WO2025135095A1 - Organometallic complex, and preparation method and use thereof - Google Patents

Abstract

Provided are: a novel organometallic complex useful as an active ingredient of a bactericide applied to agricultural and horticultural crops; and a preparation method thereof.　The novel organometallic complex comprises triflumizole, metal cations, and organic acid anions.　The organometallic complex can be prepared by mixing triflumizole and/or a salt thereof with at least one selected from the group consisting of an organic acid metal salt, a combination of an organic acid and a metal compound, and a combination of an organic acid salt and a metal compound.　Examples of the metal elements of the metal cations include zinc, copper, magnesium, calcium, nickel, cobalt, iron, and manganese.

Description

Organometallic complexes and their production methods and uses

The present invention relates to an organometallic complex, and a method for producing and using the same. More specifically, the present invention relates to an organometallic complex useful as an active ingredient of a fungicide applied to agricultural and horticultural crops, and a method for producing and using the same.
This application claims priority to Japanese Patent Application No. 2023-217302, filed on December 22, 2023, the contents of which are incorporated herein by reference.

Organometallic complexes are used as catalysts for various chemical reactions, including amidation reactions.
For example, US Pat. No. 5,399,633 discloses zinc-imidazole-carboxylate complexes which catalyze the urethane reaction and can be prepared by reacting zinc(II) biscarboxylate with an imidazole compound.

US Pat. No. 5,399,433 discloses a zinc complex represented by formula (A) which is useful as a synthesis catalyst.

On the other hand, compounds containing an imidazole group are useful as active ingredients of fungicides applied to agricultural and horticultural crops. For example, Patent Document 3 discloses a compound containing an imidazole group represented by formula (B). This compound is also described in agriculturally acceptable salt forms, including hydrochloride, sulfate, metal salts, and addition complexes of compounds such as iron, chromium, and zinc, Patent Document 3 states.

Patent Document 4 discloses azolylmethyloxiranes (eg, epoxiconazole) represented by formula (C) and plant-tolerable acid addition salts and metal complexes thereof.

Special table 2014-510174 publication WO 2014/157524 A1 Japanese Patent Application Publication No. 7-285943 Special Publication No. 4-74355

Triflumizole is easily decomposed by acids and bases and has a low melting point, making it difficult to formulate.
An object of the present invention is to provide a novel organometallic complex which is useful as an active ingredient of a fungicide to be applied to agricultural and horticultural crops, and a method for producing the same.

The present invention includes the following aspects:

[1] An organometallic complex comprising triflumizole, a metal cation and an organic acid anion.
[2] The organometallic complex according to [1], wherein the metal element of the metal cation is one selected from the group consisting of zinc, copper, magnesium, calcium, nickel, cobalt, iron and manganese.
[3] The organometallic complex according to [1] or [2], wherein the organic acid of the organic acid anion is at least one selected from the group consisting of acetylacetone and its tautomers, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid, 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione and its tautomers, 2,6-pyridinedicarboxylic acid, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, N-ethyl-N-phenyldithiocarbamic acid, propionic acid, and isobutyric acid.

[4] Triflumizole and/or a salt thereof,
and mixing at least one selected from the group consisting of an organic acid metal salt, a combination of an organic acid and a metal compound, and a combination of an organic acid salt and a metal compound.
A method for producing an organometallic complex comprising triflumizole, a metal cation and an organic acid anion.

[5] The method according to [4], wherein the molar ratio at the time of mixing is 0.5 to 2 mol of metal cation derived from the metal compound and 0.25 to 4 mol of organic acid anion derived from the organic acid and/or organic acid salt, per 1 mol of triflumizole derived from triflumizole and/or a salt thereof.
[6] The method according to [4] or [5], wherein the metal element of the metal cation is one selected from the group consisting of zinc, copper, magnesium, calcium, nickel, cobalt, iron and manganese.
[7] The method according to [4] or [5], wherein the organic acid of the organic acid anion is at least one selected from the group consisting of acetylacetone and its tautomers, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid, 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione and its tautomers, 2,6-pyridinedicarboxylic acid, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, N-ethyl-N-phenyldithiocarbamic acid, propionic acid, and isobutyric acid.

[8] A composition comprising an organometallic complex consisting of triflumizole, a metal cation and an organic acid anion.
[9] A composition comprising triflumizole, an organometallic complex consisting of a metal cation and an organic acid anion, and water.

[10] An agricultural and horticultural fungicide containing, as active ingredients, an organometallic complex consisting of triflumizole, a metal cation, and an organic acid anion.

The organometallic complex of the present invention is less likely to volatilize, has a longer-lasting bactericidal effect, is less likely to cause phytotoxicity, and is less likely to stain agricultural and horticultural crops than triflumizole or its salts. The organometallic complex of the present invention is less difficult to formulate. The pesticide composition of the present invention has a high residual rate of triflumizole, the active ingredient of the fungicide applied to agricultural and horticultural crops, and therefore has a long-lasting bactericidal effect.

FIG. 1 shows a diffraction chart of triflumizole. FIG. 1 is a diagram showing a diffraction chart of zinc benzoate. FIG. 2 is a diffraction chart of the solid product produced in Example 1. FIG. 1 is a diagram showing a diffraction chart of zinc diethyldithiocarbamate. FIG. 2 is a diffraction chart of the solid product produced in Example 2. FIG. 1 shows a diffraction chart of zinc N-ethyl-N-phenyldithiocarbamate. FIG. 2 is a diffraction chart of the solid product produced in Example 3. FIG. 1 shows a diffraction chart of zinc acetylacetonate. FIG. 2 is a diffraction chart of the solid product produced in Example 4. FIG. 1 is a diagram showing a diffraction chart of zinc adipate. FIG. 1 shows a diffraction chart of the solid product produced in Example 5. FIG. 1 is a diagram showing a diffraction chart of zinc maleate. FIG. 1 shows a diffraction chart of the solid product produced in Example 6. FIG. 1 shows a diffraction chart of zinc succinate. FIG. 1 shows a diffraction chart of the solid product produced in Example 7. FIG. 1 shows a diffraction chart of zinc malonate. FIG. 1 shows a diffraction chart of the solid product produced in Example 8. FIG. 1 is a diagram showing a diffraction chart of zinc terephthalate. FIG. 1 shows a diffraction chart of the solid product produced in Example 9. FIG. 1 shows a diffraction chart of zinc glutarate. FIG. 1 shows a diffraction chart of the solid product produced in Example 10. FIG. 1 shows a diffraction chart of 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione zinc salt. FIG. 1 shows a diffraction chart of the solid product produced in Example 11. FIG. 1 is a diagram showing a diffraction chart of 2,6-pyridinedicarboxylic acid. FIG. 1 is a diagram showing a diffraction chart of zinc oxide. FIG. 1 shows a diffraction chart of the solid product produced in Example 12. FIG. 1 shows a diffraction chart of phthalic acid. FIG. 1 shows a diffraction chart of zinc chloride. FIG. 1 shows a diffraction chart of the solid product produced in Example 13. FIG. 1 is a diagram showing a diffraction chart of zinc dimethyldithiocarbamate. FIG. 1 shows a diffraction chart of the solid product produced in Example 14. FIG. 1 shows a diffraction chart of benzoic acid. FIG. 1 is a diagram showing a diffraction chart of copper(II) hydroxide. FIG. 1 shows a diffraction chart of the solid product produced in Example 15. FIG. 1 shows a diffraction chart of the solid product produced in Example 16. FIG. 1 shows a diffraction chart of the solid product produced in Example 17. FIG. 1 shows a diffraction chart of the solid product produced in Example 18. FIG. 2 shows a diffraction chart of the solid product produced in Example 19. FIG. 1 is a diagram showing a diffraction chart of terephthalic acid. FIG. 2 shows a diffraction chart of the solid product produced in Example 20. FIG. 1 shows a diffraction chart of maleic acid. FIG. 2 shows a diffraction chart of the solid product produced in Example 21.

The organometallic complex of the present invention consists of triflumizole, a metal cation, and an organic acid anion.

One embodiment of the method for preparing the organometallic complex of the present invention comprises combining triflumizole and/or a salt thereof with an organic acid metal salt.
Another aspect of the method for preparing the organometallic complexes of the present invention comprises combining triflumizole and/or a salt thereof, an organic acid, and a metal compound.
Another aspect of the method for preparing the organometallic complex of the present invention comprises combining triflumizole and/or a salt thereof, an organic acid salt, and a metal compound.

Triflumizole is a compound known as the active ingredient of imidazole fungicides applied to horticultural crops. Triflumizole is a compound represented by formula (I) ((E)-N-[4-chloro-2-(trifluoromethyl)phenyl]-1-(1H-imidazol-1-yl)-2-propoxyethan-1-imine).

The salt of triflumizole is not particularly limited as long as it is agriculturally and horticulturally acceptable, and examples thereof include salts with inorganic acids such as hydrochloric acid and sulfuric acid; salts with organic acids such as acetic acid and lactic acid; salts with alkali metals such as lithium, sodium and potassium; salts with alkaline earth metals such as calcium and magnesium; salts with other metals; ammonium; and salts with organic bases such as triethylamine, tributylamine, pyridine and hydrazine. The metal salt of triflumizole can be used as a source of metal cations constituting the organometallic complex of the present invention and triflumizole.

In the organometallic complex of the present invention, it is presumed that triflumizole and/or its salt is contained in the organometallic complex as a ligand.

Organic acids are organic compounds that exhibit acidity. Examples of organic acids include carboxylic acids, sulfonic acids, dithiocarboxylic acids, compounds having an enol, compounds having a hydroxyl group, and compounds having a hydrothio group. Among these, preferred ones include acetylacetone and its tautomers, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid, 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione and its tautomers, 2,6-pyridinedicarboxylic acid, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, N-ethyl-N-phenyldithiocarbamic acid, propionic acid, and isobutyric acid. These can be used alone or in combination of two or more. Of these, adipic acid, maleic acid, and 2,6-pyridinedicarboxylic acid are more preferred.

The organic acid salt is not particularly limited as long as it is agriculturally and horticulturally acceptable, and examples thereof include salts with alkali metals such as lithium, sodium, and potassium; salts with alkaline earth metals such as calcium and magnesium; salts with other metals; ammonium; and salts with organic bases such as triethylamine, tributylamine, pyridine, and hydrazine. An organic acid metal salt, which is one type of organic acid salt, can be used as a source of metal cations and organic acid anions that constitute the organometallic complex of the present invention.

The metal element of the metal cation is preferably at least one metal element selected from the group consisting of elements of Groups 2 to 13 of the periodic table, and among these, a divalent or trivalent metal element is more preferred.
Examples of divalent metal elements include zinc, copper, magnesium, calcium, nickel, cobalt, iron, manganese, etc. Examples of trivalent metal elements include iron, copper, aluminum, etc.
In particular, zinc, copper, magnesium, calcium, nickel, cobalt, iron and manganese are preferred.

There are no particular limitations on the metal compound, so long as it can provide a metal cation as the central metal of the complex.
As the metal compound used in the present invention, zinc compounds are exemplified below.
Examples of the zinc salts include organic acid zinc salts such as zinc acetylacetonate, zinc malonate, zinc succinate, zinc glutarate, zinc adipate, zinc maleate, zinc benzoate, zinc phthalate, zinc terephthalate, zinc 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione zinc salt, zinc 2,6-pyridinedicarboxylate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, and zinc N-ethyl-N-phenyldithiocarbamate; and inorganic zinc compounds such as zinc chloride, zinc nitrate, zinc carbonate, zinc oxide, and zinc hydroxide. Of these, the organic acid zinc salts are preferred.
As for other metal elements, the same compounds as those in the case of zinc element can be exemplified.

In the production of the organometallic complex of the present invention, the molar ratio at the time of mixing is preferably 0.5 to 2 moles, more preferably 0.8 to 1.25 moles, and even more preferably 0.9 to 1.1 moles of metal cations derived from metal compounds per mole of triflumizole derived from triflumizole and/or its salts, and preferably 0.25 to 4 moles, more preferably 1.5 to 2.5 moles, and even more preferably 1.8 to 2.2 moles of organic acid anions derived from organic acids and/or organic acid salts. Since divalent organic acids have two organic acid anions per molecule, the molar ratio at the time of mixing is half the above number of moles of divalent organic acid per mole of triflumizole derived from triflumizole and/or its salts, that is, preferably 0.125 to 2 moles, and more preferably 0.75 to 1.25 moles.

The organometallic complex of the present invention contains preferably 1 to 4 moles of triflumizole and preferably 1 to 2 moles of an organic acid anion (-C(=O) ^O- , -C(=S)S-, ^-S (=O) _2O- , -C ⁼ C-O- ^, etc.) per mole of a metal cation which is a central metal. In the organometallic complex of the present invention, it is presumed that the nitrogen at the 3-position of the 1H-imidazol-1-yl group of triflumizole is coordinately bonded to the metal cation. In addition, in the organometallic complex of the present invention, it is presumed that the oxygen anion or sulfur anion in the organic acid anion such as carboxylate (-C(=O) ^O- ), dithiocarboxylate (-C(=S) ^S- ), ^sulfonate (-S(=O) _2O- ), enolate (-C=C- ^O- ) or the like is bonded to the metal cation.

In producing the organometallic complex of the present invention, a solvent consisting of only an organic solvent, a solvent consisting of an organic solvent and water, a solvent consisting of a surfactant and water, or a solvent consisting of an organic solvent, a surfactant and water can be used.
Examples of the organic solvent include protic polar organic solvents such as methanol, ethanol, isopropanol, n-butanol, and nitromethane; aprotic polar organic solvents such as acetone, anone, N-methylpyrrolidone, dichloromethane, tetrahydrofuran, ethyl acetate, dimethyl sulfoxide, dimethylformamide, acetonitrile, propylene carbonate, and triethylamine; and nonpolar organic solvents such as toluene, benzene, hexane, 1,4-dioxane, chloroform, and diethyl ether. Among these organic solvents, polar organic solvents are preferred.

Surfactants that can be used in the solvent include anionic surfactants such as carboxylates, sulfonates (LAS, AOS, MES, sulfosuccinates, etc.), and sulfate ester salts (AS, AES, etc.); cationic surfactants such as amine salts and quaternary ammonium salts; nonionic surfactants such as esters (glycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, etc.), ethers (polyoxyethylene (or POE) alkyl ethers, polyoxyethylene (or POE) alkyl phenyl ethers, etc.), and ester ethers; and amphoteric surfactants such as amino acid types and betaine types.

The mixing in the production of the organometallic complex of the present invention can be carried out by a known mixing means, such as an agitator, homogenizer, ultrasonic grinder, line mixer, bead mill, ball mill, line mill, etc.
The temperature of the mixture during mixing is not particularly limited, but is preferably 5 to 50°C, for example.

The composition of the present invention contains triflumizole, an organometallic complex consisting of a metal cation and an organic acid anion, and water as necessary. The composition of the present invention can be used as an agricultural and horticultural fungicide, etc.

The agricultural and horticultural fungicide of the present invention contains an organometallic complex consisting of triflumizole, a metal cation, and an organic acid anion as an active ingredient (hereinafter referred to as active ingredient (I)). There are no particular limitations on the amount of active ingredient (I) contained in the agricultural and horticultural fungicide of the present invention, so long as it exhibits a bactericidal effect.

The agricultural and horticultural fungicide of the present invention can be used to control plant diseases caused by a wide variety of filamentous fungi, such as fungi belonging to the classes Oomycetes, Ascomycetes, Deuteromycetes, Basidiomycetes, and Zygomycetes.

Examples of plant diseases (pathogens) that can be controlled are shown below.
Sugar beet: Cercospora beticola, Aphanomyces cochlioides, Root rot (Thanatephorus cucumeris), Leaf rot (Thananatephorus cucumeris), Rust (Uromyces betae), Powdery mildew (Oidium sp.), Spot disease (Ramularia beticola), Seedling damping off (Aphanomyces cochlioides, Pythium Groundnut: Mycosphaerella arachidis, Ascochyta sp., Puccinia arachidis, Pythium debaryanum, Alternaria alternata, Sclerotium rolfsii, Mycosphaerella berkeleyi, Calonectria ilicicola) etc. Cucumber: Powdery mildew (Sphaerotheca fuliginea), Downy mildew (Pseudoperonospora cubensis), Vine wilt (Mycosphaerella melonis), Vine splitting (Fusarium oxysporum), Sclerotinia sclerotiorum, Gray mold (Botrytis cinerea), Anthracnose (Colletotrichum orbiculare), Black spot (Cladosporium cucumerinum), Brown spot (Corynespora cassiicola), Seedling damping-off (Pythium debaryanum, Rhizoctonia solani Kuhn), Phomopsis root rot (Phomopsis sp.), Bacterial spot (Pseudomonas syringae pv. Lachrymans), etc. Tomato: Gray mold (Botrytis cinerea), Leaf mold (Cladosporium fulvum), Phytophthora infestans), Verticillium albo-atrum, Verticillium dahliae, Powdery mildew (Oidium neolycopersici), Ring blight (Alternaria solani), Sooty mold (Pseudocercospora fuligena), Bacterial wilt (Ralstonia solanacearum), Sclerotinia sclerotiorum, etc. Eggplant: Gray mold (Botrytis cinerea), Black blight (Corynespora melongenae), Powdery mildew (Erysiphe cichoracearum), Sooty mold (Mycovellosiella nattrassii), Sclerotinia sclerotiorum, Verticillium dahliae, Brown spot (Phomopsis vexans), etc. Pepper: Phytophthora capsici, Gray mold (Botrytis cinerea), Sclerotinia sclerotiorum, Anthracnose (Colletotrichum aenigma, Colletotrichum capsici, Colletotrichum fructicola, Colletotrichum jiangxiense), Powdery mildew (Leveillula taurica), etc. Strawberry: Gray mold (Botrytis cinerea), Powdery mildew (Sphaerotheca humuli), Anthracnose (Colletotrichum acutatum, Colletotrichum fragariae), Blight (Phytophthora cactorum), Soft rot (Rhizopus stolonifer), Yellows (Fusarium oxysporum), Wilt (Verticillium dahliae), Sclerotinia sclerotiorum), etc. Onion: Gray rot (Botrytis allii), Gray mold (Botrytis cinerea), Botrytis squamosa, Peronospora destructor, Phytophthora porri, Ciborinia allii, Botrytis squamosa, Fusarium oxysporum, Pyrenochaeta terrestris, Sclerotium cepivorum), rust (Puccinia allii), white silk rot (Sclerotium rolfsii), etc. Allium: soft rot (Pectobacterium carotovorum), downy mildew (Peronospora destructor), leaf blight (Pleospora allii), black rot sclerotium (Sclerotium cepivorum), rust (Puccinia allii), white spot leaf blight (Botrytis) squamosa), Sclerotium rolfsii), pink root rot (Pyrenochaeta terrestris), etc. Cabbage: Clubroot (Plasmodiophora brassicae), soft rot (Erwinia carotovora), black rot (Xanthomonas campesrtis pv. campestris), black spot bacterial disease (Pseudomonas syringae pv. maculicola, P. s. pv. alisalensis), downy mildew (Peronospora parasitica), sclerotinia sclerotiorum, sooty mildew (Alternaria brassicicola), gray mold (Botrytis cinerea), root rot (Phoma lingam), Pythium rot (Pythium aphanidermatum, Pythium ultimum), white rust (Albugo macrospora), etc. Lettuce: Rot (Pseudomonas cichorii, Pseudomonas marginalis), soft rot (Pectobacterium carotovorum), downy mildew (Bremia lactucae), gray mold (Botrytis cinerea), sclerotinia sclerotiorum, big-vein disease (Mirafiori lettuce big-vein ophiovirus), root rot (Fusarium oxysporum), bottom rot (Rhizoctonia solani), powdery mildew (Golovinomyces orontii), etc. Beans: Sclerotinia sclerotiorum, gray mold (Botrytis cinerea), anthracnose (Colletotrichum lindemuthianum), angular spot (Phaeoisariopsis griseola), etc. Peas: Brown spot (Mycosphaerella blight), gray mold (Botrytis cinerea), sclerotinia sclerotiorum), powdery mildew (Erysiphe pisi), etc.

Apple: Powdery mildew (Podosphaera leucotricha), black spot (Venturia inaequalis), Monilinia mali, black spot (Mycosphaerella pomi), canker (Valsa mali), leaf spot (Alternaria mali), red spot (Gymnosporangium yamadae), ring spot (Botryosphaeria berengeriana), anthracnose (Glomerella cingulata, Colletotrichum acutatum), brown spot (Diplocarpon mali), sooty spot (Zygophiala jamaicensis), sooty spot (Gloeodes pomigena), purple root rot (Helicobasidium mompa), white root rot (Rosellinia necatrix), gray mold (Botrytis cinerea), fire blight (Erwinia amylovora), silver leaf disease (Chondrostereum purpureum), crown gall (Rhizobium radiobacter, Rhizobium rhizogenes), etc. Plum: black spot (Cladosporium carpophilum), gray mold (Botrytis cinerea), brown spot (Monilinia mumecola), sooty spot (Peltaster sp.), pustule disease (Taphrina pruni), brown hole (Phloeosporella padi), etc. Persimmon: powdery mildew (Phyllactinia kakicola), anthracnose (Gloeosporium kaki), angular leaf spot (Cercospora kaki), circular leaf spot (Mycosphaerella nawae), gray mold (Botrytis cinerea), sooty spot (Zygophiala jamaicensis), etc. Peach: brown spot (Monilinia fructicola, Monilia fructigena), black spot (Cladosporium Almond: Monilinia laxa), Stigmina carpophila, Cladosporium carpophilum, Polystigma rubrum, Alternaria alternata, Colletotrichum gloeospoides, etc. Hawthorn: Monilinia fructicola, Colletotrichum acutatum, Alternaria sp.), Monilinia sp. Grapes: Gray mold (Botrytis cinerea), Powdery mildew (Uncinula necator), Late rot (Glomerella cingulata, Colletotrichum acutatum), Downy mildew (Plasmopara viticola), Black rot (Elsinoe ampelina), Brown spot (Pseudocercospora vitis), Black rot (Guignardia bidwellii), White rot (Coniella castaneicola), Rust (Phakopsora ampelopsidis), White cotton snow disease (pathogen unidentified), Crown gall (Rhizobium radiobacter, Rhizobium vitis), etc. Pears: Black spot (Venturia nashicola), Red spot (Gymnosporangium asiaticum), black spot (Alternaria kikuchiana), ring blight (Botryosphaeria berengeriana), powdery mildew (Phyllactinia mali), trunk blight (Phomopsis fukushii), brown spot (Stemphylium vesicarium), anthracnose (Glomerella cingulata), etc. Tea: ring blight (Pestalotiopsis longiseta, P. theae), anthracnose (Colletotrichum theae-sinensis), net blight (Exobasidium reticulatum), red burn (Pseudomonas syringae), blight (Exobasidium vexans), etc. Citrus: scab (Elsinoe fawcettii), blue mold (Penicillium italicum), green mold (Penicillium digitatum), gray mold (Botrytis cinerea), black spot (Diaporthe citri), canker (Xanthomonas campestris pv.Citri), powdery mildew (Oidium sp.), blight (Phytophthora citrophthora), anthracnose (Colletotrichum fioriniae), etc. Kiwifruit: blossom rot bacterial disease (Pseudomonas marginalis, Pseudomonas syringae, Pseudomonas viridiflava), canker (Pseudomonas syringae), gray mold (Botrytis cinerea), fruit soft rot (Botryosphaeria dothidea, Diaporthe sp., Lasiodiplodia theobromae), sooty spot (Pseudocercospora actinidiae), etc. Olive: anthracnose (Colletotrichum acutatum, Colletotrichum gloeosporioides), peacock spot (Spilocaea oleaginea), etc. Chestnut: anthracnose (Colletotrichum gloeosporioides, etc.

Wheat: Powdery mildew (Blumeria graminis f.sp. tritici), Fusarium head blight (Gibberella zeae, Fusarium avenaceum, Fusarium culmorum, Fusarium crookwellense, Microdochium nivale), Fusarium rust (Puccinia recondita), Yellow rust (Puccinia striiformis), Brown snow rot (Pythium iwayamai), Monographella nivalis, Pseudocercosporella herpotrichoides, Septoria tritici, Leptosphaeria nodorum, Typhula incarnata, Myriosclerotinia borealis, Gaeumannomyces graminis), ergot disease (Claviceps purpurea), smut (Tilletia Barley: Spotted leaf disease (Pyrenophora graminea), Seedling blight (Pythium spp., Fusarium spp., Rhizoctonia), Seedling blight (Pythium spp., Fusarium spp., Rhizoctonia spp.) spp.) etc. Rice: Pyricularia spp. oryzae), Rhizoctonia solani, Gibberella fujikuroi, Cochliobolus miyabeanus, Pythium graminicola, Xanthomonas oryzae, Burkholderia plantarii, Acidovorax avenae, Burkholderia glumae, Cercospora oryzae, Ustilaginoidea virens, Alternaria alternata, Curvularia intermedia, Alternaria padwickii, Epicoccum purpurascens, etc. Tobacco: Sclerotinia sclerotiorum, Erysiphe cichoracearum, Phytophthora nicotianae, etc. Tulips: Gray mold (Botrytis cinerea), brown spot (Botrytis tulipae), leaf rot (Rhizoctonia solani), bulb rot (Fusarium oxysporum), skin rot (Rhizoctonia solani), etc. Roses: black spot (Diplocarpon rosae), powdery mildew (Erysiphe simulans, Podosphaera pannosa), gray mold (Botrytis cinerea), etc. Chrysanthemums: gray mold (Botrytis cinerea), white rust (Puccinia horiana), downy mildew (Paraperonospora minor, Peronospora danica), Pythium damping-off (Pythium aphanidermatum, Pythium dissotocum, Pythium helicoides, Pythium oedochilum, Pythium sylvaticum), damping-off (Rhizoctonia solani), Fusarium wilt (Fusarium solani), etc. Gerbera: Gray mold (Botrytis cinerea), Powdery mildew (Podosphaera xanthii), etc. Lily: Leaf blight (Botrytis elliptica, Pestalotiopsis sp.), Gray mold (Botrytis cinerea), etc. Sunflower: Downy mildew (Plasmopara halstedii), Sclerotinia sclerotiorum, Gray mold (Botrytis cinerea), etc. Bentgrass: Snow mold large sclerotinia (Sclerotinia borealis), Large patch (Rhizoctonia solani), Brown patch (Rhizoctonia solani), Dollar spot (Sclerotinia homoeocarpa), Blast (Pyricularia sp.), Red burn (Pythium aphanidermatum), Anthracnose (Colletotrichum graminicola), etc. Orchard grass: Powdery mildew (Erysiphe graminis), etc. Soybean: Purple spot (Cercospora kikuchii), Downy mildew (Peronospora manshurica), Stem rot (Phytophthora sojae), Rust (Phakopsora pachyrhizi), Sclerotinia sclerotiorum, Anthracnose (Colletotrichum truncatum), Gray mold (Botrytis cinerea), Black rot (Elsinoe glycines), Black spot (Diaporthe phaseolorum var. sojae), Damping off (Pythium spp., Fusarium spp., Rhizoctonia spp.), Seedling blight (Pythium spp., Fusarium spp., Rhizoctonia spp.), etc. Potato: Late blight (Phytophthora infestans), summer blight (Alternaria solani), black spot (Thanatephorus cucumeris), half-leaf wilt (Verticillium albo-atrum, V. dahliae, V. nigrescens), black leg disease (Pectobacterium atrosepticum), soft rot (Pectobacterium carotovorum), gray mold (Botrytis cinerea), scab (Streptomyces spp.), sclerotinia sclerotiorum), etc. Yam: leaf blight (Cylindrosporium dioscoreae), anthracnose (Colletotrichum gloeosporioides), blue mold (Penicillium sclerotigenum), etc. Sweet potato: purple root rot (Helicobasidium mompa), vine split (Fusarium oxysporum), etc. Taro: blight (Phytophthora colocasiae), stem rot (Rhizoctonia solani), etc. Ginger: rhizome rot (Pythium ultimum, Pythium myriotylum), white spot (Phyllosticta zingiberis), etc. Banana: Panama disease (Fusarium oxysporum), Sigatoka disease (Mycosphaerella fijiensis, M. musicola), etc. Mango: anthracnose (Colletotrichum aenigma), canker (Xanthomonas campestris), stem rot (Diaporthe pseudophoenicicola, Lasiodiplodia theobromae, Lasiodiplodia spp., Neofusicoccum parvum, Neofusicoccum sp.), gray mold (Botrytis cinerea), etc. Rapeseed: sclerotinia sclerotiorum, root rot (Phoma lingam), black spot (Alternaria brassicae), powdery mildew (Erysiphe cruciferarum, Erysiphe cichoracearum, Oidium matthiolae), downy mildew (Peronospora parasitica), etc. Coffee: rust (Hemileia vastatrix), anthracnose (Colletotrichum coffeanum), brown eye (Cercospora coffeicola), etc. Sugarcane: brown rust (Puccinia melanocephala), etc. Corn: hail leaf spot (Gloeocercospora sorghi), rust (Puccinia sorghi), southern rust (Puccinia polysora), smut (Ustilago maydis), brown spot (Cochliobolus heterostrophus), sooty leaf spot (Setosphaeria turcica), damping off (Pythium spp., Fusarium spp., Rhizoctonia spp.), Seedling blight (Pythium spp., Fusarium spp., Rhizoctonia spp.), etc. Cotton: Seedling damping-off (Pythium sp.), Rust (Phakopsora gossypii), White mold (Mycosphaerella areola), Anthracnose (Glomerella gossypii), etc. Hops: Downy mildew (Pseudoperonospora humuli), Powdery mildew (Oidium sp., Podosphaera macularis), Gray mold (Botrytis cinerea), etc.

The agricultural and horticultural fungicide of the present invention is preferably used on plants such as grains, vegetables, root vegetables, potatoes, fruit trees, trees such as tea, coffee, and cacao, pasture grasses, turf grasses, and cotton.

The agricultural and horticultural fungicide of the present invention can be applied to various parts of plants, such as leaves, stems, stalks, flowers, buds, fruits, seeds, sprouts, roots, tubers, tuberous roots, shoots, cuttings, etc. It can also be applied to improved varieties and varieties of these plants, cultivated varieties, and even mutants, hybrids, and genetically modified organisms (GMOs).

The agricultural and horticultural fungicide of the present invention can be used for seed treatment, foliage spray, soil application, water surface application, etc., to control various diseases that occur in agricultural and horticultural crops, including flowers, turf, and pasture grass.

The agricultural and horticultural fungicide of the present invention may contain other components other than the active ingredient (I). Examples of other components include known carriers used for formulation. Examples of other components include conventionally known fungicides, insecticides/acaricides, nematicides, soil pesticides, plant regulators, synergists, fertilizers, soil conditioners, animal feed, etc. (hereinafter sometimes referred to as active ingredient (II)). The agricultural and horticultural fungicide of the present invention may exhibit a synergistic effect by containing the active ingredient (I) and the active ingredient (II).
The agricultural and horticultural fungicide of the present invention can be mixed or used in combination with an agricultural and horticultural agent containing the active ingredient (II). By using them in combination or in combination, a synergistic effect may be obtained.

Specific examples of the fungicide as the active ingredient (II) are shown below.
(1) Nucleic acid biosynthesis inhibitors:
(a) RNA polymerase I inhibitors: benalaxyl, benalaxyl-M, furalaxyl, metalaxyl, metalaxyl-M, oxadixyl, clozylacon, ofrace;
(b) Adenosine deaminase inhibitors: bupirimate, dimethirimol, ethirimol;
(c) DNA/RNA synthesis inhibitors: hymexazole, octhilinone;
(d) DNA topoisomerase II inhibitors: oxolinic acid;

(2) Mitosis inhibitors and cytostatic agents:
(a) β-tubulin polymerization inhibitors: benomyl, carbendazim, chlorphenazole, fuberidazole, thiabendazole, thiophanate, thiophanate methyl, diethofencarb, zoxamide, ethaboxam;
(b) Cytostatic agent: pencycuron;
(c) Spectrin-like protein delocalization inhibitors: fluopicolide, fluopimomide;

(3) Respiratory inhibitors:
(a) Complex I-NADH oxidoreductase inhibitors: diflumetrim, tolfenpyrad;
(b) Complex II-succinate dehydrogenase inhibitors: benodanil, flutolanil, mepronil, isofetamide, fluopyram, fenfuram, flumecyclox, carboxin, oxycarboxin, thifluzamide, benzovindiflupyr, bixafen, fluxapyroxad, furametpyr, isopyrazam, penflufen, penthiopyrad, sedaxane, boscalid, pydiflumetofen, isoflucipram, pyraziflumide, impirfluxam;
(c) Complex III - ubiquinol oxidase Qo inhibitors: azoxystrobin, cumoxystrobin, cumethoxystrobin, enoxastrobin, flufenoxystrobin, picoxystrobin, pyraoxystrobin, pyraclostrobin, pyrametostrobin, triclopyricarb, kresoxim-methyl, trifloxystrobin, dimoxystrobin, phenaminestrobin, metominostrobin, orysastrobin, famoxadone, fluoxastrobin, fenamidone, pyribencarb, methyltetraprole, mandestrobin;
(d) Complex III-ubiquinol reductase Qi inhibitors: cyazofamid, amisulbrom, fenpicoxamide;
(e) Uncouplers of oxidative phosphorylation: binapacryl, meptyldinocap, dinocap, fluazinam, ferimzone;
(f) Oxidative phosphorylation inhibitors (inhibitors of ATP synthase): fentin acetate, fentin chloride, fentin hydroxide;
(g) ATP production inhibitor: silthiofam;
(h) Complex III: Qx (unknown) inhibitor of cytochrome bc1 (ubiquinone reductase): ametoctrazine;

(4) Amino acid and protein synthesis inhibitors:
(a) Methionine biosynthesis inhibitors: andoprim, cyprodinil, mepanipyrim, pyrimethanil;
(b) protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride, streptomycin, oxytetracycline;

(5) Signal transduction inhibitors:
(a) Signal transduction inhibitors: quinoxyfen, proquinazid;
(b) MAP/histidine kinase inhibitors in osmotic signaling: fenpiclonil, fludioxonil, clozolinate, iprodione, procymidone, vinclozolin;

(6) Lipid and cell membrane synthesis inhibitors:
(a) Phospholipid biosynthesis, methyltransferase inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothiolane;
(b) Lipid peroxidants: biphenyl, chloroneb, dicloran, quintozene, tecnazene, tolclofos-methyl, etridiazole;
(c) Agents acting on cell membranes: iodocarb, propamocarb, propamocarb hydrochloride, propamocarb fossetylate, prothiocarb;
(d) Microorganisms that disrupt pathogen cell membranes: Bacillus subtilis, Bacillus subtilis QST713, Bacillus subtilis FZB24, Bacillus subtilis MBI600, Bacillus subtilis D747, Bacillus amyloliquefaciens;
(e) Cell membrane disrupting agents: Tea Tree extract;

(7) Cell membrane sterol biosynthesis inhibitors:
(a) Demethylation inhibitors at C14 position in sterol biosynthesis: triforine, pyrifenox, pyrisoxazole, fenarimol, flurprimidol, nuarimol, imazalil, imazalil sulfate, oxpoconazole, oxpoconazole fumarate, pefurazoate, prochloraz, triflumizole, biniconazole, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazol, difenoconazole, diniconazole, diniconazole-M, epoxi Siconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, fluconazole, fluconazole-cis, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, fluquinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, prothioconazole, voriconazole, mefentrifluconazole;
(b) Inhibitors of Δ14 reductase and Δ8→Δ7-isomerase in sterol biosynthesis: aldimorph, dodemorph, dodemorph acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
(c) 3-ketoreductase inhibitors in the C4 demethylation of sterol biosynthesis: fenhexamid, fenpyrazamine;
(d) Squalene epoxidase inhibitors of the sterol biosynthesis system: pyributicarb, naftifine, terbinafine;

(8) Cell wall synthesis inhibitors:
(a) trehalase inhibitor: validamycin;
(b) Chitin synthase inhibitors: polyoxins, polyoxolim;
(c) Cellulose synthase inhibitors: dimethomorph, flumorph, pyrimorph, benthiavalicarb, benthiavalicarb isopropyl, iprovalicarb, valifenalate, mandipropamide;

(9) Melanin biosynthesis inhibitors (a) Reductase inhibitors of melanin biosynthesis: fthalide, pyroquilon, tricyclazole;
(b) Dehydratase inhibitors of melanin biosynthesis: carpropamid, diclocymet, fenoxanil;
(c) Polyketide synthesis inhibitor of melanin biosynthesis: tolprocarb;

(10) Resistance inducer of host plant:
(a) Agents acting on the salicylic acid synthesis pathway: acibenzolar-S-methyl;
(b) Other: probenazole, tiadinil, isotianil, diclobenthiazox, ipfentrifluconazole, laminarin, knotweed extract, phosphorous acid, phosphites;

(11) Agents of unknown action: cymoxanil, fosetylaluminum, phosphoric acid, phosphate salts, tecloftalam, triazoxide, flusulfamide, diclomedine, metasulfocarb, cyflufenamid, metrafenone, pyriophenone, dodine, dodine free base, fluthianil;

(12) Agents with multiple sites of action: copper (copper salts), Bordeaux mixture, copper hydroxide, copper naphthalate, copper oxide, copper oxychloride, copper sulfate, sulfur, sulfur products, calcium polysulfide, ferbam, mancozeb, maneb, mancopper, metiram, polycarbamate, propineb, thiram, zineb, ziram, captan, captafol, folpet, chlorothalonil, dichlofluanid, tolylfluanid, guazatine, guazatine triacetate (also known as iminoctadine triacetate), iminoctadine triarylbesylate, anilazine, dithianone, chinomethionate, fluoroimide;

(13) Other agents: DBEDC, fluorofolpet, guazatine acetate, copper (II) bis(8-quinolinolato), propamidine, chloropicrin, cyprofuram, agrobacterium, bethoxadin, diphenylamine, methylisothianate (MITC), mildeomycin, capsaicin, khufuraneb, cyprosulfamide, dazomet, debacarb, dichlorophen, difenzoquat, difenzoquat methylsulfonate, flumetober, fosetyl calcium, fosetyl sodium, irumamycin, natamycin, nitrotar isopropyl, oxamocarb, pyrrolnitrin, tebufloquine, tolnifanide, zaliramide, argofase, amical Thiazole, oxathiapiproline, fluoxapiproline, metiram zinc, benthiazole, trichlamide, uniconazole, oxyfenthiin, picarbutrazox, diclobentiazox, quinofumelin, thiuram, ambam, Agrobacterium radiobacter, Coniothyrium minitans, Pseudomonas fluorescens, Pseudomonas rhodesia, Talaromyces flavus, Trichoderma atroviride, non-pathogenic Erwinia carotovora, Bacillus simplex, Variovorax paradoxus, Lactobacillus plantarum, florylpicoxamide, pyrapropoin, fluindapyr, aminopyrifen, pyridaclomethyl, ipflufenoquin, dipimethitron;

Specific examples of insecticides, acaricides, nematicides, soil pesticides, anthelmintics, etc. as the active ingredient (II) are shown below.

(1) Acetylcholinesterase (AChE) inhibitors (a) Carbamate acetylcholinesterase (AChE) inhibitors:
Alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC, xylylcarb, fenothiocarb, MIPC, MPMC, MTMC, aldoxycarb, alixycarb, aminocarb, bufencarb, cloethocarb, metam sodium, promecarb;
(b) Organophosphorus acetylcholinesterase (AChE) inhibitors:
Acephate, Azamethiphos, Azinphos-ethyl, Azinphos-methyl, Cadusafos, Chlorethoxyphos, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos-methyl, Coumaphos, Cyanophos, Demeton-S-methyl, Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Dimethylvinphos, Disulfoton, EPN, Ethion, Ethoprophos, Fenflur, Fenamiphos, Fenitrothion, Fenthion, Fosthiazate, Heptenophos, Imicyaphos, Isofenphos, Isocarbophos, Isopropyl O-(methoxyaminothiophosphoryl)salicylate, Isoxathion, Malathion, Mecarbam, Methamidophos, Methidathion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Para Thionemethyl, Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimiphos-methyl, Profenofos, Propetamphos, Prothiofos, Pyraclofos, Pyridafenthion, Quinalphos, Sulfotep, Tebupirimphos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Trichlorfon, Vamidothion, Bromophos-ethyl, BRP, Carbophenothion, Cyanofenphos, CYAP, Demeton-S-methylsulfone, Diarifos, Diclofenthion, Dioxabenzophos, Etrimphos, Fensulfothion, Flupyrazophos, Fonofos, Formothion, Fosmetilan, Isazophos, Iodofenphos, Methacrifos, Pirimiphos-ethyl, Phosphocarb, Propafos, Protoate, Sulprofos;

(2) GABAergic chloride ion (chloride ion) channel blockers:
Acetoprole, chlordane, endosulfan, ethiprole, fipronil, pyrafluprole, pyriprole, camphechlor, heptachlor, dienochlor, flufiprole;

(3) Sodium channel modulators (a) Pyrethroid sodium channel modulators:
Acrinathrin, allethrin, d-cis-trans-allethrin, d-trans-allethrin, bifenthrin, bioallethrin, bioallethrin-S-cyclopentenyl-isomer, bioresmethrin, cycloprothrin, cyfluthrin, β-cyfluthrin, cyhalothrin, λ-cyhalothrin, γ-cyhalothrin, cypermethrin, α-cypermethrin, β-cypermethrin, θ-cypermethrin Permethrin, ζ-cypermethrin, cyphenothrin [(1R)-trans isomer], deltamethrin, empenthrin [(EZ)-(1R)-isomer], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadesrin, permethrin, phenothrin thrin [(1R)-trans isomer], prallethrin, pyrethrum, pyrethrin, resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)-isomer], tralomethrin, transfluthrin, allethrin, pyrethrin I, pyrethrin II, profluthrin, dimefluthrin, bioethanomethrin, biopermethrin, transpermethrin, fenfluthrin, fenpyrithrin, flubrocythrinate, flufenprox, metofluthrin, protrifenbut, pyresmethrin, terallethrin, κ-bifenthrin, chloroprallethrin, heptafluthrin, meperfluthrin, ε-metofluthrin, monfluorothrin, ε-monfluorothrin, κ-tefluthrin, tetramethylfluthrin, bioethanomethrin;
(b) Sodium channel modulators (DDTs):
DDT, methoxychlor;

(4) Nicotinic acetylcholine receptor (nAChR) competitive modulators:
Acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid, thiamethoxam, nicotine, sulfoxaflor, flupyradifurone, triflumezopyrim, dichloromezothiaz, flupirimine;
(5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators:
Spinetoram, spinosad;
(6) Glutamate-gated chloride channel (GluCl) allosteric modulator:
Abamectin, Emamectin, Emamectin Benzoate, Lepimectin, Milbemectin, Ivermectin, Selamectin, Doramectin, Eprinomectin, Ivermectin, Moxidectin, Selamectin, Milbemycin, Milbemycin Oxime, Nemadectin;

(7) Juvenile hormone mimetics:
Hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen, diofenolan, epofenonane, triprene;
(8) Other non-specific (multi-site) inhibitors:
Methyl bromide, alkyl halides, chloropicrin, sodium aluminum fluoride, sulfuryl fluoride, borax, boric acid, disodium octaborate, sodium borate, sodium metaborate, tartar emetic, dazomet, metam, metam potassium salt, metam sodium salt;
(9) Chordotonal organ TRPV channel modulators:
Flonicamid, pymetrozine, pyrifluquinazone, afidopiropen;
(10) Mite growth inhibitor:
Clofentezine, diflavidazine, hexythiazox, etoxazole;
(11) Microorganism-derived insect midgut membrane disrupting agent:
Proteins in Bacillus thuringiensis subspecies israelenci, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, Bt crops: Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Ab1/Cry35Ab1; Bacillus sphaericus;

(12) mitochondrial ATP synthase inhibitors:
Diafenthiuron, azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon;
(13) Oxidative phosphorylation uncouplers that disrupt the proton gradient:
Chlorfenapyr, DNOC, sulfuramide, binapacryl, dinobuton, dinocap;
(14) Nicotinic acetylcholine receptor (nAChR) channel blockers:
Bensultap, Cartap hydrochloride, Nereistoxin, Thiocyclam, Thiosultap-sodium salt;
(15) Chitin biosynthesis inhibitor, type 0:
Bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron, buprofezin, fluazuron;
(16) Chitin biosynthesis inhibitor, type 1:
Buprofezin;
(17) Molting inhibitor:
Cyromazine;
(18) Ecdysone receptor agonist:
Chromafenozide, halofenozide, methoxyfenozide, tebufenozide;

(19) Octopamine receptor agonists:
Amitraz, demiditraz, chlordimeform;
(20) Mitochondrial electron transport complex III inhibitors:
Hydramethylnon, acequinocyl, fluacrypyrim, bifenazate;
(21) Mitochondrial electron transport complex I inhibitor (METI):
Fenazaquin, fenpyroximate, pyridaben, pyrimidifen, tebufenpyrad, tolfenpyrad, rotenone;
(22) Voltage-dependent sodium channel blockers:
Indoxacarb, metaflumizone;
(23) Acetyl-CoA carboxylase inhibitors:
Spirodiclofen, spiromesifen, spirotetramat, spiropydione;
(24) mitochondrial electron transport complex IV inhibitors:
Aluminum phosphide, calcium phosphide, zinc phosphide, phosphine, cyanide, calcium cyanide, sodium cyanide, potassium cyanide;
(25) Mitochondrial electron transport complex II inhibitors:
Cyenopyrafen, cyflumetofen, piflubumid;

(28) Ryanodine receptor modulators:
Chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide, cyhalodiamide, tetrachlorantraniliprole, tetraniliprole;
(29) Chord tone organ modulator Target site unspecified:
Flonicamid;
(30) GABA-gated chloride ion (chloride ion) channel allosteric modulators:
Broflanilide, fluxametamide, isocycloceram, afoxolaner, fluralaner, lotineral, sarolaner;
(31) Other insecticides and acaricides:
Azadirachtin, benzoximate, bifenazate, bromopropylate, chinomethionate, cryolite, dicofol, lime sulfur, mancozeb, pyridalyl, benclothiaz, sulfur, amidoflumet, 1,3-dichloropropene, DCIP, phenisobromorate, benzomate, metaldehyde, chlorbenzilate, clothiazobene, dicyclanil, fenoxacrim, fentrifanil, flubenzimine, fluphenazine, gossiplura, japonirua, methoxadiazone, petroleum (oil), potassium oleate, tetrasulf, triarane, afidopiropen, flufivrol, fluensulfone, meperfluthrin, tetramethylfluthrin, tralopyril, dimefluthrin, methylneodecane Amides, fluralaner, afoxolaner, fluxametamide, 5-[5-(3,5-dichlorophenyl)-5-trifluoromethyl-4,5-dihydroisoxazol-3-yl]-2-(1H-1,2,4-triazol-1-yl)benzonitrile (CAS: 943137-49-3), broflanilide, other metadiamides, Steinernema carpocapsae, Steinernema glacerai, Pasteuria penetrans, Pecilomyces tenuipes, Pecilomyces fumosoroseus, Beauveria bassiana, Beauveria brongniartii, Metarhizium anisopliae, Verticillium lecanii, acinonapyr, benzpyrimoxane, flometoquin, fluhexafon, oxazosulfil, cyclopyrazoflor.

(32) Anthelmintic agent:
(a) Benzimidazoles: fenbendazole, albendazole, triclabendazole, oxibendazole, mebendazole, oxfendazole, perbendazole, flubendazole, febantel, netobimin, thiophanate, thiabendazole, cambendazole;
(b) Salicylanilides: closantel, oxyclozanide, rafoxanide, niclosamide;
(c) Substituted phenols: nitroxynil, nitrosanoate;
(d) Pyrimidines: pyrantel, morantel;
(e) Imidazothiazoles: levamisole, tetramisole;
(f) Tetrahydropyrimidines: praziquantel, epsiprantel;
(g) Other anthelmintics: Cyclodienes, ryanine, clorsulon, metronidazole, demiditraz, piperazine, diethylcarbamazine, dichlorophene, monepantel, tribendimidine, amidantel, thiacetarsamide, melarsomine, and arsenamide.

Specific examples of plant regulators as the active ingredient (II) are shown below.
Abscisic acid, kinetin, benzylaminopurine, 1,3-diphenylurea, forchlorfenuron, thidiazuron, chlorfenuron, dihydrozeatin, gibberellin A, gibberellin A4, gibberellin A7, gibberellin A3, 1-methylcyclopropane, N-acetylaminoethoxyvinylglycine (also known as abiglycine), aminooxyacetic acid, silver nitrate, cobalt chloride, IAA, 4-CPA, cloprop, 2,4-D, MCPB, indole-3-butyric acid, dichlorprop, phenoty Ol, 1-naphthylacetamide, ethychlozate, cloxyfonac, maleic hydrazide, 2,3,5-triiodobenzoic acid, salicylic acid, methyl salicylate, (-)-jasmonic acid, methyl jasmonate, (+)-strigol, (+)-deoxystrigol, (+)-orobanchol, (+)-sorgolactone, 4-oxo-4-(2-phenylethyl)aminobutyric acid, ethephon, chlormequat, mepiquat chloride, benzyladenine, 5-aminolevulinic acid, daminozide.

{Formulation}
The agricultural and horticultural fungicide of the present invention is not particularly limited by its formulation. For example, it can be in the form of wettable powder, emulsifiable concentrate, powder, granule, water-soluble powder, suspension, granular wettable powder, tablet, etc. The preparation method of the formulation is not particularly limited, and a known preparation method can be adopted according to the formulation.

Auxiliary components that may be contained in compositions containing the organometallic complexes of the present invention include surfactants, bulking agents, efficacy enhancing agents, antioxidants, UV absorbers, stabilizers, etc.

  Surfactants that may be contained in the composition containing the organometallic complex of the present invention include, for example, nonionic surfactants such as polyoxyethylene-added alkyl phenyl ethers, polyoxyethylene-added alkyl ethers, polyoxyethylene-added higher fatty acid esters, polyoxyethylene-added sorbitan higher fatty acid esters, polyoxyethylene-added tristyryl phenyl ethers, sulfate salts of polyoxyethylene-added alkyl phenyl ethers, alkylbenzene sulfonates, sulfate salts of higher alcohols, alkylnaphthalene sulfonates, polycarboxylates, lignin sulfonates, formaldehyde condensates of alkylnaphthalene sulfonates, and isobutylene-maleic anhydride copolymers.

Examples of extenders that may be contained in the composition containing the organometallic complex of the present invention include the following.
solvent:
Water, glycerin, ethylene glycol, propylene glycol, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, alcohol, aliphatic hydrocarbons, aromatic hydrocarbons, etc.;
Thickeners, stabilizers and binders:
Polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, polyethylene glycol, carboxymethyl cellulose, hydroxypropyl cellulose, gum arabic, xanthan gum, gelatin, casein, pectin, sodium alginate, etc.;
Solid Support:
Mineral powders such as talc, clay, bentonite, kaolinite clay, montmorillonite, pyroferrite, acid clay, diatomaceous earth, vermiculite, apatite, gypsum, mica, silica sand, calcium carbonate, and pumice powder;
White carbon (amorphous silica), titanium dioxide, and other synthetic products;
Vegetable powders such as crystalline cellulose, starch, wood flour, cork, and coffee husks;
Polymer compounds such as polyvinyl chloride and petroleum resins;
Water soluble ingredients:
Ammonium sulfate, ammonium nitrate, ammonium chloride, potassium phosphate, potassium chloride, urea, sugars; etc.

Below are some formulation examples. Note that the formulations shown below are merely examples and may be modified within the scope of the present invention, and the present invention is in no way limited by the formulation examples below. "Parts" means "parts by mass" unless otherwise specified.

(Formulation Example 1: Wettable powder)
40 parts of the organometallic complex of the present invention, 53 parts of diatomaceous earth, 4 parts of higher alcohol sulfate, and 3 parts of alkylnaphthalene sulfonate are uniformly mixed and then finely ground to obtain a wettable powder containing 40% by weight of the active ingredient.

(Formulation Example 2: Granules)
5 parts of the organometallic complex of the present invention, 40 parts of talc, 38 parts of clay, 10 parts of bentonite, and 7 parts of sodium alkyl sulfate are uniformly mixed and then finely ground, and then granulated to a particle diameter of 0.5 to 1.0 mm to obtain a granule containing 5% by mass of the active ingredient.

(Formulation Example 3: Granules)
5 parts of the organometallic complex of the present invention, 73 parts of clay, 20 parts of bentonite, 1 part of dioctyl sulfosuccinate sodium salt, and 1 part of potassium phosphate are mixed uniformly, pulverized, and then water is added thereto and kneaded.Then, the mixture is granulated and dried to obtain a granule containing 5% by mass of the active ingredient.

(Formulation Example 4: Suspension)
10 parts of the organometallic complex of the present invention, 4 parts of polyoxyethylene alkyl allyl ether, 2 parts of sodium polycarboxylate, 10 parts of glycerin, 0.2 parts of xanthan gum, and 73.8 parts of water are mixed and wet-pulverized until the particle size becomes 3 microns or less, to obtain a suspension containing 10% by mass of the active ingredient.

(Formulation Example 5: Granular Water Dispersible)
40 parts of the organometallic complex of the present invention, 36 parts of clay, 10 parts of potassium chloride, 1 part of sodium alkylbenzenesulfonate, 8 parts of sodium ligninsulfonate, and 5 parts of formaldehyde condensate of sodium alkylbenzenesulfonate are mixed uniformly and pulverized finely. Then, an appropriate amount of water is added to the mixture, and the mixture is kneaded to form a clay-like substance. The clay-like substance is granulated, and then dried to obtain a granular water dispersible agent containing 40% by weight of active ingredient.

Next, the present invention will be explained in more detail with reference to examples. However, the present invention is not limited in any way by the following examples. Note that "parts" are values based on mass.

In this example, the solid product was evaluated by the following method.
[X-ray Powder Diffraction]
The sample was filled into the sample filling section of a silicon non-reflective test plate, and a diffraction chart was obtained by measuring the sample at a scan speed of 24°/min using a powder X-ray diffractometer (D2 PHASER, manufactured by Bruker) equipped with an X-ray source (Cu, 30 kV-10 mA). Figure 1 shows the diffraction chart of triflumizole. In the diffraction chart, the vertical axis represents intensity and the horizontal axis represents diffraction angle.

Example 1
1 part of triflumizole, 0.89 parts of zinc benzoate (about 1 mole of zinc cation and about 2 moles of benzoate anion per mole of triflumizole), 30 parts of dichloromethane and 20 parts of methanol were placed in a recovery flask and mixed by stirring. The solvent was removed from the obtained liquid using an evaporator to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of zinc cation and about 2 moles of benzoate anion). Figure 2 shows the diffraction chart of zinc benzoate. Figure 3 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 5.34°, 9.48°, 10.92°, 11.19°, 14.46°, 15.23°, 16.86°, 18.92°, 19.75°, 19.98°, 23.87°, 24.41° and 25.84°. The solid product has a different crystal structure than triflumizole and zinc benzoate.

Example 2
0.50 parts of triflumizole, 0.52 parts of zinc diethyldithiocarbamate (about 1 mole of zinc cation and about 2 moles of diethyldithiocarbamate anion per mole of triflumizole) and 20 parts of dichloromethane were placed in a recovery flask and mixed by stirring. The solvent was removed from the obtained liquid using an evaporator to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of zinc cation and about 2 moles of diethyldithiocarbamate anion). Figure 4 shows the diffraction chart of zinc diethyldithiocarbamate. Figure 5 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 9.34°, 12.10°, 13.92°, 14.53°, 15.86°, 16.55°, 17.77°, 19.69°, 21.34°, 23.30° and 27.91°. The solid product has a different crystal structure than triflumizole and zinc diethyldithiocarbamate.

Example 3
0.51 parts of triflumizole, 0.66 parts of zinc N-ethyl-N-phenyldithiocarbamate (approximately 1 mole of zinc cations and approximately 2 moles of N-ethyl-N-phenyldithiocarbamate anions per mole of triflumizole), 30 parts of dichloromethane, and 10 parts of methanol were placed in a recovery flask and mixed with stirring. The solvent was removed from the resulting liquid using an evaporator to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cations, and approximately 2 moles of N-ethyl-N-phenyldithiocarbamate anions). FIG. 6 shows a diffraction chart of zinc N-ethyl-N-phenyldithiocarbamate. FIG. 7 shows a diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 6.61°, 6.99°, 12.44°, 14.18°, 14.61°, 17.33°, 18.33°, 20.45°, 21.44°, 21.82° and 24.56°. The solid product has a crystal structure different from that of triflumizole and zinc N-ethyl-N-phenyldithiocarbamate.

Example 4
0.51 parts of triflumizole, 0.38 parts of zinc acetylacetonate (about 1 mole of zinc cation and about 2 moles of acetylacetonate anion per mole of triflumizole) and 20 parts of dichloromethane were placed in a recovery flask and mixed by stirring. The solvent was removed from the obtained liquid using an evaporator to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of zinc cation and about 2 moles of acetylacetonate anion). Figure 8 shows the diffraction chart of zinc acetylacetonate. Figure 9 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 6.64°, 9.36°, 11.93°, 13.95°, 18.01°, 20.22°, 22.79°, 23.62°, 23.47° and 24.25°. The solid product has a crystal structure different from that of triflumizole and zinc acetylacetonate.

Example 5
One part of triflumizole, 0.6 parts of zinc adipate (about 1 mole of zinc cation and about 1 mole of adipate anion per mole of triflumizole) and 0.5 parts of water were put into a mortar and pulverized. 0.5 parts of methanol was added thereto, and the mixture was further pulverized and mixed. The mixture was then air-dried to obtain a solid product (a complex containing 2 moles of triflumizole, about 1 mole of zinc cation and about 1 mole of adipate anion). Figure 10 shows the diffraction chart of zinc adipate. Figure 11 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 4.30°, 10.65°, 12.11°, 16.21°, 16.76°, 18.18°, 19.90°, 21.24° and 21.85°. The solid product has a crystal structure different from that of triflumizole and zinc adipate.

Example 6
1 part of triflumizole, 0.6 parts of zinc maleate (about 1 mole of zinc cation and about 1 mole of maleic acid anion per mole of triflumizole) and 0.5 parts of water were put into a mortar and pulverized. 0.5 parts of methanol was added thereto, and the mixture was further pulverized and mixed. The mixture was then air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of zinc cation and about 1 mole of maleic acid anion). FIG. 12 shows the diffraction chart of zinc maleate. FIG. 13 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 7.30°, 10.10°, 11.78°, 14.04°, 14.52°, 15.37°, 16.72°, 19.33°, 20.78°, 21.77°, 22.92° and 25.94°. The solid product has a different crystal structure than triflumizole and zinc maleate.

Example 7
1 part of triflumizole, 0.5 parts of zinc succinate (about 1 mole of zinc cation and about 1 mole of succinic acid per mole of triflumizole) and 0.5 parts of water were put into a mortar and pulverized. 0.2 parts of methanol was added thereto, and the mixture was further pulverized and mixed. The mixture was then air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of zinc cation and about 1 mole of succinic acid anion). Figure 14 shows the diffraction chart of zinc succinate. Figure 15 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 7.52°, 9.87°, 10.33°, 15.33°, 18.30°, 19.95°, 20.84°, 21.58°, 22.45°, 23.21° and 25.52°. The solid product has a different crystal structure than triflumizole and zinc succinate.

Example 8
1 part of triflumizole, 0.5 parts of zinc malonate (about 1 mole of zinc cation and about 1 mole of malonate anion per mole of triflumizole) and 0.5 parts of water were put into a mortar and pulverized. 0.1 parts of methanol was added thereto, and the mixture was further pulverized and mixed. The mixture was then air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of zinc cation and about 1 mole of malonate anion). FIG. 16 shows the diffraction chart of zinc malonate. FIG. 17 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 4.40°, 8.73°, 15.24°, 15.97°, 17.08°, 18.34°, 20.04°, 22.63°, 24.82° and 30.04°. The solid product has a crystal structure different from that of triflumizole and zinc malonate.

Example 9
1 part of triflumizole, 0.7 parts of zinc terephthalate (about 1 mole of zinc cation and about 1 mole of terephthalic acid anion per mole of triflumizole) and 0.5 parts of water were put into a mortar and pulverized. 0.6 parts of methanol was added thereto, and the mixture was further pulverized and mixed. The mixture was then air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of zinc cation and about 1 mole of terephthalic acid anion). FIG. 18 shows a diffraction chart of zinc terephthalate. FIG. 19 shows a diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 8.69°, 9.88°, 11.92°, 13.31°, 15.08°, 16.05°, 20.61°, 21.30°, 21.76° and 25.23°. The solid product has a crystal structure different from that of triflumizole and zinc terephthalate.

Example 10
1 part of triflumizole, 0.6 parts of zinc glutarate (about 1 mole of zinc cation and about 1 mole of glutarate anion per mole of triflumizole) and 0.5 parts of water were put into a mortar and pulverized. 0.2 parts of methanol was added thereto, and the mixture was further pulverized and mixed. The mixture was then air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of zinc cation and about 1 mole of glutarate anion). Figure 20 shows the diffraction chart of zinc glutarate. Figure 21 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 10.76°, 11.34°, 11.65°, 12.53°, 19.92°, 20.52°, 20.83°, 22.34°, 22.71° and 24.72°. The solid product has a different crystal structure from triflumizole and zinc glutarate.

Example 11
1 part of triflumizole, 0.6 parts of 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione zinc salt (about 1 mole of zinc cation and about 2 moles of 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione anion per mole of triflumizole) and 0.5 parts of water were placed in a mortar and pulverized. 0.2 parts of methanol was added thereto, and the mixture was further pulverized and mixed. The mixture was then air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of zinc cation and about 2 moles of 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione anion). FIG. 22 shows a diffraction chart of 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione zinc salt. FIG. 23 shows a diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 4.89°, 7.62°, 9.89°, 11.32°, 11.71°, 13.31°, 14.82°, 18.62°, 18.90°, 20.44°, 23.23° and 24.50°. The solid product has a crystal structure different from that of triflumizole and 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione zinc salt.

Example 12
1 part of triflumizole, 0.5 parts of 2,6-pyridinedicarboxylic acid (about 1 mole of 2,6-pyridinedicarboxylic acid per mole of triflumizole), 0.2 parts of zinc oxide (about 1 mole of zinc oxide per mole of triflumizole) and 0.5 parts of water were placed in a mortar and pulverized. 0.1 parts of methanol was added thereto, and the mixture was further pulverized and mixed. The mixture was then air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of zinc cations and about 1 mole of 2,6-pyridinedicarboxylic acid anions). FIG. 24 shows a diffraction chart of 2,6-pyridinedicarboxylic acid. FIG. 25 shows a diffraction chart of zinc oxide. FIG. 26 shows a diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 6.17°, 10.57°, 11.32°, 13.73°, 14.07°, 17.76°, 19.35°, 20.60°, 20.89° and 21.75°, and had a crystal structure different from those of triflumizole, 2,6-pyridinedicarboxylic acid and zinc oxide.

Example 13
10 parts of triflumizole, 4.8 parts of phthalic acid (about 1 mole of phthalic acid per mole of triflumizole), 2.4 parts of zinc chloride (about 1 mole of zinc chloride per mole of triflumizole), 6.4 parts of triethylamine and 160 parts of methanol were placed in an Erlenmeyer flask and stirred overnight at room temperature to mix. The resulting liquid was filtered to obtain a residue, which was washed with methanol to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of zinc cations and about 1 mole of phthalic acid anions). Figure 27 shows a diffraction chart of phthalic acid. Figure 28 shows a diffraction chart of zinc chloride. Figure 29 shows a diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 4.94°, 7.49°, 11.18°, 13.89°, 15.07°, 18.46°, 19.56°, 20.32°, 20.68° and 24.77°. The solid product has a different crystal structure from triflumizole, phthalic acid and zinc chloride.

Example 14
0.50 parts of triflumizole, 0.44 parts of zinc dimethyldithiocarbamate (about 1 mole of zinc cation and about 2 moles of dimethyldithiocarbamate anion per mole of triflumizole) and 20 parts of dichloromethane were placed in a recovery flask and mixed by stirring. The solvent was removed from the obtained liquid using an evaporator to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of zinc cation and about 2 moles of dimethyldithiocarbamate anion). Figure 30 shows the diffraction chart of zinc dimethyldithiocarbamate. Figure 31 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 5.90°, 10.59°, 11.67°, 11.92°, 13.63°, 15.65°, 17.52°, 18.84°, 20.40°, 21.54° and 24.40°. The solid product has a different crystal structure from triflumizole and zinc dimethyldithiocarbamate.

Example 15
1 part of triflumizole, 0.7 parts of benzoic acid (about 2 moles of benzoic acid per mole of triflumizole), 0.3 parts of copper(II) hydroxide (about 1 mole of copper(II) hydroxide per mole of triflumizole) and 0.3 parts of methanol were placed in a vial and stirred with a stirrer for one hour. The suspension was then filtered and air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of copper(II) cations and about 2 moles of benzoic acid anions). Figure 32 shows a diffraction chart of benzoic acid. Figure 33 shows a diffraction chart of copper(II) hydroxide. Figure 34 shows a diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 5.43°, 6.21°, 9.75°, 12.99°, 14.91°, 14.75°, 17.48°, 19.37°, 21.08° and 23.58°, and had a different crystal structure from triflumizole, benzoic acid and copper(II) hydroxide.

Example 16
1 part of triflumizole, 0.4 parts of propionic acid (approximately 2 moles of propionic acid per mole of triflumizole), 0.2 parts of zinc oxide (approximately 1 mole of zinc oxide per mole of triflumizole) and 0.3 parts of methanol were placed in a vial and stirred with a stirrer for one hour. The suspension was then filtered and air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cations and approximately 2 moles of propionate anions). Figure 35 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 5.16°, 10.42°, 11.26°, 12.97°, 15.70°, 16.54°, 19.07°, 21.46°, 22.55° and 26.02°. It had a crystal structure different from that of triflumizole and zinc oxide.

Example 17
One part of triflumizole, 0.4 parts of propionic acid (about 2 moles of propionic acid per mole of triflumizole), 0.3 parts of copper(II) hydroxide (about 1 mole of copper(II) hydroxide per mole of triflumizole) and 0.3 parts of methanol were placed in a vial and stirred with a stirrer for one hour. The suspension was then filtered and air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of copper(II) cations and about 2 moles of propionate anions). Figure 36 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 6.69°, 9.18°, 12.18°, 13.82°, 17.53°, 18.39°, 19.99°, 20.19°, 22.95° and 26.06°. It had a different crystal structure from triflumizole and copper(II) hydroxide.

Example 18
1 part of triflumizole, 0.5 parts of isobutyric acid (about 2 moles of isobutyric acid per mole of triflumizole), 0.2 parts of zinc oxide (about 1 mole of zinc oxide per mole of triflumizole) and 0.3 parts of methanol were placed in a vial and stirred with a stirrer for one hour. The suspension was then filtered and air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of zinc cation and about 2 moles of isobutyric acid anion). Figure 37 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 6.30°, 7.31°, 8.31°, 12.72°, 14.52°, 14.75°, 17.55°, 19.21°, 19.75° and 21.03°. It had a different crystal structure from triflumizole and zinc oxide.

Example 19
1 part of triflumizole, 0.5 parts of phthalic acid (about 1 mole of phthalic acid per mole of triflumizole), and 0.3 parts of copper(II) hydroxide (about 1 mole of copper(II) hydroxide per mole of triflumizole) were placed in a vial, 0.4 parts of methanol was added, and the mixture was stirred with a stirrer for one hour (at room temperature). The suspension was then filtered and air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of copper cations, and about 1 mole of phthalic acid anions). Figure 38 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 7.17°, 8.29°, 9.16°, 10.16°, 11.19°, 12.26°, 14.27°, 17.78°, 24.71°, and 28.17°. The solid product had a different crystal structure from triflumizole, phthalic acid, and copper hydroxide.

Example 20
1 part of triflumizole, 0.5 parts of terephthalic acid (1 mole of terephthalic acid per mole of triflumizole), and 0.3 parts of copper(II) hydroxide (1 mole of copper(II) hydroxide per mole of triflumizole) were placed in a vial, 0.4 parts of methanol was added, and the mixture was stirred with a stirrer for 1 hour (at room temperature). The suspension was then filtered and air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of copper cations, and about 1 mole of terephthalic acid anions). Figure 39 shows the diffraction chart of terephthalic acid. Figure 40 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 8.13°, 10.82°, 12.08°, 12.49°, 15.70°, 16.52°, 18.17°, 20.68°, 24.09°, and 27.37°. It had a different crystal structure from triflumizole, terephthalic acid and copper hydroxide.

Example 21
1 part of triflumizole, 0.3 parts of maleic acid (about 1 mole of maleic acid per mole of triflumizole), and 0.3 parts of copper(II) hydroxide (about 1 mole of copper(II) hydroxide per mole of triflumizole) were placed in a vial, 0.4 parts of methanol was added, and the mixture was stirred with a stirrer for one hour (at room temperature). The suspension was then filtered and air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, about 1 mole of copper cations, and about 1 mole of maleic acid anions). Figure 41 shows the diffraction chart of maleic acid. Figure 42 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 10.90°, 12.27°, 13.17°, 14.15°, 14.68°, 18.42°, 19.01°, 20.16°, 23.34°, and 25.16°. It had a different crystal structure from triflumizole, maleic acid and copper hydroxide.

In the present examples, the compositions were evaluated by the following methods.
[Triflumizole remaining rate]
The mass (C0) of triflumizole contained in the composition immediately after preparation was measured using high performance liquid chromatography.
The composition was then allowed to stand in a thermostatic chamber at 54° C. for 2 weeks. The mass (C2) of triflumizole contained in the composition after 2 weeks of standing was measured using high performance liquid chromatography (HPLC), and the residual rate (a2) of triflumizole was calculated. A higher residual rate (a2) indicates better chemical stability.
Triflumizole residual rate a2 (%) = C2/C0 × 100

[Particle size]
The volume-based 50% particle size (d0) of triflumizole in the composition immediately after preparation was measured using a laser diffraction particle size distribution analyzer (Shimadzu Corporation, SALD-2300).
The composition was then allowed to stand in a thermostatic chamber at 54° C. for 2 weeks. The volume-based 50% particle size (d2) of triflumizole in the composition after 2 weeks of standing was measured using a laser diffraction particle size distribution analyzer (Shimadzu Corporation, SALD-2300). The smaller the change in particle size, the more excellent the stability.

Example 22
In a container equipped with an agitator, 16.6 parts of the solid product obtained in Example 13, 5 parts of antifreeze, 0.5 parts of dioctyl sulfosuccinic acid metal salt, 2 parts of POA allylphenyl ether, 45.6 parts of water, 0.2 parts of antifoaming agent, and 0.1 parts of preservative were placed and stirred at 50-55°C for 2 hours. The mixture obtained was cooled to room temperature and subjected to a wet grinding treatment to obtain a suspension. A mixture consisting of 0.3 parts of thickener, 29.6 parts of water, and 0.1 parts of preservative was added to the suspension and mixed to obtain a composition. The evaluation results of the composition are shown in Table 1.

Example 23
In a container equipped with an agitator, 16.6 parts of the solid product obtained in Example 9, 5 parts of antifreeze, 0.5 parts of dioctyl sulfosuccinic acid metal salt, 2 parts of polyoxyethylene arylphenyl ether ammonium sulfate, 45.6 parts of water, 0.2 parts of antifoaming agent, and 0.1 parts of preservative were placed and stirred at 50 to 55°C for 2 hours. The mixture obtained was cooled to room temperature and subjected to a wet grinding treatment to obtain a suspension. A mixture consisting of 0.3 parts of thickener, 29.6 parts of water, and 0.1 parts of preservative was added to the suspension and mixed to obtain a composition. The evaluation results of the composition are shown in Table 1.

Example 24
In a container equipped with an agitator, 15.2 parts of the solid product obtained in Example 6, 5 parts of antifreeze, 0.5 parts of dioctyl sulfosuccinic acid metal salt, 2 parts of polyoxyethylene arylphenyl ether ammonium sulfate, 47 parts of water, 0.2 parts of antifoaming agent, and 0.1 parts of preservative were placed and stirred at room temperature for 30 minutes. The mixture obtained was subjected to wet grinding treatment to obtain a suspension. A mixture consisting of 0.3 parts of thickener, 29.6 parts of water, and 0.1 parts of preservative was added to the suspension, and mixed to obtain a composition. The evaluation results of the composition are shown in Table 1.

Comparative Example 1
In a container equipped with an agitator, 10 parts of triflumizole, 5 parts of antifreeze, 0.5 parts of dioctyl sulfosuccinic acid metal salt, 2 parts of polyoxyethylene arylphenyl ether sulfate ammonium salt, 52.2 parts of water, 0.2 parts of defoamer, and 0.1 parts of preservative are put and stirred for 2 hours. The mixture obtained is subjected to wet grinding to obtain a suspension. The mixture of 0.3 parts of thickener, 29.6 parts of water, and 0.1 parts of preservative is added to the suspension, and mixed to obtain a composition. The evaluation results of the composition are shown in Table 1.

Claims (10)

An organometallic complex consisting of triflumizole, a metal cation, and an organic acid anion. The organometallic complex according to claim 1, wherein the metal element of the metal cation is one selected from the group consisting of zinc, copper, magnesium, calcium, nickel, cobalt, iron and manganese. The organometallic complex according to claim 1 or 2, wherein the organic acid of the organic acid anion is at least one selected from the group consisting of acetylacetone and its tautomers, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid, 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione and its tautomers, 2,6-pyridinedicarboxylic acid, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, N-ethyl-N-phenyldithiocarbamic acid, propionic acid, and isobutyric acid. Triflumizole and/or a salt thereof,
and at least one selected from the group consisting of an organic acid metal salt, a combination of an organic acid and a metal compound, and a combination of an organic acid salt and a metal compound.
A method for producing an organometallic complex comprising triflumizole, a metal cation and an organic acid anion. The method according to claim 4, wherein the molar ratio during mixing is 0.5 to 2 moles of metal cations derived from the metal compound and 0.25 to 4 moles of organic acid anions derived from the organic acid and/or organic acid salt, per 1 mole of triflumizole derived from triflumizole and/or its salt. The method according to claim 4 or 5, wherein the metal element of the metal cation is one selected from the group consisting of zinc, copper, magnesium, calcium, nickel, cobalt, iron and manganese. The method according to claim 4 or 5, wherein the organic acid of the organic acid anion is at least one selected from the group consisting of acetylacetone and its tautomers, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid, 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione and its tautomers, 2,6-pyridinedicarboxylic acid, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, N-ethyl-N-phenyldithiocarbamic acid, propionic acid, and isobutyric acid. A composition containing an organometallic complex consisting of triflumizole, a metal cation, and an organic acid anion. A composition comprising triflumizole, an organometallic complex consisting of a metal cation and an organic acid anion, and water. An agricultural and horticultural fungicide containing as its active ingredient an organometallic complex consisting of triflumizole, a metal cation, and an organic acid anion.