JP6286693B2 - 6-Substituted nicotinic acid ester derivatives and fungicides containing the same as active ingredients - Google Patents

Description

  The present invention relates to a 6-substituted nicotinic acid ester derivative and a fungicide containing the same 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, pesticides that have been widely used in the past do not necessarily satisfy the requirements such as the effect, spectrum, residual effect, etc., and further, the number of applications and the reduction of the applied dose. 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, rice, etc. Various pathogens that have developed resistance to mold-type disinfectants 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 show sufficient control effects at low doses and have little negative impact on the environment against various pathogens that have developed resistance to conventional agricultural and horticultural fungicides is always desired. It is rare.

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

(特許文献１) Patent Document 1 discloses a carboxamide derivative represented by the following structural formula having bactericidal activity. However, the compound described in Patent Document 1 has a carboxamide bond at the 3-position of the pyridine ring, and does not have an ester bond.

(Patent Document 1)

(特許文献２) Patent Document 2 discloses a carboxamide derivative represented by the following structural formula having bactericidal activity. However, the compound described in Patent Document 2 has a carboxamide bond at the 3-position of the pyridine ring, and does not have an ester bond.

(Patent Document 2)

(特許文献３) Patent Document 3 discloses a carboxamide derivative represented by the following structural formula having bactericidal activity. However, the compound described in Patent Document 3 has a carboxamide bond at the 3-position of the pyridine ring, and does not have an ester bond.

(Patent Document 3)

(特許文献４、医薬活性) Patent Document 4 discloses the following ester derivative having an amino group at the 2-position of the pyridine ring as a reaction intermediate (page 265, Example 35, Compound No. 757). This compound does not have a substituent at the 6-position of the pyridine ring, and Patent Document 4 does not disclose a 6-substituted nicotinic acid ester derivative. In addition, this compound is disclosed only as an intermediate for producing a pharmaceutically active compound of Patent Document 4, and the 4-methoxybenzyl group is merely used as a protective group (leaving group) for carboxylic acid. Therefore, this compound is not included in the claims of Patent Document 4, and Patent Document 4 does not describe any bactericidal activity.

(Patent Document 4, pharmaceutical activity)

(特許文献５、殺虫活性) Patent Documents 5 to 9 disclose the following ester derivatives as specifically synthesized compounds. Representative examples thereof include the following compounds. Although these compounds are disclosed to have insecticidal or herbicidal activity, they have never been reported to have bactericidal activity.
Patent Document 5 discloses the following compound (compound No. 1.59, page 43). However, Patent Document 5 relates to the use as an insecticide, and the compound has a chlorine atom at the para position of the ester group of the pyridine ring.

(Patent Document 5, insecticidal activity)

(特許文献６、殺虫活性) Patent Document 6 discloses the following compounds (compounds 270 and 271 on page 33). However, Patent Document 6 relates to the use as an insecticide, and the compound does not have a substituent at the para position of the ester group of the pyridine ring.

(Patent Document 6, insecticidal activity)

(特許文献７、除草活性) Patent Document 7 discloses the following compound (Compound No. 1.3717 on page 78). However, Patent Document 7 relates to the use as a herbicide, and the compound has a substituent at the meta position of the ester group of the pyridine ring.

(Patent Document 7, herbicidal activity)

(特許文献８、除草活性) Patent Document 8 discloses the following compound (Compound No. 229, page 42). However, Patent Document 8 relates to the use as a herbicide, and the compound does not have a substituent at the para position of the ester group of the pyridine ring.

(Patent Document 8, herbicidal activity)

(特許文献９、除草活性) Patent Document 9 discloses the following compound having an amino group at the 2-position of the pyridine ring. However, Patent Document 9 relates to a herbicide, and in the compound, the 6-position of the pyridine ring is limited to a fluorine atom.

(Patent Document 9, herbicidal activity)

(特許文献１０、殺菌活性) Patent Document 10 or Patent Document 11 discloses the following compounds as specific compounds having bactericidal activity.
Specifically, Patent Document 10 discloses the following compound (Compound No. 48 on page 50). However, this compound is a compound having a chlorine atom at the para position of the ester group of the pyridine ring.

(Patent Document 10, bactericidal activity)

(特許文献１１、殺菌活性) Patent Document 11 discloses the following compound (Compound No. 22 on page 40). However, this compound is a compound having a benzyloxy group at the para position of the ester group of the pyridine ring.

(Patent Document 11, bactericidal activity)

(特許文献１２、医薬活性) Patent Documents 12 to 17 specifically disclose the following compounds having pharmaceutical activity. Specifically, Patent Document 12 discloses the following compound (Beispiel 186, page 42). However, the compound does not have a substituent at the para position of the substituted benzyl ester group of the pyridine ring, and the compound of Patent Document 12 is only disclosed as a pharmaceutically active substance.

(Patent document 12, pharmaceutical activity)

(特許文献１３、医薬活性) Patent Document 13 specifically discloses the following compounds (compounds on the right side of the reaction formula of Step 3 on page 32). However, this compound does not have a substituent at the para position of the ester group of the pyridine ring, and this compound is only disclosed as a reaction intermediate.

(Patent Document 13, Pharmaceutical activity)

(特許文献１４、医薬活性) Patent Document 14 discloses the following compound as pro-3-nicotinoyl (page 17). However, the compound does not have a substituent at the para position of the ester group of the pyridine ring, and the compound of Patent Document 14 is only disclosed as a pharmaceutically active substance.

(Patent Document 14, pharmaceutical activity)

(特許文献１５、医薬活性) Patent Document 15 discloses the following compound (E step 1 on page 51). However, this compound has a spiropiperidine group at the para position of the ester group of the pyridine ring, and Patent Document 15 only discloses this compound as an intermediate, and the compound of Patent Document 15 is disclosed as a pharmaceutically active substance. I'm just doing it.

(Patent Document 15, pharmaceutical activity)

(特許文献１６、医薬活性) Patent Document 16 discloses the following compound (page 56 (I-17b)). However, the compound has a carboxyamino group at the para position of the ester group of the pyridine ring, and the compound of Patent Document 16 is only disclosed as a pharmaceutically active substance.

(Patent Document 16, pharmaceutical activity)

(特許文献１７、医薬活性) Patent Document 17 discloses the following compound (page 93, synthesis scheme). However, the compound has a carboxyamino group at the para position of the ester group of the pyridine ring, and Patent Document 17 discloses this compound only as an intermediate, and the compound of Patent Document 17 is a pharmaceutically active substance. It is only disclosed.

(Patent Document 17, pharmaceutical activity)

  Non-Patent Document 1 relates to a pharmaceutically active compound used as a therapeutic agent for Chagas disease. Non-Patent Document 1 discloses a pharmaceutically active compound having a phenoxybenzyloxy skeleton. However, there is no disclosure of a compound incorporating nicotinic acid in this skeleton.

JP 2010-083861 A JP 2010-285351 A JP 2010-285352 A WO2008-082490 pamphlet WO2004-056735 pamphlet WO2002-002515 pamphlet WO2000-015615 pamphlet Japanese Patent Laid-Open No. 2004-051628 US4383851 pamphlet WO1994-029267 pamphlet WO1998-033772 pamphlet EP1995-650961 pamphlet WO1998-057946 pamphlet WO2003-101980 pamphlet WO2007-133561 pamphlet WO2010-029461 pamphlet WO2011-083304 pamphlet

Journal of Medicinal Chemistry, 43, 1826 (2000)

  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. Accordingly, an object of the present invention is to provide a highly safe substance in which problems such as residual toxicity and environmental pollution are reduced.

[Ｉ]
(式中、Ｒ¹は、Ｃ₁〜Ｃ₄のアルキル基、Ｃ₁〜Ｃ₄のアルコキシ基、Ｃ₁〜Ｃ₄のアルコキシメチル基またはアミノ基を示し、Ｒ²は、水素原子、Ｃ₁〜Ｃ₄のアルキル基またはアミノ基を示し、Ｒ³は、Ｃ₁〜Ｃ₄のアルキル基、Ｃ₁〜Ｃ₄のアルコキシ基、ベンジルオキシ基または

を示し、Ｒ⁴は、水素原子、ハロゲン原子、Ｃ₁〜Ｃ₄のアルキル基またはＣ₁〜Ｃ₄のアルコキシ基を示し、ただし、Ｒ¹がＣ₁〜Ｃ₄のアルキル基を示す場合は、Ｒ²は水素原子またはＣ₁〜Ｃ₄のアルキル基を示す。) で表される6-置換ニコチン酸エステル誘導体 (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ものである。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a 6-substituted nicotinic acid ester derivative defined by the following formula is a compound having characteristics capable of meeting the above demands. The invention has been completed.
That is, the present invention provides the following formula [I],

[I]
(In the formula, R ¹ represents a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ alkoxy group, a C _{1 to} C ₄ alkoxymethyl group or an amino group, and R ² represents a hydrogen atom, C ₁ an alkyl group or an amino group -C _4, R ³ is an alkyl group of C ₁ -C _4, alkoxy group of C ₁ -C _4, benzyloxy group or

R ⁴ represents a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group, provided that R ¹ represents a C ₁ -C ₄ alkyl group , R ² represents a hydrogen atom or a C ₁ -C ₄ alkyl group. And 6-substituted nicotinic acid ester derivatives (hereinafter also referred to as “compounds of the present invention”) and fungicides containing the same as active ingredients.

  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, tert-butyl group and the like. Examples of the halogen atom represented by R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the C ₁ -C ₄ alkoxy group represented by R ¹ , R ³ and R ⁴ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a sec-butoxy group. Group, tert-butoxy group and the like. The C ₁ -C ₄ alkoxymethyl group represented by R ¹ means a methyl group substituted with the aforementioned C ₁ -C ₄ alkoxy group.
The compound of the present invention is a novel compound not described in any literature, and can be produced, for example, from a known starting compound according to the following reaction formula.

[II] [III] [Ｉ] Reaction formula

[II] [III] [I]

(Wherein R ¹ , R ² and R ³ are as defined in the above formula [I].)
The nicotinic acid derivative represented by the general formula [II] is reacted with the alcohol derivative represented by the general formula [III] in the presence of a condensing agent and a base in an inert solvent, thereby being represented by the general formula [I]. The nicotinic acid ester derivative of the present invention 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.
The reaction temperature in this reaction is usually in the range of −20 ° C. to 120 ° C., preferably 0 ° C. to 40 ° 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 used in a range of 1 to 5 times mol, preferably 1 to 1.5 times mol for the nicotinic acid derivative represented by the general formula [II].

  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. The amount used is usually 1 with respect to the nicotinic acid derivative represented by the general formula [II]. It is used in a range of ˜3 times mol, preferably 1 to 1.5 times mol.

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 used in a range of 1 to 10 times mol, preferably 1 to 2 times mol for the nicotinic acid derivative represented by the general formula [II].
This reaction may or may not use a solvent, but when a solvent is used, various solvents can be used without any particular limitation as long as they do not significantly inhibit this reaction. Examples of such solvents include linear or cyclic ethers such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as benzene, toluene, and xylene; Halogenated hydrocarbons such as chloroform and carbon tetrachloride; nitriles such as acetonitrile; esters such as methyl acetate, ethyl acetate and butyl acetate; N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, Preferred examples include polar solvents such as 1,3-dimethyl-2-imidazolidinone, These inert solvents may be used singly or as mixtures of two or more kinds.
After the reaction, the target compound can be easily isolated from the reaction system containing it by a conventional method. For example, the target compound can be prepared by recrystallization, purification by column chromatography, or the like.
The nicotinic acid derivative represented by the general formula [II] used in this reaction can be immediately synthesized from a known compound according to, for example, the method described in JP 2010-083861 A (Patent Document 1). it can.
The alcohol derivative represented by the general formula [III] used in this reaction is publicly known in accordance with, for example, the method described in Journal of Medicinal Chemistry, 43, 1826 (2000) (Non-patent Document 1). It can be synthesized immediately from the compound.

  The compounds of the present invention can be obtained from fruit trees such as avocado, apricot, fig, yokokan, ume, Unshu mandarin, oyster, pumpkin, kiwifruit, plum, western none, mandarin orange, dekopon, none, natsumikan, nectarine, hakusaku. , Papaya, loquat, grapes, grapes, mango, peach, yuzu, apples, lemon, etc .: cereals, such as barley, wheat, paddy rice, corn, pigeons, rye, upland rice, etc .: potatoes, eg, potatoes, potatoes , Satoimo, Yamano potato, etc .: Vegetables, such as red bean, strawberry, Japanese bean, peas, okra, turnip, pumpkin, cabbage, cucumber, burdock, pigtail, sushi, watermelon, celery, broad bean, daikon, Japanese radish, onion, sugar beet, red pepper, carrot, tomato, eggplant, Japanese garlic, carrot Green onions, hakusai, parsley, green pepper, hechima, melon, lettuce, etc .: Special crops such as sugar cane, turf, tobacco, tea, rapeseed, pop, etc .: Flowers, 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, ginger, rosemary, etc .: trees Can be used to control diseases of reptiles, maples, swords, wigs, firewood, zelkova, cherry, cypresses, azaleas, camellia, noodles, hannoki, and eel.

  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 scab (Rhynchosporium secalis), Leaf blight (Septoria tritici), dry blight (Leptosphaeria nodorum), net blotch (Pyrenophora teres),

Scabies (Helminthosporium zonatum Ikata), black spot (Pseudomonas syringae pv. Japonica), etc .; citrus black spot (Diaporthe citri), scab (Elsinoe fawcetti), fruit rot (Penicillium digitatum, P. italicum) , Brown rot (Phytophthora citrophthora, P. nicotianae), black scab (Phyllostictina citricarpa), scab (Xanthomonas campestris pv. Citri), etc .; apple monilinia mali, rot (Valsa mali), mildew (Podosphaera leucotricha), spotted leaf disease (Alternaria mali), black spot disease (Venturia inaequalis), black spot disease (Mycospherella pomi), anthracnose (Colletotrichum acutatum), ring rot (Botryosphaeria berengeriana), red star disease (Gymnosporangium yamae) Black streak (Venturia nashicola, V. pirina), black spot (Alternaria kikuchiana), red streak (Gymnosporangium haraeanum), black streak (Monilinia fructigena), etc .; Disease (Monilinia fructicola), black spot disease (Cladosporium c) arpophilum),

Phomopsis spoilage disease (Phomopsis sp.), Perforated bacterial disease (Xanthomonas campestris pv. Pruni), etc .; Grape black rot (Elinoe ampelina), late rot (Colletotrichum acutatum), powdery mildew (Uncinula necator), rust disease ( 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 .;

Purple purpura (Cercospora kikuchii), black scab (Elsinoe glycines), black spot (Diaporthe phaseolorum var. Sojae), spot bacterial disease (Pseudomonas savastanoi pv. Glycinea), leaf blight (Xanthomonas campestris pv. Glycines), etc. ; Anthracnose (Colletotrichum lindemthianum), pod blight (Pseudomonas savastanoi pv. Phaseolicola), leaf burn (Xanthomonas campestris pv. Phaseoli), etc .; black scab (Cercospora personata), brown spot ( Cercospora arachidicola), etc .; powdery mildew (Erysiphe pisi), etc .; Colletotrichum lagenarium, powdery mildew (Sphaerotheca fuliginea, Oidiopsis taurica), vine blight (Didymella bryoniae), vine split Disease (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), plague (Phytophthora sp.), Seedling blight (Pythium sp.), Spotted bacterial disease (Pseudomonas syringae pv. Lachrymans), brown spot bacterial disease (Xanthomonas campestris p cucuribitae), etc .; Ring tomato disease (Alterna) ria solani), leaf mold (Cladosporium fulvum), plague (Phytophthora infestans), bacterial wilt (Ralstonia colanacearum),

Scab (Clavibacter michiganense subsp. Michiganense), stem rot (Pseudomonas corrugata), soft rot (Erwinia carotovora subsp. Carotovora), etc .; eggplant brown spot (Phomopsis vexans), powdery mildew (Erysiphe cichoracearum), blue Blight (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 Diseases (Pseudomonas syringae pv. Marginalis) etc .; Green rust (Puccinia allii) etc .; 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 (Ra lstonia colanacearum) Bacterial blight (Pseudomonas marginalis pv. marginalis), keratobacterial disease (Xanthomonas campestris, Xanthomonas fragariae), etc .; syringae pv. theae), blight (Ralstonia solanacearum), scab (Xanthomonas campestris pv. theicola), etc .;

Tobacco red rot (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina), plague (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), mildew (Rhizobacter dauci), streptomyces scabies (Streptomyces scabies), rose Black spot disease (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa), Agrobacterium tumefaciens, etc .; Brown spot disease (Septoria chrysanthemi-indici), white rust (Puccinia horiana), root Agrobacterium tumefaciens, etc .; various crops such as gray mold disease (Botrytis cinerea), mycorrhizal disease (Sclerotinia sclerotiorum), etc., but are not limited to the fungi listed here .

  The compounds of the present invention can be used in various dosage forms. In order to obtain these dosage forms, various agricultural chemical adjuvants conventionally used in the technical field of agricultural and horticultural fungicides can be appropriately used. Examples of dosage forms of agricultural and horticultural fungicides include emulsions, wettable powders, granular wettable powders, aqueous solvents, liquids, powders, flowables, dry flowables, fine granules, granules, tablets, oils, Sprays, fumes, etc. Of course, the compound of this invention can also be mix | blended as an active ingredient by combining 1 type (s) or 2 or more types.

  Such agrochemical adjuvants can be used for the purpose of, for example, improving the effects, stabilizing, and improving dispersibility of agricultural and horticultural fungicides. Examples of the agricultural chemical adjuvant include a carrier (diluent), a spreading agent, an emulsifier, a wetting agent, a dispersing agent, a disintegrating agent, and the like. 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, methyl Mention may be made of naphthalene, cyclohexane, animal and vegetable oils, fatty acids and the like. As the solid carrier, clay, kaolin, 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, lauryl betaine, etc. Cationic surfactants, nonionic surfactants, amphoteric surfactants, and the like can be used. Further, spreading agents; wetting agents such as dialkyl sulfosuccinate; fixing agents such as carboxymethyl cellulose and polyvinyl alcohol; disintegrating agents such as sodium lignin sulfonate and sodium lauryl sulfate can be used.
The content of the compound of the present invention as an active ingredient in an agricultural and horticultural fungicide is, for example, 0.01 to 99.5% by mass, preferably selected from the range of 0.5 to 90% by mass, such as formulation form, application method, etc. It may be appropriately determined according to various conditions. For example, about 0.5 to 20% by weight, preferably 1 to 10% by weight for powders, about 1 to 90% by weight for wettable powders, preferably about 10 to 10% by weight. In the case of an emulsion, it can be produced so as to contain an active ingredient of about 1 to 90% by mass, preferably 10 to 40% by mass.

  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, which can be further diluted with water to a predetermined concentration before use. . In the case of powders, 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 granules, 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.

For agricultural and horticultural fungicides, in addition to the compounds of the present invention which are active ingredients, other active ingredients such as other fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers, soil conditioners, etc. May be blended. The application method of the disinfectant comprising the compound of the present invention is not particularly limited, and can be applied by any method such as foliage spraying, soil treatment, in-house smoke, or 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 2-methylphenoxybenzyl 6-aminonicotinate
To a solution of 6-aminonicotinic acid (0.14 g) in methylene chloride (10 ml), 2-methylphenoxybenzyl alcohol (0.21 g), 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (0.23 g) and 4-Dimethylaminopyridine (0.15 g) was added, and the mixture was heated to reflux for 3 hours. After cooling to room temperature, the mixture was 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. 3) described in Table 1, 0.26 g, mp78-80 ° C. In addition, the compound of the present invention was synthesized in the same manner. Table 1 below lists the compounds of the present invention that were produced.

[Ｉ]

上記表１において、「mp」欄において付された括弧の番号は、以下の括弧の番号と対応し、それぞれ以下のＮＭＲデータで示される化合物を意味する。
1) ¹H-NMR(CDCl₃)δppm：2.62(3H,s)、5.35(2H,s)、6.99-7.05(4H,m)、7.12(1H,t)、7.25(1H,t)、7.32-7.38(2H,m)、7.42(2H,d)、8.20(1H,d)、9.13(1H,s)。
2) ¹H-NMR(CDCl₃)δppm：3.88(3H,s)、5.25(2H,s)、6.02(1H,d)、6.99-7.19(4H,m)、7.11(1H,t)、7.32-7.42(4H,m)、8.03(1H,d)。
3) ¹H-NMR(CDCl₃)δppm：1.01(6H,d)、2.02-2.15(1H,m)、2.61(3H,s)、3.74(2H,d)、5.31(2H,s)、6.91(2H,d)、7.22(1H,d)、7.38(2H,d)、8.18(1H,d)、9.11(1H,s)。
4) ¹H-NMR(CDCl₃)δppm：2.12(1H,m)、2.58(3H,s)、2.81(3H,d)、3.75(2H,d)、5.31(2H,s)、6.91(2H,d)、7.00(1H,d)、7.38 (2H,d)、8.11(1H,d)。
5) ¹H-NMR(CDCl₃)δppm：4.91(2H,s)、5.08(2H,s)、5.16(2H,s)、6.45(1H,d)、6.97(2H,m)、7.28-7.46(7H,m)、8.02(1H,d)、8.74(1H,s)。 Table 1

[I]

In Table 1 above, the numbers in parentheses given in the “mp” column correspond to the numbers in the following parentheses and mean the compounds indicated by the following NMR data, respectively.
1) ¹ H-NMR (CDCl ₃ ) δ ppm: 2.62 (3H, s), 5.35 (2H, s), 6.99-7.05 (4H, m), 7.12 (1H, t), 7.25 (1H, t), 7.32 -7.38 (2H, m), 7.42 (2H, d), 8.20 (1H, d), 9.13 (1H, s).
2) ¹ H-NMR (CDCl ₃ ) δ ppm: 3.88 (3H, s), 5.25 (2H, s), 6.02 (1H, d), 6.99-7.19 (4H, m), 7.11 (1H, t), 7.32 -7.42 (4H, m), 8.03 (1H, d).
3) ¹ H-NMR (CDCl ₃ ) δ ppm: 1.01 (6H, d), 2.02-2.15 (1H, m), 2.61 (3H, s), 3.74 (2H, d), 5.31 (2H, s), 6.91 (2H, d), 7.22 (1H, d), 7.38 (2H, d), 8.18 (1H, d), 9.11 (1H, s).
4) ¹ H-NMR (CDCl ₃ ) δ ppm: 2.12 (1H, m), 2.58 (3H, s), 2.81 (3H, d), 3.75 (2H, d), 5.31 (2H, s), 6.91 (2H , d), 7.00 (1H, d), 7.38 (2H, d), 8.11 (1H, d).
5) ¹ H-NMR (CDCl ₃ ) δ ppm: 4.91 (2H, s), 5.08 (2H, s), 5.16 (2H, s), 6.45 (1H, d), 6.97 (2H, m), 7.28-7.46 (7H, m), 8.02 (1H, d), 8.74 (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 Chemicals 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.

化合物 A （特許文献１に記載の化合物） Next, it is shown by test examples that the compound of the present invention is useful as an active ingredient of a fungicide. The compounds of the present invention are indicated by the compound numbers shown in Table 1, and the compounds used for comparison are indicated by the following compound symbols.

Compound A (compound described in Patent Document 1)

Test Example 1: Cucumber gray mold disease A cucumber 12 days after seeding (variety: Sagamihanjiro) was prepared for the test. 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 diluted solution having a predetermined concentration. 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

  As shown in Table 2 above, the compound of the present invention has higher bactericidal activity than Compound A.

Claims (4)

The following formula [I]

[I]
(Wherein R ¹ represents a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ alkoxy group, a C _{1 to} C ₄ alkoxymethyl group or an amino group, and R ² represents a hydrogen atom or C ₁ an alkyl group -C _4, R ³ is an alkyl group of C ₁ -C _4, alkoxy group of C ₁ -C _4, benzyloxy group or

The indicated, R ⁴ is a hydrogen atom, shows the halogen atom, alkyl group or C ₁ -C ₄ alkoxy group C ₁ -C _4. A 6-substituted nicotinic acid ester derivative represented by :
However,
A compound in which R ¹ is an amino group, R ² is a hydrogen atom, and R ³ is a methoxy group;
A compound wherein R ¹ is a methoxy group, R ² is a hydrogen atom, and R ³ is a methyl group; and
Excluding compounds wherein R ¹ is a methoxy group, R ² is a hydrogen atom, and R ³ is an isopropyl group,
The 6-substituted nicotinic acid ester derivative . The following formula [I]

(In the formula, R ¹ represents a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ alkoxy group, a C _{1 to} C ₄ alkoxymethyl group or an amino group, and R ² represents a hydrogen atom, C ₁ an alkyl group or an amino group -C _4, R ³ represents an alkyl group or a C ₁ -C ₄ alkoxy group C ₁ -C _4, provided that, R ¹ is an alkyl group of C ₁ -C ₄ R ² represents a hydrogen atom or a C ₁ -C ₄ alkyl group, in which case a 6-substituted nicotinic acid ester derivative represented by:
However,
A compound in which R ¹ is an amino group, R ² is a hydrogen atom, and R ³ is a methoxy group;
A compound wherein R ¹ is a methoxy group, R ² is a hydrogen atom, and R ³ is a methyl group; and
Excluding compounds wherein R ¹ is a methoxy group, R ² is a hydrogen atom, and R ³ is an isopropyl group,
The 6-substituted nicotinic acid ester derivative. The following formula [I]

(Wherein R ¹ represents a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ alkoxy group, a C _{1 to} C ₄ alkoxymethyl group or an amino group, and R ² represents a hydrogen atom or C ₁ an alkyl group -C _4, R ³ is an alkyl group of C ₁ -C _4, alkoxy group of C ₁ -C _4, benzyloxy group or

R ⁴ represents a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. And a 6-substituted nicotinic acid ester derivative represented by the formula: The following formula [I]

(In the formula, R ¹ represents a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ alkoxy group, a C _{1 to} C ₄ alkoxymethyl group or an amino group, and R ² represents a hydrogen atom, C ₁ an alkyl group or an amino group -C _4, R ³ represents an alkyl group or a C ₁ -C ₄ alkoxy group C ₁ -C _4, provided that, R ¹ is an alkyl group of C ₁ -C ₄ In the case of showing, R ² represents a hydrogen atom or a C ₁ -C ₄ alkyl group.) A fungicide characterized by containing a 6-substituted nicotinic acid ester derivative represented by: