WO2012169522A1

WO2012169522A1 - Agricultural or horticultural chemical agent, method for controlling plant disease, and product for controlling plant disease

Info

Publication number: WO2012169522A1
Application number: PCT/JP2012/064547
Authority: WO
Inventors: 秀明竪石; 須藤　敬一; 久菅野; 荒木　信行; 山崎　徹
Original assignee: 株式会社クレハ
Priority date: 2011-06-07
Filing date: 2012-06-06
Publication date: 2012-12-13

Abstract

This agricultural or horticultural chemical agent contains various active ingredients, one of which being an azole derivative represented by general formula (I). (In the formula, R¹ represents a cyclopropyl group or an alkyl group substituted with said cyclopropyl group. Said cyclopropyl group may be substituted with a substituent selected from among a bromine atom, a chlorine atom, and a methyl group. R² represents a cyclopropyl group or an alkyl group substituted with the cyclopropyl group. Said cyclopropyl group may be substituted with a chlorine atom.)

Description

Agricultural and horticultural chemicals, plant disease control methods, and plant disease control products

The present invention relates to an agricultural and horticultural chemical and a method for controlling plant diseases. More specifically, it is an agricultural and horticultural drug containing at least one azole compound as an active ingredient, and relates to an agricultural and horticultural drug that can be used for disease control of wheat, paddy rice, fruit trees, sugar beet and the like. . The present invention also relates to a product for controlling plant diseases containing at least two active ingredients separately.

Conventionally, as an active ingredient of an agricultural and horticultural fungicide, a hydroxyethylazole derivative which is a hetero 5-membered ring containing one or more nitrogen atoms in the ring, and a cycloalkyl group or cyclohexane is further bonded to the carbon atom to which the hydroxy group is bonded. Many derivatives in which an alkyl group substituted with an alkyl group is bonded have been proposed (see, for example, Patent Documents 1 to 13).

Further, some 2-substituted-5-benzyl-1-azolylmethylcyclopentanol derivatives are known to exhibit bactericidal activity (see, for example, Patent Documents 14 and 15).

European Patent Application No. 0015756 European Patent Application Publication No. 0052424 European Patent Application Publication No. 0061835 European Patent Application No. 0297345 European Patent Application Publication No. 0047594 European Patent Application No. 0212605 Japanese Patent Publication “JP-A-56-97276” Japanese Patent Publication “JP-A-61-226049” Japanese Patent Publication “JP-A-2-286664” Japanese Patent Publication “JP 59-98061 A” Japanese Patent Publication “Japanese Patent Laid-Open No. 61-271276” European Patent Application No. 0229642 Japanese Patent Publication “JP-A-4-230270” Japanese Patent Publication “JP-A-1-93574” Japanese Patent Publication “Japanese Patent Laid-Open No. 1-186871” Japanese Patent Publication “JP-A-5-271197” Japanese Patent Publication “JP-A-1-301664”

In disease control with agricultural and horticultural fungicides, there are problems such as the effects on non-target organisms and the environment, and the appearance of drug-resistant bacteria. In order to reduce the toxicity to non-target organisms and the burden on the environment, and to suppress the appearance of drug resistance, a bactericide that can exert a high control effect while reducing the amount of drug sprayed is desired.

The present invention has been made in view of the above-described problems, and provides an agricultural and horticultural medicine that reduces the amount of spraying required to obtain the same level of effect as compared to conventional medicines. Main purpose.

In order to solve the above problems, the present inventors synthesized a large number of azole derivatives and examined the chemical structure and physiological activity in detail. As a result, the present inventors have used an azole derivative represented by the following general formula (I) as a mixture with a conventionally used azole compound (especially at least one of metconazole and epoxiconazole). The present invention has been completed.

That is, the agricultural and horticultural agent according to the present invention is an agricultural and horticultural agent containing a plurality of active ingredients, and one of the active ingredients is an azole derivative represented by the following general formula (I). .

(In formula (I), R ¹ represents a cyclopropyl group or an alkyl group having 1 or 2 carbon atoms in which one hydrogen atom is substituted with the cyclopropyl group. At least one of the cyclopropyl groups in R ¹ The hydrogen atom may be substituted with a substituent selected from a bromine atom, a chlorine atom and a methyl group, and R ² represents a carbon number in which a cyclopropyl group or one hydrogen atom is substituted with the cyclopropyl group. Represents an alkyl group of 1 or 2. At least one hydrogen atom of the cyclopropyl group in R ² may be substituted with a chlorine atom.
The azole derivative represented by the above general formula (I) exhibits a controlling effect against a wide range of plant diseases. Furthermore, the azole derivative represented by the general formula (I) is used in combination with other active ingredients and exhibits a synergistic effect as compared with the case where each is used alone. Therefore, in the agricultural and horticultural medicine containing the azole derivative represented by the general formula (I) as one of the active ingredients, the amount of spray for obtaining the same effect as that of the conventional medicine can be reduced.

In addition, as a combined preparation for using a mixture of a plurality of active ingredients, a product for controlling plant diseases comprising the azole derivative represented by the above general formula (I) and other active ingredients separately is also included in the present invention. Included in the category.

Furthermore, a plant disease control method including a procedure for performing foliage treatment or non-foliage treatment using the above agricultural and horticultural chemicals is also included in the scope of the present invention.

In the present specification, the symbols defining the same substituent, functional group or atom in each general formula are assigned the same symbol, and details such as substitution indicated by the symbol are not redundantly described. For example, the R ¹ represented in the general formula (I), R ¹ shown in the general formula (II) represents the same substituent, functional group or atom.

The agricultural and horticultural medicine according to the present invention contains at least an azole derivative represented by the above general formula (I) as an active ingredient. Agricultural and horticultural drugs containing at least the azole derivative represented by the general formula (I) are more effective against many bacteria causing plant diseases than when other drugs contained as active ingredients are used alone. Show a synergistic bactericidal effect. As a result, the agricultural and horticultural medicine according to the present invention has an effect of reducing the amount of the medicine sprayed to show the same degree of control effect as compared with the case where the conventional medicine is used alone. In addition, the agricultural and horticultural medicine according to the present invention also has the effect of reducing the toxicity to non-target organisms and the burden on the environment, and suppressing the appearance of pathogenic bacteria having drug resistance.

2 is a drawing-substituting graph showing the results of a test for controlling effect on wheat red mold of Test Example 1. FIG. 5 is a drawing-substituting graph showing the results of a test for controlling effect on wheat red mold of Test Example 2. FIG. 6 is a drawing-substituting graph showing the results of a test for controlling effect on wheat red mold of Test Example 4. FIG. FIG. 6 is a drawing-substituting graph showing the results of a control effect test for wheat leaf mold when using Compound I-4 and metconazole in Test Example 5. FIG. FIG. 5 is a drawing-substituting graph showing the results of a control effect test for wheat leaf blight when using Compound I-8 and metconazole in Test Example 5. FIG. It is a figure which shows the equal effect curve in the control value of the plant disease control composition in Test Example 21.

Hereinafter, preferred embodiments for carrying out the present invention will be described. In addition, embodiment described below shows an example of typical embodiment of this invention, and, thereby, the range of this invention is not interpreted narrowly.

In the present embodiment, the same terms are used with the same meaning unless otherwise specified. The same applies to symbols indicating substituents, functional groups or atoms, or symbols indicating the number thereof in the general formula.

1. Admixture The agricultural and horticultural agent according to the present invention is a so-called admixture and contains a plurality of active ingredients. One of the active ingredients is an azole derivative represented by the following general formula (I). That is, the agricultural and horticultural agent according to the present invention contains at least one compound as an active ingredient in addition to the azole derivative represented by the general formula (I).

In addition, the active ingredient contained in the agricultural and horticultural medicine according to the present invention is not particularly limited as long as it is two kinds (components) or more. However, in the agricultural and horticultural medicine according to the present invention, the compound contained as an active ingredient in addition to the azole derivative represented by the general formula (I) is a compound having an ergosterol biosynthesis inhibitory ability, an succinate dehydrogenase inhibitory ability. It is preferable to be at least one selected from a compound having a compound, a strobilurin-based compound, a benzimidazole compound, and metalaxyl. Specific examples of the active ingredient contained in the agricultural and horticultural chemical according to the present invention will be described in detail below.

2. Azole derivatives, etc. (1) Compound (I)
The azole derivative represented by the general formula (I) (hereinafter referred to as compound (I)) blended as an active ingredient in the agricultural and horticultural medicine according to the present invention will be described.

Hereinafter, the definition content and specific examples of each symbol (R ¹ and R ² ) of compound (I) will be described.

(1-1) R ¹ and R ²
R ¹ represents a cyclopropyl group or an alkyl group having 1 or 2 carbon atoms in which one hydrogen atom is substituted with a cyclopropyl group. At least one hydrogen atom of these cyclopropyl groups may be substituted with one or more substituents selected from a bromine atom, a chlorine atom and a methyl group, for example, 1 to 4 substituents.

Specific examples of the alkyl group having 1 or 2 carbon atoms substituted with a cyclopropyl group include a cyclopropylmethyl group and a 2- (cyclopropyl) ethyl group.

R ² represents a cyclopropyl group or an alkyl group having 1 or 2 carbon atoms in which one hydrogen atom is substituted with a cyclopropyl group. At least one hydrogen atom of these cyclopropyl groups may be substituted with a chlorine atom, for example, 1 or 2 substituted.

In the azole derivative represented by the general formula (I), the number of substitutions by a substituent in the cyclopropyl group in R ¹ is 1 to 4, and the number of substitutions by a chlorine atom in the cyclopropyl group in R ² is 1 or 2. Is preferable from the viewpoint of activity.

(1-2) Isomer In the compound (I), when R ¹ and R ² are different, the carbon atom to which the hydroxy group is bonded is an asymmetric carbon. That is, optical isomers exist in compound (I). In addition to the asymmetric carbon, an asymmetric carbon may exist in R ¹ and R ² . In this case, since compound (I) has a plurality of asymmetric carbons, diastereomer exists in compound (I). In the present specification and the like, the “diastereomer” refers to a stereoisomer produced by the presence of a plurality of asymmetric carbon atoms in a molecule and having no mirror image relationship. The compound (I) in the present specification and the like may consist of any isomers present or may contain each isomer in an arbitrary ratio.

(1-3) Specific Examples Specific examples of the compound (I) are shown below.

(2) Ergosterol Biosynthesis Inhibitory Compound Subsequently, a case where a compound having an ergosterol biosynthesis inhibition (EBI) ability (ergosterol biosynthesis inhibition compound) is included as an active ingredient of the agricultural and horticultural medicine according to the present invention will be described. To do. The agricultural and horticultural medicine according to the present invention contains the following ergosterol biosynthesis inhibiting compound and compound (I) as active ingredients, so that the ergosterol biosynthesis inhibiting compound shown below is used as a single agent. Thus, it is possible to reduce the spraying amount of the medicine necessary for obtaining the same effect.

Examples of ergosterol biosynthesis inhibiting compounds include azaconazole, viteltanol, bromconazole, difenoconazole, cyproconazole, diniconazole, fenarimol, fenbuconazole, fenpropidin, fenpropimorph, flukinconazole, flusilazole, flutriafor, hexa Conazole, imazalyl, imibenconazole, metconazole, ipconazole, microbutanyl, nuarimol, oxpoconazole, pefazoate, penconazole, prochloraz, propiconazole, prothioconazole, epoxiconazole, cimeconazole, spiroxamine, tebuconazole, tetraconazole Triadimephone, Triadimenol, Triflumizole, Trifolin, Triticonazole, Fenhe Samido, mention may be made of dodemorph, the fenpropimorph and tridemorph. Among these, an azole compound or fenpropimorph is preferable, and metconazole, epoxiconazole, ipconazole, prothioconazole, prochloraz, tebuconazole, or fenpropimorph is more preferable. Agricultural and horticultural drugs including metconazole, epoxiconazole, ipconazole, prothioconazole, prochloraz, tebuconazole or fenpropimorph exhibit particularly high activity.

(2-1) Metoconazole Metoconazole (see the following structural formula) is known as a triazole compound that exhibits a high control effect on diseases such as wheat, fruit trees, sugar beet, shiba and rice. Metoconazole may be produced by a conventionally known method.

(2-2) Epoxyconazole Epoxyconazole (see the structural formula below) is known as a triazole compound that exhibits a high control effect on diseases such as wheat. Epoxyconazole may be produced by a conventionally known method.

(3) SDHI compound Further, the agricultural and horticultural agent according to the present invention may contain a compound having an ability to inhibit succinate dehydrogenase (also referred to as an SDHI compound) as an active ingredient.

The SDHI compound may be included instead of the above azole compound, or may be included together with the above azole compound. The agricultural and horticultural medicine according to the present invention contains the SDHI compound and the compound (I) shown below as active ingredients, so that it is comparable to the case of using the SDHI compound shown below as a single agent. It is possible to reduce the spray amount of the medicine necessary for obtaining the effect.

Examples of SDHI compounds include bixafen, boscalid, pentiopyrad, isopyrazam, fluopyram, furametopyl, tifluzamide, flutolanil, mepronil, fenfuran, carboxin, oxycarboxyne and benodanyl. Among these, bixafen (see the structural formula below) is particularly preferable. Bixafen is known as an SDHI compound that exhibits a high control effect on diseases of vegetables such as cucumber. Bixafen may be produced by a conventionally known method. Agricultural and horticultural drugs including bixafen, boscalid, pentiopyrad, isopyrazam, fluopyram, furametopil, or benodanyl show particularly high activity.

(4) Strobilurin-based compound Furthermore, the agricultural or horticultural agent according to the present invention may contain a strobilurin-based compound as an active ingredient. A strobilurin-based compound is a compound that inhibits the electron transport system of pathogenic bacteria.

The strobilurin compound may be included in place of the above azole compound and the above SDHI compound, or may be included together with at least one of the above azole compound and the above SDHI compound. . The agricultural and horticultural agent according to the present invention contains the following strobilurin-based compound and compound (I) as active ingredients, so that it is comparable to when using the strobilurin-based compound shown below as a single agent. It is possible to reduce the spray amount of the medicine necessary for obtaining the effect.

Examples of strobilurin-based compounds include pyraclostrobin, azoxystrobin, dimethoxystrobin, famoxadone, floxastrobin, metminostrobin, orisatrobin, pyraclostrobin, trifloxystrobin, dimoxystrobin, fenamidone, and Mention may be made of cresoxime methyl. Among these, pyraclostrobin (see the following structural formula), azoxystrobin, or cresoxime methyl is preferable. Pyraclostrobin is known as a strobilurin-based compound that exhibits a high control effect on a wide range of diseases such as rice, wheat, vegetables, and fruit trees. Note that pyraclostrobin may be produced by a conventionally known method. Agricultural and horticultural agents including pyraclostrobin, azoxystrobin or cresoxime methyl show particularly high activity.

(5) Benzimidazole Compound Furthermore, the agricultural and horticultural agent according to the present invention may contain a benzimidazole compound as an active ingredient.

The benzimidazole compound may be included instead of the above azole compound, the above SDHI compound and the above strobilurin compound, or the above azole compound, the above SDHI compound and the above strobilurin compound. It may be included together with at least one of these. The agricultural and horticultural medicine according to the present invention contains the following benzimidazole compound and compound (I) as active ingredients, so that it is comparable to the case where the benzimidazole compound shown below is used alone. It is possible to reduce the spray amount of the medicine necessary for obtaining the effect.

Examples of benzimidazole compounds include benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate methyl, and dietofencarb. Among these, thiophanate methyl is preferable.

(6) Metalaxyl Furthermore, the agricultural and horticultural agent according to the present invention may contain metalaxyl as an active ingredient. Metalaxyl may be included instead of the above azole compound, the above SDHI compound, the above strobilurin compound and the above benzimidazole compound, or the above azole compound, the above SDHI compound, or the above. And at least one of the above-mentioned strobilurin-based compounds and the above-described benzimidazole compounds. The agricultural and horticultural medicine according to the present invention contains metalaxyl and compound (I) as active ingredients, so that it is necessary to spread the medicine necessary for obtaining the same effect as when using metalaxyl alone. The amount can be reduced.

The active ingredient contained in the agricultural and horticultural medicine according to the present invention may be three or more. In this case, the agricultural and horticultural agent according to the present invention contains at least two kinds of the above-described compounds in addition to the compound (I). Of course, different series of compounds may be included. However, in order to make use of the effect of the compound (I), it is preferable that at least one of metconazole, epoxiconazole, bixaphene and pyractostrobin is contained.

In addition, each compound mentioned above is an example, and even if it is a compound which is not mentioned above, if it has the same activity, it can be contained as an active ingredient in the agricultural and horticultural medicine which concerns on this invention.

3. Production Method of Compound (I) (1) Step A1
Next, the manufacturing method of compound (I) is demonstrated. One embodiment of this production method includes a step of reacting an oxirane compound represented by the following general formula (II) with 1,2,4-triazole represented by the following general formula (III) (step A1). (See the following reaction formula (1)). Hereinafter, the oxirane compound represented by the general formula (II) is referred to as “compound (II)”, and the 1,2,4-triazole represented by the general formula (III) is referred to as “compound (III)”.
Reaction formula (1)

Here, the definition contents of R ¹ and R ² are as described above.

M represents a hydrogen atom or an alkali metal.

In this step, a carbon atom in the oxirane ring of compound (II) is reacted with compound (III) to form a carbon-nitrogen bond between the carbon atom in the oxirane ring of compound (II) and the nitrogen atom of compound (III). Is generated.

At this time, the solvent used is not particularly limited.

The amount of compound (III) used relative to compound (II) is, for example, 0.5 to 10 times mol, preferably 0.8 to 5 times mol. Moreover, you may add a base if desired. In this case, the amount of the base used relative to compound (III) is, for example, 0 to 10 times mol (excluding 0), preferably 0.5 to 5 times mol.

The reaction temperature and reaction time can be appropriately set depending on the type of solvent and base used.

(2) Process A2
As a suitable first synthesis method of the compound (II) used in the step A1, a halohydrin compound represented by the general formula (VI) (hereinafter referred to as “compound (VI)”) is dissolved in a solvent in the presence of a base. (See the following reaction formula (2)).
Reaction formula (2)

Here, the definition contents of R ¹ and R ² are as described above. X represents a halogen atom.

Bases used include alkali metal or alkaline earth metal hydroxide salts such as sodium hydroxide, potassium hydroxide and calcium hydroxide; alkali metal carbonates or hydrogen carbonates such as sodium carbonate and potassium carbonate, etc. Can be preferably used, but is not limited thereto.

The amount of the base is preferably 0.5 to 20 times mol, more preferably 0.8 to 5 times mol for the compound (VI).

The solvent is not particularly limited. When an aqueous base solution is used with a hydrophobic solvent, phase transfer of quaternary ammonium salts such as tetrabutylammonium salt, trimethylbenzylammonium salt and triethylbenzylammonium salt, crown ether and the like, etc. into the reaction mixture. It is also possible to carry out the reaction by adding a catalyst.

(3) Process A3
The compound (VI) used in step A2 is a compound represented by the general formula (IV) with respect to the carbonyl group of the compound represented by the general formula (VII) (hereinafter referred to as “compound (VII)”) (hereinafter referred to as “compound (VII)”). , Referred to as “compound (IV)”, to produce a carbon-carbon bond (see the following reaction formula (3)).
Reaction formula (3)

Here, the definition contents of R ¹ and R ² are as described above.

L includes alkali metal, alkaline earth metal-Q ₁ (Q ₁ is a halogen atom), 1/2 (Cu alkali metal), zinc-Q ₂ (Q ₂ is a halogen atom), etc. Is possible. Examples of the alkali metal include lithium, sodium, and potassium, and it is preferable to use lithium. Examples of the alkaline earth metal include magnesium.

The solvent used is not particularly limited as long as it is an inert solvent under the reaction conditions. When an aqueous solution is used with a hydrophobic solvent, a phase transfer catalyst such as a quaternary ammonium salt such as tetrabutylammonium salt, trimethylbenzylammonium salt and triethylbenzylammonium salt, crown ether and the like is added to the reaction mixture. It is also possible to carry out the reaction by adding.

The amount of compound (IV) to be used relative to compound (VII) is, for example, 0.5 to 10 times mol, preferably 0.8 to 5 times mol. In addition, it is preferable to use the compound (IV) prepared immediately before. Further, when L is zinc-Q ₂ (Q ₂ is a halogen atom), the reaction can be carried out while generating compound (IV) in the reaction system.

Further, a Lewis acid may be added if desired. The amount of the Lewis acid used relative to compound (IV) is, for example, 0 to 5 times mol (excluding 0), preferably 0.1 to 2 times mol. Examples of the Lewis acid used include aluminum chloride, zinc chloride, and cerium chloride.

The reaction temperature and reaction time can be appropriately set depending on the solvent used, the type of compound (VII), the type of compound (IV), and the like.

The compound (IV) and compound (VII) used here may be produced by existing techniques.

(4) Process A2a
Among the compounds (II) used in the step A1, a compound having a gem-dihalocyclopropane structure in the molecule represented by the general formula (II-a) (hereinafter referred to as “compound (II-a)”) Can be obtained by the following suitable second synthesis method. That is, it can be synthesized from an oxirane compound having a double bond in the molecule represented by the general formula (VIII) (hereinafter referred to as “compound (VIII)”) by reaction of trihalomethane with a base such as sodium hydroxide. it can. Alternatively, it can be synthesized from compound (VIII) by addition reaction of halocarbenes generated by thermal decomposition of trihaloacetate. These reactions are shown in the following reaction formula (4).
Reaction formula (4)

Here, the definition content of R ² is as described above.

R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² each independently represent a hydrogen atom, a bromine atom, a chlorine atom, or a methyl group.

n represents an integer of 0 to 2. Here, when n is 2, there are a plurality of R ¹¹ and R ¹² , but their definition contents independently represent the definition contents of R ¹¹ and R ¹² .

X ¹ and X ² each independently represent a halogen atom.

Hereinafter, a method of synthesizing compound (II-a) by reaction of trihalomethane with a base such as sodium hydroxide will be described.

Examples of the trihalomethane used include chloroform, bromoform, chlorodifluoromethane, dichlorofluoromethane, and dibromofluoromethane. The amount of trihalomethane used for compound (VIII) is not particularly limited.

As the solvent, trihalomethane itself, or other solvents such as dichloromethane or toluene inert to the reaction can be used.

When adding a base, when using an aqueous solution such as an aqueous sodium hydroxide solution, it is preferable to use a phase transfer catalyst. The phase transfer catalyst that can be used is not particularly limited. The amount of the phase transfer catalyst used is, for example, 0.001 to 5 times mol, preferably 0.01 to 2 times mol, of the compound (VIII).

Also, the base used is not particularly limited. The amount of the base to be used is, for example, 0.1 to 100 times mol, preferably 0.8 to 50 times mol, of compound (VIII). The concentration of the aqueous alkali metal hydroxide solution at this time is, for example, 10% to a saturated aqueous solution, preferably 30% to a saturated aqueous solution.

The reaction temperature is, for example, 0 ° C. to 200 ° C., preferably 10 ° C. to 150 ° C. The reaction time is 0.1 hour to several days, preferably 0.2 hour to 2 days.

(5) Process A4
Compound (VIII) used in step A2a can be obtained by the following first preferred synthesis method. First, the above-mentioned compound (VII) is reacted with an organometallic compound represented by the general formula (X) (hereinafter referred to as “compound (X)”), and the organometallic compound to the carbonyl carbon atom of the compound (VII) A carbon-carbon bond is formed by a nucleophilic addition reaction by. Thereby, a halohydrin compound represented by the general formula (IX) (hereinafter referred to as “compound (IX)”) is obtained. Next, compound (IX) is oxiraneed in the presence of a base to obtain compound (VIII) (see the following reaction formula (5)).
Reaction formula (5)

Here, the definition contents of R ² , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , L, X, and n are as described above.

Hereinafter, the reaction of reacting compound (VII) with compound (X) to obtain compound (IX) will be described.

The solvent used is not particularly limited as long as it is an inert solvent. These solvents can also be used as a mixture. Moreover, when using water for reaction, it is also possible to mix and use with an organic solvent. When water is used together with a hydrophobic organic solvent, a quaternary ammonium salt such as tetrabutylammonium salt, trimethylbenzylammonium salt and triethylbenzylammonium salt, crown ether and the like, etc. are added to the reaction mixture as necessary. A phase transfer catalyst may be added.

The amount of compound (X) used relative to compound (VII) is, for example, 0.5 to 10-fold mol, preferably 0.8 to 5-fold mol. It is preferable to use the compound (X) prepared immediately before. Further, when L is zinc-Q ₂ (Q ₂ is a halogen atom), the reaction can be carried out while generating the compound (X) in the reaction system.

If desired, a Lewis acid may be added. In this case, the amount of Lewis acid used relative to compound (VII) is, for example, 0 to 5 times mol (excluding 0), preferably 0.1 to 2 moles. Examples of the Lewis acid used include aluminum chloride, zinc chloride, and cerium chloride.

The reaction temperature and reaction time can be appropriately set depending on the type of solvent used, compound (VII), compound (X), and the like.

The oxiraneation of compound (IX) in this step can be carried out under the same conditions as the synthesis of compound (II) from compound (VI) in step A2.

As the compound (X) used here, a compound that can be produced by an existing synthesis technique such as conversion of an alkenyl halide compound to an organometallic reagent may be used. For example, when L in compound (X) is zinc-Q ₂ (Q ₂ is a halogen atom), the method shown in the following reaction formula (6) can be employed.

In order to generate compound (Xa), a method of reacting alkenyl halide represented by compound (XVII) with zinc in the system is suitable. That is, compound (Xa) is prepared by mixing in a solvent in the presence of compound (XVII).
Reaction formula (6)

Here, the definition contents of R ² , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , Q ₂ , X, and n are as described above.

Here, the solvent used is not particularly limited. Moreover, when using water for reaction, it is also possible to mix and use with an organic solvent. When water is used together with a hydrophobic organic solvent, a quaternary ammonium salt such as tetrabutylammonium salt, trimethylbenzylammonium salt and triethylbenzylammonium salt, crown ether and the like, etc. are added to the reaction mixture as necessary. You may make it react by adding a phase transfer catalyst.

As an example of a more preferable production method of compound (Xa), an organic solvent containing compound (VII) and an aqueous solution containing an additive that promotes activation of zinc such as a salt containing hydrogen halide or hydrogen halide, And alkenyl halide represented by the compound (XVII) and zinc can be mixed under the conditions of contact with each other.

Examples of the salt containing hydrogen halide include ammonium chloride and ammonium bromide. Examples of the hydrogen halide include hydrogen chloride and hydrogen bromide.

The amount of compound (XVII) used at this time is, for example, 0.5 to 20-fold mol, preferably 0.8 to 10-fold mol based on compound (VII). The amount of zinc used is, for example, 0.5 to 20-fold mol, preferably 0.8 to 10-fold mol based on compound (VII).

The reaction temperature is preferably 0 ° C. to 150 ° C., more preferably 5 ° C. to 100 ° C. The reaction time is preferably 0.1 to 24 hours, and more preferably 0.5 to 12 hours.

The compound (VII) used in this step may be one produced by existing technology.

(6) Process A4a
Among the compounds (VIII) used in step A2a, the oxirane compound represented by the general formula (VIII-a) (hereinafter referred to as compound (VIII-a)) is prepared by the following second suitable synthesis method. Obtainable. That is, with respect to the methyl ketone compound represented by the general formula (XV) (hereinafter referred to as “compound (XV)”), in the presence of a base, a dialkyl carbonate compound represented by the general formula (XVI) (hereinafter referred to as “compound (XVI)”). And a ketoester compound represented by the general formula (XIII) (hereinafter referred to as “compound (XIII)”). Next, nucleophilicity to the halogenated alkenyl compound represented by the general formula (XIV) (hereinafter referred to as “compound (XIV)”) of the carbon atom bonded to the alkoxycarbonyl group in the compound (XIII) in the presence of a base A carbon-carbon bond is generated by a substitution reaction to obtain an alkenylated ketoester compound represented by the general formula (XII) (hereinafter referred to as “compound (XII)”). Then, the compound (XII) is hydrolyzed and decarboxylated to obtain a carbonyl compound represented by the general formula (XI) (hereinafter referred to as “compound (XI)”). Finally, compound (XI) is oxiraneed to give compound (VIII-a). These reactions are shown in the following reaction formula (7).
Reaction formula (7)

Here, the definition content of R ² is as described above.

R ¹³ represents an alkyl group having 1 to 4 carbon atoms. R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ each independently represent a hydrogen atom, a bromine atom, a chlorine atom, or a methyl group.

m represents 1 or 2. Here, when m is 2, there are a plurality of R ¹⁷ and R ¹⁸ , but their definition contents independently represent the definition contents of R ¹⁷ and R ¹⁸ .

X ³ represents a halogen atom.

First, the reaction of obtaining compound (XIII) by reacting compound (XV) with compound (XVI) in the presence of a base will be described.

This reaction can be carried out in a solvent or using compound (XVI) as a solvent.

The amount of the compound (XVI) used relative to the compound (XV) is, for example, 0.5 times to 20 times mol, preferably 0.8 times to 10 times mol.

The base used is not particularly limited. The amount of the base used relative to compound (XV) is, for example, 0.5 to 10 times mol, preferably 0.8 to 5 times mol.

The reaction temperature is, for example, 0 ° C. to 250 ° C., preferably room temperature to 150 ° C. The reaction time is, for example, 0.1 hour to several days, preferably 0.5 hour to 24 hours.

The compound (XV) and compound (XVI) used here may be those synthesized by methods known in the literature.

Next, the reaction for producing a compound (XII) by producing a carbon-carbon bond by nucleophilic substitution reaction of the carbon atom bonded to the alkoxycarbonyl group in the compound (XIII) to the compound (XIV) will be described.

This reaction is usually performed in a solvent in the presence of a base.

The amount of compound (XIV) used relative to compound (XIII) is, for example, 0.5 times to 10 times mol, preferably 0.8 times to 5 times mol.

The base used is not particularly limited.

The amount of the base used for compound (XIII) is, for example, 0.5 to 10 times mol, preferably 0.8 to 5 times mol.

In the reaction for obtaining compound (XIII) from the above-mentioned compound (XV) in the presence of a base, the acidity of the hydrogen atom in the methylene moiety between the carbonyl group and the ester group of the produced compound (XIII) is the compound ( Since the acidity of the hydrogen atom of the acetyl group of XV) is higher, an alkali metal salt of compound (XIII) is formed in the course of the reaction, so the reaction solution of compound (XIII) is used without isolation as it is. You can also. In that case, it is also possible to react without adding a new base.

The reaction temperature is, for example, 0 ° C. to 250 ° C., preferably room temperature to 150 ° C., and the reaction time is, for example, 0.1 hour to several days, preferably 0.5 hour to 24 hours.

Subsequently, the reaction of hydrolyzing and decarboxylating compound (XII) to obtain compound (XI) will be described.

This hydrolysis and decarboxylation reaction can be carried out in a solvent under basic conditions or acidic conditions.

When the reaction is carried out under basic conditions, an alkali metal base such as sodium hydroxide or potassium hydroxide is usually used as the base. As the solvent, water containing alcohol or the like is usually used in addition to water.

When the reaction is carried out under acidic conditions, the acid catalyst is preferably an inorganic acid such as hydrochloric acid, hydrobromic acid and sulfuric acid, or an organic acid such as acetic acid. The solvent is usually added by adding water or an organic acid such as acetic acid to water.

The reaction temperature is, for example, 0 ° C. to the reflux point, preferably 10 ° C. to the reflux point. The reaction time is, for example, 0.1 hour to several days, preferably 0.5 hour to 24 hours.

Finally, a reaction in which the compound (XI) is oxiraneated to obtain the compound (VIII-a) will be described.

As this reaction, a method in which the compound (XI) is reacted with a sulfur ylide such as a sulfonium methylide such as dimethylsulfonium methylide or a sulfoxonium methylide such as dimethylsulfoxonium methylide in a solvent can be employed.

The sulfonium methylide or sulfoxonium methylide used is a sulfonium salt (for example, trimethylsulfonium iodide or trimethylsulfonium bromide) or a sulfoxonium salt (for example trimethylsulfoxonium iodide or trimethylsulfone) in a solvent. Xoxonium bromide and the like) and a base can be reacted.

The amount of the sulfonium methylides or sulfoxonium methylides is, for example, 0.5 to 10 times mol, preferably 0.8 to 5 times mol for the compound (XI).

The solvent used is not particularly limited. Two or more kinds of solvents can be mixed and used.

Also, when water is used in the reaction, it can be used by mixing with an organic solvent. When water is used together with a hydrophobic organic solvent, a quaternary ammonium salt such as tetrabutylammonium salt, trimethylbenzylammonium salt and triethylbenzylammonium salt, crown ether and the like, etc. are added to the reaction mixture as necessary. It is also possible to carry out the reaction by adding a phase transfer catalyst.

The base used for the production of sulfonium methylides and sulfoxonium methylides is not particularly limited.

The reaction temperature and reaction time can be appropriately set depending on the type of the solvent used, compound (XI), sulfonium salt or sulfoxonium salt, base and the like.

In the steps of the production method according to the present invention described above, the solvents, bases, acids, and the like used can be as follows unless otherwise specified.

[solvent]
The solvent used is not particularly limited. For example, halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic ethers such as petroleum ether, hexane and methylcyclohexane. Hydrocarbons, amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidinone, ethers such as diethyl ether, tetrahydrofuran and dioxane, and alcohols such as methanol and ethanol Is mentioned. In addition, examples of the solvent include water, carbon disulfide, acetonitrile, ethyl acetate, pyridine, and dimethyl sulfoxide. These solvents can be used as a mixture of two or more.

Further, as the solvent, a solvent composition comprising a solvent that does not form a uniform layer with each other can be mentioned. For example, a phase transfer catalyst such as a quaternary ammonium salt such as tetrabutylammonium salt, trimethylbenzylammonium salt and triethylbenzylammonium salt, crown ether and the like may be added to the reaction mixture to perform these reactions. it can. In this case, the solvent to be used is not particularly limited, but benzene, chloroform, dichloromethane, hexane, toluene, tetrahydrofuran and the like can be used as the oil phase.

[Base / acid]
You may add a base or an acid to the above-mentioned solvent.

Although the base used is not particularly limited, for example, alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate; alkaline earth metal carbonates such as calcium carbonate and barium carbonate; Alkali metal hydroxides such as sodium and potassium hydroxide; alkali metals such as lithium, sodium and potassium; alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; sodium hydride, potassium hydride And alkali metal hydrides such as lithium hydride; organometallic compounds of alkali metals such as n-butyllithium and methylmagnesium bromide; alkali metal amides such as lithium diisopropylamide; and triethylamine Pyridine, 4-dimethylaminopyridine, N, N-dimethylaniline and 1,8-diazabicyclo-7- [5.4.0] Organic amines such as undecene, and the like.

The acid to be used is not particularly limited. For example, inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid and sulfuric acid, organic acids such as formic acid, acetic acid, butyric acid and p-toluenesulfonic acid, and chloride Examples include Lewis acids such as lithium, lithium bromide, rhodium chloride, zinc chloride, iron chloride and aluminum chloride.

4). Plant Disease Control Composition (1) Triazole Compound The plant disease control composition according to the present invention may be a plant disease control composition containing two types of triazole derivatives as its active ingredients. One triazole derivative is a compound represented by the following formula (I ′) (hereinafter referred to as “compound (I ′)”). The other triazole derivative is, for example, a compound represented by the following formula (XVIII) (hereinafter referred to as “compound (XVIII)”).

In formula (I ′), R ²⁵ represents a cyclopropyl group in which at least one hydrogen atom is substituted with a halogen atom, a methyl group or an ethyl group, or a carbon in which one hydrogen atom is substituted with the cyclopropyl group. R ²⁶ represents an alkyl group having 1 to 4 and R ²⁶ represents a cyclopropyl group in which at least one hydrogen atom is substituted with a halogen atom, or a carbon number in which one hydrogen atom is substituted with the cyclopropyl group 1 to 3 alkyl groups are represented.

In Formula (XVIII), R ¹⁹ represents a haloalkyl group having 1 to 4 carbon atoms or a haloalkenyl group having 2 to 4 carbon atoms. Examples of R ¹⁹ include a chloromethyl group, a bromomethyl group, a chloroethyl group, and a 2-chloro-2-propenyl group.

In formula (XVIII), R ²⁰ represents an alkyl group or haloalkyl group having 1 to 4 carbon atoms, or an alkenyl group or haloalkenyl group having 2 to 4 carbon atoms. Examples of R ²⁰ include a methyl group, an ethyl group, and a chloromethyl group.

In the formula (XVIII), Y represents a halogen atom. Of these, a fluorine atom, a chlorine atom and a bromine atom are preferable. P represents an integer of 0 to 3, preferably 0, 1 or 2, and more preferably 0 or 1. When p is 2 or 3, the plurality of Y may be the same halogen atom as each other or different from each other. There is no restriction | limiting in particular in the position of Y in a benzyl group.

Compound (I ′) may have optical isomers and diastereomers as in Compound (I). Compound (I ′) includes both those containing these isomers alone and those containing each isomer in an arbitrary ratio.

In addition, compound (XVIII) has a stereoisomer based on the configuration of the organic group bonded to the cyclopentane ring, and an optical isomer exists for each stereoisomer. Therefore, the compound (XVIII) includes both those containing these isomers alone and those containing each isomer in an arbitrary ratio.

Examples of one form of the compound (I ′) include a compound represented by the following formula (Ia ′).

Here, X ⁵ to X ⁷ represent a halogen atom or a hydrogen atom, and at least one of X ⁵ to X ⁷ is a halogen atom. When X ⁵ is a hydrogen atom, it is preferable that both X ⁶ and X ⁷ are halogen atoms. s ¹ represents 0 or 1, and s ² represents 0, 1 or 2. R ²⁷ represents a hydrogen atom or a methyl group. When s ² is 2, each other there are two ^{R 27} may be different. R ²⁸ to R ³⁰ represent a hydrogen atom, a halogen atom or a methyl group, and are preferably a hydrogen atom or a halogen atom. X ⁸ and X ⁹ represent a halogen atom, and it is preferable that X ⁸ and X ⁹ are the same halogen atom species.

More specific examples of compound (I ′) are the same as the specific examples of compound (I) described above.

Specific examples of the compound (XVIII) are shown below.

(2) Method for Producing Compound (XVIII) Compound (XVIII) in the present embodiment is a compound represented by the following formula (XX) that can be produced using a known method as shown in the following Scheme 1 (hereinafter referred to as compound) (Referred to as (XX)). Note that the compound represented by the following formula (XVIIIb) has substantially the same structure as the compound represented by the formula (XVIII).

In the compounds shown in Scheme 1, R ²¹ represents a methylene group, a halomethylene group, an alkylene group or haloalkylene group having 2 to 4 carbon atoms, or an alkenylene group or haloalkenylene group having 2 to 4 carbon atoms. Represents. Also, q denotes the number of hydroxy groups bonded to a functional group represented by R ²¹ in formula (XX). Further, R ²² is a hydrogen atom an alkyl group of 1-3 1 carbon atoms which may be substituted, represents a phenyl group or a naphthyl group. X ⁴ represents a halogen atom.

Of the compounds (XX), a compound represented by the following formula (XXa) having a hydroxymethyl group at the 2-position (hereinafter referred to as “compound (XXa)”) is a compound represented by the following formula ( XXVII) can be suitably obtained by the following synthesis method (see Scheme 2 below).

In the compounds shown in Scheme 2, R ²³ and R ²⁴ each independently represents an alkyl group having 1 to 4 carbon atoms. R ²³ is the same functional group as R ²⁰ in compound (X).

5. Agricultural and horticultural chemicals Compound (I) blended as an active ingredient in the agricultural and horticultural chemicals according to the present invention exhibits a controlling effect against a wide range of plant diseases. Furthermore, compound (I) is used in combination with an ergosterol biosynthesis inhibitor compound, SDHI compound, strobilurin compound, benzimidazole compound, metalaxyl, etc., and has a synergistic effect as compared with the case where each is used alone. Demonstrate.

Since compound (I) has a 1,2,4-triazolyl group, it forms an acid addition salt with an inorganic acid or an organic acid, or a metal complex. Compound (I) may be used in the form of these acid addition salts and metal complexes.

Furthermore, at least one of diastereomers or enantiomers present in the compound (I) can be used as an active ingredient such as an agricultural or horticultural agent.

(1) Plant disease control effect The usefulness as an agricultural and horticultural agent according to the present invention will be described.

A drug containing at least compound (I) as an active ingredient exhibits a control effect against a wide range of plant diseases. Examples of applicable diseases include the following.

Soybean rust (Phakopsora pachyrhizi, Phakopsora meibomiae), rice blast (Pyricularia grisea), rice sesame leaf blight (Cochliobolus miyabeanus), rice white leaf blight (Xanthomonas oryzae), rice rot (Rhizoctonia sol) Nuclear disease (Helminthosporium sigmoideun), rice idiot seedling (Gibberella fujikuroi), rice seedling blight (Pythium aphanidermatum), apple powdery mildew (Podosphaera leucotricha), apple black rot (Venturia inaequalis), apple peach linear Apple spotted leaf blight (Alternaria alternata), apple rot blight (Valsa mali), pear black blight (Alternaria kikuchiana), pear powdery mildew (Phyllactinia pyri), pear red blight (Gymnosporangium asiaticum), pear black blight , Grape powdery mildew (Uncinula necator), grape mildew (Plasmopara viticola), grape late rot (Glomerella cingulata), barley powdery mildew (Erysiphe grami) nis f. sp hordei), barley black rust disease (Puccinia graminis), barley yellow rust disease (Puccinia striiformis), barley spotty disease (Pyrenophora graminea), barley cloud shape disease (Rhynchosporium secalis), wheat .Spsp tritici), wheat red rust (Puccinia ), Wheat leaf blight (Septoria tritici), cucumber powdery mildew (Sphaerotheca fuliginea), cucumber anthracnose (Colletotrichum lagenarium), cucumber downy mildew (Pseudoperonospora cubensis), cucumber gray plague (Phytophthora capsi Erysiphe cichoracearum, tomato ring-rot disease (Alternaria solani), eggplant powdery mildew (Erysiphe cichoracearum), strawberry powdery mildew (Sphae rotheca humuli), tobacco powdery mildew (Erysiphe cichoracearum), sugar beet brown spot (Cercospora beticola), corn smut (Ustillaga maydis), berries of Monasteria fruit tree (Monilinia fructicola), gray mold that causes various crops (Botrytis cinerea), and Sclerotinia sclerotiorum, etc.

In addition, grape rust (Phakopsora ampelopsidis), watermelon vine split (Fusarium oxysporum f.sp.niveum), cucumber vine split (Fusarim oxysporum f.sp.cucumerinum), radish yellow (Fusarium oxysporum f. sp.raphani), tobacco red star disease (Alternaria longipes), pea mosquito summer rot (Alternaria solani), soybean brown spot (Septoria ines glycines), and soybean purpura (Cercospora kikuchii).

Examples of applied plants include wild plants, plant cultivars, plants and plant cultivars obtained by conventional biological breeding such as crossbreeding or protoplast fusion, genetically modified plants and plant cultivars obtained by genetic manipulation. Can be mentioned. Examples of genetically modified plants and plant cultivars include herbicide-tolerant crops, pest-tolerant crops incorporating insecticidal protein production genes, disease-resistant crops incorporating resistance-inducing substance production genes for diseases, improved crops, improved yields Examples include crops, preservative-enhancing crops, and yield-enhancing crops. Specific examples of genetically modified plant cultivars include those containing registered trademarks such as ROUNDUP READY, LIBERTY LINK, CLEARFIELD, YIELDGARD, HERCULEX, and BOLLGARD.

Furthermore, a drug containing at least compound (I) as an active ingredient exhibits an excellent effect of protecting the material from a wide range of harmful microorganisms that invade industrial materials.

(2) Formulation In the agricultural and horticultural medicine according to the present invention, the mixing ratio of compound (I) to metconazole and / or epoxiconazole is 100: 1 to 1: 100, preferably 5: 2 to 50: 3. The same mixing ratio can be used for ergosterol biosynthesis inhibiting compounds other than metconazole and epoxiconazole, SDHI compounds, strobilurin compounds, benzimidazole compounds and metalaxyl. In addition, when the agricultural and horticultural medicine according to the present invention includes a plurality of active ingredients in addition to the compound (I), the mixing ratio of the active ingredients other than the compound (I) may be appropriately set according to the intended use of the medicine. .

Also, the agricultural and horticultural preparation may contain various components and can be mixed with a solid carrier, a liquid carrier, a surfactant, or other preparation adjuvant. Examples of the dosage form of the agricultural and horticultural preparation include various forms such as powders, wettable powders, granules, and emulsions.

In these preparations, the active ingredient is preferably contained in an amount of 0.1 to 95% by weight, more preferably 0.5 to 90% by weight, and more preferably 2 to 80% by weight based on the total amount of the preparation. Is more preferable.

When mixing other ingredients with agricultural and horticultural chemicals to form various preparations, not only the method of formulating a mixture of each active ingredient, but formulating each of the active ingredients separately and mixing them By doing so, it can also be prepared as an agricultural and horticultural preparation in the form of a preparation containing a plurality of active ingredients. Therefore, a product for controlling plant diseases which contains Compound (I) and other active ingredients separately as a combined preparation for use in mixture in plant disease control is also included in the scope of the present invention. When three or more active ingredients are contained, the active ingredients other than the compound (I) may be separate.

Examples of carriers, diluents, and surfactants used as formulation adjuvants include talc, kaolin, bentonite, diatomaceous earth, white carbon, and clay as solid carriers. Liquid diluents include water, xylene, toluene, chlorobenzene, cyclohexane, cyclohexanone, dimethyl sulfoxide, dimethylformamide, and alcohol. Surfactants should be properly used depending on the effect, such as polyoxyethylene alkylaryl ether and polyoxyethylene sorbitan monolaurate as emulsifiers, lignin sulfonate and dibutyl naphthalene sulfonate as dispersants, Examples of the wetting agent include alkyl sulfonates and alkyl phenyl sulfonates.

The preparation may be used as it is, or diluted to a predetermined concentration with a diluent such as water. When used after diluting, the concentration of the active ingredient is desirably in the range of 0.001 to 1.0% with respect to the total amount of drug after dilution.

In addition, the amount of compound (I) used in the agricultural and horticultural agent according to the present invention is 20 to 5000 g, more preferably 50 to 2000 g, per 1 ha of agricultural and horticultural land such as fields, rice fields, orchards, and greenhouses. What is necessary is just to set suitably about content of the other active ingredient contained in the said agricultural and horticultural medicine based on the usage-amount of compound (I). Since these use concentrations and amounts vary depending on the dosage form, use time, use method, use place, target crop, etc., they can be increased or decreased without sticking to the above range.

Furthermore, the agricultural and horticultural medicine according to the present invention is combined with other active ingredients (active ingredients contained in bactericides, insecticides, acaricides and herbicides) shown below in addition to the above-mentioned active ingredients, It can also be used with improved performance as a pharmaceutical agent.

<Antimicrobial substances>
The following compounds as melanin biosynthesis inhibitors (MBI agents).

Carpropamide, diclocimet, phenoxanyl, fusalide, pyroxylone, and tricyclazole.

The following compounds are other compounds.

Acibenzoral-S methyl, amisulbrom, 2-phenylphenol (OPP), bench avaricarb isopropyl, Bordeaux solution, borax, bicarbonate, biphenyl, blasticidin-S, bronopol, bupyrimeate, secbutyramine, calcium polysulfide, captafor, captan , Carboxin, quinomethionate, chloronebu, chloropicrin, chlorothalonil, clozolinate, cyazofamide, cyflufenamide, simoxanyl, cyprodinil, dazomet, debacarb, diclofluanid, diclomedin, dichlorane, diflumethrin, dinocup, diphenylamine, dithianone, dodemol Fenphos, etapoxam, ethoxyquin, etridiazole, energy Strobulin, fenpicuronyl, fentin, ferbam, ferrimzone, fluazinam, fludioxonil, furmorph, fluoroimide, flusulfamide, folpette, fosetyl-aluminum, flaxyl, fluopicolide, guazatine, hexachlorobenzene, himexazole, iminoctazine, iprobenfos, iprodicarb , Isopyrazam, Isothianyl, Kasugamycin, Copper preparations (eg copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper), crezooxime methyl, mancopper, mancozeb, maneb, mandipropamide, mepanipyrim , Mepronil, methylam, myrdiomycin, nitrotal-isopropyl, off-race, oxadixyl, o Solinic acid, oxycarboxin, oxytetracycline, pencyclon, pyribencarb, picoxystrobin, piperalin, polyoxin, probenazole, procymidone, propamocarb, propineb, proquinazide, pyrazophos, pyrifenox, pyrimethanil, quinoxyphene, quintozene, silthiophane, sulfur and sulfur Preparations, teclophthalam, technazene, thiram, thiazinyl, tolurophos-methyl, tolylfluanid, triazoxide, validamycin, vinclozolin, dineb, diram, zoxamide, amisulbrom, fluthianyl, varifenal, amethoctrazine, metolaphenone, hydroxyisoxazole, tifluzamide As well as metasulfocarb.

<Insecticide / acaricide / nematicide>
Abamectin, Acephate, Acrinathrin, Alanicarb, Aldicarb, Alletrin, Amitraz, Avermectin, Azadirachtin, Azamethifos, Azinphos-ethyl, Azinphos-methyl, Azocycline, Bacillus filmus, Bacillus subtilis, Bacillus thuringibulbbenthulbenbencarb , Benzoxymate, Bifenazite, Bifenthrin, Bioallethrin, Bioresmethrin, Bistriflurone, Buprofezin, Butocaboxin, ButoxyCarboxin, Kazusafos, Carbaryl, Carbofuran, Carbosulfan, Cartap, CGA 50439, Chlordein, Chloretifos, Chlorphenapal Chlorfenvin foss, chlorfluazuron , Chlormefos, Chlorpyrifos, Chlorpyrifosmethyl, Chromaphenozide, Chlofenthedin, Clothianidin, Chlorantraliniprole, Counpafos, Cryolite, Cyanophos, Cycloproton, Cyfluthrin, Cyhalothrin, Cihexatin, Cipermethrin, Ciphenothrin , Cyromazine, ciazapyr, sienopyrfen, DCIP, DDT, deltamethrin, demeton-S-methyl, diafenthiuron, diazinon, dichlorophen, dichloropropene, dichlorovos, dicofol, dicrotophos, dicyclanil, diflubenzuron, dimethoate, dimethylvinphos, dinobutone Dinotefuran, emamectin, endosulfan, EPN, esfenvalerate, etiophencarb, ethion, Tiprol, etofenprox, etoprofos, etoxazole, famflu, fenamifos, phenazaquin, fenbutatin oxide, fenitrothion, fenocarb, phenothiocarb, phenoxycarb, fenpropatrine, fenpyroximate, fenthionate, fenvalerate, fipronil, flunipyamide Ron, flucitrinate, flufenoxuron, flumethrin, fulvalinate, fulvendiamide, formethanate, fostiazate, halfenprox, furthiocarb, halohenozide, gamma-HCH, heptenofos, hexaflumuron, hexithiazox, hydramethylnon , Imidacloprid, imiprothrin, indoxacarb, isoproca Bu, isoxathion, lufenuron, malathion, mecarbam, metham, methamidophos, methidathione, metiocarb, methomyl, methoprene, methosrine, methoxyphenozide, metorcarb, milbemectin, monocrotofos, nared, nicotine, nitenpyram, novalflumetron, oxyflumetron Tonmethyl, parathion, permethrin, phentoate, folate, fosaron, fosmet, fosfamidon, foxime, pirimicarb, pirimiphos methyl, profenofos, propoxur, prothiophos, pymetrozine, pyracrofos, pyrethrin, pyridaben, pyridalyl, pyrimidifene, pyriproxy Fen, Pyrifluquinazone, Pyriprole, Quinarfos, Shirafu Luofen, Spinosad, Spirodiclofen, Spiromesifene, Spirotetramat, Sulfamide, Sulfotep, SZI-121, Tebufenozide, Tebufenpyrad, Tebupyrimfos, Teflubenzuron, Tefluthrin, Temefos, Terbufos, Tetrachlorbinfos, Thiacloprid, Thiamethoxam Fanox, thiometone, tolfenpyrad, tralomethrin, tralopyril, triazamate, triazophos, trichlorphone, triflumuron, bamidthione, varifenal, XMC, xylylcarb, imisiaphos, and lepimectin.

<Plant growth regulator>
Ansimidol, 6-benzylaminopurine, paclobutrazole, diclobutrazole, uniconazole, methylcyclopropene, mepiquat chloride, ethephone, chlormequat chloride, inabenfide, prohexadione and salts thereof, and trinexa Pack ethyl etc. Moreover, jasmonic acid, brassinosteroid, gibberellin and the like as plant hormones.

(3) Plant disease control method using agricultural and horticultural chemicals In addition to the foliage treatment such as foliage spraying, the agricultural and horticultural chemicals according to the present embodiment are obtained by non-foliage treatment such as seed treatment, irrigation treatment, and water surface treatment. Can also be applied. Therefore, the plant disease control method according to the present embodiment is a method including a procedure for performing foliage treatment or non-foliage treatment using the above-mentioned agricultural and horticultural chemicals. In addition, when performing a non-foliage process, a labor can be reduced compared with the case where a foliage process is performed.

In application by seed treatment, a wettable powder or powder is mixed with the seed and stirred, or the seed is immersed in a diluted wettable powder to attach the drug to the seed. The combined use amount of the active ingredients in the seed treatment is 0.01 to 10000 g, preferably 0.1 to 1000 g, per 100 kg of seeds. In addition, what is necessary is just to utilize the seed processed with the agricultural and horticultural chemical | medical agent which concerns on this invention similarly to a normal seed.

Application by irrigation is performed by treating the planting hole and its surroundings with granules, etc. at the time of transplanting seedlings, or treating the soil around the seeds or plants with granules or wettable powder. . The total use amount of the active ingredients in the irrigation treatment is 0.01 to 10000 g, preferably 0.1 to 1000 g, per 1 m ^{2 of} agricultural and horticultural land.

Application by water surface treatment is performed by treating the surface of paddy fields with granules. The combined use amount of active ingredients in the case of water surface treatment is 0.1 to 10000 g, preferably 1 to 1000 g, per paddy field 10a.

When used for foliage spraying, the total amount of active ingredients used is 20 to 5000 g, more preferably 50 to 2000 g, per ha of agricultural and horticultural lands such as fields, fields, orchards and greenhouses. The concentration and amount used vary depending on the dosage form, time of use, method of use, place of use, target crop, etc., and can be increased or decreased without sticking to the above range.
(Additional notes)
The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims. That is, embodiments obtained by combining technical means appropriately modified within the scope of the claims are also included in the technical scope of the present invention.

Hereinafter, the present invention will be specifically described with reference to production examples, formulation examples, and test examples. In addition, this invention is not limited to the following manufacture examples, formulation examples, and test examples, unless the summary is exceeded.

When two or more asymmetric carbons are present in compound (I), a plurality of diastereomers are produced as isomers. It is difficult to separate and assign all these diastereomers. Therefore, in the following production examples, only diastereomers that can be assigned are described in alphabetical order. There is no particular meaning to the order in alphabetical order. For example, compound I-1a, compound I-1b and the like are described in the assigned order.

<Test Example 1: Control effect test against wheat leaf mold>
Epoxyconazole and a compound represented by the following chemical formula (Compound I-4 of Production Example 4 below) were mixed at a predetermined ratio, and the cooperative effect on wheat red mold was tested.

The ears of wheat at the flowering stage (variety: Norin 61) were cut from the top of the leaf and inserted into a 10 cm long test tube to which hydroponics (hyponex) was added (3 cut ears / test tube). After weighing a predetermined amount, each compound was dissolved in acetone and mixed to prepare a spray solution (acetone 10%, spreading agent (Guramin S) 60 ppm). The sprayed liquid was sprayed on the cut ears at a liquid volume equivalent to 1000 L / ha (one ward three-track system). After the spray solution was dried at room temperature, wheat spores spores (5 × 10 ⁵ / ml) were spray-inoculated on the cut ears. After that, it is kept in a 20 ° C wet box for 5 days, and the severity of the disease is investigated by the disease index of Ban & Suenaga (see Ban & Suenaga Euphyitica 113, p87-99, (2000)). The control value was calculated based on

Judgment of the cooperation effect by mixing was performed according to the iso-effect curve method described in the literature (see Pesticide Experiment Method Vol. 3, Soft Science, p109-116). From the control values when epoxiconazole and compound I-4 were used in combination at different concentrations, an isoeffect curve showing a certain control value was prepared. When the straight line of the equal effect is linear, the effect is determined to be additive, when it is curved upward, it is determined to be antagonistic, and when it is curved downward, it is determined to be synergistic.

The test results are shown in FIG. FIG. 1 shows an equi-effect curve that gives a control value of 90 when epoxiconazole and compound I-4 are used in combination at different concentrations. The isoeffect curve is curved downward, revealing that compound I-4 and epoxiconazole have a synergistic effect.

<Test Example 2: Control effect test against wheat leaf mold>
Pyraclostrobin and the above compound I-4 were mixed at a predetermined ratio, and the cooperative effect on wheat leaf mold was tested.

A chemical solution containing pyraclostrobin and compound I-4 was prepared and sprayed on the cut ears so as to obtain a predetermined dose. The other test methods and the determination method of the cooperation effect are the same as in Test Example 1.

The test results are shown in FIG. FIG. 2 shows an equivalent effect curve in which a control value of 70 is obtained when pyraclostrobin and compound I-4 are used in combination at different concentrations. The isoeffect curve is curved downward, revealing that compound I-4 and pyraclostrobin have a synergistic effect.

<Test Example 3: Control effect test against wheat leaf mold>
Bixafen and the aforementioned compound I-4 were mixed at a predetermined ratio, and the cooperative effect on wheat red mold was tested.

Cut ears were prepared from flowering wheat plants (variety: Norin 61). A medicinal solution containing bixaphene and compound I-4 was prepared and sprayed on the cut ears to give a predetermined dosage. Other test methods are the same as in Test Example 1.

Using the Colby formula (see the following formula), the theoretical value of the control value in the case of mixed spraying was calculated from the control value in the case of separately spraying bixafen and compound I-4. Then, it was judged that the effect was synergistic if the control value at the time of actual mixed spraying was larger than the theoretical value, additive if it was equivalent, and antagonistic if it was small.

Control value at the time of mixing spraying (theoretical value) = α + ((100−α) × β) / 100
In the formula, α and β are the control values when each agent is sprayed alone.

The results are shown in Table 1. The control value of the mixture sprayed with Bixafen and Compound I-4 is larger than the theoretical value calculated from the control value of each sprayed alone, and Compound I-4 and Bixafen have a synergistic effect. It became clear to show.

<Test Example 4: Control effect test against wheat leaf mold>
Methoconazole and Compound I-2 were mixed at a predetermined ratio, and the cooperative effect on wheat red mold was tested.

Cut ears were prepared from flowering wheat plants (variety: Norin 61). A medicinal solution containing metconazole and compound I-2 was prepared and sprayed on the cut ears so as to obtain a predetermined dose. The cut ears were dried at room temperature for about 1 hour, and then sprayed and inoculated with a Fusarium graminearum ascospore suspension (1 × 10 ⁵ cells / ml). It was kept in a room box at 20 ° C., and after 5 days, the disease was investigated according to the evaluation method described in the literature (see Ban & Suenaga Euphyitica 113, p87-99, (2000)). The test scale was three cut ears and one treatment zone.

Using the Colby formula (see the following formula), the theoretical value of the control value when mixed sprayed was calculated from the control value when metconazole and compound I-2 were sprayed individually. Then, it was judged that the effect was synergistic if the control value at the time of actual mixed spraying was larger than the theoretical value, additive if it was equivalent, and antagonistic if it was small.

The test results are shown in FIG. The control value when metconazole and compound I-2 were mixed and sprayed was larger than the theoretical value calculated from the control value when each was sprayed alone, and compound I-2 and metconazole showed a synergistic effect. It became clear.

<Test Example 5: Control effect test on wheat leaf mold>
A control effect test for wheat leaf blight was conducted in the same manner as in Test Example 4 except that Compound I-4 or Compound I-8 was used instead of Compound I-2. The results when using Compound I-4 are shown in FIG. 4, and the results when using Compound I-8 are shown in FIG.

Also in the case of using Compound I-4 or Compound I-8, the control value when mixed and sprayed is larger than the theoretical value calculated from the control value when spraying each alone, It was revealed that Compound I-8 and metconazole have a synergistic effect.

<Test Example 6: In vitro antibacterial activity test>
Boscalid and compound I-4 were mixed in PDA medium to a predetermined concentration. A 4 mm diameter flora disk was cut out from the vicinity of the colony of the wheat leaf blight fungus (Microdocum nivale) that had been pre-cultured in a PDA medium, and inoculated on the PDA medium mixed with the drug. After culturing at 25 ° C. for 3 days, the diameter of the grown colonies was measured, and the mycelial growth inhibition rate was determined by comparing with the colony diameter on the medium not containing the drug. The determination of the cooperation effect was performed by a method using the Colby equation as in Test Example 1.

The results are shown in Table 2. The growth inhibition rate when boscalid and compound I-4 were mixed was larger than the theoretical value calculated from the inhibition rate when each was used alone, and compound I-4 and boscalid had a synergistic effect. It became clear to show.

<Test Example 7: In vitro antibacterial activity test>
Isopyrazam and compound I-4 were mixed in a PDA medium at a predetermined concentration, and the mycelial growth inhibition rate of the wheat fungus (Microdocum nivale) was determined. The test method is the same as in Test Example 6. The determination of the cooperation effect was performed by a method using the Colby equation as in Test Example 1.

The results are shown in Table 3. The growth inhibition rate when isopyrazam and compound I-4 are mixed is larger than the theoretical value calculated from the inhibition rate when each is used alone, and compound I-4 and isopyrazam have a synergistic effect. It became clear to show.

<Test Example 8: In vitro antibacterial activity test>
Fluopyram and compound I-4 were mixed in PDA medium to a predetermined concentration. A 4 mm diameter bacterial flora disc was cut out from around the colony of rice rot (Rhizoctonia oryzae) pre-cultured in PDA medium and inoculated on PDA medium mixed with the drug. After culturing at 25 ° C. for 1 day, the diameter of the grown colonies was measured, and the mycelial growth inhibition rate was determined by comparing with the colony diameter on the medium not containing the drug. The determination of the cooperation effect was performed by a method using the Colby equation as in Test Example 1.

The results are shown in Table 4. The growth inhibition rate when fluopyram and compound I-4 are mixed is larger than the theoretical value calculated from the inhibition rate when each is used alone, and compound I-4 and fluopyram have a synergistic effect. It became clear to show.

<Test Example 9: In vitro antibacterial activity test>
Frametopyr and the above compound I-4 were mixed in a PDA medium so as to have a predetermined concentration. A 4 mm-diameter flora disk was cut out from around a colony of wheat eye spot fungus (Pseudocercoporella herpotrichoides) that had been pre-cultured in PDA medium in advance, and inoculated on PDA medium mixed with the drug. After culturing at 20 ° C. for 7 days, the diameter of the grown colonies was measured, and the mycelial growth inhibition rate was determined by comparing with the colony diameter on the medium not containing the drug. The determination of the cooperation effect was performed by a method using the Colby equation as in Test Example 1.

The results are shown in Table 5. The growth inhibition rate when mixing flametopil and compound I-4 is larger than the theoretical value calculated from the inhibition rate when each is used alone, and compound I-4 and flametopil have a synergistic effect. It became clear to show.

<Test Example 10: In vitro antibacterial activity test>
Benodanil and compound I-4 were mixed in PDA medium to a predetermined concentration. A 4 mm diameter bacterial flora disc was cut out from around the colony of wheat blight (Phaeosphaeria nodorum) that had been pre-cultured in a PDA medium, and inoculated on a PDA medium mixed with the drug. After culturing at 20 ° C. for 7 days, the diameter of the grown colonies was measured, and the mycelial growth inhibition rate was determined by comparing with the colony diameter on the medium not containing the drug. The determination of the cooperation effect was performed by a method using the Colby equation as in Test Example 1.

The results are shown in Table 6. The growth inhibition rate when benodanyl and compound I-4 were mixed was larger than the theoretical value calculated from the inhibition rate when each was used alone, and compound I-4 and benodanyl had a synergistic effect. It became clear to show.

<Test Example 11: In vitro antibacterial activity test>
Penthiopyrad and compound I-4 were mixed in PDA medium to a predetermined concentration. A 4 mm-diameter flora disk was cut out from around the colony of a wheat blight fungus (Gaeumannomyces graminis) that had been pre-cultured in a PDA medium in advance and inoculated on a PDA medium mixed with the drug. After culturing at 20 ° C. for 3 days, the diameter of the grown colonies was measured, and the mycelial growth inhibition rate was determined by comparing with the colony diameter on the medium not containing the drug. The determination of the cooperation effect was performed by a method using the Colby equation as in Test Example 1.

The results are shown in Table 7. The growth inhibition rate when penthiopyrad and compound I-4 are mixed is larger than the theoretical value calculated from the inhibition rate when each is used alone, and compound I-4 and penthiopyrad have a synergistic effect. It became clear to show.

<Test Example 12: In vitro antibacterial activity test>
Azoxystrobin and compound I-4 were mixed in a PDA medium at a predetermined concentration, and the mycelial growth inhibition rate of the wheat fungus (Microdocum nivale) was determined. The test method is the same as in Test Example 7. The determination of the cooperation effect was performed by a method using the Colby equation as in Test Example 1.

The results are shown in Table 8. The growth inhibition rate when azoxystrobin and compound I-4 were mixed was larger than the theoretical value calculated from the inhibition rate when each was used alone, and compound I-4 and azoxystrobin Was shown to have a synergistic effect.

<Test Example 13: In vitro antibacterial activity test>
Cresoxime methyl and compound I-4 were mixed in a PDA medium at a predetermined concentration, and the mycelial growth inhibition rate of the wheat fungus (Microdocum nivale) was determined. The test method is the same as in Test Example 7. The determination of the cooperation effect was performed by a method using the Colby equation as in Test Example 1.

The results are shown in Table 9. The growth inhibition rate when mixing cresoxime methyl and compound I-4 is larger than the theoretical value calculated from the inhibition rate when each is used alone, and compound I-4 and cresoxime methyl have a synergistic effect. It became clear to show.

<Test Example 14: In vitro antibacterial activity test>
Ipconazole and Compound I-4 were mixed in a PDA medium at a predetermined concentration, and the mycelial growth inhibition rate of the wheat fungus (Microdocum nivale) was determined. The test method is the same as in Test Example 7. The determination of the cooperation effect was performed by a method using the Colby equation as in Test Example 1.

The results are shown in Table 10. The growth inhibition rate when mixing ipconazole and compound I-4 is larger than the theoretical value calculated from the inhibition rate when each is used alone, and compound I-4 and ipconazole have a synergistic effect. It became clear to show.

<Test Example 15: In vitro antibacterial activity test>
Prochloraz and compound I-4 were mixed in a PDA medium to a predetermined concentration, and the mycelial growth inhibition rate of the wheat fungus (Microdocum nivale) was determined. The test method is the same as in Test Example 7. The determination of the cooperation effect was performed by a method using the Colby equation as in Test Example 1.

The results are shown in Table 11. The growth inhibition rate when prochloraz and compound I-4 were mixed was larger than the theoretical value calculated from the inhibition rate when each was used alone, and compound I-4 and prochloraz had a synergistic effect. It became clear to show.

<Test Example 16: In vitro antibacterial activity test>
Prothioconazole and Compound I-4 were mixed in PDA medium to a predetermined concentration. A 4 mm diameter flora disk was cut out from around the colony of Botrytis cinerea pre-cultured in PDA medium, and inoculated on PDA medium mixed with the drug. After culturing at 20 ° C. for 2 days, the diameter of the grown colonies was measured, and the mycelial growth inhibition rate was determined by comparing with the colony diameter on the medium not containing the drug. The determination of the cooperation effect was performed by a method using the Colby equation as in Test Example 1.

The results are shown in Table 12. The growth inhibition rate when prothioconazole and compound I-4 are mixed is larger than the theoretical value calculated from the inhibition rate when each is used alone, and compound I-4 and prothioconazole synergistically It became clear that it showed the effect.

<Test Example 17: In vitro antibacterial activity test>
Fenpropimorph and compound I-4 were mixed in a PDA medium at a predetermined concentration, and the mycelial growth inhibition rate of wheat leaf blight fungus (Gaeumannomyces graminis) was determined. The method is the same as in Test Example 11. The determination of the cooperation effect was performed by a method using the Colby equation as in Test Example 1.

The results are shown in Table 13. The growth inhibition rate when fenpropimorph and compound I-4 were mixed was larger than the theoretical value calculated from the inhibition rate when each was used alone, and compound I-4 and fenpropimorph were synergistic. It became clear to show the effect.

<Test Example 18: In vitro antibacterial activity test>
Thiophanate methyl and compound I-4 were mixed in a PDA medium so as to have a predetermined concentration, and the mycelial growth inhibition rate of the wheat fungus (Microdocum nivale) was determined. The test method is the same as in Test Example 7. The determination of the cooperation effect was performed by a method using the Colby equation as in Test Example 1.

The results are shown in Table 14. The growth inhibition rate when thiophanate methyl and compound I-4 were mixed was larger than the theoretical value calculated from the inhibition rate when each was used alone, and compound I-4 and thiophanate methyl had a synergistic effect. It became clear to show.

<Test Example 19: In vitro antibacterial activity test>
Tebuconazole and Compound I-4 were mixed in a PDA medium to a predetermined concentration, and the mycelial growth inhibition rate of the wheat fungus (Microdocum nivale) was determined. The test method is the same as in Test Example 7. The determination of the cooperation effect was performed by a method using the Colby equation as in Test Example 1.

The results are shown in Table 15. The growth inhibition rate when tebuconazole and compound I-4 were mixed was larger than the theoretical value calculated from the inhibition rate when each was used alone, and compound I-4 and tebuconazole had a synergistic effect. It became clear to show.

<Test Example 20: In vitro antibacterial activity test>
Metalaxyl and compound I-4 were mixed in a PDA medium to a predetermined concentration. A 4 mm diameter bacterial flora disk was cut out from around the colony of rice seedling blight (Pythium aphanidermatum) that had been pre-cultured in PDA medium in advance and inoculated on PDA medium mixed with the drug. After culturing at 25 ° C. for 3 days, the diameter of the grown colonies was measured, and the mycelial growth inhibition rate was determined by comparing with the colony diameter on the medium not containing the drug. The determination of the cooperation effect was performed by a method using the Colby equation as in Test Example 1.

The results are shown in Table 16. The growth inhibition rate when mixing metalaxyl and compound I-4 is larger than the theoretical value calculated from the inhibition rate when each is used alone, and compound I-4 and metalaxyl have a synergistic effect. It became clear to show.

<Test Example 21: Wheat red mold control effect test by foliar spray treatment of plant disease control composition>
Cut ears were prepared from flowering wheat plants (variety: Norin 61). A preparation in the form of a wettable powder such as Mixed Preparation Example 1 described later containing Compound I-2 and Compound XVIII-1 at a predetermined concentration is prepared, diluted and suspended to a predetermined concentration with water, and a ratio of 1,000 L / ha Scattered with. After air-drying the ear portion, (adjusted to 1 × 10 ⁵ cells / ml, including Grameen S final concentration 60 ppm) spores of wheat Fusarium fungus were sprayed inoculated, 20 ° C., and held in high humidity conditions. On the fifth day after inoculation, the morbidity of wheat red mold was investigated, and the control value was calculated by the following formula.
Control value (%) = (1− (average morbidity in sprayed area / average illness in non-sprayed area)) × 100
In addition, the test scale was carried out with three cut ears and three treatment zones.

Determination of the cooperative effect by mixing Compound I-2 and Compound XVIII-1 is based on the effect of mixing by the isoeffect curve method described in Agricultural Chemical Experiment Method Vol. 3 (Soft Science, March 1981), pages 109-116. The judgment method was used as a reference. According to this determination method, if the combination of the two compounds is additive, the isoeffect curve becomes linear, and if it is antagonistic, the curve curves upward (convex curve), and is cooperative (synergistic). ), The curve curves downward (concave curve).

From the control effect by the combination of the concentration of each compound, an iso-effect curve showing a control value of 60% was prepared. The created equal effect curve is shown in FIG.

As shown in FIG. 6, the equivalent effect curve when compound I-2 (compound A in the figure) and compound XVIII-1 (compound B in the figure) are mixed and dispersed is a concave curve curved downward. Indicated. That is, it was shown that when compound I-2 and compound XVIII-1 were mixed, a cooperative control effect was obtained.

Compound I-2 used in this Test Example and the following Reference Test Example is a compound of Compound No. I-2a obtained in Production Example 2 described later.
<Reference test example: Wheat red mold control effect test by foliar spray treatment>
Cut ears were prepared from flowering wheat plants (variety: Norin 61). A preparation in the form of a wettable powder containing only compound I-2 of compound I-2 and compound XVIII-1 was prepared, diluted and suspended in water to a prescribed concentration (500 mg / L), and a ratio of 1,000 L / ha Scattered with. After air-drying the head, spray inoculated with wheat spore mold spores (adjusted to 2 × 10 ⁵ cells / ml, containing Gramine S with a final concentration of 60 ppm and sucrose with a final concentration of 0.5%), 20 ° C., Maintained under high humidity conditions. On the 4th to 7th day after inoculation, the morbidity of wheat red mold was investigated, and the control value was calculated by the following formula.
Control value (%) = (1− (average morbidity in sprayed area / average illness in non-sprayed area)) × 100
As a result, the preparation containing Compound I-2 showed a control value of 90% or more.

In addition, a preparation in the form of a wettable powder containing only Compound XVIII-1 out of Compound I-2 and Compound XVIII-1 was prepared and subjected to the same test.

As a result, the formulation containing compound XVIII-1 also showed a control value of 90% or more.
<Production Example 1>
Synthesis of 1- (1-chlorocyclopropyl) -1- (2,2-dichlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) ethanol (Compound No. I-1) 1) Intermediate, 1-chloro-2- (1-chlorocyclopropyl) -3-buten-2-ol (compound (IX-1) (compound (IX), R ² = 1-chlorocyclopropyl, R ⁸ = H , R ⁹ = H, R ¹⁰ = H, X = Cl, n = 0)) Under a nitrogen stream, 2-chloro-1- (1-chlorocyclopropyl) ethanone (compound (VII), R ² = 1 -Chlorocyclopropyl, X = Cl) (4.38 mmol) in anhydrous THF (5 ml) was cooled to -20 ° C. To this solution, add 0.75 M vinylmagnesium bromide (compound (X), R ⁸ = H, R ⁹ = H, R ¹⁰ = H, L = MgBr, n = 0) (9.38 mmol) in anhydrous THF (6 ml). The diluted solution was added dropwise so that the reaction temperature did not increase. After completion of the dropwise addition, the mixture was slowly heated to 0 ° C and then stirred at 0 ° C for 1 hour. A saturated ammonium chloride solution was added to the reaction solution while cooling with ice water, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated aqueous sodium hydrogen carbonate, water and saturated brine, and dried over anhydrous sodium sulfate, and the solvent was evaporated. The obtained oil was purified by silica gel column chromatography to obtain the desired product.
(2) Intermediate, 2- (1-chlorocyclopropyl) -2- (2,2-dichlorocyclopropyl) oxirane (compound (II-a-1) (compound (II-a), R ² = 1- Chlorocyclopropyl, R ⁸ = H, R ⁹ = H, R ¹⁰ = H, X ¹ = Cl, X ² = Cl, n = 0)) Compound (IX-1) (2.93 mmol) in chloroform (2.4 ml) And benzyltriethylammonium chloride (0.15 mmol) was added. A solution obtained by dissolving sodium hydroxide (45.0 mmol) in water (1.8 ml) was added to this solution, and the mixture was vigorously stirred at 60 ° C. for 8 hours. Thereafter, the reaction temperature was raised to 70 ° C., and the mixture was further stirred for 4 hours and the reaction temperature at 80 ° C. for 20 hours. After the reaction, the mixture was extracted with chloroform, and the organic layer was washed with water and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting oil was purified by silica gel column chromatography to obtain the desired product as two isomers.
(3) 1- (1-chlorocyclopropyl) -1- (2,2-dichlorocyclopropyl) -2- (1H-1,2,4-triazol-1-yl) ethanol (Compound No. I-1a) Synthesis of 1H-1,2,4-triazole (compound (III), M = H) (0.22 mmol), potassium carbonate (0.22 mmol), potassium t-butoxide (0.02 mmol) under NMP (2 ml) ). A solution of compound (II-a-1) (0.16 mmol) in NMP (1 ml) was added and stirred at 80 ° C. for 5 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography to obtain the desired product.
Yield: 25%
NMR δ _H (400 MHz, CDCl ₃ ):
0.74-0.87 (m, 2H), 1.09-1.15 (m, 1H), 1.35-1.41 (m, 2H), 1.52 (dd, J = 11.0, 7.1Hz, 1H), 2.20 (dd, J = 11.0, 9.1 Hz, 1H), 3.75 (s, 1H), 4.51 (d, J = 14.2Hz, 1H), 4.60 (d, J = 14.2Hz, 1H), 7.98 (s, 1H), 8.22 (s, 1H).
<Production Example 2>
2- (1-Chlorocyclopropyl) -1- (2,2-dibromocyclopropyl) -3- (1H-1,2,4-triazol-1-yl) propan-2-ol (Compound No. I-2 ) (1) Intermediate, 1-chloro-2- (1-chlorocyclopropyl) -4-penten-2-ol (compound (IX-2) (compound (IX), R ² = 1-chlorocyclopropyl, Synthesis of R ⁸ = H, R ⁹ = H, R ¹⁰ = H, R ¹¹ = H, R ¹² = H, X = Cl, n = 1)) 2-chloro-1- (1-chloro Cyclopropyl) ethanone (compound (VII), R ² = 1-chlorocyclopropyl, X═Cl) (0.0098 mol) was dissolved in diethyl ether (20 ml) and cooled to about −50 ° C. Allylmagnesium bromide (compound (X), R ⁸ = H, R ⁹ = H, R ¹⁰ = H, R ¹¹ = H, R ¹² = H, L = MgBr, n = 1) 1M diethyl ether solution (0.0098 x 1.8 mol) was added, and the mixture was stirred at the same temperature for about 20 minutes while gradually raising the temperature for 1 hour. Further, after stirring for 1 hour under ice cooling, ice water and a saturated aqueous ammonium chloride solution were added. After extraction with diethyl ether, the organic layer was extracted with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, and concentrated to obtain a crude product.
(2) Intermediate, 2- (1-chlorocyclopropyl) -2- (2,2-dibromocyclopropylmethyl) oxirane (compound (II-a-2) (compound (II-a), R ² = 1) -chlorocyclopropyl, R ⁸ = H, R ⁹ = H, R ¹⁰ = H, R ¹¹ = H, R ¹² = H, X ¹ = Br, X ² = Br, n = 1)) ) (0.0031 mol) was added bromoform (9.2 mmol), 50% aqueous sodium hydroxide solution (2 g) and benzyltriethylammonium chloride (0.154 mmol), and then at room temperature for 1 hour, about 60 ° C for 1 hour, and further about 80 ° C. For 1 hour. Water was added to the reaction mixture, and the mixture was extracted with diethyl ether. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated. Bromoform (9.2 mmol), 50% aqueous sodium hydroxide solution (2 g) and benzyltriethylammonium chloride (0.30 mol) were added to the resulting crude product, and the mixture was stirred at about 80 ° C. for 4 hours. Water was added to the reaction mixture, and the mixture was extracted with diethyl ether. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated. Purification by silica gel column chromatography gave a crude product.
(3) 2- (1-chlorocyclopropyl) -1- (2,2-dibromocyclopropyl) -3- (1H-1,2,4-triazol-1-yl) propan-2-ol (compound number) Synthesis of I-2) After potassium carbonate (2.7 mmol) was added to DMF (3 ml) and suspended, t-BuONa (0.36 mmol), 1,2,4-triazole (compound (III), M = H) 2.7 mmol) was added. Compound (II-a-2) (0.0018 mol) dissolved in DMF (3 ml) was added, and the mixture was stirred at 90 ° C. for 2 hours. Ethyl acetate and water were added and partitioned, and the organic layer was washed with saturated brine. The aqueous layer was extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate and concentrated. Purification was performed by silica gel column chromatography, and the less polar isomer a was isolated from the two isomers.
[Compound No. I-2a]
Yield: 9%
NMR δ _H (400 MHz, CDCl ₃ ):
0.28-0.38 (m, 1H), 0.42-0.52 (m, 1H), 0.73-0.84 (m, 1H), 1.02-1.12 (m, 1H), 1.42 (app.t, J = 7.6 Hz, 1H), 1.88 (dd, J = 7.3, 10.6 Hz, 1H), 1.92-2.19 (m, 3H), 4.36 (s, 1H), 4.39 (d, J = 14.2 Hz, 1H,), 4.95 (d, J = 14.2 Hz, 1H), 8.04 (s, 1H), 8.28 (s, 1H).
<Production Example 3>
Synthesis of 1,3-bis (2,2-dichlorocyclopropyl) -2- (1H-1,2,4-triazol-1-ylmethyl) propan-2-ol (Compound No. I-3) (1) Intermediate Synthesis of 4-chloromethylhepta-1,6-dien-4-ol In a nitrogen stream, anhydrous diethyl ether (10 ml) was added to magnesium (24 mmol), and allyl bromide (22.3 mmol) was added to diethyl A solution dissolved in ether (25 ml) was added dropwise so that the reaction solution continued to gently reflux, and then stirred at room temperature for 30 minutes. A solution of chloroacetyl chloride (10.6 mmol) dissolved in anhydrous diethyl ether (10 ml) was cooled to −40 ° C., and the previously prepared allylmagnesium bromide solution was added dropwise so that the reaction solution temperature did not increase. After completion of dropping, the mixture was stirred at -40 ° C for 2 hours, and then slowly heated to 0 ° C. A saturated ammonium chloride solution was added to the reaction solution while cooling with ice water, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated aqueous sodium hydrogen carbonate, water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain the desired product.
(2) Intermediate, 2,2-bis (2,2-dichlorocyclopropylmethyl) oxirane (compound (II-1) (compound (II), R ¹ = 2,2-dichlorocyclopropylmethyl, R ² = 2,2 Synthesis of 4-dichlorocyclopropylmethyl)) 4-Chloromethylhepta-1,6-dien-4-ol (6.6 mmol) was dissolved in chloroform (11 ml), and benzyltriethylammonium chloride (0.66 mmol) was added. A solution of sodium hydroxide (130 mmol) dissolved in water (5 ml) was added and stirred vigorously at 60 ° C. for 15 hours. After the reaction, the mixture was extracted with chloroform, and the organic layer was washed with water and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain the desired product as a diastereomer mixture.
(3) Synthesis of 1,3-bis (2,2-dichlorocyclopropyl) -2- (1H-1,2,4-triazol-1-ylmethyl) propan-2-ol (Compound No. I-3) Nitrogen Under a stream of air, 60% sodium hydride (3.0 mmol) was washed with hexane, suspended in anhydrous DMF (5.0 ml), and cooled with ice to 1H-1,2,4-triazole (compound (III), M = H) (2.9 mmol) was added. After stirring at room temperature for 30 minutes, a solution of compound (II-1) (2.0 mmol) in anhydrous DMF (3.0 ml) was added, and the mixture was stirred at 90 ° C. for 8 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography to obtain the desired product.
[Compound No. I-3a]
Yield: 11%
NMR δ _H (400 MHz, CDCl ₃ ):
1.30 (t, J = 7.4Hz, 2H), 1.69-1.74 (m, 4H), 1.84-1.85 (m, 4H), 3.98 (s, 1H), 4.44 (s, 2H), 8.04 (s, 1H) , 8.18 (s, 1H).
[Compound No. I-3b]
Yield: 26%
NMR δ _H (400 MHz, CDCl ₃ ):
1.03-1.07 (m, 1H), 1.17-1.21 (m, 1H), 1.46-1.56 (m, 1H), 1.64-1.68 (m, 1H), 1.72-1.81 (m, 4H), 1.95-1.99 (m , 1H), 2.08 (dd, J = 4.1, 14.8Hz, 1H), 4.01 (d, J = 1.4Hz, 1H), 4.39 (d, J = 14.1Hz, 1H), 4.45 (d, J = 14.1Hz , 1H), 8.03 (s, 1H), 8.17 (s, 1H).
<Production Example 4>
2- (1-Chlorocyclopropyl) -4- (2,2-dichlorocyclopropyl) -1- (1H-1,2,4-triazol-1-yl) butan-2-ol (Compound No. I-4 ) (1) Intermediate, methyl 3- (1-chlorocyclopropyl) -3-oxopropionate (compound (XIII-1) (compound (XIII), R ² = 1-chlorocyclopropyl, R ¹³ = Me)) ) Under nitrogen flow, 60% sodium hydride (95.0 mmol) was washed with hexane, suspended in dimethyl carbonate (compound (XVI), R ¹³ = Me) (80 ml), and anhydrous methanol (0.5 ml) was added. And heated to 80 ° C. A solution of 1- (1-chlorocyclopropyl) ethanone (compound (XV), R ² = 1-chlorocyclopropyl) (86.0 mmol) dissolved in dimethyl carbonate (compound (XVI), R ¹³ = Me) (6 ml) The mixture was further stirred at 80 ° C. for 3 hours. After allowing to cool, acetic acid (10 ml) was added to the reaction solution, and then poured into ice water to separate the organic layer. The aqueous layer was extracted with diethyl ether, and the organic layers were washed with water and saturated brine, and then dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the desired product was obtained by distillation under reduced pressure.
(2) Intermediate, methyl 2- (2-propenyl) -3- (1-chlorocyclopropyl) -3-oxopropionate (compound (XII-1) (compound (XII), R ² = 1-chlorocyclopropyl, R ¹⁴ = H, R ¹⁵ = H, R ¹⁶ = H, R ¹⁷ = H, R ¹⁸ = H, R ¹³ = Me, m = 1))) 60% sodium hydride (33.0 mmol) under nitrogen Was washed with hexane and suspended in anhydrous DMF (70 ml). A solution of compound (XIII-1) (30.0 mmol) dissolved in anhydrous DMF (15 ml) was added, and the mixture was stirred at room temperature for 1.5 hours. After stirring, allyl bromide (compound (XIV), R ¹⁴ = H, R ¹⁵ = H, R ¹⁶ = H, R ¹⁷ = H, R ¹⁸ = H, X ³ = Br, m = 1) (33.0 mmol) A solution dissolved in anhydrous DMF (15 ml) was added, and the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into ice water and extracted with hexane. The organic layer was washed with water and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain the desired product.
(3) Intermediate, 1- (1-chlorocyclopropyl) -4-penten-1-one (compound (XI-1) (compound (XI), R ² = 1-chlorocyclopropyl, R ¹⁴ = H, R ¹⁵ = H, R ¹⁶ = H, R ¹⁷ = H, R ¹⁸ = H, m = 1)) Compound (XII-1) (28.5 mmol) was dissolved in isopropanol (10 ml). A solution of sodium hydroxide (55.0 mmol) dissolved in water (11 ml) was added and stirred at 80 ° C. for 4.5 hours. After allowing to cool, the reaction solution was poured into ice water and extracted with hexane, and the organic layer was washed with water and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain the desired product.
(4) Intermediate, 2- (3-butenyl) -2- (1-chlorocyclopropyl) oxirane (compound (VIII-a-1) (compound (VIII-a), R ² = 1-chlorocyclopropyl, R ¹⁴ = H, R ¹⁵ = H, R ¹⁶ = H, R ¹⁷ = H, R ¹⁸ = H, m = 1)) Under nitrogen flow, 60% sodium hydride (43.7 mmol) was washed with hexane Suspended in DMSO (70 ml). Trimethylsulfoxonium bromide (43.4 mmol) was added and stirred at room temperature for 1.5 hours. A solution of compound (XI-1) (31.5 mmol) in anhydrous DMSO (30 ml) was added, and the mixture was further stirred at room temperature for 3 hours. The reaction solution was poured into ice water and extracted with hexane. The organic layer was washed with water and saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting oil was distilled under reduced pressure to obtain the desired product.
(5) Intermediate, 2- (1-chlorocyclopropyl) -2- [2- (2,2-dichlorocyclopropyl) ethyl] oxirane (compound (II-a-3) (compound (II-a), R ² = 1-chlorocyclopropyl, R ⁸ = H, R ⁹ = H, R ¹⁰ = H, R ¹¹ = H, R ¹² = H, X ¹ = Cl, X ² = Cl, n = 2)) (VIII-a-1) (110 mmol) and benzyltriethylammonium chloride (2.26 mmol) were dissolved in chloroform (63 ml), and a solution of sodium hydroxide (577 mmol) / water (23.5 ml) was added at 60 ° C. Stir for 2 hours. The reaction solution was poured into ice water and extracted with chloroform. The organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by distillation under reduced pressure, and the residue was purified by silica gel column chromatography to obtain the desired product.
(6) 2- (1-chlorocyclopropyl) -4- (2,2-dichlorocyclopropyl) -1- (1H-1,2,4-triazol-1-yl) butan-2-ol (compound number) I-4) Synthesis Under nitrogen stream, 1H-1,2,4-triazole (compound (III), M = H) (2.06 mmol), potassium carbonate (1.96 mmol), potassium t-butoxide (0.13 mmol) Suspended in DMF (2 ml). A solution of compound (II-a-3) (1.54 mmol) in DMF (2 ml) was added, and the mixture was stirred at 70 ° C. for 5 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography to obtain the desired product as two diastereomers.
[Compound No. I-4a]
Yield: 8%
NMR δ _H (400 MHz, CDCl ₃ ):
0.24 (ddd, J = 11.0, 7.2, 6.0Hz, 1H), 0.45 (ddd, J = 10.7, 7.5, 6.0Hz, 1H), 0.83 (ddd, J = 10.7, 7.2, 5.7Hz, 1H), 1.06 ( ddd, J = 11.0, 7.5, 5.7Hz, 1H), 1.12 (bs, 1H), 1.5-1.6 (m, 2H), 1.6-1.8 (m, 1H), 1.8-2.1 (m, 3H), 4.06 ( s, 1H), 4.27 (d, J = 14.2Hz, 1H), 4.71 (d, J = 14.2Hz, 1H), 8.01 (s, 1H), 8.24 (s, 1H).
[Compound No. I-4b]
Yield: 11%
NMR δ _H (400 MHz, CDCl ₃ ):
0.24 (ddd, J = 11.0, 7.2, 6.0Hz, 1H), 0.44 (ddd, J = 10.8, 7.5, 6.0Hz, 1H), 0.85 (ddd, J = 10.8, 7.2, 5.7Hz, 1H), 1.07 ( ddd, J = 11.0, 7.5, 5.7Hz, 1H), 1.1-1.2 (m, 1H), 1.5-1.6 (m, 2H), 1.7-1.8 (m, 2H), 1.8-2.0 (m, 1H), 2.2-2.3 (m, 1H), 4.08 (s, 1H), 4.26 (d, J = 14.2Hz, 1H), 4.71 (d, J = 14.2Hz, 1H), 8.02 (s, 1H), 8.24 (s , 1H).
Compounds (I) shown in the following “Table 17” to “Table 20” were synthesized by the method according to the above Production Examples 1 to 4.

<Production Example 5>
(1,2-cis, 1,5-cis) -5- (4-chlorobenzyl) -2-chloromethyl-2-methyl-1- (1H-1,2,4-triazol-1-ylmethyl) cyclo Pentanol (R ²⁰ = CH ₃ , (Y) p = 4-Cl, R ²¹ = CH ₂ , X ⁴ = Cl, q = 1, 1,2-cis, 1,5-cis compound ( XVIIIb), Compound No .: XVIII-1) (1) 1- (4-Chlorobenzyl) -3-methyl-3-hydroxymethyl-2-oxocyclopentanecarboxylic acid methyl ester (compound (XXVI-1) ( Synthesis of Compound (XXVI), R ²³ = CH ₃ , R ²⁴ = CH ₃ , (Y) p = 4-Cl)) Methyl 1- (4-chlorobenzyl) -3-methyl-2-oxocyclopentanecarboxylate Ester (compound (X ^{_{^{_{VII): R 23 = CH 3}}}} , R 24 = CH 3, the addition of (Y) p = 4-Cl ) ( in 4.0 mmol), 37% aqueous formaldehyde (12 mmol) and potassium carbonate (2.0 mmol), Stir vigorously at room temperature for 4 hours. After completion of the reaction, water was added and extracted with ethyl acetate (30 ml). The organic layer was washed with saturated brine (10 ml) and then dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain compound (XXVI-1) as two isomers.

(2) 5- (4-Chlorobenzyl) -2-methoxymethoxymethyl-2-methylcyclopentanone (Compound (XXIV-1) (Compound (XXIV), R ²³ = CH ₃ , (Y) p = 4- Synthesis of Cl, G = CH ₂ OCH ₃ )) Compound (XXVI-1) (0.60 mmol) was dissolved in methylene chloride (5.6 ml), and dimethoxymethane (2.8 ml) was added thereto. This was cooled in a water bath, diphosphorus pentoxide (372 mg) was added, and the mixture was vigorously stirred at room temperature for 10 minutes. After completion of the reaction, the reaction mixture was added to saturated brine and extracted with diethyl ether. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off and the residue was dried under reduced pressure to obtain crude 1- (4-chlorobenzyl) -3-methoxymethoxymethyl-3-methyl-2-oxocyclopentanecarboxylic acid methyl ester (compound (XXV-1) (compound ( XXV), R ²³ = CH ₃ , R ²⁴ = CH ₃ , (Y) p = 4-Cl, G = CH ₂ OCH ₃ )) (195 mg).

188.8 mg of the obtained compound (XXV-1) was dissolved in isopropanol (0.53 ml), 2M aqueous sodium hydroxide solution (1.12 mmol) was added thereto, and the mixture was stirred at 60 ° C. for 1 hour. After completion of the reaction, water was added and extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain compound (XXIV-1) as a mixture of two isomers.

(3) 5- (4-Chlorobenzyl) -2-methoxymethoxymethyl-2-methyl-1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol (compound (XXI-1) ( Synthesis of Compound (XXI), R ²³ = CH ₃ , (Y) p = 4-Cl, G = CH ₂ OCH ₃ )) 1H-1,2,4-triazole sodium salt (13.1 mmol) was added to NMP (7 ml) And the temperature was raised to an internal temperature of 115 ° C. Compound (XXIV-1) (8.76 mmol) was added thereto, and washing was performed with NMP (1.8 ml). After the internal temperature returned to 115 ° C., sodium t-butoxide (5.26 mmol) and trimethylsulfoxonium bromide (1.476 mmol) were added in portions over about 3 hours. After completion of the addition, the mixture was stirred at the same temperature for 75 minutes. The reaction solution was cooled to 35 ° C., water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain compound (XXI-1).

(4) 5- (4-Chlorobenzyl) -2-hydroxymethyl-2-methyl-1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol (compound (XXa-1) (compound Synthesis of (XXa), R ²³ = CH ₃ , (Y) p = 4-Cl)) Compound (XXI-1) (1.66 mmol) was dissolved in methanol (6.3 ml), and 10% hydrogen chloride was added thereto. -Methanol (1.73 mmol) was added and stirred at room temperature for 48 hours. After completion of the reaction, the solvent was distilled off and water was added. Further, ethyl acetate (80 ml) was added, and then an aqueous sodium hydroxide solution was added until the pH reached 10. The organic layer was separated, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off to give compound (XXa-1) as a plurality of isomers ((compound (XXa-1a) (1,2-cis, 1,5-cis form): compound (XXa-1b) (1, 2-trans, 1,5-cis type): other geometric isomers = 6: 3: 1) In this production example, “1,2-cis”, “1,5-cis” And “1,2-trans” means that the hydroxy group at position 1 of the cyclopentane ring, the hydroxymethyl group at position 2 and the substituted or unsubstituted benzyl group at position 5 in compound (XXa), or compound (XXa) Mention is made of functional groups corresponding to these groups in the derivatives.

(5) (1,2-cis, 1,5-cis) -5- (4-chlorobenzyl) -2-methyl-2-[(4-methylphenyl) sulfonyloxymethyl] -1- (1H-1 , 2,4-Triazol-1-ylmethyl) cyclopentanol (compound (XIX-1) (compound (XIX), R ²⁰ = CH ₃ , (Y) p = 4-Cl, R ²¹ = CH ₂ , R ²² = 4-methylphenyl, q = 1, 1,2-cis, 1,5-cis)) In an argon atmosphere, sodium hydride (1.83 mmol) was washed with hexane, and then dehydrated in THF (4 ml). It was suspended and cooled with ice water. Then, compound (XXa-1a) (1.52 mmol) dissolved in dehydrated THF (5 ml) was added dropwise. It returned to room temperature and stirred for 30 minutes. After cooling with ice water again, p-toluenesulfonyl chloride (1.97 mmol) was added and stirred at the same temperature for 1.5 hours and then at room temperature for 0.5 hour. Water (20 ml) was added to the reaction mixture to stop the reaction, and the mixture was partitioned with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. Purification by silica gel chromatography gave compound (XIX-1).

(6) Synthesis of Compound (XVIII-1) Compound (XIX-1) (0.0245 mmol) was dissolved in dehydrated DMF (0.24 ml) under an argon atmosphere. To this was added lithium chloride (0.245 mmol), and the mixture was stirred at 100 ° C. for 1.5 hours. Ethyl acetate (2 ml) was added to the reaction mixture, and the mixture was washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate and concentrated. Purification by silica gel column chromatography gave compound (XVIII-1).
Yield: 58%
¹ H-NMR (400 MHz, CDCl ₃ ) δ:
1.18 (3H, s), 1.46 (2H, m), 1.70 (1H, m), 1.92 (2H, m), 2.35 (2H, m), 3.26 (1H, d, J = 10.8Hz), 3.57 (1H , d, J = 10.8Hz), 4.06 (1H, s), 4.25 (1H, d, J = 14.2Hz), 4.54 (1H, d, J = 14.2Hz), 6.98 (2H, d, J = 8.4Hz) ), 7.21 (2H, d, J = 8.4Hz), 8.02 (1H, s), 8.19 (1H, s).
Next, mixed preparation examples are shown. The carrier (diluent) and auxiliary agent, and the mixing ratio thereof can be changed within a wide range. “Parts” in each formulation example represents parts by weight.
<Mixed preparation example 1 (wettable powder)>
Compound (I) 25 parts metconazole 25 parts lignin sulfonate 5 parts alkyl sulfonate 3 parts diatomaceous earth 42 parts are pulverized and mixed to obtain a wettable powder, diluted with water and used.
<Mixed preparation example 2 (powder)>
Compound (I) 3 parts metconazole 3 parts clay 40 parts talc 54 parts are ground and mixed and used as dust.
<Mixed preparation example 3 (granule)>
Compound (I) 2.5 parts metconazole 2.5 parts bentonite 43 parts clay 45 parts lignin sulfonate 7 parts uniformly mixed, water added and kneaded, processed into granules in an extrusion granulator, dried and granulated Use as an agent.
<Mixed formulation example 4 (emulsion)>
Compound (I) 5 parts metconazole 5 parts polyoxyethylene alkyl aryl ether 10 parts polyoxyethylene sorbitan monolaurate 3 parts Xylene 77 parts are mixed and dissolved uniformly to give an emulsion.

The agricultural and horticultural medicine according to the present invention can be suitably used as a medicine for plant diseases such as wheat red mold.

Claims

An agricultural and horticultural medicine containing a plurality of active ingredients, wherein one of the active ingredients is an azole derivative represented by the following general formula (I).

(In formula (I), R 1 represents a cyclopropyl group or an alkyl group having 1 or 2 carbon atoms in which one hydrogen atom is substituted with the cyclopropyl group. At least one of the cyclopropyl groups in R 1 The hydrogen atom may be substituted with a substituent selected from a bromine atom, a chlorine atom and a methyl group, and R 2 represents a carbon number in which a cyclopropyl group or one hydrogen atom is substituted with the cyclopropyl group. Represents an alkyl group of 1 or 2. At least one hydrogen atom of the cyclopropyl group in R 2 may be substituted with a chlorine atom.
The agricultural and horticultural agent according to claim 1, wherein the compound contained as the active ingredient in addition to the compound represented by the general formula (I) is a compound having an ergosterol biosynthesis inhibitory ability.
The agricultural and horticultural agent according to claim 2, wherein the compound having the ability to inhibit ergosterol biosynthesis is at least one of an azole compound and fenpropimorph.
The agricultural and horticultural agent according to claim 3, wherein the azole compound is at least one of metconazole, epoxiconazole, ipconazole, prothioconazole, tebuconazole and prochloraz.
5. The compound according to claim 1, wherein the compound contained as the active ingredient in addition to the compound represented by the general formula (I) is a compound having an ability to inhibit succinate dehydrogenase. Agricultural and horticultural chemicals as described.
The agricultural and horticultural agent according to claim 5, wherein the compound having an ability to inhibit succinate dehydrogenase is at least one of bixaphene, boscalid, pentiopyrad, isopyrazam, fluopyram, furametopil, and benodanyl.
The agricultural or horticultural agent according to any one of claims 1 to 6, wherein the compound contained as the active ingredient in addition to the compound represented by the general formula (I) is a strobilurin-based compound.
The agricultural and horticultural agent according to claim 7, wherein the strobilurin-based compound is at least one of pyraclostrobin, azoxystrobin and cresoxime methyl.
The agricultural or horticultural agent according to any one of claims 1 to 8, wherein the compound contained as the active ingredient in addition to the compound represented by the general formula (I) is a benzimidazole compound.
10. The agricultural and horticultural agent according to claim 9, wherein the benzimidazole compound is thiophanate methyl.
The agricultural and horticultural agent according to any one of claims 1 to 10, wherein the compound contained as the active ingredient in addition to the compound represented by the general formula (I) is metalaxyl.
In the formula (I), the number of substitutions of the cyclopropyl group in R 1 by the substituent is 1 to 4, and the number of substitutions of the cyclopropyl group in R 2 by a chlorine atom is 1 or 2. The agricultural or horticultural agent according to any one of claims 1 to 11, wherein:
The agricultural and horticultural agent according to any one of claims 1 to 12, wherein the agent is used as a disinfectant.
A product for controlling plant diseases characterized by comprising separately an azole derivative represented by the following general formula (I) and another active ingredient as a combined preparation for using a mixture of a plurality of active ingredients.

(In the formula (I), R 1 represents a cyclopropyl group or an alkyl group having 1 or 2 carbon atoms substituted with the cyclopropyl group. The cyclopropyl group includes a bromine atom, a chlorine atom and a methyl group. R 2 represents a cyclopropyl group or an alkyl group having 1 or 2 carbon atoms that is substituted with the cyclopropyl group, and the cyclopropyl group is a chlorine atom. May be substituted with.)
A plant disease control method comprising a step of performing a foliage treatment or a non-foliage treatment using the agricultural and horticultural chemical according to any one of claims 1 to 13.