of barley powdery mildew on the first leaf was investigated, and the control value (%) was calculated by the following formula 1. And according to the following Table 4, the control value was converted into the evaluation value. This test was conducted in a triple system of 1 pot per 1 chemical solution concentration. The average evaluation value of the control effect was obtained.

In addition, the degree of chemical damage was investigated according to the following criteria.
Survey index of chemical damage level (assessment based on 6 levels)
5: Excitement 4: Acupuncture 3: Many 2: Slight 1: Slightly 0: None This investigation index of the degree of phytotoxicity was also applied to Test Examples 2 to 3.

  These results are shown in Table 5 below.

In addition, the comparative medicine A in Table 5 shows the following compound. This comparative drug A is described in International Publication No. 01/42201 pamphlet, formulated according to the examples of the present invention, and subjected to a biological test. This comparative drug A is also used as a comparative drug in Test Examples 2-3.

(Test Example 2)
Wheat red rust control effect test A dilute solution of wettable powder prepared according to Example 4 on a 1-leaf seedling of wheat (variety: Norin 61) grown in a plastic pot with a diameter of 6 cm in a greenhouse ( (100 ppm) was sprayed 10 ml per pot (stem and leaf spraying). The day after the drug treatment, a pot sprayed with a spore suspension (spore concentration 5 × 10 ⁵ cells / ml) of summer spore of wheat rust (Puccinia recondita) previously formed on another wheat leaf On the top, 5 ml per pot was spray-inoculated, and the disease was controlled in an artificial climate room at 20 ° C. Ten days after the inoculation, the number of lesions on the first leaf was examined, and the control value (%) was calculated by the following formula 2. And according to said Table 4, the control value was converted into the evaluation value. This test was conducted in a triple system of 1 pot per 1 chemical solution concentration. The average evaluation value of the control effect was obtained.

Moreover, the investigation index (evaluation in six steps) of the degree of phytotoxicity to wheat was investigated according to the above.
These results are shown in Table 6 below.

(Test Example 3)
Cucumber gray mold control effect test A cucumber (variety: Sagamihanjiro) 1.5 leaf stage seedling cultivated in a plastic pot with a diameter of 6 cm in a greenhouse was treated with a wettable powder prepared according to Example 4. 10 ml of diluted solution (100 ppm) was sprayed per pot (stem and leaf spraying). The day after the drug treatment, inoculated on the first leaf of the cucumber with an agar piece (diameter 5 mm) of a cucumber gray mold (Botrytis cinerea) previously cultured on a potato broth medium. Put in the greenhouse. Four days after the inoculation, the lesion diameter (cm) was measured, and the control value (%) was calculated by the following formula 3. And according to said Table 4, the control value was converted into the evaluation value. This test was conducted in a triple system of 1 pot per 1 chemical solution concentration. The average evaluation value of the control effect was obtained.

In addition, a survey index (assessed in 6 stages) of the degree of phytotoxicity to cucumber was investigated according to the above.
These results are shown in Table 7.

(Test Example 4)
Rice blast control effect test Diluted liquid of wettable powder prepared in accordance with Example 4 (500 ppm) on the three leaf seedlings of rice (variety: Asahi) cultivated in a plastic pot with a diameter of 6 cm in a greenhouse 10 ml per one pot was sprayed (foliage spray). The day after the drug treatment, the spore suspension (spore concentration: 1 × 10 ⁶ / ml) of conidia of rice blast fungus (Pyricularia oryzae) previously formed on oatmeal agar medium was sprayed with the drug. 5 ml per pot was spray-inoculated on the pot, and the disease was controlled in an artificial weather room at 24 ° C. Five days after the inoculation, the number of rice blast spots on the third leaf was examined, and the control value (%) was calculated by the following formula 4. And according to following Table 4, the control value (%) was converted into the evaluation value. This test was conducted in a triple system of 1 pot per 1 chemical solution concentration. The average evaluation value of the control effect was obtained.

In addition, a survey index (assessment based on 6 levels) of the degree of phytotoxicity to paddy rice was investigated according to the above.
These results are shown in Table 8 below.

Claims (3)

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

[Wherein X represents an oxygen atom or a direct bond, and Y and Z each independently contains one or two or more atoms selected from the group consisting of a phenyl group, an oxygen atom, a sulfur atom or a nitrogen atom. And a phenyl group, a hetero 5-membered ring or a hetero 6-membered ring may be unsubstituted or substituted with a halogen atom, an alkyl group or a haloalkyl group. . ]   In the general formula (I), Y is a phenyl group which may be unsubstituted or substituted with a halogen atom, an alkyl group or a haloalkyl group, and Z is unsubstituted or a halogen atom, an alkyl The azine derivative or a salt thereof according to claim 1, which is a thiazole ring optionally substituted with a group or a haloalkyl group.   An agricultural and horticultural fungicide comprising the azine derivative according to claim 1 and / or a salt thereof.