WO2021230382A1 - (-)-enantiomer of triazole derivative, agricultural or horticultural chemical, and industrial material protectant - Google Patents

Abstract

Provided is a plant disease control agent which has low toxicity to humans and animals and high safety in handling and which exhibits excellent antimicrobial effects, even at a low application dose, on a large number of microorganisms causing plant diseases. The present invention pertains to the (-)-enantiomer of a compound represented by general formula (I) or an agrochemically acceptable salt thereof.

Description

Triazole derivative (-)-enantiomers, agricultural and horticultural agents and industrial material protectants

The present invention relates to a triazole derivative (-)-enantiomer, and an agricultural and horticultural agent containing the triazole derivative as an active ingredient, and an industrial material protective agent.

Conventionally, there is a demand for agricultural and horticultural chemicals that are less toxic to humans and animals, have excellent handling safety, and have a high control effect against a wide range of plant diseases. Under such circumstances, Patent Document 1 discloses a novel triazole derivative which is an active ingredient of an agricultural and horticultural drug.

International release WO2019 / 093522

However, even with the compound described in Patent Document 1, if the applied amount is low, a sufficient effect may not be obtained.

Therefore, the present invention has been made in view of the above problems, and an object thereof is to provide a compound having high antibacterial activity against plant diseases, which can be expected to have a high control effect against plant diseases even at a low application amount. To do.

In order to solve the above problems, the compound according to the present invention is a (-)-enantiomer of a triazole derivative represented by the following general formula (I) or a pesticide-acceptable salt thereof.

[In formula (I),
R ¹ is -OR ⁴ or -NR ⁵ R ⁶ ;
R ⁴ , R ⁵ and R ⁶ are independently hydrogen, C _1- C ₆ -alkyl group, C _2- C ₆ -alkenyl group, C _2- C ₆ -alkynyl group, C _3- C ₈ -cyclo. Alkyne group, C _3- C ₈ -cycloalkyl-C _1- C ₄ -alkyl group, phenyl group, phenyl-C _1- C ₄ -alkyl group, phenyl-C _2- C ₄ -alkenyl group or phenyl-C ₂ -C _4- It is an alkynyl group, and R ⁵ and R ⁶ may form a ring;
Here, the ^{aliphatic groups in R 4} , R ⁵ and R ⁶ may have 1, 2, 3 or the maximum possible number of the same or different groups R ^a , where R ^a is a halogen group. , cyano group, nitro _group, C 1 -C ₄ - alkoxy and _C 1 -C ₄ - is selected from haloalkoxy groups independently of each other;
R ² is a halogen group, a cyano group, a nitro group, a phenyl group, a phenyl-oxy group, a C _1- C ₄ -alkyl group, a C _1- C ₄ -haloalkyl group, a C _1- C ₄ -alkoxy group, and a C _1-. C ₄ -haloalkoxy group, -SOR ⁷ or -SF ₅ ;
R ³ is a halogen group, a cyano group, a nitro group, an amino group, a phenyl group, a phenyl-oxy group, a C _1- C ₄ -alkyl group, a C _1- C ₄ -haloalkyl group, and a C _1- C ₄ -alkoxy group. or _C 1 -C ₄ - haloalkoxy _group, C 1 -C ₄ - alkylamino _group, C 1 -C ₄ - dialkylamino _group, C 1 -C ₄ - alkyl acyl amino group, in -SOR ⁷ or -SF ₅ can be;
The cycloalkyl and phenyl group moieties in R ⁴ , R ⁵ , and R ^{6 and the phenyl group moieties in R 3} have 1, 2, 3, 4, 5 or the maximum number of possible identical or different groups R ^b . may also be, ^{R b} is halogen, cyano, _nitro, C 1 -C ₄ - alkyl _group, C 1 -C ₄ - alkoxy _group, C 1 -C ₄ - haloalkyl and _C 1 -C _4- Selected independently of each other from the haloalkoxy group;
Wherein, ^{R 7} _is, C 1 -C ₄ - alkyl group or a _C 1 -C ₄ - haloalkyl group;
n is 0,1,2,3, or 4;
m is 1,2,3,4 or 5,
An asterisk (*) refers to an asymmetric carbon atom. ]

The (-)-enantiomer of the triazole derivative according to the present invention has an excellent bactericidal action against many bacteria that cause diseases to plants even at a low application amount.

Hereinafter, the (-)-enantiomer of the triazole derivative according to the present invention will be described in detail. It should be noted that the embodiments described below show an example of a typical embodiment of the present invention, and the scope of the present invention is not narrowly interpreted by this.

[1. Triazole derivative enantiomer]
The (-)-enantiomer of the triazole derivative according to the present embodiment is the (-)-enantiomer (hereinafter, triazole derivative (-) in the triazole derivative represented by the following general formula (I) (hereinafter referred to as triazole derivative (I))). ) -Called an enantiomer). The asterisk (*) in the following general formula (I) refers to an asymmetric carbon atom. In the present specification, the "(-)-enantiomer" refers to an enantiomer that rotates the vibration plane of the linearly polarized light of the sodium D line to the left, and the "(+)-enantiomer" refers to the sodium D line. Refers to an enantiomer that rotates the vibrating plane of linearly polarized light to the right.

In general formula (I),
R ¹ is -OR ⁴ or -NR ⁵ R ⁶ , preferably -OR ⁴ .

R ⁴ , R ⁵ and R ⁶ are independently hydrogen, C _1- C ₆ -alkyl group, C _2- C ₆ -alkenyl group, C _2- C ₆ -alkynyl group, C _3- C ₈ -cyclo. Alkyl group, C _3- C ₈ -cycloalkyl-C _1- C ₄ -alkyl group, phenyl group, phenyl-C _1- C ₄ -alkyl group, phenyl-C _2- C ₄ -alkenyl group or phenyl-C ₂ -C ₄ -Alkynyl group. R ⁵ and R ⁶ may form a ring together with the nitrogen atom to which R ⁵ and R ^{6 are bonded.}

C ₁ -C ₆ - alkyl group is a straight chain or branched chain alkyl group with a carbon number 1-6, for example, a methyl group, an ethyl group, a 1-methylethyl group, 1,1-dimethyl Ethyl group, propyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, butyl group, 1-methylbutyl group, 2- Methylbutyl group, 3-methylbutyl group, 3,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,1-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, pentyl group, 1-methylpentyl group , 2-Methylpentyl group, 3-methylpentyl group and 4-methylpentyl group.

C ₂ -C ₆ - alkenyl group is a linear or branched alkenyl group having a carbon atom is 2-6, for example, ethenyl, 2-propenyl group, 1-methyl-2-propenyl group , 2-Methyl-2-propenyl group, 1-butenyl group, 2-butenyl group, 3-methyl-2-butenyl group, 1-methyl-2-butenyl group, 3-butenyl group, 1-pentenyl group, 2- Examples include a pentanyl group, a 1-hexenyl group and a 5-hexenyl group.

C ₂ -C ₆ - alkynyl group, a linear or branched chain alkynyl group having a carbon atom is 2-6, for example, ethynyl group, 1-propynyl, 2-propynyl, 1-butynyl Examples include groups, 2-butynyl groups, 3-butynyl groups, pentynyl groups and 1-hexynyl groups.

The C _3- C ₈ -cycloalkyl group is a cyclic alkyl having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Be done.

The C _3- C ₈ -cycloalkyl-C _1- C ₄ -alkyl group consists of a cyclic cycloalkyl group having 3 to 8 carbon atoms and a linear or branched-chain alkyl group having 1 to 4 carbon atoms. Indicates that they are combined. For example, cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, 2-cyclopropylethyl group, 1-cyclopropylethyl group, 2-cyclohexylethyl group, 3-cyclopropylpropyl group, 2-cyclo Examples thereof include a propylpropyl group and a 4-cyclopropylbutyl group.

The phenyl-C _1- C ₄ -alkyl group is a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a phenyl group, for example, a phenylmethyl group, a 2-phenylethyl group, and the like. Examples include 3-phenylpropyl group and 4-phenylbutyl group.

The phenyl-C _2- C ₄ -alkenyl group has a linear or branched alkenyl group having 2 to 4 carbon atoms bonded to the phenyl group, for example, a phenylethenyl group or a phenyl-1-propenyl. Groups include groups, phenylisopropenyl groups, and phenylbutenyl groups.

The phenyl-C _2- C ₄ -alkynyl group has an alkynyl group having 2 to 4 carbon atoms bonded to the phenyl group, and is, for example, a phenylethynyl group, a phenyl-1-propynyl group, or a phenyl-2-propynyl group. , Phenyl-1-butynyl group, phenyl-2-butynyl group, and phenyl-3-butynyl group.

R ⁴ is _preferably, C 1 -C ₆ - alkyl group.

The aliphatic groups in R ¹ , R ⁴ , R ⁵ and R ⁶ may have 1, 2, 3 or the maximum possible number of the same or different groups R ^a , where R ^a is a halogen group. , cyano group, nitro _group, C 1 -C ₄ - independently of each other selected from haloalkoxy group - alkoxy group and _C 1 -C _4.

Examples of the halogen group include a chlorine group, a bromine group, an iodine group or a fluorine group. For example, a chloromethyl group, a 2-chloroethyl group, a 2,3-dichloropropyl group, a bromomethyl group, a chlorodifluoromethyl group, a trifluoromethyl group, and a 3,3,3-trifluoropropyl group can be mentioned.

C 1 _-C 4 _- alkoxy group is a linear or branched alkoxy group having 1 to 4 carbon atoms, e.g., methoxy, ethoxy, n- propoxy, isopropoxy, n- butoxy Examples include a group, a sec-butoxy group, and a tert-butoxy group.

C 1 _-C 4 _- haloalkoxy group, the aforementioned C ₁ -C 4 _{- 1} or more halogen atoms at positions which can replace the alkoxy group is substituted, if a halogen group which is substituted in the 2 or more The halogen groups may be the same or different.

R ² is a halogen group, a cyano group, a nitro group, a phenyl group, a phenyl-oxy group, a C _1- C ₄ -alkyl group, a C _1- C ₄ -haloalkyl group, a C _1- C ₄ -alkoxy group, and a C ₁ -C ₄ -haloalkoxy group, -SOR ⁷ or -SF ₅ .

_Halogen, C 1 -C ₄ - alkyl _group, C 1 -C ₄ - haloalkyl _group, C 1 -C ₄ - alkoxy groups, and _C 1 -C ₄ - haloalkoxy group, an organic group represented by ^{R a} The groups mentioned as an example of the above can be mentioned.

R ² is preferably a halogen group, a cyano _group, C 1 -C ₄ - alkyl _group, C 1 -C ₄ - haloalkyl _group, C 1 -C ₄ - alkoxy group, an -SOR ^7, or -SF _5, more preferably, a halogen group, a cyano _group, C 1 -C ₄ - alkoxy group - alkyl _group, C 1 -C ₄ - haloalkyl group or a _C 1 -C _4.

R ⁷ _is, C 1 -C ₄ - alkyl group or a _C 1 -C ₄ - haloalkyl group. The substitution position of R ² is the 2nd, 3rd, 5th or 6th position, preferably the 2nd position. n is 0, 1, 2, 3 or 4, preferably 1.

R ³ is a halogen group, a cyano group, a nitro group, an amino group, a phenyl group, a phenyl-oxy group, a C _1- C ₄ -alkyl group, a C _1- C ₄ -haloalkyl group, and a C _1- C ₄ -alkoxy group. , _C 1 -C ₄ - haloalkoxy _group, C 1 -C ₄ - alkylamino _group, C 1 -C ₄ - dialkylamino _group, C 1 -C ₄ - alkyl acyl amino group, -SOR ^7, or -SF ₅ Yes, the halogen group, C _1- C ₄ -alkyl C _1- C ₄ -haloalkyl group, C _1- C ₄ -alkoxy group or C _1- C ₄ -halo alkoxy group, and -SOR ⁷ are represented by ^{R 2.} Examples of the organic groups mentioned above can be mentioned.

R ³ is preferably a halogen group, a nitro group, an amino _group, C 1 -C ₄ - alkyl _group, C 1 -C ₄ - haloalkyl _group, C 1 -C ₄ - alkoxy _group, C 1 -C ₄ - halo alkoxy _groups, C 1 -C ₄ - alkylamino _group, C 1 -C ₄ - dialkylamino _group, C 1 -C ₄ - alkyl acyl amino group, an -SOR ^7, or -SF _5, more preferably a halogen group , C _1- C ₄ -alkyl group, C _1- C ₄ -haloalkyl group, C _1- C ₄ -alkoxy group or C _1- C ₄ -haloalkoxy group.

C 1 _-C 4 _- alkylamino group is one of an amino group substituted with a straight-chain or branched alkyl group having 1 to 4 carbon atoms of the hydrogen atom of the amino group, e.g., methylamino Examples include groups, ethylamino groups, n-propylamino groups, isopropylamino groups, and tert-butylamino groups.

C 1 _-C 4 _- dialkylamino group is an amino group in which a hydrogen atom of two co-having amino group substituted by a straight or branched chain alkyl group having 1 to 4 carbon atoms, e.g., N , N-dimethylamino group, N, N-diethylamino group, N, N-di-n-propylamino group, N, N-diisopropylamino group, and N, N-di-tert-butylamino group.

C 1 _-C 4 _- alkyl acyl amino group, it is one or two amino groups substituted with a linear or branched alkyl acyl group of 1 to 4 carbon atoms of the hydrogen atom of the amino group For example, methyl acylamino group, ethyl acylamino group, n-propyl acylamino group, isopropyl acylamino group, tert-butyl acylamino group, N, N-dimethylacylamino group, N, N-diethylacylamino group, Examples thereof include N, N-di-n-propyl acylamino groups, N, N-diisopropyl acylamino groups, and N, N-di-tert-butyl acylamino groups.

The cycloalkyl or phenyl group moiety in R ⁴ , R ⁵ , R ^{6 or the phenyl group moiety in R 3} has 1, 2, 3, 4, 5 or the maximum number of possible identical or different groups R ^b . may also be, ^{R b} is halogen, cyano, _nitro, C 1 -C ₄ - alkyl _group, C 1 -C ₄ - alkoxy _group, C 1 -C ₄ - haloalkyl and _C 1 -C _4- Selected independently of each other from the haloalkoxy group. _Halogen, C 1 -C ₄ - alkyl _group, C 1 -C ₄ - alkoxy _group, C 1 -C ₄ - haloalkyl and _C 1 -C ₄ - haloalkoxy group, the organic group represented by ^{R a} The groups given as an example can be mentioned.

From the above, the triazole derivative (-) - as a preferred embodiment of the enantiomers, in the general formula (I), ^{R 1} is located at -OR ^{4; R 2} is halogen, _cyano, C 1 -C ₄ - Alkoxy group, C _1- C ₄ -haloalkyl group, C _1- C ₄ -alkoxy group, -SOR ⁷ or -SF ₅ ; R ³ is halogen group, nitro group, cyano group, amino group, C _1- C ₄ - alkyl _group, C 1 -C ₄ - haloalkyl _group, C 1 -C ₄ - alkoxy _group, C 1 -C ₄ - haloalkoxy _group, C 1 -C ₄ - alkylamino _group, C 1 -C ₄ - dialkylamino _group, C 1 -C ₄ - alkyl acyl amino group, an -SOR ^7, or -SF _5, triazole derivative (-) - include enantiomers.

Further, as a more preferable embodiment of the triazole derivative (-)-enantiomer, in the general formula (I), R ¹ is -OR ⁴ and R ⁴ is a C _1- C ₆ -alkyl group; R ² is a halogen group, a cyano group, a C _1- C ₄ -alkyl group, a C _1- C ₄ -haloalkyl group or a C _1- C ₄ -alkoxy group; R ³ is a halogen group, a cyano group, C. Examples thereof include a triazole derivative (-)-enantiomer which is a _1- C ₄ -alkyl group, a C _1- C ₄ -haloalkyl group, a C _1- C ₄ -alkoxy group or a C _1- C _{4-haloalkoxy group.}

Agriculturally acceptable salts of triazole derivative (-)-enantiomers, in particular salts of these cations or acids thereof, whose cations and anions do not adversely affect the action of the triazole derivative (-)-enantiomer. Includes acid addition salts of. Suitable cations are particularly ammonium ions of alkali metals (preferably sodium and potassium), alkaline earth metals (preferably calcium, magnesium and barium), transition metals (preferably manganese, copper, zinc and iron) and also. 1 to 4 C ₁ -C if desired 4 _- alkyl substituents and / or one phenyl substituent or benzyl substituent optionally may ammonium ions (preferably diisopropyl ammonium have, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium), furthermore phosphonium ions, sulfonium ions (preferably tri _(C 1 -C ₄ - alkyl) sulfonium), and sulfoxonium ions (preferably tri _(C 1 -C ₄ - alkyl) sulfonium It is also (xonium). The anions of useful acid addition salts are mainly chloride ion, bromide ion, fluoride ion, hydrogen sulfate ion, sulfate ion, dihydrogen phosphate ion, hydrogen phosphate ion, phosphate ion, nitrate ion, bicarbonate. ions, carbonate ions, hexafluorosilicic acid ion, hexafluorophosphate ion, benzoate ion, and C ₁ -C 4 _- anions of alkanoic acids, preferably ion formic acid, acetate, propionate and butyrate. These can be formed by reacting the triazole derivative (-)-enantiomer with the corresponding anionic acid (preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid).

[2. Triazole derivative (-)-Production method of enantiomer]
[1. Preparation of triazole derivative (-)-enantiomer by optical resolution]
The triazole derivative (-)-enantiomer can be obtained by preparative separation from the racemate of the triazole derivative (I). The racemate of the triazole derivative (I) can be obtained, for example, according to the method described in Patent Document 1. When the triazole derivative is produced according to the method described in Patent Document 1, the obtained triazole derivative is a racemate.

Examples of the method for separating enantiomers include a method for separating by chiral chromatography. Specifically, amylostris (3,5-dimethylphenylcarbamate), cellulosetris (3,5-dimethylphenylcarbamate), cellulosetris (3,5-dichlorophenylcarbamate), amylostris [(S) -α-methyl Benzyl carbamate], cellulose tris (4-methylbenzoate), amylose tris (5-chloro-2-methylphenyl carbamate) or cellulose tris (3-chloro-4-methylphenyl carbamate) on a stationary phase immobilized on a silica gel carrier. Then, using hexane / ethanol (100/0 to 0/100), hexane / isopropanol (100/0 to 0/100), ethanol, methanol or acetonitrile as the mobile phase, the triazole derivative (I) is separated from the racemic form. By taking and separating, a triazole derivative (-)-enantiomer can be prepared.

The optical rotation of the separated (-)-enantiomer may be determined according to a conventionally known method.

[2. Preparation of triazole derivative (-)-enantiomer by chemical synthesis]
(Overall scheme)

Hereinafter, each process will be described. In the following description, the compound represented by the general formula (N) (where N is an arbitrary Roman numeral) in the overall scheme is referred to as compound (N).

(Step 1)
In step 1, a compound (VII) is obtained by introducing a methyl group into the compound (VIII). Wherein, ^{R 7} in the compound (VIII) is _C 1 -C ₆ - alkyl group. One example is a method in which a methylation reagent is added to a solution of compound (VIII) at a low temperature (for example, −78 ° C.) and reacted.

Examples of the methylation reagent include trimethylaluminum, methylmagnesium chloride, methylmagnesium bromide, and methyllithium.

Examples of the solvent in step 1 include ethers such as tetrahydrofuran, dioxane and diethyl ether, and organic solvents such as toluene and hexane which are inert to the reaction.

(Step 2)
In step 2, a compound (VI) is obtained by forming an exoolefin from the compound (VII) by a dehydration reaction using an acid catalyst.

As an example, in a reaction vessel equipped with a Dean-Stark apparatus, a method of reacting while dehydrating under reflux conditions using paratoluenesulfonic acid monohydrate as an acid catalyst and toluene as a solvent can be mentioned. , Not limited to this.

(Step 3)
In step 3, the ester portion of compound (VI) is reduced to alcohol to obtain compound (V). Specifically, the compound (V) is obtained by mixing the compound (VI) and the hydride reducing agent in a solvent at a low temperature (for example, 0 ° C.) or at room temperature.

Examples of the solvent in step 3 include ethers such as tetrahydrofuran, dioxane and diethyl ether, reaction-inactive toluene and dichloromethane, and organic solvents such as a mixture thereof.

Examples of the hydride reducing agent include lithium aluminum hydride and diisobutylaluminum hydride.

(Step 4)
In step 4, compound (IV) is obtained by epoxidizing the olefin moiety of compound (V).

As an example, titanium (IV) tetraisopropoxide, diethyl L- (+)-diethyl tartrate and tert-butyl hydroperoxide are mixed in dichloromethane at a low temperature (for example, -20 ° C.), and compound (V) is added thereto. Examples thereof include, but are not limited to, a method of adding and reacting at a low temperature.

(Step 5)
In step 5, compound (III) is obtained by oxidizing the alcohol moiety of compound (IV) to a carboxylic acid. Specifically, compound (III) is obtained by mixing ruthenium trichloride, sodium periodate and compound (IV) in a solvent at room temperature.

Examples of the solvent in step 5 include water, carbon tetrachloride, acetonitrile and ethyl acetate, and a mixed solvent composed of these solvents.

(Step 6)
In step 6, compound (II) is obtained from compound (III). When R ¹ is OR ⁴ and R ⁴ is hydrogen, the compound (II) and the compound (III) are the same, so that this step is not necessary.

First, when R ¹ is OR ⁴ and R ⁴ is alkyl, a method of obtaining compound (II) by alkylating compound (III) can be mentioned. As an example, in a solvent, a dialkyl sulfate ^{(R 4 OS (= O)} OR 4) as carbonate and alkylating reagent or with ^R 4 -LG, and a method for the reaction at room temperature.

Examples of carbonates include sodium carbonate, potassium carbonate, cesium carbonate and lithium carbonate.

LG has a leaving group that can be substituted nucleophilically, for example, a leaving group selected from a halogen group, an alkylsulfonyloxy group and an arylsulfonyloxy group.

Next, when R ¹ is NR ⁵ R ⁶ , compound (II) is obtained by condensing compound (III) with an amine. Specific examples thereof include a method in which compound (III), an amine, a base and a condensing agent are mixed in a solvent and reacted at room temperature.

Examples of the solvent in step 6 include amides such as N, N-dimethylacetamide, N-methylpyrrolidone and N, N-dimethylformaldehyde, and organic solvents such as dichloromethane and dichloroethane which are inert to the reaction.

Examples of the base include trisubstituted amines such as triethylamine, diisopropylethylamine and N, N-dimethyl-4-aminopyridine.

Examples of the condensing agent include 1- [bis (dimethylamino) methylene] -1H-1,2,3-triazolo [4,5-b] pyridinium 3-oxide hexafluorophosphate (HATU) and 1- [bis. (Dimethylamino) Methylene] -1H-benzotriazolinium 3-oxide hexafluorophosphate (HBTU) and 1H-benzotriazole-1-yloxytripyrrolidinophosphonium hexafluorophosphate (PyBOP) and the like.

(Step 7)
In step 7, the oxylan ring in the compound (II) is obtained by mixing the compound (II) and the azole compound in a solvent by a known method (for example, the method described in Patent Document: Japanese Patent Application Laid-Open No. 2013-100238). The compound (I), that is, the triazole derivative (I) is produced by forming a carbon-nitrogen bond between the carbon atom constituting the compound and the nitrogen atom of the azole compound.

Examples of the azole compound include 1,2,4-triazole or an alkali metal salt thereof.

The solvent of step 7 is not particularly limited, and for example, alcohols such as methanol and ethanol, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, N, N-dimethylacetamide, N-methylpyrrolidone and N, N. -Amids such as dimethylformaldehyde, as well as dimethylsulfoxide can be mentioned.

Further, a base may be added if desired. Examples of the base include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide and potassium t-butoxide, and potassium carbonate and the like.

[3. Agricultural and horticultural chemicals]
Since the triazole derivative (-)-enantiomer has a 1,2,4-triazolyl group, it forms an acid addition salt or metal complex of an inorganic acid and an organic acid. Therefore, it can be used as an active ingredient of agricultural and horticultural chemicals as a part of an acid addition salt and a metal complex.

[1. Plant disease control effect]
The fungicide for agriculture and horticulture in the present embodiment exhibits a control effect against a wide range of plant diseases.

Examples of applicable diseases include the following. The parentheses after each disease indicate the main pathogens that cause the disease. Soybean rust (Phakopsora pachyrhizi, Phakopsora meibomiae), soybean brown spot disease (Zymoseptria glycines), soybean purple spot disease (Cercospora kikuchiri), soybean brown spot disease (Alter) spot (Cercocopora sojina), soybean lysoctonia root rot (Rhizoctonia soly), soybean leaf rot (Rhizoctonia soly), soybean black spot disease (Diaporthe phaselorum), soybean stalk epidemic (Phoseolorum) Rapeseed Phoma leaf
spot / stem canker (Leptosphaeria maculans, Leptosphaeria biglobosa), Light leaf of rapeseed
spot (Pyrenopeziza brassicae), rapeseed root-knot disease Clubloot (Plasmodiophora brassicae), rapeseed verticillium wilt disease (Verticillium lonei rape), rapeseed Bla Cochliobolus miyabeanus, rice white leaf blight (Xanthomonas oryzae), rice crest blight (Rhizoctonia solani), rice small black fungus nucleus disease (Helminthosporium sigmoideun), rice seedlings , Phythium glaminicola, Omugi udonko disease (Erysipe graminis f. Sphordei), Omugi black rust (Puccinia graminis), Omugi Fusarium head blight (Puccinia), Fusarium head blight (Puccinia) Wilt disease (Rynchosporium secalis), Naked black scab (Ustilago nuda), Puccinia teres, Fusarium head blight (Fusarium head blight) , Puccinia recondita, Puccinia striformis, Pseudocercosporella herpotorichoides, Fusarium head blight, Fusarium head blight, Fusarium head blight, Fusarium head blight Blight (Zymoseptria tritici), Fusarium head blight (Microdochium nivale), Fusarium head blight (Gaeumanomyces graminis), Wheat black spot (Epicoccum spp), Wheat yellow spot (Puccinia) ritici-repentis, wheat small sclerotium nuclear disease (Typula incarnate, Cyphula ishikariensis), Shivadar spot disease (Sclerotinia homoeocarpa), Shivalaji patch disease (Rhizoctonia) ), Gray leaf Spot (Pyricularia grisea) of Shiva, Necrotic ring spot disease of Shiva (Ophiosphaerella korrae), Red threat (Laetisaria fuciformis) of Shiva, Rhizoctonia (Phizoctonia) , Sheba of Root decline of warm-season grasses (Gaeumannomyces graminis), lawn of brown ring patch (Waitea circinata), grass Fairy ring disease (Agaricus, Calvatia, Chlorophyllum, Clitocybe, Lepiota, Lepista, Lycoperdon, Marasmius, Scleroderma, Tricholoma, such as ), Shiva Rhizoctonia (Microdochium nivale), Shiva snow rot small sclerotia (Typhula incarnate, Typhula ishikariensis), Shiva Rhizoctonia leaf blight (Curvalaria sp.). ), Shiva pseudo-leaf rot (Ceratobasis sp.), Shiva blight (Zoysia decline), corn scab (Ustilago maydis), corn charcoal scab (Colletotrichum glaminicola), corn brown spot (Kaba) Diseases (Cercospora zeae-maydis), corn panama disease (Setosphaeria turcica), corn northern spot disease (Cochliobolus carbonum), corn spot disease (Physodorma maidis), corn rust (Pysodorma maidis), corn rust (Pusc) , Corn yellow sesame leaf blight (Phyllosticta maydis), corn red mold (Gibberella zeae), sugar cane rust (Puccinia spp), uri stag beetle (Sphaerotheca fusarium) ), Pseudoperonospora cubensis, Phytophthora capsici, Fusarium oxysporum f.sp.cuburiminum, watermelon panama disease, watermelon panama disease (Fustilago) Diseases (Podosphaera leucolicha), apple scab (Venturia inaequualis), apple morinia disease (Moniliina mari), apple spot foliar disease (Alternaria alternatea apple pathalia) , Pear Udonko disease (Phyllactinia pyri), Pear red scab (Gymnosporangium asiaticum), Pear scab (Ventria nashikola), Strawberry Udonko disease (Sphaerotheca funa) ), Erysiphe blue mold (Pencillium italicum), Uncinula necator, Plasmopara viticola, Glomerella chingulata, Glamella sigatoka, Phakops Black sigatoka) (Mycosphaerella fijiensis, Mycosphaerella mycosphaerella), Erysiphe cychoracearum, Tomato ring scab (Alternaria solani), Nasuta sickness (Erysiphe) (Collettricum cocodes), Erysiphe spp, Leveillula tarica, Mycosphaerella influenza, Tobacco sigatoka (Erysiphe sigatoka) Erysiphe betae, Thanatephorus cucumeris, Thanatephorus cucumeris, Aphanomyces cochlioides, Dycon wilt disease. sp. raphani), Cha charcoal scab (Discula thee-sinensis), Chamochi disease (Exobasidedium vexans), Cha brown circle disease (Pseudocercospora ocelata, Cercospora chaae), Chacospora chiapes (Exobasideium reticleutum), Wata black spot disease Alternaria leaf spot (Alternaria spp), Wata charcoal spt (Glomerella spp), Wata ring crest disease (Ascochyta gossypi), Wata spi leaf spot (Cercospora spp), Wata's Diplopia ball rot (Diplopia spp), Wata's Hard lock (Fusarium spp), Wata's Phoma blitz (Phoma spl) black sp. Cercosporidium personatum, Cercospora arachidicola, Cercospora lorfsi, Puccinia arachidis, Banana yellow shigatoka, Mycosphaerella Gray mold (Botrytis sinerea), disease of the genus Pythium (Pythium spp) and mycosphaerella (Cercospora), etc. that damage various crops. In addition, the genus Aspergillus, the genus Cochliobolus, the genus Corticium, the genus Diplodia, the genus Pencillum, the genus Gibberala, the genus Mucor, the genus Phoma, the genus Phomopsis, the genus Pyrenophora, and the genus Pyrenophora. Seed-borne diseases or early-growth diseases of various plants caused by the genus Trichoderma, the genus Ustylago, and the like.

Among the above-mentioned diseases, the fungicide for agriculture and gardening according to the present embodiment exhibits a particularly excellent control effect against the diseases of wheat such as wheat leaf blight and barley Fusarium head blight. Therefore, agricultural and horticultural fungicides are suitably used for controlling wheat, but are not limited thereto.

The agricultural and horticultural fungicides in this embodiment can be used for all plants, and examples of applicable plants include the following. Rice, wheat, barley, lime, embaku, triticale, corn, morokoshi (sorghum), sugar cane, shiva, bentgrass, Bermudagrass, fescue and ryegrass and other rice families, soybeans, lacquer, green beans, pea, azuki and alfalfa Mame family, Hirugao family such as sweet potato, Capsicum family such as pepper, pepper, tomato, eggplant, potato and tobacco, Tade family such as buckwheat, Kiku family such as sunflower, Ukogi family such as Chosen carrot, Abranaceae such as rapeseed, hakusai, cub, cabbage and daikon, red-spotted family such as tensai, blue-spotted family such as cotton, red-spotted family such as coffee tree, blue-spotted family such as cacao, camellia family such as cha, Uri families such as watermelons, melons, cucumbers and pumpkins, lilies such as onions, onions and garlic, roses such as strawberries, apples, almonds, apricots, sea urchins, peaches, peaches, peaches and pears, carrots, etc. Seri family, Satoimo family such as Satoimo, Urushi family such as mango, Pineapple family such as pineapple, Papaya family such as papaya, Kakinoki family such as oyster, Tsutsuji family such as blueberry, Walnut such as Pekan Family, Basho family such as banana, Mokusei family such as olive, Palm family such as Coco palm and Natsume palm, Mikan family such as tangerine, orange, grapefruit and lemon, Grape family such as grape, Flowers and ornamental plants), trees other than fruit trees, and other ornamental plants. In addition, wild plants, plant cultivars, plants and plant cultivars obtained by conventional biological breeding such as crossbreeding or progenitor fusion, and genetically modified plant cultivars obtained by genetic engineering and approved in each country can be mentioned. .. Examples of such genetically modified plant cultivars include those accumulated in the database of the International Agribio Corporation (ISAAA). Specifically, Roundup Ready, Liberty Link, IMI, SCS, Clearfield, Enlist, B.I. t. , BXN, Poast Compatible, AgriSure, Genuity, Optimum, Powercore, DroughtGard, YieldGard, Herculex, WideStrike, Twinlink, VipCot, GlyTol, Newleaf, KnockOut, BiteGard, BtXtra, StarLink, Nucotn, NatureGard, Protecta, SmartStax, Power core, InVigor And those including registered trademarks such as Bollgard.

[2. pharmaceutical formulation〕
The agricultural and horticultural chemicals are prepared by mixing the triazole derivative (-)-enantiomer according to the present embodiment, which is an active ingredient, with a solid carrier or a liquid carrier (diluent), a surfactant, other pharmaceutical adjuncts, and the like, and powder and water. It is formulated and used in various forms such as Japanese preparations, granules and emulsions.

These preparations contain the triazole derivative (-)-enantiomer as an active ingredient in an amount of 0.05 to 95% by weight, preferably 0.25 to 90% by weight, and more preferably 1 to 80% by weight. Examples of solid carriers, liquid carriers and surfactants used as formulation aids are as follows. First, solid carriers are used as powder carriers, granular carriers and the like, and clay, talc, diatomaceous earth, zeolite, montmorillonite, bentonite and acidic. Minerals such as white clay, active white clay, attapargit, calculus, vermiculite, pearlite, pebbles, silica sand; synthetic organic substances such as urea; salts such as calcium carbonate, sodium carbonate, sodium sulfate, limestone, and baking soda; amorphous such as white carbon. Synthetic inorganic substances such as quality silica and titanium dioxide; plants such as wood flour, corn stalk (cob), walnut shell (hard fruit hull), fruit nucleus, fir, oak, bran, soybean flour, powdered cellulose, starch, dextrin, sugar, etc. Sex carriers; crosslinked lignin, cationic gels, gelatin gelled with heating or polyvalent metal salts, water-soluble polymer gels such as agar, and chlorinated polyethylene, chlorinated polypropylene, polyvinyl acetate, polyvinyl chloride, ethylene-vinyl acetate. Examples thereof include various polymer carriers such as copolymers and urea-aldevido resins.

Liquid carriers include fatty acid solvents (paraffins), aromatic solvents (xylene, alkylbenzene, alkylnaphthalene, solvent naphtha, etc.), mixed solvents (kerosene), machine oils (refined high boiling fatty acid hydrocarbons), alcohols (alcohols). Methanol, ethanol, isopropanol, cyclohexanol, etc.), polyhydric alcohols (ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, etc.), polyhydric alcohol derivatives (propylene-based glycol ether, etc.), ketones Classes (acetone, acetophenone, cyclohexanone, methylcyclohexanone, γ-butyrolactone, etc.), esters (fatty acid methyl ester (palm oil fatty acid methyl ester), ethyl hexyl lactate, propylene carbonate, dibasic acid methyl ester (succinic acid dimethyl ester, glutamate dimethyl ester) (Ester, adipic acid dimethyl ester)), nitrogen-containing carriers (N-alkylpyrrolidones), fats and oils (palm oil, soybean oil, rapeseed oil, etc.), amide-based solvents (dimethylformamide, (N, N-dimethyloctaneamide, etc.) N, N-dimethyldecaneamide, 5- (dimethylamino) -2-methyl-5-oxo-valeric acid methyl ester, N-acylmorpholin-based solvent (CAS No. 887947-29-7, etc.), dimethylsulfoxide acetonitrile , Water, etc.

Examples of the nonionic surfactant include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene resin acid ester, and polyoxyethylene fatty acid diester. , Polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene dialkylphenyl ether, polyoxyethylene alkylphenyl ether formalin condensate, polyoxyethylene / polyoxypropylene block polymer, alkylpolyoxyethylene / polyoxypropylene block Polymer ether, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, polyoxyethylene fatty acid bisphenyl ether, polyoxyethylene benzylphenyl (or phenylphenyl) ether, polyoxyethylene styrylphenyl (or phenylphenyl) ether, polyoxyethylene Examples thereof include ether and ester-type silicon and fluorine-based surfactants, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, and alkyl glycosides. Anionic surfactants include alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, polyoxyethylene benzyl (or styryl) phenyl (or phenylphenyl) ether sulfate, polyoxyethylene, and polyoxypropylene. Salts of sulfates such as block polymer sulfate, paraffin (alkane) sulfonate, α-olefin sulfonate, dialkyl sulfosuccinate, alkylbenzene sulfonate, mono or dialkylnaphthalene sulfonate, naphthalene sulfonate formalin condensate, alkyldiphenyl ether disulfonate, lignin sulfonate, Salts of sulfonates such as polyoxyethylene alkylphenyl ether sulfonates, polyoxyethylene alkyl ether sulfosuccinic acid half esters, fatty acids, salts of fatty acids such as N-methyl-fatty acid sarcosinates, resin acids, polyoxyethylene alkyl ether phosphates, Polyoxyethylene mono or dialkylphenyl ether phosphate, polyoxyethylene benzyl (or styryl) phenyl (or phenylphenyl) ether phosphate, polyoxyethylene / polyoxypropylene block polymer, phosphatidylcholine phosphatidylethanolimine (resitin), alkyl phosphate, etc. Kind of salt and the like. Cationic surfactants include ammonium salts such as alkyltrimethylammonium chloride, methylpolyoxyethylene alkylammonium chloride, alkyl N-methylpyridium bromide, mono or dialkylmethylated ammonium chloride, alkylpentamethylpropylenediaminedichloride and alkyldimethyl. Examples thereof include benzalkonium salts such as benzalkonium chloride and benzethonium chloride (octylphenoxyethoxyethyldimethylbenzylammonium chloride). In addition, conventionally known biosurfactants (for example, mannosylargitol lipid, sophorolipid, ramnolipid, trehalose lipid, cellobiose lipid, glucose lipid, oligosaccharide fatty acid ester, surfactin, serauetchin, lykencin, arslofactin, spiclesporic acid, corinomicol). Acid, agaric acid, emalzan, etc.) may be contained as a surfactant.

Other pharmaceutical aids include inorganic salts such as sodium and potassium as pH adjusters, fluorine-based and silicone-based defoaming agents, water-soluble salts such as salt, and xattan gum and guar gum used as thickeners. Water-soluble polymers such as carboxymethyl cellulose, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic polymer, polyvinyl alcohol, starch derivatives, polysaccharides, alginic acid and its salts, metal stearate used as a disintegrant dispersant, sodium tripolyphosphate, hexametallin Acid soda and others include preservatives, colorants, antioxidants, UV absorbers, and chemical damage reducing agents.

There are two types of pharmaceutical products, one that is used as it is and the other that is diluted to a predetermined concentration with a diluent such as water. The concentration of the triazole derivative (-)-enantiomer when diluted and used is preferably in the range of 0.0005 to 1.0%.

The amount of the triazole derivative (-)-enantiomer used is 10 to 5000 g, more preferably 25 to 2000 g per 1 ha of horticultural land such as fields, rice fields, orchards and greenhouses. Since these concentrations and amounts used vary depending on the dosage form, timing of use, method of use, place of use, target crop, etc., they can be increased or decreased without being particular about the above range.

[3. Other active ingredients]
The agricultural and horticultural agent containing the triazole derivative (-)-enantiomer (I) in the present embodiment can be used in combination with other known active ingredients to enhance the performance as the agricultural and horticultural agent. Other known active ingredients include known active ingredients contained in fungicides, insecticides, acaricides, nematodes, and plant growth regulators.

Known active ingredients contained in bactericides include nucleic acid synthesis and metabolism inhibitors, threaded nucleus division / cell division inhibitors, respiratory inhibitors, amino acid / protein biosynthesis inhibitors, signal transduction inhibitors, lipid biosynthesis or transport / Examples include cell membrane structure or function inhibitors, cell membrane sterol biosynthesis inhibitors, cell wall biosynthesis inhibitors, melanin biosynthesis inhibitors, host plant resistance inducers, and multi-action point bactericides.

Examples of the nucleic acid synthesis metabolism inhibitor include benaraxil, benaraxyl M, furaxyl, offrace, bupirimate, dimethyrimol, etilimol, octylinone, metalaxil, metalaxil-M, oxadixil and himexazole, and are at least one selected from these. obtain.

Examples of the filamentous fission / cell division inhibitor include benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate, thiophanate-methyl, dietofencarb, zoxamide, etaboxam, pencyclon, fluoricorid, phenamaclyl, metrafenone and pyriophenone. Can be at least one.

Respiratory inhibitors include tolfenpyrado, diflumethrim, phenazakin, pidiflumethofen, fenfuran, carboxin, oxycarboxin, benodanyl, flutranil, mepronil, isofetamide, benzobindiflupill, bixaphen, fluindapyl, fluxapyroxado, Flametopill, isopyrazam, penflufen, penthiopyrado, sedaxan, isoflusiplum, boscalid, fluopirum, thyfluzamide, pyraziflumid, pyribencarb, fluoxastrobin, phenamiden, mandestrobin, azoxystrobin, spumoxystrobin, enoxastrobin, full Phenoxystrobin, picoxystrobin, pyracrostrobin, pyraoxystrobin, trichloropyricalve, famoxadon, dymoxystrobin, phenaminestrobin, metminostrobin, orisastrobin, cresoxime-methyl, trifluorostrobin, siazophamid, Amisulbrom, fenpicoxamide, florylpicoxamide, binapacryl, meptyldinocup, dinocup, fluazinum, triphenyltin acetate, triphenyltin chloride, triphenyltin hydroxide, silthiofam, amethoctrazine, methyltetraplol, pyrapropoin and Impilfluxam and the like can be mentioned and at least one selected from these.

Examples of the amino acid / protein biosynthesis inhibitor include cyprodinyl, mepanipyrim, pyrimethanyl, blastsidedin, kasugamycin, streptomycin, oxytetracycline and the like, and may be at least one selected from these.

Examples of the signal transduction inhibitor include quinoxyphen, proquinazide, clozoline, dimethacron, phenpicronyl, fludioxonyl, iprodion, procymidone, vinclozoline and the like, and may be at least one selected from these.

Lipid biosynthesis or transport / cell membrane structure or function inhibitors include isoprothiolan, edifenphos, iprobenphos (IBP), pyrazophos, biphenyl, chloroneb, dichloran, quintozen (PCNB), technazen (TCNB), torquelophos- Methyl, etridiazole, prothiocarb, propamocarb, natamycin, oxathiapiproline, fluoxapiproline and the like can be mentioned and may be at least one selected from these.

Cell membrane sterol biosynthesis inhibitors include imazalyl, oxpoconazole, pefrazoate, prochloraz, triflumizole, trifolin, pyrifenox, pyrisoxazole, phenalimol, nuarimol, azaconazole, bitertanol, bromconazole, cyproconazole, Diphenoconazole, diniconazole, epoxyconazole, etaconazole, fenbuconazole, fluconazole, fluconazole, flutrifolin, hexaconazole, imibenconazole, metconazole, ipconazole, microbutanyl, penconazole, propiconazole, simeconazole, tebuconazole, tetra. Nazole, Triazimefon, Triazimenol, Triticonazole, Mefentrifluconazole, Prothioconazole, Tridemorph, Fenpropimorph, Fenpropidine, Piperline, Spiroxamine, Fempyrazamine, Fenhexamide, Naftiffin, Turbinafin, Pyribycarb and Examples include ipfentrifluconazole and the like, and may be at least one selected from these.

Examples of the cell wall biosynthesis inhibitor include polyoxin, dimethmorph, fulmorph, pyrimorph, mandipropamide, benchavaricarb, iprovaricarb, and varifenalate, and may be at least one selected from these.

Examples of the melanin biosynthesis inhibitor include fusalide, tricyclazole, pyrochyron, carpropamide, diclosimet, phenoxanyl, tolprocarb and the like, and may be at least one selected from these.

Host plant resistance inducers include acibenzolar-S-methyl, probenazole, thiazinyl, laminarin, isothianyl, laminarin, phocetyl-Al, phosphoric acid and phosphate, with at least one selected from these. could be.

Multi-action point fungicides include simoxanyl, tecrophthalam, triazoxide, flusulfamide, dichromedin, siflufenamide, dodine, fluthianyl, ferlimzone, tebuflokin, picalbutrazox, varydamycin, mineral oil, baking soda, potassium carbonate, copper and copper compounds, sulfur, Farbam, Manzeb, Manneb, Metylum, Propineb, Thiram, Dineb, Diram, Captan, Captan, Folpet, Chlorotalonyl (TPN), Guazatin, Iminoctadine acetate, Iminoctadine albesylate, Anilazine, Dithianone, Fluorimide, Metasulfocarb , Florylpicoxamide, fluopimomid, ipflufenokin, quinomethionate, pyridaclomethyl, aminopyridene, diclobenazox, quinofmerin, dipimethitron and the like, and may be at least one selected from these.

In addition, as compounds for other fungicide applications, fenamiden, fenitropan, halpin, isonial, diclobenazox, picalbutrazox, hydroxyisoxazole, fluorimide, quinomethionate, chloroinconazide, trichoderma mycelium extract, Gosei Kayupte (tea tree) extract, vegetable oil (eugenol, geraniol, timol), Oitadori extract, cell wall of Saccharomyces cerevisiae LAS117 strain and biopesticides (Agrobacterium radiobacter, Pseudomonas fluorescens, Pseudomonas rodesia, Pseudomonas chlororafis AFS009 strain, Bacillus subtilis, Bacillus symplex, Bacillus amyloliquefaciens, Bacillus mycoides, non-pathogenic Elvinia carotbora, Lactobacillus plantarum, Barrioborax paradox, Swingrea glutinosa extract , Trichoderma atroviride LU132 strain, Trichoderma atroviride SC1 strain, Trichoderma asperellam T34 strain, Gliocladium catenuratam or chronostakis rosea, Streptomyces glyceobilides K61 strain, Streptomyces lydicus WYEC108, etc.) Can be mentioned.

Known active ingredients in pesticides include nicotinic acetylcholine receptor antagonist modulators, sodium channel modulators, lianodine receptor modulators, acetylcholinesterase inhibitors, oxidative phosphorylation uncouplers, and mitochondrial electron transport chain complex I. Inhibitors and the like can be mentioned.

Examples of the nicotinic acetylcholine receptor antagonist modulator include acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam, sulfoxaflor, flupyradiflon, and triflumezopyrim, and may be at least one selected from these.

Examples of the sodium channel modulator include pyrethroid compounds, and examples of the pyrethroid compounds include acrinathrin, arereslin, cypermethrin, bifenthrin, cycloprothrin, cyhalothrin, deltamethrin, dimefluthrin, esphenvalerate, etofenprox, and fenpropathrin. , Fenvalerate, flubrocitrinate, flucitrinate, fluvalinate, halfenprox, cyhalothrin, metoflutrin, monfluorothrin, permethrin, profluthrin, tefluthrin, tralomethrin, imiprothrin, pyrethrin and ciphenothrin, chloropralesrin, epsilonmethrin Trin and epsilon monfluorothrin and the like can be mentioned and may be at least one selected from these.

Examples of the ryanodine receptor modulator include chloranthraniliprole, cyantraniliprole, flubendiamide, sihalodiamide, and the like, and may be at least one selected from these.

Acetylcholinesterase inhibitors include acephate, azinephos-methyl, kazusaphos, chlorethoxyphos, chlorfenbinphos, chlorpyriphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos (DDVP), dicrotophos, dimethote, disulfoton, etion, etoplophos. , EPN, phenamiphos, fenitrothion (MEP), fenthion (MPP), hostizate, imiciaphos, isofenphos, isoxathione, malathion, metamidphos, metidathion, mevinphos, monochromotophos, ometoate, oxydemethonemethyl, parathion, parathion-methyl, pholate, , Hosalon, Hosmet, Phosfamidon, Hoxime, Pyrimiphosmethyl, Profenophos, Prothiophos, Pyraclophos, Pyridafenthion, Kinalphos, Tebupyrimhos, Telbuhos, Triazophos and Trichlorfon (DEP), Aranicarb, Ardicalve, Benfracarb, BPMC, Carbofuran, Carbofuran , Cartap, phenoxycarb (BPMC), formethanate, isoprocarb (MIPC), methiocarb, mesomil, oxamil, pyrimicalve, thiodicalve, XMC, bendiocarb, ethiophencarb, phenobucarb, phenothiocarb, fratiocarb, metorcarb and xylylcarb. It can be at least one selected from these.

Examples of the oxidative phosphorylation uncoupler include chlorfenapyr, DNOC, sulflamide and the like, and may be at least one selected from these.

Examples of the mitochondrial electron transport chain complex I inhibitor include tebufenpyrado, tolfenpyrado, phenazakin, phenpyroxymate, pyridaben, pyrimidiphen and rotenone, and may be at least one selected from these.

Known active ingredients in plant growth regulators include aminoethoxyvinylglycine, chlormecoat, chlorpropham, cyclanilide, dikegrac, daminogit, etephone, fluluprimidol, flumethrolin, holchlorphenurone, gibberellin, hydrazide maleate. Salts, mepicort chloride, methylcyclopropham, benzylaminopurine, paclobutrazol, prohexadione, thydiazulone, tributylphosphorotrithioate, trinexacacethyl and uniconazole, and the like, and at least one selected from these. Can be one.

Known active ingredients (mite-killing active ingredients) contained in the acaricide include, for example, acequinocil, hydramethylnon, amideflumet, amitraz, azocyclotin, biphenazate, bromopropirate, clofentezine, quinomethionate, phenisobromolate, and the like. Benzoximate, clofentezine, cyenopyraphen, siflumethofen, cyhexatin, difluorovidazine, dienochlor, etoxazole, phenazakin, fenbutatin oxide, phenpyroximate, phenothiocarb, fluaclipirim, hexitiazox, propargite (BPPS), piflubumid, pyridaben Examples include fen, tebufenpyrado, tetradiphon, asinonapill, cyhexatinifene, flupentiophenox, blended oil and the like.

Known active ingredients (nematode active ingredients) contained in nematode nematodes include, for example, DD (1,3-dichloropropene), DCIP (dichlorodiisopropyl ether), methylisothiocyanate, carbam sodium salt, and the like. C.

In addition, as compounds for other pesticide applications, avelmectin, tetrachlorolantraniliplol, diafentiurone, ethiprol, fipronil, fronicamid, fluenesulfone, indoxacarb, metaflumison, metaaldehyde, pimetrodin, pyridalyl, pyrifluquinazone, silafluofen. , Spirosion, Spirotetramato, Sulfoxaflor, Afidopyropen, Brofuranilide, Cycraniliprol, Dichloromesothiaz, Frometkin, Fluazindridin, Fluhexaphon, Fluxametamide, Pyryprol, Tetraniliprol, Hydroprene, Kinoprene, Metoprene, Ticropira Zoflo (tyclopyrazoflor), flupyrimin, spiropidione, benzpyrimoxane, isocycloselam, sulfurulamide, nicofluprol, gympropyridas, methyl bromide, chlorpicrin, cryolite, sulfryl fluoride, boric acid, boric acid, sodium octaborate , Sodium metaborate, Insecticide, Dazomet, Metam, Aluminum phosphide, Calcium phosphate, Hosphin, Zinc phosphate, Calcium cyanide, Potassium cyanide, Sodium cyanide, Ciproflanilide, Kodlinga granule disease virus, Kodlinga modoki granule disease virus, Boric acid beetle nuclear polymorphism virus, Tobacco moth nuclear polymorphic disease virus, GS-omega / kappa HXTX-Hv1a peptide, azadilactin, dicohol, lime sulfur mixture, Burkhorderia spp. Examples include compounds, fatty acid monoesters with glycerin or propanediol, neem oil, boberia baciana, metallidium anisoprie, pequiromyces fumosoloseus, diatomaceous soil and the like.

[4. Plant disease control method]
The agricultural and horticultural chemicals in this embodiment can be used in cultivated or non-agricultural lands such as fields, paddy fields, lawns, and orchards. Further, the agricultural and horticultural chemicals in the present embodiment can be applied not only by foliage treatment such as foliage spraying, but also by non-foliage treatment such as seed treatment including treatment of bulbs and tubers, irrigation treatment, and water surface treatment. Therefore, the method for controlling plant diseases in the present embodiment is a method including a procedure for performing foliage treatment or non-foliage treatment using the above-mentioned agricultural and horticultural agents. In addition, when the non-foliage treatment is performed, the labor can be reduced as compared with the case where the foliage treatment is performed.

In the application by seed treatment, the chemicals are attached to the seeds by mixing the wettable powder and powder with the seeds and stirring, or by immersing the seeds in the diluted wettable powder. It also includes a seed coating process. The amount of the active ingredient used in the seed treatment is, for example, 0.005 to 10000 g, preferably 0.05 to 1000 g per 100 kg of seeds. Seeds treated with agricultural and horticultural chemicals may be used in the same manner as normal seeds.

The application by irrigation treatment is performed by treating the planting hole or its surroundings with granules, etc. at the time of transplanting seedlings, or treating the soil around the seeds or plants with granules, wettable powders, etc. .. The amount of the active ingredient used in the irrigation treatment is, for example, 0.005 to 10000 g, preferably 0.05 to 1000 g per ^{1 m 2 of agricultural and horticultural land.}

Application by water surface treatment is performed by treating the surface water of the paddy field with granules or the like. The amount of the active ingredient used in the water surface treatment is, for example, 0.05 to 10000 g, preferably 0.5 to 1000 g per paddy field 10a.

The amount of the active ingredient used for foliage spraying is, for example, 10 to 5000 g, more preferably 25 to 2000 g per 1 ha of agricultural and horticultural fields such as fields, rice fields, orchards and greenhouses.

Since the concentration and amount of use differ depending on the dosage form, timing of use, method of use, place of use, target crop, etc., it is possible to increase or decrease without being particular about the above range.

The liquid carrier is not particularly limited as long as it does not react with the active ingredient. Examples of the liquid carrier include water, alcohols (eg, methyl alcohol, ethyl alcohol, ethylene glycol, cellosolve, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), ethers (eg, dimethyl ether, diethyl ether, dioxane, hydrocarbon, etc.). Etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, methylnaphthalene, etc.), aliphatic hydrocarbons (eg, gasoline, kerosine, kerosene, machine oil, fuel oil, etc.), acid amides (eg, dimethylformamide). , N-Methylpyrrolidone, etc.) Halogenated hydrocarbons (eg, chloroform, carbon tetrachloride, etc.), esters (eg, ethyl acetate esters, fatty acid glycerin esters, etc.), nitriles (eg, acetonitrile, etc.) and dimethylsulfoxide. And so on.

As the solid carrier, fine powders or granules such as kaolin clay, bentonite, acidic clay, pyrophyllite, talc, diatomaceous earth, calcite, urea, and ammonium sulfate can be used.

As emulsifiers and dispersants, surfactants such as soaps, alkylsulfonic acids, alkylarylsulfonic acids, dialkylsulfosuccinic acids, quaternary ammonium salts, oxyalkylamines, fatty acid esters, polyalkylene oxides, and anhydrosorbitols. Can be used.

When the triazole derivative (-)-enantiomer is contained in the pharmaceutical product as an active ingredient, the content ratio varies depending on the dosage form and the purpose of use, but is 0.1 to 99.9% by weight based on the total amount of the pharmaceutical product. do it. In actual use, the treatment concentration is usually adjusted to 0.0025 to 5% by weight, preferably 0.005 to 1% by weight by appropriately adding a solvent, a diluent, a bulking agent or the like. It is preferable to do so.

As explained above, the triazole derivative (-)-enantiomer shows an excellent bactericidal action against many bacteria that cause plant diseases. That is, the agricultural and horticultural disease control agent containing the triazole derivative (-)-enantiomer as an active ingredient has low toxicity to humans and animals, is excellent in handling safety, and can exhibit a high control effect on a wide range of plant diseases.

[4. Industrial material protectant]
[1. Industrial material protection effect]
The triazole derivative (-)-enantiomer according to the present embodiment can also be used as an industrial material protectant because it exhibits an excellent effect of protecting the material from a wide range of harmful microorganisms that attack the industrial material. Examples of such microorganisms include the following microorganisms.

Paper and pulp-deteriorating microorganisms (including slime-forming microorganisms), Aspergillus sp., Trichoderma sp., Penicillium sp., Geotrichum sp., Chaetomium sp. (Cadophora
sp. ), Ceratostomella sp., Cladosporium sp., Corticium sp., Lentinus sp., Lentinus sp., Phomatics sp. Polysticus sp., Pulularia sp., Stereum sp., Trichosporium sp., Aerobacter sp., Bacillus sp., Desulfobibrio sp. , Pseudomonas sp., Flavobacterium sp., Micrococcus sp., and other fiber-degrading microorganisms such as Aspergillus sp., Penicillium sp., Penicillium sp. ), Micrococcium sp., Curvularia sp., Gliomatics sp., Memnoniella sp., Sarcopodium sp., Sarcopodium sp. Stereum sp., Zygorhynchus sp., Bacillus sp., Staphylococcus sp. Aspergillus sp., Penicillium sp., Rhizopus sp., Aureobasidium sp., Gliocladum sp., Cladosporium sp. Aspergillus (Asp), which is a leather-deteriorating microorganism such as Chaetomium sp.) And Trichoderma sp. erguillussp. ), Penicillium sp., Chaetomium sp., Cladosporium sp., Mucor sp., Paecilomyces sp., Pilobus sp. ), Trichosporon sp., Trichothecium sp., Aspergillus sp., Penicillium sp., Rhizopus sp., Trichothecium sp., Trichothecium sp., Trichothecium sp. , Chaetomium sp., Myrothecium sp., Streptomyces sp., Pseudomonas sp., Bacillus sp., Bacillus sp., Micrococcus sp. .), Margarinomyces sp., Monascus sp., And other paint-degrading microorganisms such as Aspergillus sp., Penicillium sp., Cladosporium sp., Cladosporium sp. Sidium (Aureobasideium sp.), Gliocladium sp., Botriodiplodia sp., Macrosporium sp., Monilia sp., Forma (Ph) , Pluraria sp., Sporotrichum sp., Trichoderma sp., Bacillus sp., Proteus sp., Pseudomonas sp., Serra, Pseudomonas sp.

[2. pharmaceutical formulation〕
The industrial material protective agent containing the triazole derivative (-)-enantiomer as an active ingredient according to the present embodiment may contain various components other than the triazole derivative (-)-enantiomer. The industrial material protectant containing the triazole derivative (-)-enantiomer as an active ingredient can be dissolved or dispersed in a suitable liquid carrier, or mixed with a solid carrier for use. The industrial material protectant containing the triazole derivative (-)-enantiomer as an active ingredient may further contain an emulsifier, a dispersant, a spreading agent, a penetrant, a wetting agent, a stabilizer and the like, if necessary. Examples of the dosage form of the industrial material protective agent containing the triazole derivative (-)-enantiomer as an active ingredient include wettable powders, powders, granules, tablets, pastes, suspensions and spray materials. can. The industrial material protective agent containing the triazole derivative (-)-enantiomer as an active ingredient may contain other fungicides, insecticides, deterioration inhibitors and the like.

The liquid carrier is not particularly limited as long as it does not react with the active ingredient. Examples of the liquid carrier include water, alcohols (eg, methyl alcohol, ethyl alcohol, ethylene glycol, cellosolve, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), ethers (eg, dimethyl ether, diethyl ether, dioxane, hydrocarbon, etc.). Etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, methylnaphthalene, etc.), aliphatic hydrocarbons (eg, gasoline, kerosine, kerosene, machine oil, fuel oil, etc.), acid amides (eg, dimethylformamide). , N-Methylpyrrolidone, etc.) Halogenated hydrocarbons (eg, chloroform, carbon tetrachloride, etc.), esters (eg, ethyl acetate esters, fatty acid glycerin esters, etc.), nitriles (eg, acetonitrile, etc.), dimethylsulfoxide, etc. Can be mentioned.

As the solid carrier, fine powders or granules such as kaolin clay, bentonite, acidic clay, pyrophyllite, talc, diatomaceous earth, calcite, urea and ammonium sulfate can be used.

As emulsifiers and dispersants, surfactants such as soaps, alkylsulfonic acids, alkylarylsulfonic acids, dialkylsulfosuccinic acids, quaternary ammonium salts, oxyalkylamines, fatty acid esters, polyalkylene oxides and anhydrosorbitols Can be used.

When the triazole derivative (-)-enantiomer is contained in the pharmaceutical product as an active ingredient, the content ratio varies depending on the dosage form and the purpose of use, but is 0.05 to 99.9% by weight based on the total amount of the pharmaceutical product. do it. In actual use, the treatment concentration is usually adjusted to 0.0025 to 5% by weight, preferably 0.005 to 1% by weight by appropriately adding a solvent, a diluent, a bulking agent, or the like. It is preferable to do so.

[summary]
The compound according to the present invention is a (-)-enantiomer of the triazole derivative represented by the above general formula (I) or a pesticide-acceptable salt thereof.

In one aspect of the compound according to the present invention, in the general formula (I),
R ¹ is -OR ⁴ ;
R ² is a halogen group, a cyano group, a C _1- C ₄ -alkyl group, a C _1- C ₄ -haloalkyl group, a C _1- C ₄ -alkoxy group, -SOR ⁷ or -SF ₅ ;
R ³ is a halogen group, a nitro group, a cyano group, an amino group, a C _1- C ₄ -alkyl group, a C _1- C ₄ -haloalkyl group, a C _1- C ₄ -alkoxy group, and a C _1- C ₄ -halo. alkoxy _groups, C 1 -C ₄ - alkyl acyl amino group, the compound or a salt thereof -SOR ⁷ or -SF ₅ - alkylamino _group, C 1 -C ₄ - dialkylamino _group, C 1 -C _4.

In one embodiment of the compounds according to the present invention, in the general formula (I), ^{R 4} _is, C 1 -C ₆ - an alkyl group;
R ² is halogen, _cyano, C 1 -C ₄ - alkyl _group, C 1 -C ₄ - haloalkyl group or a _C 1 -C ₄ - alkoxy group;
R ³ is halogen, _cyano, C 1 -C ₄ - haloalkoxy group - alkyl _group, C 1 -C ₄ - haloalkyl _group, C 1 -C ₄ - alkoxy group or a _C 1 -C _4.

Agricultural and horticultural agents or industrial material protective agents containing the triazole derivative (-)-enantiomer according to the present invention as an active ingredient are also included in the category of the present invention.

Examples are shown below, and embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible for details. Further, the present invention is not limited to the above-described embodiment, and various modifications can be made within the scope of the claims, and the present invention also relates to an embodiment obtained by appropriately combining the disclosed technical means. It is included in the technical scope of the invention. In addition, all of the documents described in this specification are incorporated by reference.

<Production Example 1: Preparation of triazole derivative (-)-enantiomer by optical resolution>
Methyl 2- (2-chloro-4- (4-chlorophenoxyphenyl) phenyl) -2-hydroxy-3- (1H-1,2,4-triazole-1-yl) propanoate with reference to Patent Document 1. (Hereinafter referred to as compound 1 (racemic)) was obtained.

Compound 1 (racemi) was dissolved in methanol and subjected to high performance liquid chromatography (HPLC) in which amylose tris (3-chloro-5-methylphenylcarbamate) was connected to a preparative column immobilized on a silica gel carrier. Separation was performed.

The specific conditions are as follows.
High Performance Liquid Chromatograph: Preparative Column: Product Name "CHIRALPAK IG", manufactured by Daicel Chemical Industries, Ltd., Inner diameter 4.6 mm, Length 250 mm, Particle size 5 μm
Sample concentration: 0.5 mg / mL
Mobile phase: 100% methanol flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detection wavelength: 230nm

When separated under the above conditions, two peaks with different elution times were detected. As a result of measuring the specific rotation of the compound derived from each peak, the compound eluted first was (+)-enantiomer, and the compound eluted later was (-)-enantiomer. Hereinafter, the (-)-enantiomer and the (+)-enantiomer are referred to as compound 1 (-) and compound 1 (+), respectively.

The specific rotation was measured using P-1020 (manufactured by JASCO Corporation, Na lamp: 589 nm). The specific measurement results are as follows.

(+)-Specific rotation of enantiomers:
[Α] ²⁰ _D = + 120.8 ° (10 mg per 1 mL of chloroform)
(-)-Specific rotation of enantiomers:
[Α] ²⁰ _D = -123.1 ° (10 mg per 1 mL of chloroform)

<Production Example 2: Preparation of triazole derivative (-)-enantiomer by chemical synthesis>
Synthesis of 2- (2-chloro-4- (4-chlorophenoxy) phenyl) propa-2-en-1-ol (reaction scheme 1)

Dissolve 5.0 g of 2- (2-chloro-4- (4-chlorophenoxy) phenyl) -2-oxoacetate in 76.9 mL of tetrahydrofuran (THF) and cool to -78 ° C in a dry ice / acetone bath. bottom. 17.2 mL of 1.07 M / methylmagnesium bromide / THF solution was slowly added dropwise to the obtained solution, and the mixture was stirred for 1 hour. The reaction was stopped by adding an aqueous ammonium chloride solution to the reaction solution. For the obtained solution, the aqueous layer was extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 5.38 g of a crude product A of methyl 2- (2-chloro-4- (4-chlorophenoxy) phenyl) -2-hydroxypropanoate.

Subsequently, 5.38 g of the crude product A was dissolved in 92.3 mL of toluene. 1.46 g of paratoluenesulfonic acid monohydrate was added thereto, and the mixture was stirred under reflux conditions in an oil bath heated to 130 ° C. One hour after the start of the reaction, the reaction solution was allowed to cool to room temperature, and then a saturated aqueous sodium hydrogen carbonate solution was added to stop the reaction. For the obtained solution, an aqueous layer was extracted with toluene and washed with saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off to obtain 4.83 g of a crude product of methyl 2- (2-chloro-4- (4-chlorophenoxy) phenyl) acrylate.

2.43 g of crude product B was dissolved in 18.5 mL of toluene, cooled in a dry ice / acetone bath, and then 18.5 mL of 1.0 M / diisopropylaluminum hydride / toluene solution was added. After stirring for 1 hour under cooling, the reaction solution was added to hydrochloric acid (1N) to stop the reaction. Further, water and potassium sodium tartrate were added, and the mixture was stirred at room temperature for 1 hour. For the obtained solution, the aqueous layer was extracted with toluene, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product C ₁ . Further, in another batch, the same crude product C ₂ was obtained by performing the same operation as the above operation. Together, they were purified as crude product C by silica gel column chromatography (silica gel 40 g hexane / ethyl acetate: 20 → 50%) to obtain 3.68 g of the title compound as a colorless liquid. ^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.34-7.30 (m, 2H), 7.18 (d, J = 8.4 Hz, 1H), 7.00-6.92 (m, 3H) ), 6.89 (dd, J = 8.4, 2.0Hz, 1H), 5.37 (s, 1H), 5.18 (s, 1H), 4.41 (d, J = 6.4Hz) , 2H), OH signal disappeared due to H / D exchange.

(2- (2-Chloro-4- (4-chlorophenoxy) phenyl) oxylan-2-yl) Methanol synthesis (reaction scheme 2)

10.5 mL of dichloromethane was placed in a flask containing 306 mg of Molecular Sieves 4A, which had been heat-dried under vacuum conditions, and cooled by ice cooling. After adding 1.23 mL of titanium (IV) tetraisopropoxide and 0.89 mL of diethyl L- (+)-tartarate to the solution, the mixture was transferred to a low temperature constant temperature bath at −20 ° C. and stirred for 10 minutes while cooling. To the obtained solution, 17.9 mL of 1.16 M / tert-butyl hydroperoxide / anhydrous dichloromethane solution was added, and the mixture was further stirred for 20 minutes to obtain a reaction solution A. Subsequently, 613 mg of 2- (2-chloro-4- (4-chlorophenoxy) phenyl) propa-2-ene-1-ol obtained in the previous section was dissolved in 10.5 mL of dichloromethane to obtain a reaction solution B. .. The reaction solution B was added dropwise to the reaction solution A using a Pasteur pipette. After stirring for 6 hours under cooling at −20 ° C., the reaction was stopped by adding a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium sulfite solution to the reaction solution. Subsequently, an aqueous layer was extracted with ethyl acetate from the filtrate obtained by filtering the solution with Celite, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain a crude product D. The crude product D was purified by silica gel column chromatography (silica gel 16 g, hexane / ethyl acetate: 9 → 50%) to obtain 318 mg of the title compound as a colorless liquid. ^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.41 (d, J = 8.8 Hz, 1H), 7.35-7.30 (m, 2H), 7.00-6.96 (m, 3H) ), 6.89 (dd, J = 8.4,2.0Hz, 1H), 4.02-3.89 (m, 2H), 3.35 (d, J = 4.8Hz, 1H), 2 .88 (d, J = 4.8 Hz, 1H), 1.76-1.72 (m, 1H).

Synthesis of Methyl 2- (2-Chloro-4- (4-Chlorophenoxy) Phenyl) Oxylan-2-carboxylate (Reaction Scheme 3)

102 mg of (2- (2-chloro-4- (4-chlorophenoxy) phenyl) oxylan-2-yl) methanol obtained in the previous section is dissolved in 0.65 mL of carbon tetrachloride, 0.65 mL of acetonitrile, and 1.0 mL of water. Then, after adding 280 mg of sodium periodate, 7 mg of ruthenium trichloride was added. After stirring this reaction solution at room temperature for 1 hour, the reaction was stopped by adding a saturated aqueous solution of sodium hydrogen carbonate and a saturated aqueous solution of sodium sulfite to the reaction solution. Further, hydrochloric acid (1N) was added until the pH of the solution reached about 3, and the aqueous layer was extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate. The crude organism E obtained by distilling off the solvent was used as it was in the next reaction.

Crude product E was dissolved in 3.3 mL of N, N-dimethylformamide and 0.061 mL of iodomethane was added. After cooling in an ice bath, 136 mg of potassium carbonate was then added. After stirring at room temperature for 1 hour, 0.182 mL of iodomethane and then 407 mg of potassium carbonate were further added. After stirring at room temperature for 1 hour, the reaction was stopped by adding a saturated aqueous solution of ammonium chloride to the reaction solution. The aqueous layer was extracted with ethyl acetate, washed with saturated brine and dried over anhydrous sodium sulfate. The crude product F obtained by distilling off the solvent was purified by silica gel column chromatography (silica gel 7 g, hexane / ethyl acetate: 9 → 50%) to obtain 51 mg of the title compound as a colorless liquid. ^{1 1} H NMR (400 MHz, CDCl ₃ ): 7.39 (d, J = 8.5 Hz, 2H), 7.34 (d, J = 8.8 Hz, 2H), 7.01-6.96 (m, 3H), 6.88 (dd, J = 8.5, 2.4Hz, 1H), 3.79 (s, 3H), 3.59 (d, J = 6.3Hz, 1H), 3.02 ( d, J = 6.3Hz, 1H).

Synthesis of methyl 2- (2-chloro-4- (4-chlorophenoxyphenyl) phenyl) -2-hydroxy-3- (1H-1,2,4-triazole-1-yl) methyl propanoate (Compound 1) ( Reaction scheme 4)

Methyl 2- (2-chloro-4- (4-chlorophenoxy) phenyl) oxylan-2-carboxylate 51 mg obtained in the previous section was dissolved in 0.75 mL of dimethylacetamide, and 31 mg of 1,2,4-triazole was added. rice field. After cooling in an ice bath, 21 mg of potassium carbonate was then added. After stirring for 3 hours in an oil bath heated to 60 ° C., the mixture was left at room temperature for 15 hours. After stirring again in an oil bath heated to 60 ° C. for 3 hours, the reaction was stopped by adding a saturated aqueous solution of ammonium chloride to the reaction solution under ice-cooling. The aqueous layer was extracted with toluene, washed with saturated brine and dried over anhydrous sodium sulfate. By purifying the crude product G obtained by distilling off the solvent by silica gel column chromatography (silica gel 7 g, hexane / ethyl acetate: 40 → 100%), 19 mg of the title compound (Compound 1) was made into a colorless solid. Obtained. ^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 8.00 (s, 1H), 7.88 (s, 1H), 7.40 (d, J = 8.8 Hz, 1H), 7.34 (d, J = 8.7Hz, 2H), 6.99-6.95 (m, 3H), 6.81 (d, J = 8.8Hz, 1H), 5.02 (d, J = 14.3Hz, 1H) ), 4.93 (d, J = 14.3Hz, 1H), 4.88 (br, 1H), 3.80 (s, 3H).

The specific rotation of compound 1 obtained in the previous section was measured using P-1020 (Na lamp: 589 nm, manufactured by JASCO Corporation). The specific measurement results are as follows.

[Α] ²⁰ _D = −102.0 ° (8.9 mg per 1 mL of chloroform)
Compound 1 prepared in Production Example 2 was dissolved in methanol and subjected to high performance liquid chromatography (HPLC) in which a preparative column in which amylostris (3-chloro-5-methylphenylcarbamate) was immobilized on a silica gel carrier was connected. , The abundance ratio of each enantiomer contained in the obtained compound 1 was measured.

The specific conditions are as follows.
High Performance Liquid Chromatograph: Preparative Column: Product Name "CHIRALPAK IG", manufactured by Daicel Chemical Industries, Ltd., Inner diameter 4.6 mm, Length 150 mm, Particle size 5 μm
Sample concentration: 1.0 mg / mL
Mobile phase: 100% methanol flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detection wavelength: 230nm

When separated under the above conditions, two peaks with different elution times were detected. The abundance ratio of each enantiomer calculated from the area value of the peak was (-)-enantiomer: (+)-enantiomer = 95: 5.

<Formation example 1: wettable powder>
A hydrate was prepared as follows using any of the prepared triazole derivatives (-)-enantiomers described in this patent.
Triazole derivative (-)-enantiomer 20.0 parts Sodium lauryl sulfate 2 parts Sodium salt of alkylnaphthalene sulfonic acid formalin condensate 5 parts Zinc stearate 0.2 parts White carbon 3 parts Clay 69.8 parts are mixed and pulverized. It was used as a wettable powder, diluted with water.

<Pharmaceutical example 2: Emulsion>
An emulsion was prepared as follows using any of the prepared triazole derivatives (-)-enantiomers described in this patent.
Triazole derivative (-)-enantiomer 5.0 parts polyoxyalkylene alkyl ether / alkylbenzene sulfonic acid metal salt / alkylbenzene mixture 3.75 parts polyoxyalkylene alkyl ether 11.25 parts 5- (dimethylamino) -2-methyl-5 -Methyl oxopentanoate 12.0 parts N, N-dimethyloctaneamide / N, N-dimethyldecaneamide 44.0 parts Solventnaphtha 24.0 parts are uniformly mixed and dissolved to form an emulsion, which is diluted with water before use. bottom.

<Test Example 1: Antibacterial test against phytopathogens>
The antibacterial property of compound 1 (-) prepared in Production Example 1 against various plant pathogens was tested by a Petri dish test. Compound 1 (racemic) was used as a control compound. After sterilization by autoclave, compound 1 (-) or compound 1 dissolved in dimethyl sulfoxide (DMSO) so as to have a drug concentration of 2.5 mg / L in PDA medium (potato-dextrose-agar medium) cooled to around 60 ° C. (Potato) was added to PDA medium at 1% v / v. The mixture was mixed so that the drug concentration in the PDA medium was uniform, and the medium was poured into a petri dish to prepare a plate medium containing compound 1 (−) or compound 1 (racemic).

On the other hand, the flora of various phytopathogens shown in Table 1 previously cultured on the PDA medium was punched out with a cork borer having a diameter of 4 mm and inoculated into the above-mentioned drug-containing plate medium. After culturing at a temperature for a predetermined period, the bacterial flora diameter was measured on a drug-treated plate medium. The hyphal elongation inhibition rate (%) was calculated by the following formula in comparison with the diameter of the flora on the untreated plate containing no drug. The greater the rate of hyphal elongation inhibition, the better the antibacterial property.

Hyphal elongation inhibition rate (%) = (1-Diameter of flora on drug-treated plate / Diameter of flora on untreated plate) x 100
The results of the hyphal elongation inhibition rate R (%) are shown in Table 1.

<Test Example 2: Wheat red rust control effect test>
Compound 1 (-) or compound 1 (racemic) prepared in Production Example 1 was dissolved in acetone so as to have a predetermined drug concentration, and 5% v / v was added to ion-exchanged water containing Gramin S (of Gramin S). Final concentration 60 ppm). The prepared drug was sprayed at a rate of 1000 L / ha on wheat (variety: Norin 61) in the first and second leaf stages cultivated in a square plastic pot (6 cm × 6 cm) (drug treatment group). The untreated plot was obtained by spraying wheat with ion-exchanged water containing 5% acetone (final concentration of Gramin S 60 ppm) containing no compound. After spraying, the spray solution on the wheat leaves is air-dried, and the spore solution of wheat red rust fungus ( ^{prepared to 1 × 10 6} cells / ml, containing Gramin S having a final concentration of 60 ppm) is spray-inoculated, and under high humidity conditions at 20 ° C. I kept it for 24 hours. After that, it was managed in the greenhouse. On the 10th day after inoculation, the affected area of wheat red rust was investigated, and the control value was calculated from the following formula.
Control value (%) = (1-Average diseased area in drug-treated area / Average diseased area in untreated area) x 100

In Test Example 2, the control value of compound 1 (racemic) was 67% at a concentration of 0.5 g / ha, whereas the control value of compound 1 (-) was 90%.

<Test Example 3: Wheat powdery mildew control effect test>
Compound 1 (-) or compound 1 (racemic) prepared in Production Example 1 was dissolved in acetone so as to have a predetermined drug concentration, and 5% v / v was added to ion-exchanged water containing Gramin S (of Gramin S). Final concentration 60 ppm). The prepared drug was sprayed at a rate of 1000 L / ha on wheat (variety: Norin 61) in the first and second leaf stages cultivated in a square plastic pot (6 cm × 6 cm) (drug treatment group). The untreated plot was obtained by spraying wheat with ion-exchanged water containing 5% acetone (final concentration of Gramin S 60 ppm) containing no compound. After spraying, the spray liquid on the wheat leaves was air-dried, sprinkled with spores of wheat powdery mildew, and inoculated, and managed in a greenhouse. On the 10th day after inoculation, the affected area of wheat powdery mildew was investigated, and the control value (%) was calculated.

In the test example, the control value of compound 1 (racemic) was 38% at a concentration of 7.5 g / ha, whereas the control value of compound 1 (-) was 56%.

The (-)-enantiomer of the triazole derivative according to the present invention can be suitably used as an active ingredient of a fungicide for agriculture and horticulture and a protective agent for industrial materials.

Claims (4)

1. A (-)-enantiomer of a triazole derivative represented by the following general formula (I), or a pesticide-acceptable salt thereof.
   

   

   [In formula (I),
   R ¹ is -OR ⁴ or -NR ⁵ R ⁶ ;
   R ⁴ , R ⁵ and R ⁶ are independently hydrogen, C _1- C ₆ -alkyl group, C _2- C ₆ -alkenyl group, C _2- C ₆ -alkynyl group, C _3- C ₈ -cyclo. Alkyne group, C _3- C ₈ -cycloalkyl-C _1- C ₄ -alkyl group, phenyl group, phenyl-C _1- C ₄ -alkyl group, phenyl-C _2- C ₄ -alkenyl group or phenyl-C ₂ -C _4- It is an alkynyl group, and R ⁵ and R ⁶ may form a ring;
   Here, the ^{aliphatic groups in R 4} , R ⁵ and R ⁶ may have 1, 2, 3 or the maximum possible number of the same or different groups R ^a , where R ^a is a halogen group. , cyano group, nitro _group, C 1 -C ₄ - alkoxy and _C 1 -C ₄ - is selected from haloalkoxy groups independently of each other;
   R ² is a halogen group, a cyano group, a nitro group, a phenyl group, a phenyl-oxy group, a C _1- C ₄ -alkyl group, a C _1- C ₄ -haloalkyl group, a C _1- C ₄ -alkoxy group, and a C _1-. C ₄ -haloalkoxy group, -SOR ⁷ or -SF ₅ ;
   R ³ is a halogen group, a cyano group, a nitro group, an amino group, a phenyl group, a phenyl-oxy group, a C _1- C ₄ -alkyl group, a C _1- C ₄ -haloalkyl group, and a C _1- C ₄ -alkoxy group. or _C 1 -C ₄ - haloalkoxy _group, C 1 -C ₄ - alkylamino _group, C 1 -C ₄ - dialkylamino _group, C 1 -C ₄ - alkyl acyl amino group, in -SOR ⁷ or -SF ₅ can be;
   The cycloalkyl and phenyl group moieties in R ⁴ , R ⁵ , and R ^{6 and the phenyl group moieties in R 3} have 1, 2, 3, 4, 5 or the maximum number of possible identical or different groups R ^b . may also be, ^{R b} is halogen, cyano, _nitro, C 1 -C ₄ - alkyl _group, C 1 -C ₄ - alkoxy _group, C 1 -C ₄ - haloalkyl and _C 1 -C _4- Selected independently of each other from the haloalkoxy group;
   Wherein, ^{R 7} _is, C 1 -C ₄ - alkyl group or a _C 1 -C ₄ - haloalkyl group;
   n is 0,1,2,3, or 4;
   m is 1,2,3,4 or 5,
   An asterisk (*) refers to an asymmetric carbon atom. ]
2. In the above general formula (I)
   R ¹ is -OR ⁴ ;
   R ² is a halogen group, a cyano group, a C _1- C ₄ -alkyl group, a C _1- C ₄ -haloalkyl group, a C _1- C ₄ -alkoxy group, -SOR ⁷ or -SF ₅ ;
   R ³ is a halogen group, a nitro group, a cyano group, an amino group, a C _1- C ₄ -alkyl group, a C _1- C ₄ -haloalkyl group, a C _1- C ₄ -alkoxy group, and a C _1- C ₄ -halo. alkoxy _groups, C 1 -C ₄ - alkylamino _group, C 1 -C ₄ - dialkylamino _group, C 1 -C ₄ - alkyl acyl amino group, an -SOR ^7, or -SF _5, according to claim 1 (-)-Enantiomer of a triazole derivative or a salt thereof.
3. In the above general formula (I)
   R ⁴ _is, C 1 -C ₆ - an alkyl group;
   R ² is halogen, _cyano, C 1 -C ₄ - alkyl _group, C 1 -C ₄ - haloalkyl group or a _C 1 -C ₄ - alkoxy group;
   R ³ is halogen, _cyano, C 1 -C ₄ - alkyl _group, C 1 -C ₄ - haloalkyl _group, C 1 -C ₄ - alkoxy group or a _C 1 -C ₄ - haloalkoxy group, wherein Item 2. The (-)-enantiomer of the triazole derivative according to Item 2 or a salt thereof.
4. An agricultural or horticultural agent or an industrial material protective agent containing (-)-enantiomer of the triazole derivative according to any one of claims 1 to 3 as an active ingredient.