JP6331075B2 - 3-Amino-1H-pyrazole-4-carboxylic acid benzyl ester derivatives and fungicides containing the same as active ingredients - Google Patents

Description

  The present invention relates to a 3-amino-1H-pyrazole-4-carboxylic acid benzyl ester derivative and a fungicide containing this as an active ingredient.

  In the field of agriculture and horticulture, various fungicides for the purpose of controlling various pathogenic bacteria have been developed and put into practical use.

  However, it cannot be said that the conventionally used agricultural chemicals satisfy the requirements such as the effect, spectrum, residual effect, etc., or the number of application times and the reduction of the applied drug amount. In addition, the emergence of pathogenic bacteria that have developed resistance to conventional general agricultural chemicals is also a problem. For example, in the cultivation of vegetables, fruit trees, flower buds, tea, wheat and rice, for example, various types such as triazole, imidazole, pyrimidine, benzimidazole, dicarboximide, phenylamide and strobilurin Various pathogens that have developed resistance to various fungicides and the like have appeared in various places, and the control of these resistant pathogens has become difficult year by year. Therefore, the emergence of new pesticides that exhibit sufficient control effects at low doses and have little adverse environmental impact against various pathogens that have developed resistance to conventional agricultural and horticultural fungicides is always desirable. ing.

  Various new fungicides have been proposed to meet these demands, but they do not necessarily meet the above demands.

しかしながら、特許文献１および２に記載の化合物において、ピラゾール環の２−位に置換基の記載はなく、特許文献１および２には殺菌活性については全く記載されていない。 Until now, it is known that 5-amino-1H-pyrazole-4-carboxylic acid benzyl ester derivatives are used for photographic materials and the like. For example, the following documents are cited as documents disclosing 5-amino-1H-pyrazole-4-carboxylic acid benzyl ester derivatives.
In Patent Documents 1 and 2, as an intermediate of a photographic coupler, a 5-amino-1H-pyrazole-4-carboxylic acid benzyl ester derivative represented by the following structural formula (3-amino-1H in the compound of the present invention) is disclosed. -Is a tautomer of a pyrazole-4-carboxylic acid benzyl ester derivative).

However, in the compounds described in Patent Documents 1 and 2, there is no description of a substituent at the 2-position of the pyrazole ring, and Patent Documents 1 and 2 do not describe any bactericidal activity.

しかしながら、特許文献３および４に記載の化合物において、ピラゾール環の１−位は水素原子であり、特許文献３および４には殺菌活性については全く記載されていない。 Patent Documents 3 and 4 disclose a 3-amino-1H-pyrazole-4-carboxylic acid benzyl ester derivative represented by the following structural formula as a pharmaceutical production intermediate.

However, in the compounds described in Patent Documents 3 and 4, the 1-position of the pyrazole ring is a hydrogen atom, and Patent Documents 3 and 4 do not describe any bactericidal activity.

しかしながら、非特許文献１に記載の化合物において、ピラゾール環の１−位は水素原子であり、そもそも非特許文献１は合成法に関する論文であり、殺菌活性については全く記載されていない。 Non-Patent Document 1 discloses a 3-amino-1H-pyrazole-4-carboxylic acid benzyl ester derivative represented by the following structural formula.

However, in the compound described in Non-Patent Document 1, the 1-position of the pyrazole ring is a hydrogen atom, and Non-Patent Document 1 is a paper on a synthesis method in the first place, and no bactericidal activity is described.

しかしながら、非特許文献２に記載の化合物において、ピラゾール環の１−位は水素原子であり、そもそも非特許文献２はzaleplonの不純物および分解生成物に関する論文であり、殺菌活性については全く記載されていない。 Non-Patent Document 2 discloses a 3-amino-1H-pyrazole-4-carboxylic acid benzyl ester derivative represented by the following structural formula.

However, in the compound described in Non-Patent Document 2, the 1-position of the pyrazole ring is a hydrogen atom, and Non-Patent Document 2 is a paper on impurities and decomposition products of zaleplon in the first place and does not describe any bactericidal activity. Absent.

JP-A-62-195368 JP-A-62-158259 Japanese Patent Laid-Open No. 10-182615 International Publication No. 2007/111212

Journal of the Chemical Society Section C: Organic, 8, 1501 (1971) Journal of Heterocyclic Chemistry, 47, 276 (2010)

  The present invention provides a new substance useful for the control of various fungi, and in particular, exhibits a high control effect against various fungi that are resistant to conventional fungicides, and is effective at a low dose. The object is to provide a highly safe substance with reduced problems such as residual toxicity and environmental pollution.

(式中、Ｒ¹はＣ₁〜Ｃ₄のアルキル基を示し、Ｒ²は水素原子またはＣ₁〜Ｃ₄のアルキル基を示し、Ｒ³およびＲ⁴は互いに独立して水素原子、Ｃ₁〜Ｃ₄のアルキル基、Ｃ₁〜Ｃ₄のアルコキシ基、トリフルオロメチル基、トリフルオロメトキシ基、シアノ基またはハロゲン原子を示し、Ｙは酸素原子、硫黄原子またはＯＣＨ₂を示す。)で表される、３−アミノ−１Ｈ−ピラゾール−４−カルボン酸ベンジルエステル誘導体(以下、「本発明の化合物」とも言う)およびこれを有効成分として含有する殺菌剤に関する。 As a result of intensive studies to solve the above problems, the inventors of the present invention have a characteristic that a 3-amino-1H-pyrazole-4-carboxylic acid benzyl ester derivative defined by the following formula can meet the above-mentioned demands. It discovered that it was a compound and came to complete this invention.
That is, the present invention provides the following formula [I],

(In the formula, R ¹ represents a C _{1 to} C ₄ alkyl group, R ² represents a hydrogen atom or a C _{1 to} C ₄ alkyl group, R ³ and R ⁴ are each independently a hydrogen atom, C ₁ alkyl group -C _4, alkoxy group of C ₁ -C _4, a trifluoromethyl group, a trifluoromethoxy group, a cyano group or a halogen atom, Y table in an oxygen atom, a sulfur atom or OCH _2.) The present invention relates to a 3-amino-1H-pyrazole-4-carboxylic acid benzyl ester derivative (hereinafter also referred to as “the compound of the present invention”) and a fungicide containing this as an active ingredient.

  The compound of the present invention exhibits excellent effects against various fungi.

Hereinafter, the present invention will be described in detail.
In the compound of the present invention represented by the formula [I], examples of the C ₁ -C ₄ alkyl group represented by R ¹ , R ² , R ³ and R ⁴ include a methyl group, an ethyl group, and n-propyl. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. Examples of the C ₁ -C ₄ alkoxy group represented by R ³ and R ⁴ include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert -Butoxy group is mentioned. Examples of the halogen atom represented by R ³ and R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The compound of the present invention is a novel compound not described in any literature, and can be produced, for example, according to the following reaction formula.

Reaction formula

(Wherein R ¹ , R ² , R ³ , R ⁴ and Y are as defined in the above formula [I].)
The 3-amino-1H-pyrazole-4-carboxylic acid derivative represented by the above formula [II] and the benzyl alcohol derivative represented by the above formula [III] are reacted in an inert solvent in the presence of a condensing agent and a base. Thus, the 3-amino-1H-pyrazole-4-carboxylic acid benzyl ester derivative of the present invention represented by the above formula [I] can be produced.
Here, the compounds [II] and [III] are already known compounds, or compounds that can be readily synthesized by those skilled in the art from known compounds. Compound [II] can be synthesized, for example, by the method described in International Publication No. 2004/103975. Compound [III] can be synthesized, for example, in Journal of Medicinal Chemistry, 43, 1826 (2000). It can be synthesized by the method described.
The reaction temperature in this reaction is usually in the range of −20 ° C. to 120 ° C., preferably 0 ° C. to 80 ° C., and the reaction time is usually in the range of 0.2 hour to 24 hours, preferably 1 hour to 5 hours. The benzyl alcohol derivative represented by the general formula [III] is usually 1 to 5 times mol, preferably 1 to 1 mol with respect to the 3-amino-1H-pyrazole-4-carboxylic acid derivative represented by the general formula [II]. Used in a 1.5-fold molar range.

  Examples of the condensing agent used in this reaction include diethyl cyanophosphate (DEPC), carbonyldiimidazole (CDI), 1,3-dicyclohexylcarbodiimide (DCC), 1-ethyl-3- (3-dimethylamino). Propyl) carbodiimide hydrochloride, chlorocarbonates, 2-chloro-1-methylpyridinium iodide and the like, and the amount used is 3-amino-1H-pyrazole- represented by the general formula [II] It is used usually in a range of 1 to 3 times mol, preferably 1 to 1.5 times mol, of the 4-carboxylic acid derivative.

Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate; acetates such as sodium acetate and potassium acetate; potassium-t-butoxide, Metal alkoxides such as sodium methoxide and sodium ethoxide; tertiary amines such as triethylamine, diisopropylethylamine and 1,8-diazabicyclo [5,4,0] undec-7-ene; pyridine, dimethylaminopyridine and the like A nitrogen-containing aromatic compound etc. can be mentioned. The amount of the base is usually 1 to 10 times mol, preferably 1 to 2 times mol for the 3-amino-1H-pyrazole-4-carboxylic acid derivative represented by the general formula [II].
Although this reaction may or may not use a solvent, any solvent that does not significantly inhibit this reaction may be used. For example, dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, Linear or cyclic ethers such as dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; nitriles such as acetonitrile; methyl acetate and ethyl acetate And esters such as butyl acetate; polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, and their inert A solvent can be used individually or in mixture of 2 or more types.
After the reaction, the target product may be isolated from the reaction system containing the target product by a conventional method, and the target product can be produced by purification by recrystallization, column chromatography or the like, if necessary.

  The compounds of the present invention can be obtained from fruit trees such as avocado, apricot, fig, citrus, ume, mandarin orange, outo, kaki, kabosu, kiwifruit, peach, western none, kankan, dekopon, none, natsumikan, nectarine, hassaku, papaya. , Loquat, grapes, grapes, mangoes, peaches, yuzu, apples, lemons, etc .: cereals such as barley, wheat, paddy rice, corn, pigeons, rye, upland rice, etc .: potatoes such as potatoes, potatoes, sweet potatoes, yamato Potatoes, etc .: Vegetables such as red bean paste, strawberries, green beans, green beans, okra, turnip, pumpkin, cabbage, cucumber, burdock, pigtails, sardines, watermelon, celery, broad bean, daikon, daiz, onion, Ladybug, red pepper, tomato, tomato, eggplant, garlic, carrot, green onion Sai, parsley, bell pepper, hechima, melon, lettuce, etc .: special crops such as sugar cane, turf, tobacco, tea, rapeseed, pop etc .: flower buds, such as hydrangea, carnation, gerbera, gazania, kiku, snapdragon, calendula, Salvia, perennial gypsophila, sweet pea, statice, saintpaulia, dahlia, timothy, delphenium, eustoma, verbena, sunflower, roses, begonia, petunia, poinsettia, lilac, apples, rosemary, etc .: Trees such as red bean, maple, It can be used to control diseases of Scarecrow, Wig, Firewood, Keyaki, Sakura, Shinoki, Azalea, Tsubaki, Nara, Hannoki and Yanagi.

  Diseases targeted include plant parasitic fungi, bacteria and actinomycetes, specifically rice blast (Pyricularia oryzae), sesame leaf blight (Cochliobolus miyabeanus), blight (Rizoctonia) solani), bacterial wilt disease (Burcholderia glumae), white leaf blight (Xanthomonas oryzae pv. oryzae), brown streak (Acidovorax avenae subsp. avenae), inner bud browning (Erinia ananas), leaf tree browning (Pseudomonas fuscovaginae) ), Bacterial disease (Burkholderia plantarii), etc .; wheat powdery mildew (Erysiphe graminis), red mold (Gibberella zeae), red rust (Puccinia striiformis, P. graminis, P. recondita, P. hordei), Snow rot (Typhula sp., Micronectriella nivalis), Bare smut (Ustilago tritici, U. nuda), Nagisa smut (Tilletia caries), Eye rot (Pseudocercosporella herpotrichoides), Cloud shape (Rhynchosporium secalis), Leaf blight (Septoria tritici), blight (Leptosphaeria nodorum), net blotch (Pyrenophora teres), hail Diseases (Helminthosporium zonatum Ikata), black spot disease (Pseudomonas syringae pv. Japonica), etc .; citrus black spot disease (Diaporthe citri), common scab (Elsinoe fawcetti), fruit rot (Penicillium digitatum, P. italicum), brown Rot disease (Phytophthora citrophthora, P. nicotianae), black spot disease (Phyllosticta citricarpa), scab disease (Xanthomonas campestris pv. Citri), etc .; leucotricha), spotted leaf disease (Alternaria mali), black spot disease (Venturia inaequalis), black spot disease (Mycospherella pomi), anthrax disease (Colletotrichum acutatum), ring rot disease (Botryosphaeria berengeriana), red star disease (Gymnosporangium yamadae) (Monilinia fructicola), etc .; without black spot disease (Venturia nashicola, V. pirina), black spot disease (Alternaria kikuchiana), red star disease (Gymnosporangium haraeanum), asbestos disease (Monilinia fructigena), etc .; fructicola), black spot disease (Cladosporium carpophilum), Phyopsis sp., Xanthomonas campestris pv. Pruni, etc .; Grape rot (Elsinoe ampelina), late rot (Colletotrichum acutatum), powdery mildew (Uncinula necator), rust ( Phakopsora ampelopsidis), black lot disease (Guignardia bidwellii), downy mildew (Plasmopara viticola), ash scab (Monilinia fructigena), black scab (Cladosporium viticolum), gray mold (Botrytis cinerea), root cancer bacterium (Agrobacterium vitis), etc .; Oyster anthracnose (Gloeosporium kaki), deciduous leaf disease (Cercospora kaki, Mycoshaerella nawae), etc .; Japanese purpura (Cercospora kikuchii), black scab (Elsinoe glycines), black spot (Diaporthe phaseolorum var) sojae), bacterial spot disease (Pseudomonas savastanoi pv. glycinea), leaf burning (Xanthomonas campestris pv. glycines), etc .; Disease (Xanthomonas campestris pv. Phase oli), etc .; black scab (Cercospora personata), brown spot (Cercospora arachidicola), etc .; powdery mildew (Erysiphe pisi), etc .; cucumber anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea, Oidiopsis taurica), vine blight (Didymella bryoniae), vine split (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), plague (Phytophthora sp.), Seedling blight (Pythium sp.), Spots Bacterial diseases (Pseudomonas syringae pv. Lachrymans), brown spot bacterial diseases (Xanthomonas campestris pv. Cucuribitae), etc .; Ring tomato disease (Alternaria solani), leaf mold (Cladosporium fulvum), plague (Phytophthora infestans), bacterial wilt (Ralstonia solanacearum), scab (Clavibacter michiganense subsp. Michiganense), stem gangrene (Pseudomonas corrugata), soft rot (Erwinia carotovora subsp. Carotovora), etc .; ), Bacterial wilt (Ralstonia colanacearum) Etc .; Black spot disease (Alternaria japonica), white spot disease (Cercosporella brassicae), black rot (Xanthomonas campestris pv. Campestris), soft rot (Erwinia carotovora subsp. Carotovora), rot disease (Pseudomonas syringae pv.) marginalis) etc .; Onion rust (Puccinia allii), etc .; potato summer plague (Alternaria solani), plague (Phytophthora infestans), leaf rot fungus (Rhizoctonia solani), soft rot (Erwinia carotovora subsp. carotovora), black leg disease (Erwinia carotovora subsp. Atroseptica), bacterial wilt (Ralstonia colanacearum), scab (Streptomyces scabies, Streptomyces acidiscabies), etc .; strawberry powdery mildew (Sphaerotheca humuli), bacterial wilt (Ralstonia colanacearum) Pseudomonas marginalis pv. Marginalis), Xanthomonas campestris, Xanthomonas fragariae, etc .; tea net blight (Exobasidium reticulatum), white scab (Elsinoe leucospila), red blight (Pseudomonas syringae pv. Theae), withering Diseases (Ralstonia solanacearum), scab (Xanthomonas campestris pv. Theicola), etc .; tobacco red star disease (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), anthrax (Colletotrichum tabacum), downy mildew (Peronospora tabacina), epidemic (Phytophthora nicotianae), cavernous disease (Erwinia carotovora subsp. Carotovora), etc .; brown spot disease (Cercospora beticola), seedling blight (Aphanomyces cochliodes), etc .; carrot black leaf blight (Alternaria dauci), kump disease ( Rhizobacter dauci), Streptomyces scabies, rose scab (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa), root cancer (Agrobacterium tumefaciens), etc .; chrysanthemi-indici), white rust (Puccinia horiana), root scab (Agrobacterium tumefaciens) etc .; various crops such as gray mold (Botrytis cinerea), sclerotia (Sclerotinia sclerotiorum), etc. Without limitation It is not limited to the fungi described here.

  The compound of the present invention can be used as an agricultural and horticultural fungicide in the form of a composition produced by using an agricultural chemical auxiliary widely used in the industry and in various dosage forms. The form of the agricultural and horticultural fungicide is not particularly limited. For example, emulsion, wettable powder, wettable granule, aqueous solvent, liquid, powder, flowable, dry flowable, fine granule, granule, tablet It is preferable to use a form such as an oil agent, a spray agent, or an aerosol. One or more of the above compounds can be blended as an active ingredient.

  The agrochemical adjuvant used for producing the agricultural and horticultural fungicide can be used for the purpose of, for example, improving the effect, stabilizing, and improving dispersibility of the agricultural and horticultural fungicide. For example, a carrier (diluent), a spreading agent, an emulsifier, a wetting agent, a dispersing agent, a disintegrating agent, or the like can be used. Examples of liquid carriers include water, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, butanol and glycol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, and methylnaphthalene. , Cyclohexane, animal and vegetable oils, fatty acids and the like. As the solid carrier, clay, kaolinite, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, sawdust, nitrocellulose, starch, gum arabic and the like can be used.

As the emulsifier and the dispersant, a normal surfactant can be used. For example, anionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, and lauryl betaine. Cationic surfactants, nonionic surfactants, amphoteric surfactants, and the like can be used. Moreover, spreading agents; wet spreading agents such as dialkylsulfosuccinate; fixing agents such as carboxymethyl cellulose and polyvinyl alcohol; disintegrating agents such as sodium lignin sulfonate and sodium lauryl sulfate can be used.
In the agricultural and horticultural fungicide of the present invention, the content of the compound of the present invention as an active ingredient is, for example, 0.01 to 99.5%, and preferably selected from the range of 0.5 to 90%. May be appropriately determined depending on various conditions such as, for example, about 0.5 to 20% by weight, preferably about 1 to 10% by weight for powders, and about 1 to 90% by weight for wettable powders, , 10 to 80% by weight, and about 1 to 90% by weight, preferably 10 to 40% by weight, of an emulsion.

  For example, in the case of an emulsion, the compound of the present invention, which is an active ingredient, can be mixed with a solvent and a surfactant to produce a stock emulsion, and this stock solution is diluted with water to a predetermined concentration when used. Can be applied. In the case of a wettable powder, the compound of the present invention as an active ingredient, a solid carrier, and a surfactant are mixed to produce a stock solution, and this stock solution can be applied after diluting with water to a predetermined concentration when used. . In the case of a powder, the compound of the present invention, which is an active ingredient, and a solid carrier can be mixed and applied as it is. In the case of a granule, the compound of the present invention as an active ingredient, a solid carrier, and a surfactant It can be produced by mixing and granulating an agent and applied as it is. However, the manufacturing method of each of the above-mentioned preparation forms is not limited to the above-mentioned ones, and can be appropriately selected by those skilled in the art according to the type of active ingredient, application purpose, and the like.

The agricultural and horticultural fungicides of the present invention include other fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers, soil improvers and the like in addition to the compounds of the present invention which are active ingredients. These active ingredients may be blended. The application method of the disinfectant of the present invention is not particularly limited, and can be applied by any method such as foliage spraying, soil treatment, smoke in the facility, and stalk. For example, in the case of foliage spraying, for example, a solution having a concentration range of 5 to 1000 ppm, preferably 10 to 500 ppm can be used at an application rate of about 50 to 700 liters per 10 ares. In the case of soil treatment, a solution having a concentration range of 5 to 1000 ppm can be used at an application rate of about 0.1 to 1 liter per 1 m ² .

  Hereinafter, the present invention is further described in detail using Examples, Formulation Examples, and Test Examples, but the scope of the present invention is not limited by these Examples, Formulation Examples, and Test Examples.

Example 1 Synthesis of 3-amino-1-methyl-1H-pyrazole-4-carboxylic acid-4- (2-chlorophenoxy) benzyl ester 3-amino-1-methyl-1H-pyrazole-4-carboxylic acid (0.141 g) in 1,2-dichloroethane was added 4- (2-chlorophenoxy) benzyl alcohol (0.235 g), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (0.230 g). ) And 4-dimethylaminopyridine (0.146 g) were added, and the mixture was heated and stirred at 80 ° C. for 2 hours. After cooling to room temperature, water was added and extracted with methylene chloride, and the aqueous layer was further extracted with methylene chloride. The organic layers were combined and dried over anhydrous sodium sulfate. The residue obtained by concentrating under reduced pressure was purified by silica gel column chromatography to obtain the compound of the present invention (No. 1) described in Table 1, 0.267 g, mp 98-100 ° C. In the same manner, the compound of the present invention was prepared in the same manner. Table 1 below lists the compounds of the present invention that were produced.

1) ¹H-NMR(CDCl₃)δppm：2.32(3H,s)、3.65(3H,s)、4.78(2H,br)、5.21(2H,s)、6.81(2H,m)、6.92(1H,d)、6.99(2H,d)、7.20(1H,t)、7.35(2H,d)、7.56(1H,s)

2) ¹H-NMR(CDCl₃)δppm：3.71(3H,s)、3.79(3H,s)、4.68(2H,br)、5.21(2H,s)、5.99-6.06(3H,m)、7.01(2H,d)、7.22(1H,t)、7.38(2H,d)、7.58(1H,s)

3) ¹H-NMR(CDCl₃)δppm：3.70(3H,s)、3.76(6H,s)、4.66(2H,br)、5.22(2H,s)、6.18(2H,s)、6.22(1H,s)、7.01(2H,d)、7.37(2H,d)、7.58(1H,s)

4) ¹H-NMR(CDCl₃)δppm：1.40(3H,t)、3.70(2H,s)、4.00(2H,q)、4.68(2H,br)、5.21(2H,s)、6.57-6.60(2H,m)、6.04(1H,d)、7.00(2H,d)、7.21(1H,t)、7.37(2H,d)、7.58(1H,s)

5) ¹H-NMR(CDCl₃)δppm：3.63(3H,s)、4.77(2H,br)、5.21(2H,s)、6.93(1H,d)、6.96-7.52(5H,m)、7.25-7.35(3H,m)、7.53(1H,s)

6) ¹H-NMR(CDCl₃)δppm：3.70(3H,s)、4.67(2H,br)、5.22(2H,s)、7.23-7.40(9H,m)、7.58(1H,s)

7) ¹H-NMR(CDCl₃)δppm：0.90(3H,t)、1.82(2H,m)、3.83(2H,t)、4.77(2H,br)、5.23(2H,s)、7.00(4H,m)、7.13(1H,t)、7.35(4H,m)、7.58(1H,s)

8) ¹H-NMR(CDCl₃)δppm：2.39(3H,s)、3.78(3H,s)、4.65(2H,br)、5.03(2H,s)、5.20(2H,s)、6.99(2H,d)、7.20-7.28(3H,m)、7.35(2H,d)、7.40(1H,d)、7.57(1H,s) Table 1

1) ¹ H-NMR (CDCl ₃ ) δ ppm: 2.32 (3H, s), 3.65 (3H, s), 4.78 (2H, br), 5.21 (2H, s), 6.81 (2H, m), 6.92 (1H , d), 6.99 (2H, d), 7.20 (1H, t), 7.35 (2H, d), 7.56 (1H, s)

2) ¹ H-NMR (CDCl ₃ ) δ ppm: 3.71 (3H, s), 3.79 (3H, s), 4.68 (2H, br), 5.21 (2H, s), 5.99-6.06 (3H, m), 7.01 (2H, d), 7.22 (1H, t), 7.38 (2H, d), 7.58 (1H, s)

3) ¹ H-NMR (CDCl ₃ ) δ ppm: 3.70 (3H, s), 3.76 (6H, s), 4.66 (2H, br), 5.22 (2H, s), 6.18 (2H, s), 6.22 (1H , s), 7.01 (2H, d), 7.37 (2H, d), 7.58 (1H, s)

4) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.40 (3H, t), 3.70 (2H, s), 4.00 (2H, q), 4.68 (2H, br), 5.21 (2H, s), 6.57-6.60 (2H, m), 6.04 (1H, d), 7.00 (2H, d), 7.21 (1H, t), 7.37 (2H, d), 7.58 (1H, s)

5) ¹ H-NMR (CDCl ₃ ) δ ppm: 3.63 (3H, s), 4.77 (2H, br), 5.21 (2H, s), 6.93 (1H, d), 6.96-7.52 (5H, m), 7.25 -7.35 (3H, m), 7.53 (1H, s)

6) ¹ H-NMR (CDCl ₃ ) δ ppm: 3.70 (3H, s), 4.67 (2H, br), 5.22 (2H, s), 7.23-7.40 (9H, m), 7.58 (1H, s)

7) ¹ H-NMR (CDCl ₃ ) δ ppm: 0.90 (3H, t), 1.82 (2H, m), 3.83 (2H, t), 4.77 (2H, br), 5.23 (2H, s), 7.00 (4H , m), 7.13 (1H, t), 7.35 (4H, m), 7.58 (1H, s)

8) ¹ H-NMR (CDCl ₃ ) δ ppm: 2.39 (3H, s), 3.78 (3H, s), 4.65 (2H, br), 5.03 (2H, s), 5.20 (2H, s), 6.99 (2H , d), 7.20-7.28 (3H, m), 7.35 (2H, d), 7.40 (1H, d), 7.57 (1H, s)

  Next, formulation examples are shown. In addition, a part represents a mass part.

Formulation Example 1 Emulsion Compound of the present invention (10 parts), xylene (60 parts), N-methyl-2-pyrrolidone (20 parts) and Solpol 3005X (mixture of nonionic surfactant and anionic surfactant, Toho Chemical Industry Co., Ltd. (trade name) (10 parts) was uniformly mixed and dissolved to obtain an emulsion.

Formulation Example 2 Wetting Agent-1
Compound of the present invention (20 parts), Nipsil NS-K (white carbon, Tosoh Silica Co., Ltd., trade name) (20 parts), Kaolin clay (Kaolinite, Takehara Chemical Co., Ltd., trade name) (50 parts) Sun extract P-252 (sodium lignin sulfonate, Nippon Paper Chemical Co., Ltd., trade name) (5 parts) and Lunox P-65L (alkyl allyl sulfonate, Toho Chemical Co., Ltd., trade name) (5 parts) Was uniformly mixed and ground with an air mill to obtain a wettable powder.

Formulation Example 3 Wetting Agent-2

  Compound of the present invention (20 parts), nip seal NS-K (20 parts), kaolin clay (50 parts), LUNOX 1000C (naphthalene sulfonate condensate, Toho Chemical Co., Ltd., trade name) (5 parts) and Solpol 5276 (nonionic surfactant, Toho Chemical Co., Ltd., trade name) (5 parts) was uniformly mixed and pulverized with an air mill to obtain a wettable powder.

Formulation Example 4 Flowable Agent-1
Premixed propylene glycol (5 parts), Solpol 7933 (anionic surfactant, Toho Chemical Co., Ltd., trade name) (5 parts), compound of the present invention (20 parts) in water (50 parts) Was dispersed into a slurry mixture, and then this slurry mixture was wet pulverized with Dynomill (Shinmaru Enterprises Co., Ltd.), and then xanthan gum (0.2 parts) was mixed and dispersed in water (19.8 parts) in advance. Was added to obtain a flowable agent.

Formulation Example 5 Flowable Agent-2
Compound of the present invention (20 parts), Newkalgen FS-26 (mixture of dioctyl sulfosuccinate and polyoxyethylene tristyryl phenyl ether, Takemoto Yushi Co., Ltd., trade name) (5 parts), propylene glycol (8 parts), Water (50 parts) was mixed in advance, and this slurry-like mixture was wet-pulverized with a Dynomill (Shinmaru Enterprises). Next, xanthan gum (0.2 parts) was thoroughly mixed and dispersed in water (16.8 parts) to prepare a gel-like material, which was thoroughly mixed with the pulverized slurry to obtain a flowable agent.

  Next, it is shown by test examples that the compound of the present invention is useful as an active ingredient of a fungicide. In addition, the compound of this invention is shown by the compound number of Table 1.

Test Example 1 Test for Cucumber Gray Mold Disease Cucumber (variety: Sagamihanjiro) 12 days after sowing was prepared for testing. The cotyledon part was cut off leaving about 2 cm of the cucumber leaf shaft. Separately, a 32cm x 24cm x 4.5cm (vertical x horizontal x height) plastic case was laid with a paper towel sufficiently dampened with water, and a net with feet was placed on the paper towel. . On the net, the cut-out cotyledon parts were arranged so that the leaves were horizontal. 50 μl of a spore suspension (1 × 10 ⁶ / ml) of cucumber gray mold fungus (Botrytis cinerea) was added dropwise to the center of the cotyledon. Then, a 6 mm diameter paper disk was put on the cotyledon. Separately, the emulsion prepared according to Formulation Example 1 was further diluted with a 0.02% Tween20 demineralized water solution to prepare a 25 ppm diluted solution. 50 μl of this diluted solution was dropped from the top of the paper disk. After covering the plastic case for 72 hours at 20 ° C., the lesion diameter was measured, and the control value of cucumber gray mold was determined by the following formula. The results are shown in Table 2.
Control value (%) = [1− (treatment area lesion diameter / untreated area lesion diameter)] × 100

Table 2
Cucumber gray mold

Claims (2)

The following formula [I]

(In the formula, R ¹ represents a C _{1 to} C ₄ alkyl group, R ² represents a hydrogen atom or a C _{1 to} C ₄ alkyl group, R ³ and R ⁴ are each independently a hydrogen atom, C ₁ alkyl group -C _4, alkoxy group of C ₁ -C _4, a trifluoromethyl group, a trifluoromethoxy group, a cyano group or a halogen atom, Y table in an oxygen atom, a sulfur atom or OCH _2.) 3-amino-1H-pyrazole-4-carboxylic acid benzyl ester derivative.   A bactericide comprising the 3-amino-1H-pyrazole-4-carboxylic acid benzyl ester derivative according to claim 1 as an active ingredient.