JP5360244B2 - Plant disease control composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition having excellent plant disease controlling efficacy. <P>SOLUTION: The plant disease controlling agent composition contains at least one selected from 3-chloro-N-(3-chloro-5-trifluoromethyl-2-pyridyl)-&alpha;, &alpha;, &alpha;-trifluoro-2,6-dinitro-p-toluidine, 4-(2,2-difluoro-1,3-benzodioxol-4-yl)-1H-pyrrole-3-carbonitrile, N-(4,6-dimethylpyrimidin-2-yl)aniline, 4-cyclopropyl-6-methyl-N-phenyl-2-pyrimidinamine, N-(4-methyl-6-prop-1-ynyl-pyrimidin-2-yl)aniline, etc., and a certain kind of pyrazolinone compound as active ingredients. <P>COPYRIGHT: (C)2012,JPO&amp;INPIT

Description

  The present invention relates to a plant disease control composition.

  It is known that certain pyrazolinone derivatives have a plant disease control effect (Japanese Patent Application Laid-Open Nos. 8-208621, 2000-226374, 2001-11053, etc.). On the other hand, if multiple diseases occur at the same time or the resistant bacteria problem of a commercially available agent, the effect of controlling only one kind of active ingredient is insufficient, so two or more kinds of plant disease control agents are used at the same time. It is also actually applied to plants.

JP-A-8-208621 JP 2000-226374 A JP 2001-11053 A

  An object of the present invention is to provide a highly active plant disease control composition containing two or more active ingredients.

Under such circumstances, as a result of intensive studies on the plant disease control efficacy, the present inventors have found that a high effect can be found in plant disease control by using certain pyrazolinone derivatives in combination with specific compounds. It came to.
That is, the present invention relates to 3-chloro-N- (3-chloro-5-trifluoromethyl-2-pyridyl) -α, α, α-trifluoro-2,6-dinitro-p-toluidine [hereinafter referred to as Compound A 4- (2,2-difluoro-1,3-benzodioxol-4-yl) -1H-pyrrole-3-carbonitrile (hereinafter referred to as Compound B), N- (4,6 -Dimethylpyrimidin-2-yl) aniline (hereinafter referred to as Compound C), 4-cyclopropyl-6-methyl-N-phenyl-2-pyrimidinamine (hereinafter referred to as Compound D), N- (4-methyl) -6-prop-1-ynylpyrimidin-2-yl) aniline (hereinafter referred to as Compound E), 1-methylethyl = (3,4-diethoxyphenyl) carbamate (hereinafter referred to as Compound F), N -(3,5-dichloro Enyl) -1,2-dimethylcyclopropane-1,2-dicarboximide [hereinafter referred to as Compound G], 3- (3,5-dichlorophenyl) -N- (1-methylethyl) -2,4- Dioxo-1-imidazolidinecarboxamide (hereinafter referred to as Compound H), 3- (3,5-dichlorophenyl) -5-ethenyl-5-methyl-1,3-oxazolidine-2,4-dione (hereinafter referred to as Compound I) And at least one selected from 2-chloro-N- [4′-chloro- (1,1′-biphenyl) -2-yl] -3-pyridinecarboxamide (hereinafter referred to as Compound L),
Plant disease containing 1-[(2-propenylthio) carbonyl] -2- (1-methylethyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one as an active ingredient A control composition (hereinafter referred to as the present composition) is provided.
Furthermore, the plant foliage, the soil on which the plant grows, or the seed of the plant is selected from Compound A, Compound B, Compound C, Compound D, Compound E, Compound F, Compound G, Compound H, Compound I and Compound L. There is also provided a method for controlling plant diseases (hereinafter referred to as the method of the present invention) in which at least one compound and compound α are applied.

［式中、Ｒ¹は２−クロロフェニル基、２−メチルフェニル基または２，６−ジクロロフェニル基を表し、Ｒ²は１−メチルエチル基、１，１−ジメチルエチル基、１−メチルプロピル基、１−エチルプロピル基または１−メチルブチル基を表し、Ｒ³はメトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、（２−プロペニルオキシ）カルボニル基、（２−プロピニルオキシ）カルボニル基、ブトキシカルボニル基、（３−ブテニルオキシ）カルボニル基、（２−ブチニルオキシ）カルボニル基、（３−ブチニルオキシ）カルボニル基、（メチルチオ）カルボニル基、（エチルチオ）カルボニル基、（プロピルチオ）カルボニル基、（２−プロペニルチオ）カルボニル基、（２−プロピニルチオ）カルボニル基、メチルスルホニル基、エチルスルホニル基またはプロピルスルホニル基を表す。］
で示されるピラゾリノン誘導体〔以下、化合物αと記す〕とを有効成分として含有する植物病害防除組成物〔以下、本発明組成物と記す〕を提供する。
更に、植物の茎葉部、植物が生育する土壌または植物の種子に、化合物Ａ、化合物Ｂ、化合物Ｃ、化合物Ｄ、化合物Ｅ、化合物Ｆ、化合物Ｇ、化合物Ｈ、化合物Ｉ、化合物Ｊ、化合物Ｋおよび化合物Ｌから選ばれる少なくとも１種と化合物αとを施用する植物病害の防除方法〔以下、本発明方法と記す〕も提供する。

[Wherein R ¹ represents a 2-chlorophenyl group, a 2-methylphenyl group or a 2,6-dichlorophenyl group, and R ² represents a 1-methylethyl group, a 1,1-dimethylethyl group, a 1-methylpropyl group, 1-ethylpropyl group or 1-methylbutyl group, R ³ represents a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a (2-propenyloxy) carbonyl group, a (2-propynyloxy) carbonyl group, a butoxycarbonyl group, (3-butenyloxy) carbonyl group, (2-butynyloxy) carbonyl group, (3-butynyloxy) carbonyl group, (methylthio) carbonyl group, (ethylthio) carbonyl group, (propylthio) carbonyl group, (2-propenylthio) carbonyl group , (2-propynylthio) carbonyl group, methyls Honiru group, an ethylsulfonyl group or propylsulfonyl group. ]
The plant disease control composition (henceforth this invention composition) which contains the pyrazolinone derivative [henceforth compound (alpha)] shown by these as an active ingredient is provided.
Further, compound A, compound B, compound C, compound D, compound E, compound F, compound G, compound H, compound I, compound J, compound K are added to the plant foliage, the soil on which the plant grows, or the plant seed. And a method for controlling plant diseases (hereinafter referred to as the method of the present invention), which comprises applying at least one selected from compound L and compound α.

  The composition of the present invention has an excellent plant disease control effect.

Compound A is an active ingredient of a fungicide known by the general name fluazinam. Compound B is an active ingredient of a fungicide known by the general name fludioxonil. Compound C is an active ingredient of a fungicide known by the general name pyrimethanil. Compound D is an active ingredient of a fungicide known by the general name cyprodinil. Compound E is an active ingredient of a bactericide known by the general name mepanyprim. Compound F is an active ingredient of a disinfectant known by the general name dietofencarb. Compound G is an active ingredient of a fungicide known as procimideone. Compound H is an active ingredient of a fungicide known as iprodione. Compound I is the active ingredient of a fungicide known as vinclozolin. All of these compounds are commercially available (for example, Wako Pure Chemical Industries, Ltd.). Compound J and Compound K are compounds described in JP-A-9-235282. Compound L is a compound described in JP-A-5-221994.
Compound α can be produced by the method described in JP-A-2000-226374 or JP-A-2001-11053.

Specific examples of the compound α are shown below.
1-[(2-propenylthio) carbonyl] -2- (1-methylethyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one [hereinafter referred to as compound α-26] ].

  In the composition of the present invention, at least one selected from Compound A, Compound B, Compound C, Compound D, Compound E, Compound F, Compound G, Compound H, Compound I, Compound J, Compound K and Compound L and Compound α The weight ratio is usually 0.25 to 20, preferably 0.5 to 2, in terms of weight ratio, where the compound α is 1.

  The composition of the present invention comprises at least one selected from Compound A, Compound B, Compound C, Compound D, Compound E, Compound F, Compound G, Compound H, Compound I, Compound J, Compound K and Compound L, and Compound α. [Hereinafter referred to as the active ingredient of the present invention] may only be present, but in addition to these active ingredients of the present invention, a carrier, a surfactant, a formulation adjuvant, a diluting solvent, etc. may be included. , Wettable powders, flowables, powders, granules, dry flowables, emulsions, aqueous liquids, oils, microcapsules and the like.

  Examples of solid carriers used in the formulation include kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob flour, walnut shell flour, urea, Examples thereof include fine powders or granular materials such as ammonium sulfate and synthetic silicon hydroxide, and examples of the liquid carrier include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, and cellosolve. , Ketones such as acetone, cyclohexanone and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide and acetonitrile.

Examples of surfactants include anions such as alkyl sulfate esters, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphates, naphthalene sulfonate formalin condensates, and the like. Nonionic surfactants such as surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkyl polyoxypropylene block copolymers, sorbitan fatty acid esters and the like can be mentioned.
Examples of the preparation adjuvant include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), and PAP (isopropyl acid phosphate).
An example of the diluting solvent is water.

  Wettable powders, flowable powders, emulsions and the like are usually used after diluting with water, and the concentration of the active ingredient of the present invention in the preparation is usually 0.0005 to 2% by weight, preferably 0.005 to 1% by weight. Powders, granules and the like are usually applied as they are without dilution, and the concentration of the active ingredient of the present invention in the preparation is usually 0.1 to 99% by weight, preferably 1 to 90% by weight.

The method of the present invention is usually carried out by applying the composition of the present invention to plant foliage, soil on which plants grow, or plant seeds. Specifically, the liquid or powdery composition of the present invention is sprayed on the plant foliage, or the liquid composition of the present invention is poured into the soil where the plant is growing, or the powdery composition of the present invention. The composition is mixed with the soil before the plant grows, or by immersing the seeds of the plant in the liquid composition of the present invention.
Further, in the method of the present invention, compound A, compound B, compound C, compound D, compound E, compound F, compound G, compound H, plant foliage, soil on which the plant grows, or plant seeds, Also includes a form in which a composition containing at least one selected from Compound I, Compound J, Compound K and Compound L as an active ingredient and a composition containing Compound α as an active ingredient are applied substantially simultaneously. It is a waste.

  In the method of the present invention, the application amount of the active ingredient of the present invention may vary depending on the type of target plant, the type of target disease, the degree of occurrence of the disease, the formulation form, the application method, the application time, the weather conditions, etc. In application to parts, it is usually 0.1 to 50 g, preferably 1 to 10 g per are, and in the treatment to seeds, the active ingredient of the present invention is usually 0.001 to 100 parts by weight based on 1000 parts by weight of seeds. Part by weight, preferably in the range of 0.01 to 50 parts by weight.

By the method of the present invention, it is possible to control plant diseases in fields, paddy fields, orchards, tea gardens, pastures, lawns and the like. Examples of plant diseases that can be controlled include the following diseases.
Rice blast (Pyricularia oryzae), sesame leaf blight (Cochliobolus miyabeanus), blight (Rhizoctonia solani), wheat powdery mildew (Erysiphe graminis), head blight (Gibberella zeae), rust (Puccinia striiformis) , P. graminis, P. recondita, P. hordei), snow rot (Typhula sp., Micronectriella nivalis), naked smut (Ustilago tritici, U. nuda), lintel scab (Tilletia caries), Pseudocercosporella herpotrichoides), cloud disease (Rhynchosporium secalis), leaf blight (Septoria tritici), blight (Leptosphaeria nodorum),
Citrus black spot (Diaporthe citri), common scab (Elsinoe fawcetti), fruit rot (Penicillium digitatum, P. italicum),
Monilinia disease (Monilinia fructigena), rot disease (Valsa mali), powdery mildew (Podosphaera leucotricha), spotted leaf disease (Alternaria mali), black star disease (Venturia inaequalis),
Pear black spot (Venturia nashicola, V. pirina), black spot (Alternaria kikuchiana), red star (Gymnosporangium haraeanum),
Peach ash scab (Monilinia fructicola, Sclerotinia cinerea), black scab (Cladosporium carpophilum), Phomopsis sp. (Phomopsis sp.),
Grapes black rot (Elsinoe ampelina), late rot (Glomerella cingulata), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), black lot disease (Guignardia bidwellii), downy mildew (Plasmopara viticola),
Oyster anthracnose (Gloeosporium kaki), deciduous leaf disease (Cercospora kaki, Mycosphaerella nawae),
Colletotrichum lagenarium, powdery mildew (Sphaerotheca fuliginea), vine blight (Mycosphaerella melonis), vine split (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), plague (Phytophthora sp.) Seedling blight (Pythium sp.),
Tomato ring disease (Alternaria solani), leaf mold (Cladosporium fulvum), plague (Phytophthora infestans),
Eggplant brown spot (Phomopsis vexans), powdery mildew (Erysiphe cichoracearum), cruciferous vegetable black spot (Alternaria japonica), white spot (Cercosporella brassicae),
Leek rust (Puccinia allii),
Soybean purpura (Cercospora kikuchii), black scab (Elsinoe glycines), sunspot (Diaporthe phaseolorum var. Sojae),
Kidney anthracnose (Colletotrichum lindemthianum),
Peanut black astringency (Cercospora personata), brown spot (Cercospora arachidicola),
Pea powdery mildew (Erysiphe pisi),
Potato summer plague (Alternaria solani), plague (Phytophthora infestans),
Strawberry powdery mildew (Sphaerotheca humuli),
Cha net blast (Exobasidium reticulatum), white scab (Elsinoe leucospila),
Tobacco red blight (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina), plague (Phytophthora nicotianae),
Sugar beet brown spot (Cercospora beticola),
Rose scab (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa), chrysanthemum (Septoria chrysanthemi-indici), white rust (Puccinia horiana),
Various crops such as gray mold (Botrytis cinerea), sclerotia (Sclerotinia sclerotiorum), etc.

Hereinafter, although this invention is demonstrated in more detail by a manufacture example, a test example, etc., this invention is not limited only to these examples.
First, the manufacturing method of this invention composition is described below.
Production Example 1
Compound α-1, Compound α-2, Compound α-3, Compound α-4, Compound α-5, Compound α-6, Compound α-7, Compound α-8, Compound α-9, Compound α-10, Compound α-11, Compound α-12, Compound α-13, Compound α-14, Compound α-15, Compound α-16, Compound α-17, Compound α-18, Compound α-19 and Compound α-20 Each emulsion is obtained by thoroughly mixing 2.5 parts of each, 2.5 parts of Compound A, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 75 parts of xylene.

Production Example 2
Compound α-21, Compound α-22, Compound α-23, Compound α-24, Compound α-25, Compound α-26, Compound α-27, Compound α-28, Compound α-29, Compound α-30, Compound α-31, Compound α-32, Compound α-33, Compound α-34, Compound α-35, Compound α-36, Compound α-37, Compound α-38, Compound α-39 and Compound α-40 Each emulsion is obtained by thoroughly mixing 2.5 parts of each, 2.5 parts of Compound B, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 75 parts of xylene.

Formulation Example 3
Compound α-41, Compound α-42, Compound α-43, Compound α-44, Compound α-45, Compound α-46, Compound α-47, Compound α-48, Compound α-49, Compound α-50, Compound α-51, Compound α-52, Compound α-53, Compound α-54, Compound α-55, Compound α-56, Compound α-57, Compound α-58, Compound α-59 and Compound α-60 5 parts each, 5 parts of Compound C, 35 parts of a mixture of white carbon and polyoxyethylene alkyl ether sulfate ammonium salt (weight ratio 1: 1) and 55 parts of water are mixed and finely pulverized by a wet pulverization method. Thus, each flowable preparation is obtained.

Formulation Example 4
Compound α-61, Compound α-62, Compound α-63, Compound α-64, Compound α-65, Compound α-66, Compound α-67, Compound α-68, Compound α-69, Compound α-70, Compound α-71, Compound α-72, Compound α-73, Compound α-74, Compound α-75, Compound α-76, Compound α-77, Compound α-78, Compound α-79 and Compound α-80 5 parts each, 5 parts of Compound D, 35 parts of a mixture of white carbon and polyoxyethylene alkyl ether sulfate ammonium salt (weight ratio 1: 1) and 55 parts of water are mixed and finely pulverized by a wet pulverization method. Thus, each flowable preparation is obtained.

Formulation Example 5
Compound α-81, Compound α-82, Compound α-83, Compound α-84, Compound α-85, Compound α-86, Compound α-87, Compound α-88, Compound α-89, Compound α-90, Compound α-91, Compound α-92, Compound α-93, Compound α-94, Compound α-95, Compound α-96, Compound α-97 and Compound α-98 each 5 parts, Compound E 10 parts, After mixing 28.5 parts of an aqueous solution containing 1.5 parts of sorbitan trioleate and 2 parts of polyvinyl alcohol, the mixture was pulverized by a wet pulverization method, and then 0.05 parts of xanthan gum and aluminum magnesium 45 parts of an aqueous solution containing 0.1 part of silicate is added, and 10 parts of propylene glycol is further added and stirred and mixed to obtain each flowable preparation.

Formulation Example 6
Compound α-1, Compound α-2, Compound α-3, Compound α-4, Compound α-5, Compound α-6, Compound α-7, Compound α-8, Compound α-9, Compound α-10, Compound α-11, Compound α-12, Compound α-13, Compound α-14, Compound α-15, Compound α-16, Compound α-17, Compound α-18, Compound α-19 and Compound α-20 5 parts each, 10 parts of Compound F, 1.5 parts of sorbitan trioleate and 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol were mixed and pulverized by a wet pulverization method. To this, 45 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate is added, and 10 parts of propylene glycol is further added and stirred to obtain each flowable preparation.

Formulation Example 7
Compound α-21, Compound α-22, Compound α-23, Compound α-24, Compound α-25, Compound α-26, Compound α-27, Compound α-28, Compound α-29, Compound α-30, Compound α-31, Compound α-32, Compound α-33, Compound α-34, Compound α-35, Compound α-36, Compound α-37, Compound α-38, Compound α-39 and Compound α-40 1 part each, 2.5 parts of compound G, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 63.5 parts of kaolin clay are mixed well, and water is added. After kneading well, each granule is obtained by granulating and drying.

Formulation Example 8
Compound α-41, Compound α-42, Compound α-43, Compound α-44, Compound α-45, Compound α-46, Compound α-47, Compound α-48, Compound α-49, Compound α-50, Compound α-51, Compound α-52, Compound α-53, Compound α-54, Compound α-55, Compound α-56, Compound α-57, Compound α-58, Compound α-59 and Compound α-60 1 part each, 2.5 parts of compound H, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 63.5 parts of kaolin clay are mixed well, and water is added. After kneading well, each granule is obtained by granulating and drying.

Formulation Example 9
Compound α-61, Compound α-62, Compound α-63, Compound α-64, Compound α-65, Compound α-66, Compound α-67, Compound α-68, Compound α-69, Compound α-70, Compound α-71, Compound α-72, Compound α-73, Compound α-74, Compound α-75, Compound α-76, Compound α-77, Compound α-78, Compound α-79 and Compound α-80 Each wettable powder is obtained by thoroughly grinding and mixing 12.5 parts each, 37.5 parts of Compound I, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic silicon hydrous oxide.

Formulation Example 10
Compound α-81, Compound α-82, Compound α-83, Compound α-84, Compound α-85, Compound α-86, Compound α-87, Compound α-88, Compound α-89, Compound α-90, Compound α-91, Compound α-92, Compound α-93, Compound α-94, Compound α-95, Compound α-96, Compound α-97 and Compound α-98, 12.5 parts each, Compound J 37 Each wettable powder is obtained by thoroughly grinding and mixing 5 parts, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide.

Formulation Example 11
Compound α-1, Compound α-2, Compound α-3, Compound α-4, Compound α-5, Compound α-6, Compound α-7, Compound α-8, Compound α-9, Compound α-10, Compound α-11, Compound α-12, Compound α-13, Compound α-14, Compound α-15, Compound α-16, Compound α-17, Compound α-18, Compound α-19 and Compound α-20 Each powder is obtained by thoroughly grinding and mixing 1 part each, 2 parts of Compound K, 85 parts of Kaolin clay and 10 parts of talc.

Formulation Example 12
Compound α-21, Compound α-22, Compound α-23, Compound α-24, Compound α-25, Compound α-26, Compound α-27, Compound α-28, Compound α-29, Compound α-30, Compound α-31, Compound α-32, Compound α-33, Compound α-34, Compound α-35, Compound α-36, Compound α-37, Compound α-38, Compound α-39, Compound α-40 Each powder is obtained by thoroughly pulverizing and mixing 1 part each, 2 parts Compound L, 85 parts Kaolin clay and 10 parts talc.

Next, synthesis examples of the compound α are shown below.
Synthesis example 1
[1] 1- (1,1-dimethylethyl) -2- (1-methylethyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one in 107 g (313 mmol) 300 ml of normal hydrochloric acid and 100 ml of ethanol were added, and the mixture was stirred for 4 hours under reflux conditions. Thereafter, ethanol was distilled off under reduced pressure, the aqueous layer was neutralized with dilute aqueous sodium hydroxide solution, and the precipitated solid was collected by filtration. The solid was washed with water and ethyl acetate, dried under reduced pressure, and 88.4 g (309 mmol) of 2- (1-methylethyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one. )
¹ H-NMR (CD ₃ OD, TMS)
δ (ppm): 7.47 (1H), 7.33-7.36 (2H), 4.93 (2H), 4.41 (1H), 1.30 (6H)
[2] 2- (1-methylethyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one (1.57 g, 5.5 mmol) is suspended in 20 ml of 1,4-dioxane. The mixture was made turbid, and 0.30 g (7.5 mmol) of 60% oily sodium hydride was added and heated to 90 ° C. Subsequently, 0.72 g (7.6 mmol) of methyl chloroformate was added dropwise. After further stirring at the same temperature for 1 hour, the reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with water and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography, and the resulting white solid was washed with a mixed solvent of ethyl acetate and hexane to give 1- (methoxycarbonyl) -2- (1-methylethyl) -4- (2,6 -Dichlorophenyl) -5-amino-1H-pyrazol-3-one 0.13 mg (0.38 mmol) was obtained.
¹ H-NMR (CDCl ₃ , TMS)
δ (ppm): 7.33 (1H), 7.15 to 7.21 (2H), 5.74 (2H), 4.02 (1H), 3.96 (3H), 1.37 (6H)

Synthesis example 2
5.00 g (17.5 mmol) of 2- (1-methylethyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one, 1.47 g of lithium hydroxide monohydrate ( 35.0 mmol) and 4.22 g (35.0 mmol) of 2-propenyl chloroformate from 1-[(2-propenyloxy) carbonyl] -2- (1-methylethyl) -4- (2,6- 2.67 g (7.22 mmol) of dichlorophenyl) -5-amino-1H-pyrazol-3-one was obtained.
Melting point: 173.8 ° C

Synthesis example 3
2- (1-Methylethyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one 1.57 g (5.5 mmol), 60% oily sodium hydride 0.30 g (7 0.5 mmol) and 0.65 g (5.99 mmol) of ethyl chloroformate from 1- (ethoxycarbonyl) -2- (1-methylethyl) -4- (2,6-dichlorophenyl) -5-amino-1H -0.61 g (1.76 mmol) of pyrazol-3-one was obtained.
¹ H-NMR (CDCl ₃ , TMS)
δ (ppm): 7.37 (1H), 7.18-7.23 (2H), 5.71 (2H), 4.42 (2H), 4.05 (1H), 1.40-1. 47 (9H)

Synthesis example 4
Bis (trichloromethyl) = carbonate 1.41 g (4.73 mmol) was dissolved in 10 ml of 1,4-dioxane, and 1.12 g (14.2 mmol) of pyridine was added dropwise under water cooling. After stirring at room temperature for 15 minutes, 0.79 g (14.1 mmol) of 2-propyne-1-ol was added dropwise, and after further stirring for 35 minutes at room temperature, the reaction solution was filtered to obtain a filtrate. [Hereinafter, this filtrate is referred to as “filtrate A”]
2- (1-Methylethyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one 2.02 g (7.06 mmol) and lithium hydroxide monohydrate 0.59 g ( 20 ml of toluene was added to the mixture with 14.0 mmol), and the mixture was refluxed for 30 minutes while removing water by azeotropic dehydration. Toluene was distilled off under reduced pressure, 15 ml of 1,4-dioxane was added, and the above “filtrate A” was added dropwise under reflux conditions. After further stirring for 5 minutes under reflux conditions, 1,4-dioxane was distilled off under reduced pressure. Water was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed twice with water. The solvent was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography, and 1-[(2-propynyloxy) carbonyl] -2- (1-methylethyl) -4- (2,6-dichlorophenyl) -5- 0.51 g (1.44 mmol) of amino-1H-pyrazol-3-one was obtained.
Melting point: 137.4 ° C

Synthesis example 5
Bis (trichloromethyl) = carbonate 1.40 g (4.67 mmol) was dissolved in 10 ml of 1,4-dioxane, and 1.1 g (14 mmol) of pyridine was added dropwise under water cooling. After stirring at room temperature for 15 minutes, 1.03 g (14 mmol) of 3-butene-1-ol was added dropwise, and the mixture was further stirred at room temperature for 15 minutes, and then the reaction solution was filtered to obtain a filtrate. [Hereinafter, this filtrate is referred to as “filtrate D”]
2- (1-Methylethyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one 2.0 g (7.00 mmol) and lithium hydroxide monohydrate 0.59 g ( To the mixture with 14.0 mmol), 20 ml of toluene was added and refluxed for 1 hour while removing water by azeotropic dehydration. Toluene was distilled off under reduced pressure, and 10 ml of 1,4-dioxane was added. The above-mentioned “filtrate D” was added dropwise under reflux, and the mixture was further stirred for 10 minutes under reflux conditions, and 1,4-dioxane was distilled off under reduced pressure. Water was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed twice with water.
The solvent was distilled off under reduced pressure, and the residue was washed with a mixed solvent of ethyl acetate and hexane to give 1-[(3-butenyloxy) carbonyl] -2- (1-methylethyl) -4- (2,6-dichlorophenyl). 0.65 g (1.84 mmol) of -5-amino-1H-pyrazol-3-one was obtained.
Melting point: 133.1 ° C

Synthesis Example 6
Bis (trichloromethyl) = carbonate 1.40 g (4.67 mmol) was dissolved in 10 ml of 1,4-dioxane, and 1.1 g (14 mmol) of pyridine was added dropwise under water cooling. After stirring at room temperature for 30 minutes, 0.98 g (14 mmol) of 2-butyne-1-ol was added dropwise, and the mixture was further stirred at room temperature for 15 minutes, and then the reaction solution was filtered to obtain a filtrate. [Hereafter, this filtrate is referred to as “filtrate E”]
2- (1-Methylethyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one 2.0 g (7.00 mmol) and lithium hydroxide monohydrate 0.59 g ( To the mixture with 14.0 mmol), 20 ml of toluene was added and refluxed for 1 hour while removing water by azeotropic dehydration. Toluene was distilled off under reduced pressure, and 10 ml of 1,4-dioxane was added. The above-mentioned “filtrate E” was added dropwise under reflux, and the mixture was further stirred for 10 minutes under reflux conditions. Then, 1,4-dioxane was distilled off under reduced pressure. Water was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed twice with water.
The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography to give 1-[(2-butynyloxy) carbonyl] -2- (1-methylethyl) -4- (2,6-dichlorophenyl) -5-amino. 1.0 g (2.84 mmol) of -1H-pyrazol-3-one was obtained.
Melting point: 152.0 ° C

Synthesis example 7
Bis (trichloromethyl) = carbonate 1.41 g (4.67 mmol) was dissolved in 10 ml of 1,4-dioxane, and 1.1 g (14 mmol) of pyridine was added dropwise under water cooling. After stirring at room temperature for 15 minutes, 0.98 g (14 mmol) of 3-butyne-1-ol was added dropwise, and the mixture was further stirred at room temperature for 1 hour, and then the reaction solution was filtered to obtain a filtrate. [Hereafter, this filtrate is referred to as “filtrate F”]
2- (1-Methylethyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one 2.0 g (7.00 mmol) and lithium hydroxide monohydrate 0.59 g ( To the mixture with 14.0 mmol), 20 ml of toluene was added and refluxed for 1 hour while removing water by azeotropic dehydration. Toluene was distilled off under reduced pressure, and 10 ml of 1,4-dioxane was added. The above-mentioned “filtrate F” was added dropwise under reflux, and the mixture was further stirred for 10 minutes under reflux conditions. Then, 1,4-dioxane was distilled off under reduced pressure. Water was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed twice with water.
The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography to give 1-[(3-butynyloxy) carbonyl] -2- (1-methylethyl) -4- (2,6-dichlorophenyl) -5-amino. 0.58 g (1.65 mmol) of -1H-pyrazol-3-one was obtained.
Melting point: 160.3 ° C

Synthesis example 8
1.43 g (5.0 mmol) of 2- (1-methylethyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one and 0.42 g of lithium hydroxide monohydrate ( To the mixture with 10.0 mmol), 20 ml of toluene was added and the mixture was refluxed for 30 minutes while removing water by azeotropic dehydration. Toluene was distilled off under reduced pressure, 20 ml of 1,4-dioxane was added, and 1.1 ml (9.1 mmol) of S-ethyl = chlorothioformate was added dropwise under reflux. After further stirring for 10 minutes under reflux conditions, 1,4-dioxane was distilled off under reduced pressure. Water was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed twice with water. The solvent was distilled off under reduced pressure, and the residue was subjected to preparative thin layer chromatography to give 1-[(ethylthio) carbonyl] -2- (1-methylethyl) -4- (2,6-dichlorophenyl) -5-amino. 0.24 g (0.64 mmol) of -1H-pyrazol-3-one was obtained.
Melting point: 177.5 ° C

Synthesis example 8
Bis (trichloromethyl) = carbonate 0.98 g (3.29 mmol) was dissolved in 10 ml of 1,4-dioxane, and 0.79 g (10.0 mmol) of pyridine was added dropwise under water cooling. After stirring at room temperature for 30 minutes, 1.35 g (10.0 mmol) of 55% 2-propene-1-thiol was added dropwise, and after stirring for another 30 minutes at room temperature, the reaction solution was filtered to obtain a filtrate. [Hereinafter, this filtrate is referred to as “filtrate H”] 2- (1-methylethyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one 1.41 g (4.93 mmol) ) And lithium hydroxide monohydrate 0.42 g (10.0 mmol), 20 ml of toluene was added and the mixture was refluxed for 30 minutes while removing water by azeotropic dehydration. Toluene was distilled off under reduced pressure, and 10 ml of 1,4-dioxane was added. Under reflux, the above-mentioned “filtrate H” was added dropwise, and the mixture was further stirred for 10 minutes under reflux conditions, and then 1,4-dioxane was distilled off under reduced pressure. Water was added to the residue, extracted with ethyl acetate, and the organic layer was washed twice with water. The solvent was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography, and 1-[(2-propenylthio) carbonyl] -2- (1-methylethyl) -4- (2,6-dichlorophenyl) -5- 0.14 g (0.36 mmol) of amino-1H-pyrazol-3-one was obtained.
Melting point: 170.8 ° C

Synthesis Example 10
[1] To 54.6 g (181 mmol) of 1- (1,1-dimethylethyl) -2- (1-methylpropyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 3N hydrochloric acid (300 ml) and ethanol (100 ml) were added, and the mixture was stirred under reflux conditions for 4 hours. Thereafter, ethanol was distilled off under reduced pressure, the aqueous layer was neutralized with an aqueous sodium hydrogen carbonate solution, and the precipitated solid was collected by filtration. The solid was washed with water and ethyl acetate and dried under reduced pressure to give 35.3 g (144 mmol) of 2- (1-methylpropyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one. Got.
¹ H-NMR (CD ₃ OD, TMS)
δ (ppm): 7.17 (4H), 4.83 (2H), 4.1 (1H), 2.25 (3H), 1.5 to 1.9 (2H), 1.21 (3H) , 0.94 (3H)
[2] 2- (1-methylpropyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 2.45 g (10.0 mmol) and lithium hydroxide monohydrate 20 ml of toluene was added to a mixture of 84 g (20.0 mmol) and refluxed for 30 minutes while removing water by azeotropic dehydration. Toluene was distilled off under reduced pressure, 20 ml of 1,4-dioxane was added, and 2.41 g (20.0 mmol) of 2-propenyl = chloroformate was added dropwise under reflux. After further stirring for 10 minutes under reflux conditions, 1,4-dioxane was distilled off under reduced pressure. Water was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed twice with water. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography to give 1-[(2-propenyloxy) carbonyl] -2- (1-methylpropyl) -4- (2-methylphenyl) -5-amino. 0.53 g (1.88 mmol) of -1H-pyrazol-3-one was obtained.
Melting point: 102.1 ° C

Synthesis Example 11
1.22 g (5.0 mmol) of 2- (1-methylpropyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one and 0.42 g of lithium hydroxide monohydrate (10 0.0 mmol), 10 ml of toluene was added, and the mixture was refluxed for 30 minutes while removing water by azeotropic dehydration. Toluene was distilled off under reduced pressure, 10 ml of 1,4-dioxane was added, and 1.25 g (10.0 mmol) of S-ethyl = chlorothioformate was added dropwise under reflux. After further stirring for 30 minutes under reflux conditions, 1,4-dioxane was distilled off under reduced pressure. Water was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed with water. The solvent was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography, and 1-[(ethylthio) carbonyl] -2- (1-methylpropyl) -4- (2-methylphenyl) -5-amino-1H- 0.14 g (0.42 mmol) of pyrazol-3-one was obtained.
Melting point: 137.8 ° C

Synthesis Example 12
2- (1-methylpropyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 1.20 g (4.9 mmol) and lithium hydroxide monohydrate 0.41 g (9 .8 mmol) was added to 10 ml of toluene and the mixture was refluxed for 30 minutes while removing water by azeotropic dehydration. Toluene was distilled off under reduced pressure, 10 ml of 1,4-dioxane was added, and 1.0 g (7.3 mmol) of S- (2-propenyl) = chlorothioformate was added dropwise under reflux. After further stirring for 15 minutes under reflux conditions, 1,4-dioxane was distilled off under reduced pressure. Water was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed with brine. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography to give 1-[(2-propenylthio) carbonyl] -2- (1-methylpropyl) -4- (2-methylphenyl) -5-amino. 0.09 g (0.26 mmol) of -1H-pyrazol-3-one was obtained.
Melting point: 146.6 ° C

Synthesis Example 13
Bis (trichloromethyl) = carbonate 0.98 g (3.29 mmol) was dissolved in 10 ml of 1,4-dioxane, and 0.79 g (10.0 mmol) of pyridine was added dropwise under water cooling. After stirring at room temperature for 15 minutes, 0.56 g (10.0 mmol) of 2-propyne-1-ol was added dropwise, and after further stirring for 15 minutes at room temperature, the reaction solution was filtered to obtain a filtrate. [Hereinafter, this filtrate is referred to as “filtrate B”]
2- (1-methylpropyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one 1.50 g (5.00 mmol) and lithium hydroxide monohydrate 0.42 g ( To the mixture with 10.0 mmol), 20 ml of toluene was added and the mixture was refluxed for 30 minutes while removing water by azeotropic dehydration. Toluene was distilled off under reduced pressure, and 10 ml of 1,4-dioxane was added. The above-mentioned “filtrate B” was added dropwise under reflux, and the mixture was further stirred for 1 hour under reflux conditions, and 1,4-dioxane was distilled off under reduced pressure. Water was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed twice with water. The solvent was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography, and 1-[(2-propynyloxy) carbonyl] -2- (1-methylpropyl) -4- (2,6-dichlorophenyl) -5- 0.31 g (0.86 mmol) of amino-1H-pyrazol-3-one was obtained.
Melting point: 132.7 ° C

Synthesis Example 14
Bis (trichloromethyl) = carbonate 0.98 g (3.29 mmol) was dissolved in 10 ml of 1,4-dioxane, and 0.79 g (10 mmol) of pyridine was added dropwise under water cooling. After stirring at room temperature for 25 minutes, 0.72 g (10 mmol) of 3-butene-1-ol was added dropwise, and after further stirring at room temperature for 15 minutes, the reaction solution was filtered to obtain a filtrate. [Hereinafter, this filtrate is referred to as “filtrate G”]
2- (1-methylpropyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one 1.5 g (5.0 mmol) and lithium hydroxide monohydrate 0.42 g ( 10 ml of toluene was added to the mixture with 10.0 mmol), and the mixture was refluxed for 1 hour while removing water by azeotropic dehydration. Toluene was distilled off under reduced pressure, and 10 ml of 1,4-dioxane was added. The above-mentioned “filtrate G” was added dropwise under reflux, and the mixture was further stirred for 10 minutes under reflux conditions. Then, 1,4-dioxane was distilled off under reduced pressure. Water was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed twice with water.
The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography to give 1-[(3-butenyloxy) carbonyl] -2- (1-methylpropyl) -4- (2,6-dichlorophenyl) -5-amino. 0.47 g (1.18 mmol) of -1H-pyrazol-3-one was obtained.
Melting point: 127.7 ° C

Synthesis Example 15
[1] 2- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 20.00 g (0.106 mol), S-ethyl = chlorothioformate 13.84 g (0.111 mol) and toluene To 100.00 g of the mixture, 50.79 g (0.127 mol) of a 10% aqueous sodium hydroxide solution was slowly added dropwise at 25 ° C. After completion of dropping, the mixture was stirred at the same temperature for 1 hour. Thereafter, 5% aqueous hydrochloric acid was added to make the liquidity of the reaction mixture acidic, and this was extracted twice with 40.00 g of ethyl acetate. The organic layers were combined, dried over magnesium sulfate, the solvent was concentrated, the residue was subjected to silica gel column chromatography, and after concentration, the residue was washed with 200 ml of a mixture of ethyl acetate / n-hexane = 1/9. And dried to obtain 24.39 g of 1-[(ethylthio) carbonyl] -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one (LC area percentage value of 98.5%).
Melting point: 172.5 ° C
[2] 1-[(Ethylthio) carbonyl] -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 1.39 g (5 mmol) of 1,4-dioxane solution in 60 mg of lithium hydride (7.5 mmol) was added and refluxed for 10 minutes. 1-Methylethyl = methanesulfonate 1.0 g (7.2 mmol) was added and refluxed for 30 minutes. 1,4-Dioxane was distilled off under reduced pressure, water was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed with water. The solvent was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography, and 1-[(ethylthio) carbonyl] -2- (1-methylethyl) -4- (2-methylphenyl) -5-amino-1H- 1.14 g (3.57 mmol) of pyrazol-3-one was obtained.
¹ H-NMR (CDCl ₃ , TMS)
δ (ppm): 7.17 to 7.24 (4H), 5.5 (2H), 3.91 (1H), 2.95 (2H), 2.26 (3H), 1.43 (6H) , 1.36 (3H)

Synthesis Example 16
[1] 4- (2-Methylphenyl) -5-amino-1H-pyrazol-3-one 5.0 g (26 mmol), S- (2-propenyl) = chlorothioformate 3.7 g (27 mmol), toluene To a mixture of 40 g and 10 g of methanol, 25 g (32 mmol) of 5% aqueous sodium hydroxide solution was added dropwise at 25 ° C. over about 1 hour. After completion of dropping, the mixture was stirred at the same temperature for 5 hours. Thereafter, 5% aqueous hydrochloric acid was added to make the liquidity of the reaction mixture acidic. 25 ml of normal hexane was added thereto, and after stirring for about 1 hour, the crystals were filtered. The filtered product was washed with methanol water, water and normal hexane and then dried to give 1-[(2-propenylthio) carbonyl] -4- (2-methylphenyl) -5-amino-1H-pyrazole-3. -Obtained 6.1 g of ON.
¹ H-NMR (CDCl ₃ )
δ (ppm): 7.20 to 7.28 (4H), 5.80 to 5.97 (1H), 5.49 (2H), 5.14 to 5.49 (2H), 3.61 (2H) ) 2.31 (3H).
[2] 1-[(2-propenylthio) carbonyl] -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 6.0 g (20 mmol), molecular sieves 3A 3.0 g, 1- A mixture of 3.9 g (28 mmol) of methyl ethyl methanesulfonate and 30 ml of dioxane was heated to 90 ° C.
At the same temperature, 1.3 g (23 mmol) of lithium hydroxide monohydrate was added in 3 portions over 2 hours. After the addition, the mixture was stirred at the same temperature for 5 hours. Thereafter, the mixture was cooled, 97 g of 5% aqueous hydrochloric acid was added, extraction was performed with ethyl acetate, the organic layer was dried over magnesium sulfate, and then the solvent was distilled off. The residue is crystallized by adding n-hexane, filtered, washed with n-hexane, dried, 1-[(2-propenylthio) carbonyl] -2- (1-methylethyl) -4- (2- 3.8 g of methylphenyl) -5-amino-1H-pyrazol-3-one was obtained.
Melting point: 118.3 ° C
¹ H-NMR (CDCl ₃ )
δ (ppm): 7.18-7.26 (4H), 5.82-5.99 (1H), 5.60 (2H), 5.19-5.37 (2H), 3.84-3 .96 (1H), 3.60 (2H), 2.27 (3H), 1.43 (6H).

Synthesis Example 17
[1] 1.89 g (10.0 mmol) of 4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one, 1.30 g (11.8 mmol) of S-methyl chlorothioformate and toluene To 25 ml of the mixture, 7.1 g (11.4 mmol) of 6.45% aqueous sodium hydroxide was slowly added dropwise at 25 ° C. After completion of dropping, the mixture was stirred at the same temperature for 3 hours. Thereafter, 5% aqueous hydrochloric acid was added to make the liquidity of the reaction mixture acidic, and this was extracted with toluene and tert-butyl methyl ether. The organic layer was concentrated, the residue was washed with a mixed solvent of ethyl acetate and hexane, and 1-[(methylthio) carbonyl] -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 2.0 g was obtained.
¹ H-NMR (CDCl ₃ )
δ (ppm): 7.21 to 7.30 (4H), 5.49 (2H), 2.39 (3H), 2.32 (3H)
[2] Hydrogen in 10 ml of 1,4-dioxane solution of 0.34 g (1.27 mmol) of 1-[(methylthio) carbonyl] -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one Lithium chloride 15 mg (1.9 mmol) was added and refluxed for 10 minutes. 0.21 g (1.52 mmol) of 1-methylethyl methanesulfonate was added and refluxed for 1 hour. 1,4-Dioxane was distilled off under reduced pressure, 5% aqueous hydrochloric acid was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed with water. The solvent was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography, and 1-[(methylthio) carbonyl] -2- (1-methylethyl) -4- (2-methylphenyl) -5-amino-1H- 0.14 g of pyrazol-3-one was obtained.
¹ H-NMR (CDCl ₃ )
δ (ppm): 7.16 to 7.25 (4H), 5.52 (2H), 3.86 to 3.95 (1H), 2.40 (3H), 2.26 (3H), 2. 14 (3H), 1.42-1.50 (6H)

Synthesis Example 18
[1] 2- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one 20.00 g (81.97 mmol), S-ethyl chlorothioformate 10.72 g (86.07 mmol) and To a mixture of 100.00 g of toluene, 39.34 g (98.36 mmol) of a 10% aqueous sodium hydroxide solution was slowly added dropwise at 25 ° C. After completion of dropping, the mixture was stirred at the same temperature for 2 hours. Thereafter, 5% aqueous hydrochloric acid was added to make the reaction mixture acidic, and this was extracted with toluene and methyl tert-butyl ether. The organic layer was concentrated, the residue was subjected to silica gel column chromatography, and 1-[(ethylthio) carbonyl] -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one 19.16 g (LC area percentage value 98.4%) was obtained.
Melting point: 198.5 ° C
[2] 1-[(Ethylthio) carbonyl] -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one in a solution of 2.07 g (6.23 mmol) in 1,4-dioxane 85 mg (10.6 mmol) of lithium chloride was added and refluxed for 10 minutes. 1.6 g (10.5 mmol) of 1-methylpropyl methanesulfonate was added and refluxed for 1 hour. 1,4-Dioxane was distilled off under reduced pressure, water was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed with water. The solvent was distilled off under reduced pressure, and the residue was washed with a mixed solvent of ethyl acetate and hexane to give 1-[(ethylthio) carbonyl] -2- (1-methylpropyl) -4- (2,6-dichlorophenyl) -5. -1.25 g (3.22 mmol) of amino-1H-pyrazol-3-one was obtained.
¹ H-NMR (CDCl ₃ , TMS)
δ (ppm): 7.37 (1H), 7.18-7.26 (2H), 5.63 (2H), 3.63 (1H), 2.97 (2H), 1.88-2. 09 (2H), 1.35 to 1.41 (6H), 1.00 (3H)

Synthesis Example 19
[1] 2.00 g (10.6 mmol) of 4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one, 1.21 g (11.1 mmol) of ethyl chloroformate and 10.00 g of toluene To this mixture, 5.08 g (12.7 mmol) of a 10% aqueous sodium hydroxide solution was slowly added dropwise at 25 ° C. After completion of dropping, the mixture was stirred at the same temperature for 1 hour. Thereafter, 5% aqueous hydrochloric acid was added to make the liquidity of the reaction mixture acidic, and this was extracted twice with 10.00 g of ethyl acetate. The organic layers were combined, dried over magnesium sulfate, the solvent was concentrated, the residue was subjected to silica gel column chromatography, and 1- (ethoxycarbonyl) -4- (2-methylphenyl) -5-amino-1H-pyrazole- 2.10 g of 3-one (LC area percentage 98.9%) was obtained.
Melting point: 161.5 ° C
[2] To a mixture of 0.0305 g (3.80 mmol) of lithium hydride and 10.00 g of 1,4-dioxane at room temperature, 1- (ethoxycarbonyl) -4- (2-methylphenyl) -5-amino- 0.50 g (1.90 mmol) of 1H-pyrazol-3-one was added and stirred at the same temperature for 30 minutes. Thereafter, 0.58 g (3.80 mmol) of 1-methylpropyl = methanesulfonate was slowly added dropwise, and after completion of the addition, the temperature was raised to 100 ° C. and stirred at the same temperature for 4 hours. Then, it cooled, added 10.00 g of 5% hydrochloric acid water, and extracted twice with 20.00 g of toluene. The organic layers were combined, dried over magnesium sulfate, and the solvent was distilled off. The residue is crystallized by adding n-hexane, filtered, washed with n-hexane, dried, 1- (ethoxycarbonyl) -2- (1-methylpropyl) -4- (2-methylphenyl) -5- 0.25 g of amino-1H-pyrazol-3-one (LC area percentage value 95.2%) was obtained.
Melting point: 70.0 ° C

Synthesis Example 20
[1] 2.42 g (9.92 mmol) of 4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one, 1.30 g (11.8 mmol) of S-methyl chlorothioformate and 6.4 g (11.9 mmol) of a 7.46% aqueous sodium hydroxide solution was slowly added dropwise to a mixture of 20 ml of toluene at 25 ° C. After completion of dropping, the mixture was stirred at the same temperature for 3 hours. Thereafter, 5% aqueous hydrochloric acid was added to make the liquidity of the reaction mixture acidic, and this was extracted with toluene and tert-butyl methyl ether. The organic layer was concentrated, the residue was washed with a mixed solvent of ethyl acetate and hexane, and 1-[(methylthio) carbonyl] -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazole-3- 2.4 g of ON was obtained.
¹ H-NMR (DMSO)
δ (ppm): 11.0 (1H), 7.48-7.51 (2H), 7.34-7.39 (1H), 6.60 (2H), 3.32 (3H), 2. 33 (3H)
[2] To 10 ml of 1,4-dioxane solution of 0.72 g (2.25 mmol) of 1-[(methylthio) carbonyl] -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one 30 mg (3.75 mmol) of lithium hydride was added and refluxed for 10 minutes. 0.43 g (3.11 mmol) of 1-methylethyl methanesulfonate was added and refluxed for 1 hour. 1,4-Dioxane was distilled off under reduced pressure, 5% aqueous hydrochloric acid was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed with water. The solvent was distilled off under reduced pressure, and the residue was washed with a mixed solvent of ethyl acetate and hexane to give 1-[(methylthio) carbonyl] -2- (1-methylethyl) -4- (2,6-dichlorophenyl) -5. -0.46 g of amino-1H-pyrazol-3-one was obtained.
¹ H-NMR (CDCl ₃ )
δ (ppm): 7.35 to 7.39 (2H), 7.18 to 7.27 (1H), 5.67 (2H), 3.85 to 3.95 (1H), 2.40 (3H) ), 1.43-1.46 (6H).

Synthesis Example 21
Lithium hydride was added to 10 ml of 1,4-dioxane solution of 0.80 g (2.52 mmol) of 1-[(methylthio) carbonyl] -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one. 30 mg (3.75 mmol) was added and refluxed for 10 minutes. 1-Methylpropyl = methanesulfonate 0.50 g (3.29 mmol) was added and refluxed for 1 hour. 1,4-Dioxane was distilled off under reduced pressure, 5% aqueous hydrochloric acid was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed with water. The solvent was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography, and 1-[(methylthio) carbonyl] -2- (1-methylpropyl) -4- (2,6-dichlorophenyl) -5-amino-1H. -0.33 g of pyrazol-3-one was obtained.
¹ H-NMR (CDCl ₃ )
δ (ppm): 7.35 to 7.39 (2H) 7.18 to 7.27 (1H), 5.66 (2H), 3.55 to 3.66 (1H), 2.41 (3H) 1.82 to 2.13 (2H), 1.38 to 1.41 (3H), 0.97 to 1.03 (3H).

Synthesis Example 22
1-[(2-propenylthio) carbonyl] -4- (2-chlorophenyl) -5-amino-1H-pyrazol-3-one 2.0 g (6.46 mmol), molecular sieves 3A 1.0 g, 1-methylpropyl = A mixture of 1.33 g (8.72 mmol) of methanesulfonate and 10 g of dioxane was heated to 90 ° C. At the same temperature, 0.31 g (7.43 mmol) of lithium hydroxide monohydrate was added in 3 portions over 2 hours. After the addition, the mixture was stirred at the same temperature for 5 hours. Thereafter, the mixture was cooled, 8 g of 5% aqueous hydrochloric acid was added, and the mixture was extracted with ethyl acetate (4 g × 2). The organic layers were combined, dried over magnesium sulfate, and the solvent was distilled off. The residue was crystallized by adding n-hexane, filtered, washed with n-hexane, dried, 1-[(2-propenylthio) carbonyl] -2- (1-methylpropyl) -4- (2- 1.75 g of chlorophenyl) -5-amino-1H-pyrazol-3-one was obtained.
¹ H-NMR (CDCl ₃ )
δ (ppm): 7.21 to 7.44 (4H), 5.83 to 5.94 (1H), 5.76 (2H), 5.09 to 5.36 (2H), 3.60 to 3 .66 (3H), 1.81 to 2.11 (2H), 1.38 (3H), 1.00 (3H).

Synthesis Example 23
1-[(Methylthio) carbonyl] -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 0.80 g (3.06 mmol) in 1,4-dioxane solution 15 ml, lithium hydride 37 mg (4.63 mmol) was added and refluxed for 10 minutes. 0.65 g (4.28 mmol) of 1-methylpropyl methanesulfonate was added and refluxed for 1 hour. 1,4-Dioxane was distilled off under reduced pressure, 5% aqueous hydrochloric acid was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed with water. The solvent was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography, and 1-[(methylthio) carbonyl] -2- (1-methylpropyl) -4- (2-methylphenyl) -5-amino-1H- 0.42 g of pyrazol-3-one was obtained.
¹ H-NMR (CDCl ₃ )
δ (ppm): 7.18 to 7.25 (4H), 5.51 (2H), 3.68 to 3.77 (1H), 2.40 (3H), 2.27 (3H), 1. 78-1.97 (2H), 1.37-1.39 (3H), 0.92-0.97 (3H)

Synthesis Example 24
[1] 4.60 g (24.3 mmol) of 4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one and 9.8 g (97 mmol) of triethylamine were added to tetrahydrofuran, and chlorotrimethyl was added under ice cooling. Silane 2.2g (27.0mmol) was dripped and it stirred at room temperature for 3 hours. To the mixture, 3.1 g (27.0 mmol) of methanesulfonyl chloride was added dropwise under ice cooling, and the mixture was stirred at room temperature for 1 hour. The precipitate produced in the reaction mixture was removed by filtration, 1 ml of water and 1 ml of acetic acid were added to the filtrate, and the mixture was stirred for 1 hour under heating and refluxing conditions. After cooling the reaction solution to room temperature, water was added to the reaction solution and extracted with ethyl acetate, and the organic layer was washed with water and concentrated under reduced pressure. The residue was washed with ethyl acetate to obtain 1.2 g (5.1 mmol) of 1- (methylsulfonyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one.
¹ H-NMR (DMSO-d ⁶ )
δ (ppm): 7.17 to 7.24 (4H), 6.35 (2H), 3.10 (3H), 2.19 (3H)
[2] 1- (methylsulfonyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 900 mg (3.4 mmol) was dissolved in 10 ml of 1,4-dioxane and hydrogenated. Lithium 40 mg (5.0 mmol) was added, and the mixture was stirred for 10 minutes under heating under reflux. Thereafter, 770 mg (5.1 mmol) of 1-methylpropyl = methanesulfonate was added, and the mixture was further stirred for 30 minutes under the same conditions.
The reaction solution was concentrated under reduced pressure, water was added to the residue, this was extracted with ethyl acetate, and the organic layer was washed with water and concentrated under reduced pressure. The residue was washed with a mixed solvent of ethyl acetate and n-hexane to give 1- (methylsulfonyl) -2- (1-methylpropyl) -4- (2-methylphenyl) -5-amino-1H-pyrazole-3. -1.1 g (3.0 mmol) of ON were obtained.
Melting point: 154.1 ° C

Synthesis Example 25
1- (methylsulfonyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 1.5 g (5.6 mmol), lithium hydride 40 mg (5.0 mmol) and 1-methylbutyl = From 1.5 g (8.2 mmol) of methanesulfonate, 0.2 g of 1- (methylsulfonyl) -2- (1-methylbutyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one (0.59 mmol) was obtained.
_{^{1 H-NMR (CDCl 3 /}} TMS)
δ (ppm): 7.12 to 7.29 (4H), 5.14 (2H), 4.03 to 4.10 (1H), 2.99 (3H), 2.25 (3H), 2. 04 to 2.13 (1H), 1.65 to 1.75 (1H), 1.34 to 1.54 (5H), 0.92 to 0.97 (3H)

Synthesis Example 26
1- (Ethylsulfonyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 2.0 g (7.1 mmol), lithium hydride 85 mg (10.6 mmol) and 1-methylpropyl = From 1.6 g (10.5 mmol) of methanesulfonate, 1- (ethylsulfonyl) -2- (1-methylpropyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 0 Obtained .48 g (1.42 mmol).
¹ H-NMR (CDCl ₃ / TMS)
δ (ppm): 7.12 to 7.30 (4H), 5.17 (2H), 3.98 to 4.05 (1H), 3.23 to 3.30 (2H), 2.26 (3H ), 2.11 to 2.18 (1H), 1.67 to 1.82 (1H), 1.47 to 1.52 (3H), 1.33 (3H), 0.97 to 1.02 ( 3H)

Synthesis Example 27
1- (propylsulfonyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 1.6 g (5.2 mmol), lithium hydride 63 mg (7.9 mmol) and 1-methylpropyl = From 1.2 g (7.9 mmol) of methanesulfonate, 1- (propylsulfonyl) -2- (1-methylpropyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 0 Obtained .42 g (1.19 mmol).
¹ H-NMR (CDCl ₃ / TMS)
δ (ppm): 7.12 to 7.29 (4H), 5.19 (2H), 3.96 to 4.03 (1H), 3.11 to 3.22 (2H), 2.25 (3H ), 2.07 to 2.20 (1H), 1.90 to 2.02 (1H), 1.33 to 1.35 (3H), 1.08 to 1.13 (3H), 0.97 to 1.02 (3H)

Synthesis Example 28
1- (Ethylsulfonyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 1.56 g (5.5 mmol), lithium hydride 66 mg (8.3 mmol) and 1-methylbutyl = From 1.5 g (8.2 mmol) of methanesulfonate, 0.45 g of 1- (ethylsulfonyl) -2- (1-methylbutyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one (1.25 mmol) was obtained.
¹ H-NMR (CDCl ₃ / TMS)
δ (ppm): 7.11 to 7.29 (4H), 5.19 (2H), 4.04 to 4.13 (1H), 3.21 to 3.30 (2H), 2.25 (3H ), 2.0 to 2.2 (1H), 1.64 to 1.70 (1H), 1.33 to 1.52 (8H), 0.91 to 0.97 (3H)

Synthesis Example 29
1- (Methylsulfonyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 1.5 g (5.6 mmol), lithium hydride 65 mg (8.1 mmol) and 1-methylethyl = From 1.2 g (8.7 mmol) of methanesulfonate, 1- (ethylsulfonyl) -2- (1-methylethyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one 0 Obtained .4 g (1.29 mmol).
¹ H-NMR (CDCl ₃ / TMS)
δ (ppm): 7.13 to 7.30 (4H), 5.17 (2H), 4.17 to 4.26 (1H), 3.00 (3H), 2.26 (3H), 1. 42-1.47 (6H)

Synthesis Example 30
1- (methylsulfonyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one 1.27 g (4.4 mmol), lithium hydride 53 mg (6.6 mmol) and 1-methylbutyl = From 1.1 g (6.6 mmol) of methanesulfonate, 1- (methylsulfonyl) -2- (1-methylbutyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one 0 Obtained .35 g (0.97 mmol).
¹ H-NMR (CDCl ₃ / TMS)
δ (ppm): 7.24 to 7.41 (3H), 5.21 (2H), 4.02 to 4.09 (1H), 3.05 (3H), 2.06 to 2.18 (1H ), 1.64 to 1.74 (1H), 1.36 to 1.50 (5H), 0.91 to 0.96 (3H)

Synthesis Example 31
1- (methylsulfonyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazol-3-one 1.2 g (4.1 mmol), lithium hydride 50 mg (6.3 mmol) and 1-methyl From 0.93 g (6.1 mmol) of propyl methanesulfonate, 1- (methylsulfonyl) -2- (1-methylpropyl) -4- (2,6-dichlorophenyl) -5-amino-1H-pyrazole-3- 0.38 g (1.10 mmol) of ON was obtained.
¹ H-NMR (CDCl ₃ / TMS)
δ (ppm): 7.24 to 7.41 (3H), 5.20 (2H), 3.91 to 4.00 (1H), 3.06 (3H), 2.11 to 2.20 (1H) ), 1.68 to 1.82 (1H), 1.36 to 1.38 (3H), 0.99 to 1.04 (3H)

Synthesis Example 32
1- (methylsulfonyl) -4- (2-chlorophenyl) -5-amino-1H-pyrazol-3-one 0.84 g (3.1 mmol), lithium hydride 37 mg (4.6 mmol) and 1-methylbutyl = methane From 0.77 g (4.6 mmol) of sulfonate to 0.16 g of 1- (methylsulfonyl) -2- (1-methylbutyl) -4- (2-chlorophenyl) -5-amino-1H-pyrazol-3-one (0. 47 mmol) was obtained.
¹ H-NMR (CDCl ₃ / TMS)
δ (ppm): 7.26 to 7.46 (4H), 5.30 (2H), 4.02 to 4.12 (1H), 3.02 (3H), 2.04 to 2.16 (1H ), 1.66 to 1.76 (1H), 1.36 to 1.49 (5H), 0.92 to 1.03 (3H)

Synthesis Example 33
1- (methylsulfonyl) -4- (2-chlorophenyl) -5-amino-1H-pyrazol-3-one 0.99 g (3.6 mmol), lithium hydride 44 mg (5.5 mmol) and 1-methylpropyl = From 0.82 g (5.4 mmol) of methanesulfonate to 0.20 g of 1- (methylsulfonyl) -2- (1-methylpropyl) -4- (2-chlorophenyl) -5-amino-1H-pyrazol-3-one ( 0.61 mmol) was obtained.
¹ H-NMR (CDCl ₃ / TMS)
δ (ppm): 7.29 to 7.47 (4H), 5.31 (2H), 3.03 (3H), 2.11 to 2.19 (1H), 1.70 to 1.81 (1H) ), 1.36 to 1.38 (3H), 0.97 to 1.03 (3H)

Test example 1
A plastic pot was filled with sand loam, sown with cucumber (Sagamihanjiro), and grown in a greenhouse for 12 days. Compound α-1, Compound α-2, Compound α-7, Compound α-25, Compound α-28, Compound α-72, Compound α-77, Compound α-81 and Compound α-83 And the wettable powder of Compound A were each diluted with water, and then tank mixed to obtain a liquid composition having a compound α concentration of 2.5 ppm and a compound A concentration of 10 ppm. The liquid composition was sprayed on the foliage so that it sufficiently adhered to the cucumber leaf surface. After spraying, the plants were air-dried, and a spore-containing PDA medium of fluazinam-resistant cucumber gray mold was placed on the cucumber leaf surface. After inoculation at 10 ° C. under high humidity for 6 days, the control effect was investigated.
As a result, the treatment composition group of the present invention showed a higher control effect than the single treatment group of Compound α or Compound A.

Hereinafter, tests were performed according to Test Example 1. For the tested cucumber gray mold fungus, normal sensitive bacteria were used unless otherwise specified.
Test example 2
Compound α-1, Compound α-3, Compound α-14, Compound α-23, Compound α-77, Compound α-83, Compound α-85 and Compound α-86 The same experiment as in Test Example 1 was conducted using a liquid composition having a concentration of Compound α after tank mixing of 2.5 ppm and a concentration of Compound B of 1.25 ppm.
As a result, the treatment group of the present invention showed a higher control effect than the single treatment group of Compound α or Compound B.

Test example 3
Compound α-1, Compound α-2, Compound α-3, Compound α-4, Compound α-5, Compound α-6, Compound α-7, Compound α-8, Compound α-9, Compound α-10, Compound α-11, Compound α-12, Compound α-13, Compound α-14, Compound α-15, Compound α-16, Compound α-17, Compound α-18, Compound α-19 and Compound α-20 Using each wettable powder and wettable powder of Compound C, the same experiment as in Test Example 1 was performed with a liquid composition having a compound α concentration of 2.5 ppm and a compound C concentration of 10 ppm after tank mixing. It was.
As a result, the treated group of the present invention showed a higher control effect than the treated group of Compound α or Compound C alone.

Test example 4
Compound α-7, Compound α-9, Compound α-23, Compound α-72, Compound α-80 and Compound α-81 The same experiment as in Test Example 1 was performed using a liquid composition having an α concentration of 2.5 ppm and a compound D concentration of 5 ppm.
As a result, the treated group of the present invention showed a higher control effect than the treated group of Compound α or Compound D alone.

Test Example 5
Compound after tank mix using each of compound α-1, compound α-3, compound α-19, compound α-18, compound α-72, compound α-80 and compound E 80 The same experiment as in Test Example 1 was performed with a liquid composition having an α concentration of 2.5 ppm and a compound E concentration of 5 ppm.
As a result, the treated group of the present invention showed a higher control effect than the treated group of Compound α or Compound E alone.

Test Example 6
Compound after tank mixing using each of compound α-2, compound α-20, compound α-34, compound α-41, compound α-79, compound α-86 and compound F wettable powder An experiment similar to Test Example 1 was performed using a liquid composition having an α concentration of 2.5 ppm and a compound F concentration of 5 ppm.
As a result, the treated group of the present invention showed a higher control effect than the treated group of Compound α or Compound F alone.

Test Example 7
Compound α-7, Compound α-15, Compound α-23, Compound α-25, Compound α-26, Compound α-29, Compound α-38, Compound α-40, Compound α-77, Compound α-79, Using each of the wettable powders of Compound α-83 and Compound α-87 and the wettable powder of Compound G, a liquid composition in which the concentration of Compound α after tank mixing is 2.5 ppm and the concentration of Compound G is 40 ppm is used. The same experiment as in Test Example 1 was performed. However, dicarboximide drug-resistant bacteria were used as the test bacteria.
As a result, the treatment group of the present invention showed a higher control effect than the single treatment group of Compound α or Compound G.

Test Example 8
Compound α-1, Compound α-3, Compound α-14, Compound α-79, Compound α-86 and compound H wettable powders were used, and the concentration of compound α after tank mixing was 5 ppm. The same experiment as in Test Example 1 was performed using a liquid composition having a concentration of Compound H of 40 ppm.
However, dicarboximide drug-resistant bacteria were used as test bacteria. As a result, the treated group of the present invention showed a higher control effect than the treated group of Compound α or Compound H alone.

Test Example 9
Compound α-3, Compound α-25, Compound α-34, Compound α-41, Compound α-77, Compound α-81, Compound α-83 and Compound α-86 An experiment similar to that of Test Example 1 was performed using a liquid composition having a compound α concentration of 10 ppm and a compound I concentration of 40 ppm after tank mixing. However, dicarboximide drug-resistant bacteria were used as test bacteria.
As a result, the treated group of the present invention showed a higher control effect than the treated group of Compound α or Compound I alone.

Test Example 10
Compound α-7, Compound α-14, Compound α-31, Compound α-41 and Compound α-79 were each used as a wettable powder of Compound J, and the concentration of Compound α after tank mixing was 2 The same experiment as in Test Example 1 was performed using a liquid composition having a concentration of 5 ppm and a concentration of Compound J of 5 ppm.
As a result, the treated group of the present invention showed a higher control effect than the treated group of Compound α or Compound J alone.

Test Example 11
Compound α-9, Compound α-20, Compound α-26, Compound α-28, Compound α-81 and Compound α-83 The same experiment as in Test Example 1 was performed using a liquid composition having an α concentration of 2.5 ppm and a compound K concentration of 2.5 ppm.
As a result, the treated group of the present invention showed a higher control effect than the treated group of Compound α or Compound K alone.

Test Example 12
Compound α-19, Compound α-23, Compound α-25, Compound α-72, Compound α-85 and Compound α-87 The same experiment as in Test Example 1 was performed using a liquid composition having an α concentration of 2.5 ppm and a compound L concentration of 2.5 ppm.
As a result, the treatment group of the present invention showed a higher control effect than the single treatment group of Compound α or Compound L.

Claims (2)

3-chloro-N- (3-chloro-5-trifluoromethyl-2-pyridyl) -α, α, α-trifluoro-2,6-dinitro-p-toluidine, 4- (2,2-difluoro- 1,3-benzodioxol-4-yl) -1H-pyrrole-3-carbonitrile, N- (4,6-dimethylpyrimidin-2-yl) aniline, 4-cyclopropyl-6-methyl-N- Phenyl-2-pyrimidineamine, N- (4-methyl-6-prop-1-ynylpyrimidin-2-yl) aniline, 1-methylethyl = (3,4-diethoxyphenyl) carbamate, N- (3 , 5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, 3- (3,5-dichlorophenyl) -N- (1-methylethyl) -2,4-dioxo-1-imi Oxazolidinedione carboxamide, 3- (3,5-dichlorophenyl) -5-ethenyl-5-methyl-1,3-oxazolidine-2,4-dione, Contact and 2-chloro -N- [4'-chloro - (1 , 1′-biphenyl) -2-yl] -3-pyridinecarboxamide, and 1-[(2-propenylthio) carbonyl] -2- (1-methylethyl) -4- (2- A plant disease control composition comprising methylphenyl) -5-amino-1H-pyrazol-3-one as an active ingredient. 3-chloro-N- (3-chloro-5-trifluoromethyl-2-pyridyl) -α, α, α-trifluoro-2,6 is added to the plant foliage, the soil where the plant grows or the seed of the plant. -Dinitro-p-toluidine, 4- (2,2-difluoro-1,3-benzodioxol-4-yl) -1H-pyrrole-3-carbonitrile, N- (4,6-dimethylpyrimidine-2 -Yl) aniline, 4-cyclopropyl-6-methyl-N-phenyl-2-pyrimidinamine, N- (4-methyl-6-prop-1-ynylpyrimidin-2-yl) aniline, 1-methylethyl = (3,4-diethoxyphenyl) carbamate, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, 3- (3,4-dichlorophenyl)- - (1-methylethyl) -2,4-dioxo-1-imidazolidine carboxamide, 3- (3,5-dichlorophenyl) -5-ethenyl-5-methyl-1,3-oxazolidine-2,4-dione, Contact and chloro -N- [4'-chloro - (1,1'-biphenyl) -2-yl] -3 and at least one selected from pyridine carboxamide, as claimed in claim 1 1 - [( Control of plant diseases characterized by applying 2-propenylthio) carbonyl] -2- (1-methylethyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one Method.