KR101018895B1 - Fungicides in agriculture - Google Patents

Abstract

The present invention relates to an agricultural fungicide, and more particularly, to an agricultural ingredient containing substituted 1,3-thiazole derivatives having excellent effects of controlling or preventing disease by inhibiting the death or growth of phytopathogens. It is about a fungicide.

1,3-thiazole derivatives, bactericidal activity, agricultural fungicides, pseudo fungi, late blight, downy mildew

Description

Fungicides in agriculture

The present invention relates to an agricultural fungicide, and more particularly, to an agricultural ingredient containing substituted 1,3-thiazole derivatives having excellent effects of controlling or preventing disease by inhibiting the death or growth of phytopathogens. It is about a fungicide.

In spite of the excellent disinfectant effect, currently used sterilizers have become a new problem due to the increase in the resistance of target pathogens and the increase in the amount of treatment. Therefore, there is a need to develop an environmentally friendly fungicide with a wider sterilization spectrum while showing a strong sterilization effect at a low dose. According to these demands, the development of a new type of disinfectant with differentiation while compensating for the disadvantages of the existing disinfectants is urgently required.

In this regard, the present inventors have tried to develop a new sterilizing compound having excellent sterilizing effect and broad sterilizing spectrum even in a small amount compared to agricultural sterilizing agents which have been used conventionally.

In the meantime, the experiments showed that the substituted 1,3-thiazole derivatives, which have been reported by the applicants as effective agents for the treatment and prevention of TNF-α-related inflammatory diseases, exhibit potent bactericidal activity, particularly against plant fungi. By confirming through, to complete the present invention.

That is, some of the substituted 1,3-thiazole derivatives proposed by the present invention as bactericidal active compounds have anti-inflammatory or immunosuppressive activity, and thus, as a medicine for treating arthritis, enteritis, and the like, 848,205. However, no literature has been published on the use of these compounds as agricultural fungicides.

An object of the present invention is to provide an agricultural fungicide having an excellent effect of controlling or reducing disease by killing or inhibiting the growth of plant pathogens causing plant diseases such as downy mildew, late blight, wart disease, rot, root gall disease, and mozalococcal disease. There is this.

It is an object of the present invention to provide a novel use of substituted 1,3-thiazole derivatives known as agents for the treatment and prevention of TNF-α related inflammatory diseases as agricultural fungicides.

The present invention provides agricultural fungicides prepared as a mixture by further comprising one or two or more components selected from other fungicides, insecticides, herbicides, plant growth regulators and fertilizers in addition to the substituted 1,3-thiazole derivatives as active ingredients. There is a purpose.

An object of the present invention is to provide an agricultural fungicide formulated with a hydrating agent, an emulsion, a granule, a powder, a liquid hydrating agent, a granulating hydrating agent, a surface floating granule, a seed treatment hydrating agent, a fumigant, or a coating agent.

In addition, the present invention provides an excellent bactericidal activity against plant pathogens as agricultural fungicides, and provides a 1,3-thiazole derivative compound substituted as a novel compound having no chemical structure in the literature, including Korean Patent Registration No. 848,205 and the like. Its purpose is to.

The present invention provides an agricultural fungicide containing a single compound or a mixture of two or more selected from substituted 1,3-thiazole derivatives represented by the following Formula 1 and agrochemically acceptable salts thereof as an active ingredient, Could solve.

In Chemical Formula 1,

,

,

,

,

, 또는

이며, 여기서 X는 CH, C-OH, 또는 N이고, Y는 CH₂, CH-C₁~C₄의 알킬, NH, N-C₁~C₄의 알킬, N-C₁~C₄의 아미노-C₁~C₄의 알킬, N-CO-C₁~C₄의 알킬, N-CO-C₃~C₈의 시클로알킬, N-CO-C₅~C₈의 아릴, N-CO-C₁~C₄의 아미노-C₁~C₄의 알킬, 또는 N-CO-C₁~C₄의 알콕시이며; R³는 할로겐 원자, -NH-R⁴, -NH-CO-R⁵, -N-(CO-R⁵)₂, -N(C₁~C₄의 알킬)₂,

, -S(O)_n-R⁵, 또는 -O-R⁵이며; R⁴는 H, C₁~C₈의 알킬, C₃~C₈의 시클로알킬, C₃~C₈의 시클로알킬알킬, C₅~C₈의 아릴, CH(C₁~C₄의 알킬)-페닐, 또는 아민이고; 상기 아릴 및 페 닐의 방향족 고리는 할로겐, 시아노, C₁~C₄의 알콕시, HO-C₁~C₄의 알킬, 및 CO-C₁~C₄의 알콕시 중에서 선택된 치환체가 1 내지 3개 치환 또는 비치환될 수 있고; R⁵는 C₁~C₄의 알킬, C₃~C₈의 시클로알킬, C₅~C₈의 아릴, 또는 C₁~C₄의 알콕시이고; m은 1, 또는 2이며; n은 0, 1, 또는 2이다.Z is CH or N; R ¹ is a halogen atom, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ Of alkyl or C ₁ to C ₄ Alkoxy; R ² is H, a halogen atom, C ₁ ~ C ₄ Of alkyl, -NH-R ⁴ , C ₁ to C ₄ Alkyl-S (O) _n -phenyl,

,

,

,

,

, or

Wherein X is CH, C-OH, or N, and Y is CH ₂ , CH-C ₁ to C ₄ Of alkyl, NH, NC ₁ -C ₄ Alkyl, NC ₁ ~ C ₄ of the amino -C ₁ ~ C _{4 alkyl, N-CO-C 1 ~} C 4 _{alkyl, N-CO-C 3 ~} C 8 cycloalkyl, N-CO-C ₅ ~ for C ₈ aryl, _{N-CO-C 1 ~ C} 4 of the amino -C ₁ ~ C ₄ alkyl, or _{N-CO-C 1 ~ C} 4 Alkoxy; R ³ is a halogen atom, -NH-R ⁴ , -NH-CO-R ⁵ , -N- (CO-R ⁵ ) ₂ , -N (C ₁ ~ C ₄ Alkyl) ₂ ,

, -S (O) _n -R ⁵ , or -OR ⁵ ; R ⁴ is H, C ₁ ~ C ₈ Alkyl, C ₃ -C ₈ Cycloalkyl, C ₃ to C ₈ Cycloalkylalkyl, C ₅ -C ₈ aryl, CH (C ₁ -C ₄ of Alkyl) -phenyl, or amine; The aromatic ring of the aryl and phenyl may be halogen, cyano, C ₁ ~ C ₄ Alkoxy, alkyl of HO-C ₁ -C ₄ , and of CO-C ₁ -C ₄ A substituent selected from alkoxy may be substituted or unsubstituted from 1 to 3; R ⁵ is C ₁ ~ C ₄ Alkyl, C ₃ -C ₈ Cycloalkyl, C ₅ -C ₈ aryl, or C ₁ -C ₄ Alkoxy; m is 1 or 2; n is 0, 1, or 2.

In addition, the compound represented by the formula (1a) is a new compound that has not been found in any of the chemical structure, including Korean Patent Registration No. 848,205, etc. The present invention is a new compound represented by the formula (1a) and its pesticides The problem has been solved by providing a compound selected from the academically acceptable salts.

In Chemical Formula 1a,

이며; R⁴는 할로겐, 시아노, C₁~C₄의 알콕시, HO-C₁~C₄의 알킬, 및 CO-C₁~C₄ 의 알콕시 중에서 선택된 치환체가 1 내지 3개 치환된 페닐이고; m은 1, 또는 2이다.Y is NH, or NC ₁ to C ₄ Alkyl; R ³ is -NH-R ⁴ , -N (C ₁ ~ C ₄ Alkyl) ₂ , or

Is; R ⁴ is halogen, cyano, C ₁ ~ C ₄ Alkoxy, alkyl of HO-C ₁ -C ₄ , and of CO-C ₁ -C ₄ Substituents selected from alkoxy are 1-3 substituted phenyl; m is 1 or 2.

In the substituted 1,3-thiazole derivative represented by the formula (1) contained as an active ingredient in an agricultural fungicide characterized by the present invention, preferably as follows.

Z is CH or N; R ¹ is 2-F, 3-F, 4-F, 3-Cl, 3-CF ₃ , 3-CH ₃ or 4-OCH ₃ , and R ² is H, Cl, ethyl, amino, NHNH ₂ , methyl Amino, 6, N- dimethylnicotinylamino, 4-methylsulfanylphenyl, 4-methanesulfinylphenyl, 4-methanesulfonylphenyl, piperidin-1-yl, 4-methyl-piperidine-1- 1, piperidin-4-yl, N- methyl-piperidin-4-yl, N- ethyl-piperidin-4yl, N -isopropyl-piperidin-4yl, N- cyclopropylmethyl -Piperidin-4yl, N- dimethylaminoethyl-piperidin-4-yl, N- methylcarbonyl-piperidin-4-yl, N- cyclopropylcarbonyl-piperidin-4-yl , N- dimethylaminomethylcarbonyl-piperidin-4-yl, N- phenylcarbonyl-piperidin-4-yl, ethoxycarbonyl-piperidin-4-yl, N -butoxycarbonyl -Piperidin-4-yl, piperazin-1-yl, N- methyl-piperazin-1-yl, N -butoxycarbonyl-piperazin-1-yl, 4-methyl-4-oxypiperazin -1-yl, 4-hydroxy-piperidin-4-yl, N- methyl-4-hydroxy-piperidin-4-yl, N -butoxycarbonyl- 4-hydroxy-piperidin-4-yl, 2,5-diazabicyclo [2.2.1] -hept-2-yl, Nt -butoxycarbonyl-2,5-diazabicyclo [2.2.1 ] -Hept-2-yl, piperidin-4-ylamino, Nt -butoxycarbonyl-piperidin-4-ylamino, piperidin-4-yloxy or Nt -butoxycarbonyl- pipe Ferridin-4-yloxy; R ³ is F, amino, isopropylamino, 3-pentylamino, cyclopropylamino, cyclopropylmethylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cycloheptylamino, phenylamino, (3-fluorophenyl ) Amino, (4-fluorophenyl) amino, (3-cyanophenyl) amino, (3-cyanomethylphenyl) amino, (3-hydroxymethylphenyl) amino, (3- (2-hydroxyethyl) phenyl ) Amino, (3-methoxyphenyl) amino, (3-methoxycarbonylphenyl) amino, benzylamino, (S) -1-phenylethylamino, (R) -1-phenylethylamino, methylethylamino, Diethylamino, ethylcarbonylamino, N, N -diethylcarbonylamino, cyclohexylcarbonylamino, N, N- dicyclohexylcarbonylamino, phenylcarbonylamino, t -butoxycarbonylamino, pi Ralidin-1-yl, piperidin-1-yl, cyclopentyloxy, cyclohexyloxy, phenyloxy, methylsulfanyl, cyclopentylsulfanyl, cycl Hexylsulfanyl, a sulfanyl benzene, methane sulfinyl or methanesulfonyl.

Substituted 1,3-thiazole derivative represented by Formula 1 can be used in the form of agrochemically acceptable salts, for example, metal salts, salts with organic bases, salts with inorganic acids, salts with organic acids, Salts with basic or acidic amino acids. Suitable metal salts include alkali metal salts such as sodium salts, potassium salts and the like; Alkaline earth metal salts such as calcium salts, magnesium salts, barium salts, and the like; Aluminum salts; Suitable examples of salts with organic bases include, for example, trimethylamine, triethylamine, pyridine, picoline, 2,6-lutidine, ethanolamine, diethanolamine, triethanolamine, cyclohexylamine, dicyclohexyl Salts with amines, N, N -dibenzylethylenediamine and the like. Suitable examples of salts with inorganic acids are, for example, salts with hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid and the like. Suitable examples of salts with organic acids include, for example, salts with formic acid, acetic acid, trifluoroacetic acid, phthalic acid, fumaric acid, oxalic acid, tartaric acid, maleic acid, citric acid, succinic acid, methanesulfonic acid, benzenesulfonic acid, p- toluenesulfonic acid, and the like. . Suitable examples of salts with basic amino acids include, for example, salts with arginine, lysine, ornithine and the like. Suitable examples of salts with acidic amino acids are, for example, salts with aspartic acid, glutamic acid and the like. Particularly preferred salts include inorganic salts such as alkali metal salts (eg, sodium salts, potassium salts, etc.), alkaline earth metal salts (eg, calcium salts, magnesium salts, barium salts, etc.) when the compound has an acidic functional group therein, And organic salts such as ammonium salts and when the compound has a basic functional group therein, salts with inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, phthalic acid, fumaric acid, oxalic acid, tartaric acid, maleic acid, citric acid, Salts with organic acids such as succinic acid, methanesulfonic acid, p- toluenesulfonic acid and the like.

The method for preparing a substituted 1,3-thiazole derivative represented by Chemical Formula 1, which is included as an active ingredient in an agricultural fungicide characterized by the present invention, is described in Schemes 1 to 6 in Korean Patent Registration No. 848,205 and its Specific synthetic methods and structural analysis data of the synthetic compounds are described as examples, which may be referred to. In addition, the substituted 1,3-thiazole derivative represented by Chemical Formula 1a, which is claimed as a novel compound, may also be synthesized by a known method such as Korean Patent Registration No. 848,205. It can be easily synthesized by applying a known synthesis method.

On the other hand, agricultural fungicides characterized by the present invention may include the compound represented by the formula (1) alone, the active ingredient comprises 0.001 to 99% by weight, preferably 0.005 to 30% by weight and the residual amount of excipients It may further include. The excipient may be a conventional microbial agent, antimicrobial effect enhancer, diluent or carrier. In addition, other fungicides, insecticides, herbicides, plant growth regulators or fertilizers that have been commercially used or developed for the purpose of enhancing the efficacy or expanding the scope of application may be formulated in the form of a mixed agent. Drugs that can be included in the agricultural fungicide of the present invention and formulated into a mixed agent are specifically illustrated as follows, but the present invention is not limited to these drugs, and it is also possible to sufficiently substitute the other known drugs.

1) Fungicides: neoasozin, nuarimol, dazomet, dazomet, dodine, dinocap, dinoconazole, dimethato Dimethomorph, DBEDC, dichlofluanid, dithianon, difenoconazole, myclobutanil, mandipropamid , Mancozeb, metalaxyl, metalaxyl-M, metominostrobin, metconazol, metiram, mepanipyrim Mepronil, validamycin-A, benomyl, bordeaux mixture, boscalid, blasticidin-S, bitteranol ( bitertanol, vinclozolin, cyazofamid, cyproconazole, streptomycin, methyl bromide, anyl Anilazine, isoprothiolane, azoxystrobin, aliset (fosetyl-Al), edifenphos, ethaboxam, etridiazole, oxolinic acid (oxolinic acid), oxycarboxin, oxytetracycline, oxine-copper, iminoctadine tris (albesilate), iminoctadine triacetate ), Imidacloprid, imibencobazole, iprodione, iprodione, IBP, tricyclazole, thiophanate-methyl, thifluzamide Carbendazim, carpropamid, captan, copper hydroxide, cuprous oxide, kresoxim-methyl, chlorothalonil ), Clotianidine seed treatment Tetrazole, teclolftalam, tetraconazole, tolyclofos-methyl, tribasic copper sulfate, tricyclazole, triadiazole Triadimenol, triadimefon, triforine, trifloxystrobin, triflumizole, thiram, thiamethoxam, thiabendazole ), Thiophanate-methyl, thifluzamide, pyroquilon, phenarimol, phenazine oxide, phenazineanyl, fenoxanil, fenbuconazole (fenbuconazole), pencicuron, penconazole, penhexamide, fenhexamid, fosetyl-Al, polyoxin-D, polyoxin-B ), Folpet, probenazole, procymidone, prochloraz ), Propineb, propiconazole, prophalide, fthalide, fludioxonil, flusulfamide, flusilazol, fluazinam , Fluoromide, fluquinconazole, flutolanil, pyrazophos, pyraclostrobin, pyrimethanil, hymexazol ), Hexaconazole, sulfur.

2) Pesticides: machine oil, novaluron, diazinon, fonofos, demeton S-methyl, deltamethrin, dino Difurfuran, dichlorvos, dichlorvos, dimethylvinphos, dimethoate, dimethylvinphos, diafenthiuron, difenpol dicofol, dichlorvos, diflubenzuron, lambda cyhalothrin, lufenuron, mecarbam, metamidophos, methamsodium sodium, methomyl, methoxyfenozide, metaldehyde, metidathion, monocrotophos, milbemectin, betacyflutrin beta cyfluthrin, bensultap, benzoximate, benfuracarb, buprofez in), bistrifluron, bifenazate, bifenthrin, cyromazine, cypermethrin, cyfluthrin, cyhexatin , Spinosad, spirodiclofen, spiromesifen, silafluofen, silafluofen, cycloprothrin, amitraz ), Abamectin, acequinocyl, acetamiprid, acephate, azocyclotin, azinphos-methyl, acrinathrin , Alpha-cypermethrin, emamectin benzoate, esfenvalerate, bromopropylate, ethofenprox, ethoprophos, ethoxazole (ethoxazole) ethoxazole, endosulfan, omethoate, Imidacloprid, isazofos, isofenphos, isopen, EPN, indoxaacarb, zeta-cypermethrin, zeomeonat, chiodica Thiodicarb, cadusafos, carbaryl, carbosulfan, carbofuran, cartapfurchloride, cartap hydrochloride, quinalphos, chlorfenapyr , Chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, clotianidin, clofentezine, terbufos, tebufonoza Tebufenozide, tebufenpyrad, tetradifon, tetradifon, teflubenzuron, tralomethrin, triazophos, trichlofon, triflulofon (triflumuron), thiamethoxam, thiacloprid acloprid, thiodicarb, parathion ethyl, paraffinic oil,

Phenthoate, fenazaquin, fenobaucarb (BPMC), phenothiocarb, fenitrothion, fenvalerate, fenvalerate, fenbutatin, fentoate (fentoate) phenthoate, fenthion, fenpropathrin, fenpyroximate, phorate, phosmet, fosthiazate, phosphamidon, Phoxim, furathiocarb, flucythrinate, prothiofos, propargite, propenofos, primiphos-ethyl, fluacrypyrim (fluacrypyrim), flufennoxuron, pyraclofos, pyyridaben, pyridaphenthion, pyridalyl, pyridalyl, pirimicarb, pyrimifosmethyl (pirimiphos-methyl), pyridaphenthion, Pyriproxyfen, pymetrozine, blood Ronil (fipronil), halpen Prox (halfenprox), hexynyl thiazol jokseu (hexythiazox), after the louver (fluvalinate), hwenok when Cobb (fenoxycarb).

Plant growth regulators and herbicides: glufosinate ammonium, glyphosate, glyphosatepotassium, nad (1-naphthyacetic acid), napropamide, and nicosul Nicosulfuron, daminozide, diquat dibromide, decyl alcohol, dimethenamid, dimethenamid-p, dicamba (dicamba), dichloprop triethanol amine, diclobenyl, dithiopyr, dithiopyr, linuron, potassium salt of maleic hydrazide, malic hydra Zoidcholine (choline salt of maleic hydrazide), mecoprop, metabenzthiazuron, metolachlor, mettribuzin, mepiquat chloride, bensulfide ( bensulide, bentazone, benfluralin ( benfluralin, butachlor, bromacil, bispyribac-sodium, bifenox, sap-cipa (4-CPA), sulfosate, cetoxydim (sethoxydim), simazine, cyhalofop-butyl, abiglycine (aminoethoxyvinylglycine), asulamsodium soluble (Asulam), IBA, isoxaben, isoxaben Azimsulfuron, Sodium-5-mononitro-guaiacol, alachlor, S-metolarchlor, ethalfluralin, ethephon, eticlozete (ethychlozate), chlornitrofen, oryzalin, oxadiazon, oxaziclomefone, oxyfluorfen, 6-benzylaminopurine, inaben Inabenfide, imazaquin, imazapyr, isa-di (2,4-D), isa-diethylester, gibberellic acid,Fluazifop-butyl, carfentrazone-ethyl, calcium carbonate, quinoclamine, quizalofop-ethyl, quinmerac, clethodim ), Chlormequat-chloride, chlorpropham, clomazone, clomazone, cloxyfonac, terbuthylazine, trinexapac-ethyl, triclo Triclopyr, triclopyr-TEA, trifluralin, thidiazuron, thiobencarb, thifensulfuron-methyl, fatty alcohol alcohols, perfluidone, fenoxaprop-P-ethyl, pendimethalin, pentrazamide, penoxsulam, phosphoxenlam (forchlorfenuron), pretilachlor, prodiamine, prolinen, propanil, Propaquizafop, propoxydim, propisochlor, plazasulfuron, fluazifop-butyl, pyrazosulfuron-ethyl ), Pyribenzoxim, pyributicarb, haloxyfop-methyl, hexazinone, hexaconazole.

Thus, the agricultural fungicide of the present invention is in addition to the substituted 1,3-thiazole derivative represented by the formula (1) or agrochemically acceptable salts thereof, in addition to other fungicides, insecticides, herbicides, plant growth regulators or fertilizers, The effect of improving drug efficacy is expected to increase, and its scope of application is expected to greatly expand.

Plants to which the agricultural fungicide of the present invention can be applied include grains such as rice, wheat and barley; Fruit trees such as apples, pears, citrus fruits, grapes, bananas and peaches; Vegetables such as coffee, tea tree, potatoes, peppers, green peppers, tomatoes, cucumbers, watermelons, melons, lettuces, cabbages, celery, rapeseed, peanuts, cabbage, leeks, garlic, ginger, and onions; Flowers may include grass, forestry and ornamental seedlings, carnations, lilies, roses and chrysanthemums. In addition, it can be used to control or reduce the damage caused during the storage of seeds or agricultural products.

Agricultural fungicides of the present invention are excellent for controlling the disease or reducing the damage by inhibiting the death or growth of similar fungi such as Oomycetes , Plasmodiophoromycetes . Therefore, the agricultural fungicide of the present invention is effective for preventing or treating diseases such as Downy mildew, Late blight, Wart disease, Downy disease, Root-knot disease, and Mozalok disease. Specific examples of plant diseases that can be controlled by the agricultural fungicides of the present invention include melon, disease, melon, disease, cucumber, disease, cabbage, mildew, lettuce, mildew, rose, disease, grape, disease, hop disease, gerbera disease, potato blight, pepper Plague, Tomato Plague, Tobacco Plague, Sesame Plague, Apple Plague, Cabbage Root Disease, Musa Viper, Mozalok Disease, and the like. The pathogens associated with the above-mentioned plant diseases are specifically listed as follows. Melon germ disease [pathogen: Pseudoperonospora cubensis ], melon fungal disease [pathogen: Pseudoperonosporacubensis ], cucumber germ disease [pathogen: Pseudoperonospora cuvensis], Chinese cabbage fungus [pathogen: Peronospora parasitica ], lettuce fungus [pathogen: Bremia lactucae ], rose fungus [pathogen: Peronospora sparsa ], grape fungus [Pathogen: Plasmopara viticola ], hop fungal disease [pathogen: Pseudoperonospora humuli ], gerbera late disease [pathogen: Phytophthora cryptogea ], potato late blight [ pathogens: Pastry Saratov inpe Afghanistan's Tora (Phytophthora infestans)], pepper blight [pathogens: Pastry Saratov Torah kaepsi City (Phytophthora capsici), tomato late blight [hospital : Pastry Saratov Torah inpe Afghanistan's (Phytophthora infestans)], tobacco epidemic [pathogens: Pastry Saratov Torah Nico Tia four (Phytophthora nicotianae var nicotianae.)] , Sesame plague [pathogens: Pie Saratov Torah Nico Tia four (Phytophthora nicotianae var parasitica )], Apple late blight [pathogen: Phytophthora cactorum ], cabbage root disease [pathogen: Plasmodiophora brassicae ], wart disease [pathogen: Plasmodiophora] brassicae )], potato flour beetle disease [pathogen: Spongospora subterranea , mozzarella disease [pathogen: Pythium spp .], pepper anthrax [pathogen: Colletotrichum coccodes )], Cucumber anthrax [pathogen: Colletotrichum orbiculare ], rice blast [pathogen: Magnaporthe grisea ], etc. have.

Agricultural fungicides of the present invention are mainly used in the form of a formulated to increase the ease of use and safety. The form of the preparation may be prepared in a suitable formulation depending on the plant to be applied or the method of application. Suitable formulations may be formulated into hydrating agents, emulsions, granules, powders, liquid hydrating agents, granulating hydrating agents, sleeping flocculating granules, seed treatment hydrating agents, fumigants, coating agents and the like.

The content of the compound represented by Formula 1 or an agriculturally acceptable salt thereof contained as an active ingredient in the agricultural fungicide of the present invention may vary depending on the form of the preparation. For example, 1 to 90% by weight of a hydrating agent or an emulsion, a hydrating agent for seed treatment, and a liquid hydrating agent for seed treatment, 0.1 to 10% by weight for a powder, 1 to 50% by weight for a liquid hydrating agent, granules and sleeping injuries. In the case of sex granulation, it is preferable to be within 1 to 30% by weight, and to mix or separate with fertilizers (for example, fertilizers containing nitrogen, phosphoric acid and potassium) to within 25% by weight. The content rate of a component can also change a little.

In formulating the agricultural fungicide of the present invention, a carrier in a solid or liquid state may be used, and various minor ingredients may be used to enhance the adhesion and safety of the compound of the present invention, which is a main ingredient, and the safety of the drug. Can be used. As a carrier used to formulate the agricultural fungicide of the present invention, liquid carriers include water, alcohols (methanol, benzyl alcohol, furfuryl alcohol, butanol, ethylene glycol, glycerin, etc.), ketones (cyclohexanone, acetone, methyl). Ethyl ketones, etc.), ethers (dioxane, tetrahydrofuran, cellosolve, etc.), aliphatic hydrocarbons (gasoline, ketocene, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride, etc.), acid amides (dimethylformamide, etc.) , Esters (ethyl acetate, butyl acetate, ethylene glycol acetate, fatty acid glycerin esters, etc.), nitriles (acetonitrile, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), and the like, may be used alone or in combination. It can mix and use the above. And solid carriers include mineral particles (kaolin, clay, bentonite, acidic clay, talc, silica, sand, diatomaceous earth, dolomite, calcium carbonate, powdered magnesium, gypsum, etc.), vegetable powders (soybean flour, flour, sawdust, starch powder, crystals). Cellulose, etc.) can be used.

In addition, the agricultural fungicide of the present invention may further include an emulsifier, an adhesive, a dispersant or a wetting agent, and may further include an anionic, cationic, or nonionic surfactant. As the cationic surfactant, a long chain alkylammonium salt such as bromocetyltrimethylammonium salt can be used, and as anionic surfactant, alkylaryl sulfonic acid such as dodecylbenzene sulfonic acid, alkyloxy sulfonic acid such as lauryloxy sulfonic acid, Alkali sulfonic acids such as lignin sulfonic acid, naphthalene sulfonic acid and dibutyl naphthalene sulfonic acid, lauryl ether sulfate, sulfated aliphatic alcohols, fatty acids, sulfated hexadecanol, sulfated heptanedecanol and sulfated aliphatic alcohols, glycol ethers and the like , Alkaline earth metal salts or ammonium salts can be used. And as the nonionic surfactant, a condensate of castor oil, naphthalenesulfonic acid and phenol or formaldehyde containing aliphatic alcohols such as all rail alcohol and cetyl alcohol, phenol, alkylphenol, ethylene oxide or propylene oxide can be used.

In addition, when formulated for seed treatment, various binders may be used to enhance adhesion to seeds, and N -methylpyrrolidone, propylene glycol and N, N- dimethylformamide are used as solvents. Can be formulated.

Agricultural fungicides of the present invention can be applied to plants by conventional methods. When applied to plants, they can be directly treated (sprayed or applied) on the leaves, stems, branches, roots, seeds of plants (including crops, seedlings, shrubs, and trees), or in general cultivated soils such as rice fields or fields, Plants that are miscible to the medium or grown in water (eg, rice) can be treated on the surface to control disease. Specific application methods are coating treatment, dipping treatment, fumigation treatment or spraying treatment. For example, the disinfectant composition may be sprayed onto soil, leaves, stems, seeds, flowers or fruits of plants, wherein the composition is applied to water or other diluents. Can be diluted. The application time of the agricultural fungicide is preferably at the time of smooth growth of phytopathogens, which may vary depending on the type of plant on which the phytopathogens develop, it is preferable to apply at the appropriate time depending on the type of plant. Typical application times are planting, cultivation and harvesting of plants. The application amount of the agricultural fungicide composition can be appropriately adjusted according to the type of plant, pathogen and application method. For example, the composition for the disinfectant may be fertilized at 0.5 to 5 g per m ² of farmland, or 50 to 500 μg / plant may be applied based on the active ingredient.

Hereinafter, preferred examples, formulations, and experimental examples are presented to help understand the present invention. However, the following Examples, Formulation Examples and Experimental Examples are provided only to more easily understand the present invention, and the contents of the present invention are not limited thereto.

[Example]

In this example, the chemical structure and spectroscopic data of the compound of the substituted 1,3-thiazole derivative newly synthesized by the applicant are shown in Table 1 below.

The substituted 1,3-thiazole derivatives shown in Table 1 were synthesized with reference to the preparation methods and examples of Schemes 1 to 6 disclosed in Korean Patent Registration No. 848,205, and Korean Patent Registration No. 848,205 for experts in the field of organic synthesis. It is contemplated that this may be readily synthesized with reference to the method disclosed in.

[Example]

In this formulation example, the compound represented by the formula (1) is a representative example for formulating an agricultural fungicide containing an active ingredient suitable for the purpose of application. The composition of each component used in the formulation is as follows.

Formulation Example 1 Hydration

A hydrating agent was prepared by grinding and mixing 10 g of the compound of Formula 1, 10 g of NK250L (surfactant), 10 g of white carbon, and 70 g of pyrophylite (extender).

Formulation Example 2 Emulsion

An emulsion was prepared by mixing 10 g of the compound of Formula 1, 10 g of DDY2000 (surfactant), and 80 g of xylene.

Formulation Example 3 Liquid Hydrating Agent

10 g of the compound of formula 1, 10 g of HY1910 (surfactant), 5 g of propylene glycol, 0.2 g of xanthan gum, 0.15 g of KM-73 (antifoaming agent), 0.2 g of Biocide-LS (preservative), KNP (thickener) ) 0.1 g and 74.35 g of water (extender) were ground and mixed in a ball mill to prepare a liquid hydrating agent.

Formulation Example 4 Sleep Injury

Horizontal extrusion by mixing 5 g of a compound of formula 1, 7.5 g of paraffin oil, 2 g of sodium alkalsulfosuccinate (surfactant), 3 g of white carbon, 1.2 g of xanthan gum, 0.8 g of sodium polyacrylate, and 80.5 g of potassium chloride It was granulated by a molding machine and dried to prepare a surface floating granule.

Formulation Example 5

5 g of a compound of Formula 1, 2.5 g of HY1910 (surfactant), 0.2 g of NK250L (surfactant), 0.5 g of soda ash, 2.0 g of dextrin, 25 g of bentonite, 64.8 g of talc (Talc) and kneaded with water in a horizontal extrusion Granulation was carried out by granulating and drying the molding machine.

Formulation Example 6 Mixing Agent

In Formulation Examples 1 to 5, a mixture was prepared by using a single or a mixture selected from conventional fungicides, insecticides, herbicides and commercially available within the 20% by weight of the weight of the compound of Formula 1 used as the active ingredient. .

Experimental Example Bactericidal Effect Experiment

In this Experimental Example, in order to confirm the control effect of the compound represented by the formula (1) as an agricultural fungicide, Phytophthora capsici , Plasmopara viticola was examined. The controlling value of each compound was calculated by the following equation.

1) In vivo test for phytophthora capsici

Pepper bacillus was subcultured with Phytophthora capsici , which was distributed by the National Institute of Agricultural Science and Technology in 2004, and used as an inoculator. Each test compound was dissolved in 10 mL of acetone, and then mixed with 90 mL of a 250 ppm Tween 20 solution to prepare a solution having a final concentration of 30 ppm of the test compound. Experiments on the preventive effect of each compound was carried out by spraying the test substance solution evenly wet to the red pepper leaves 1 day before the inoculation of red pepper bacillus bacteria and air-dried in the greenhouse for 24 hours. Pepper pest was used as inoculum was incubated for 7 days in V-8 medium (V-8 juice 200 mL, CaCO ₃ 4.5 g, agar 20 g, distilled water 800 mL). After removing the aerial mycelium of the cultured strain and drying for 24 hours under light conditions, a large amount of zygote sac formed on the surface of the medium was collected with a brush, and the pathogen inoculum was prepared at a concentration of 10 ⁴ spores / mL, and then 1 hour at 4 ° C. It was maintained to induce the maximum outflow of the resident from the zygomatic sac. Immediately before inoculation, Tween 20 solution was added at a concentration of 100 ppm and evenly sprayed on pepper leaves of 6-8 leaves of the main leaves. After inoculation of the pathogen, the disease was transferred to a constant temperature and humidity room at 23 ° C. to induce the onset for 2 days. The control effect was calculated by examining the lesion area ratio in the foliage 2 to 5 days after inoculation, and the control value was calculated based on Equation 1, and the results are shown in Table 2 below.

2) In vitro test method for phytophthora capsici

Phytophthora capsici ( Phytophthora capsici ), which was sold at the Institute of Agricultural Science and Technology in 2004, was subcultured and used as an inoculum and tested by the Paper Disc Method. After dissolving 5 mg of each test compound in 1 mL of acetone, a solution of 5000 ppm was prepared, and the solution was added to 3 paper discs (Avantec) of 6 mm in diameter, 15 μl each, for 1 hour. It was air dried on a clean bench. Paper disks containing the test compound were placed on PDA medium (Difco) at 25 mm away from 12, 4 and 8 o'clock, respectively, and then V-8 medium (V-8 juice 200 mL, CaCO ₃ 4.5 g, 20 g of agar, 800 mL of distilled water) was strained at the center for 7 days and cultured in a 20 ° C. incubator for 4 to 5 days to determine the minimum radius (mm) of the low support formed. The results are shown in Table 2 below.

3) In vivo assay for Plasmopara viticola

Grape seedlings (Geobong) were seeded in a square pot (15 × 20 cm 2) containing horticultural soil for 2 months or longer and used for the test. Indoor cultivation is difficult hwalmul parasites of grapes packed in order to prepare the inoculum of grape downy mildew (2008, Anseong) made the suspension after collecting spores brush formed on the back of the natural onset of a grape leaf in the final inoculum concentration 1 × 10 ⁵ Dilution to spores / mL was used as inoculum. Each test compound was dissolved in 10 mL of acetone, mixed with 90 mL of a 250 ppm Tween 20 solution, and adjusted to a final concentration of 30 ppm. To confirm the prophylactic effect, the leaves were sprayed to be completely wet 1 day before inoculation and air-dried in a greenhouse for 24 hours. The prepared spore suspension was evenly inoculated on the grape leaves. After inoculation, the cells were stored in a 20 ° C. germination plant for 2 days and then moved to a 20 ° C. constant temperature and humidity chamber. The lesion area rate of the foliage was investigated, and the control value of each compound was calculated by the above equation.

_

As can be seen from the results of Table 2, the compound represented by the formula (1) has a strong bactericidal effect against red pepper bacillus ( Phytophthora capsici ), Staphylococcus aureus ( Plasmopara viticola ). Therefore, the compound of the present invention is effective as an active ingredient of agricultural fungicides to control the disease or reduce the damage by inhibiting the death or growth of phytopathogens, including similar fungi.

As described above, the agricultural fungicide of the present invention containing the compound represented by Chemical Formula 1 as an active ingredient exhibits a strong bactericidal effect at low doses against phytopathogenic bacteria causing disease in plants, thereby preventing environmental pollution. It can be usefully used as an environmentally friendly fungicide.

Claims (9)

Agricultural fungicide containing a single compound or a mixture of two or more selected from substituted 1,3-thiazole derivatives represented by the following Formula 1 and agrochemically acceptable salts thereof as an active ingredient: [Formula 1]

In Chemical Formula 1, Z is CH, or N; R ¹ is a halogen atom, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ Alkyl, or C ₁ to C ₄ Alkoxy; R ² is

, or

Wherein X is CH, or C-OH, and Y is NH, NC ₁ -C ₄ Alkyl, NC ₁ -C ₄ alkyl-N- (C ₁ -C ₄ alkyl) ₂ , N-CO-C ₁ -C ₄ alkyl, N-CO-C ₃ -C ₈ cycloalkyl, N- CO-C ₅ to C ₈ aryl, N-CO-C ₁ to C ₄ alkyl-N- (C ₁ to C ₄ alkyl) ₂ , or N-CO-C ₁ to C ₄ Alkoxy; R ³ represents a halogen atom, -NH-R ⁴ , -NH-CO-R ⁵ , -N- (CO-R ⁵ ) ₂ , -N (C ₁ -C ₄ Alkyl) ₂ ,

, -S (O) _n -R ⁵ , or -OR ⁵ ; R ⁴ is H, C ₁ ~ C ₈ Alkyl, C ₃ -C ₈ Cycloalkyl, C ₃ to C ₈ Cycloalkylalkyl, C ₅ -C ₈ aryl, CH (C ₁ -C ₄ of Alkyl) -phenyl, or amine; The aromatic ring of the aryl and phenyl is halogen, cyano, C ₁ ~ C ₄ Alkoxy, alkyl of HO-C ₁ -C ₄ , and of CO-C ₁ -C ₄ A substituent selected from alkoxy may be substituted or unsubstituted from 1 to 3; R ⁵ is C ₁ ~ C ₄ Alkyl, C ₃ -C ₈ Cycloalkyl, C ₅ -C ₈ aryl, or C ₁ -C ₄ Alkoxy; m is 1 or 2; n is 0, 1, or 2. According to claim 1, in the formula 1 Z is N; R ¹ is 2-F, 3-F, 4-F, 3-Cl, 3-CF ₃ , 3-CH ₃ , or 4-OCH ₃ ; R ² is piperidin-4-yl, N- methyl-piperidin-4-yl, N- ethyl-piperidin-4-yl, N -isopropyl-piperidin-4-yl, N- Cyclopropylmethyl-piperidin-4-yl, N- dimethylaminoethyl-piperidin-4-yl, N- methylcarbonyl-piperidin-4-yl, N- cyclopropylcarbonyl-piperidine 4-yl, N- dimethylaminomethylcarbonyl-piperidin-4-yl, N- phenylcarbonyl-piperidin-4-yl, 4-hydroxy-piperidin-4-yl, N- Methyl-4-hydroxy-piperidin-4-yl, piperidin-4-ylamino, or piperidin-4-yloxy; R ³ is F, amino, isopropylamino, 3-pentylamino, cyclopropylamino, cyclopropylmethylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cycloheptylamino, methylethylamino, diethylamino, phenyl Amino, (3-fluorophenyl) amino, (4-fluorophenyl) amino, (3-cyanophenyl) amino, (3-hydroxymethylphenyl) amino, (3- (2-hydroxyethyl) phenyl) Amino, (3-methoxyphenyl) amino, (3-methoxycarbonylphenyl) amino, benzylamino, (S) -1-phenylethylamino, (R) -1-phenylethylamino, pyrrolidine-1 -Yl, piperidin-1-yl, or methylsulfanyl; Agricultural fungicide comprising a single compound or a mixture of two or more selected from 1,3-thiazole derivatives substituted with an agrochemically acceptable salt thereof as an active ingredient. The method of claim 1, Agricultural fungicides, characterized in that prepared as a mixture, further comprising a single or a mixture selected from other fungicides, insecticides, herbicides, plant growth regulators and fertilizers as the active ingredient. The method according to any one of claims 1 to 3, Agricultural fungicides formulated with hydrating agents, emulsions, granules, powders, liquid hydrating agents, granulating hydrating agents, sleeping flocculating granules, seed treatment hydrating agents, fumigations, or coating agents. The method according to any one of claims 1 to 3, Agricultural fungicides, characterized in that the use of similar fungi to control the disease or reduce the damage by inhibiting the death or growth. The method according to any one of claims 1 to 3, Agricultural fungicides for use in the treatment and prevention of plant diseases, including downy mildew, late blight, wart disease, rot, root gall, and mozzarella. Substituted 1,3-thiazole derivatives represented by the general formula (1a) or agrochemically acceptable salts: [Formula 1a]

In Chemical Formula 1a, Y is NH, or NC ₁ to C ₄ Alkyl; R ³ is -NH-R ⁴ , -N (C ₁ ~ C ₄ Alkyl) ₂ , or

Is; R ⁴ is halogen, cyano, C ₁ ~ C ₄ Alkoxy, alkyl of HO-C ₁ -C ₄ , and of CO-C ₁ -C ₄ Substituents selected from alkoxy are 1-3 substituted phenyl; m is 1 or 2. According to claim 7, wherein in Formula 1a Y is NH, or N-CH ₃ ; R ³ is 3-pentylamino, methylethylamino, diethylamino, pyrrolidin-1-yl, piperidin-1-yl, (3-fluorophenyl) amino, (4-fluorophenyl) amino, (3-cyanophenyl) amino, (3-hydroxymethylphenyl) amino, (3- (2-hydroxyethyl) phenyl) amino, (3-methoxyphenyl) amino, or (3-methoxycarbonylphenyl ) Amino; Substituted 1,3-thiazole derivatives or agrochemically acceptable salts. According to claim 7, wherein the compound represented by Formula 1a Ethyl- {4- [4- (4-fluorophenyl) -2-piperidin-4-yl-thiazol-5-yl] pyrimidin-2-yl} methylamine (Compound 2), Diethyl- {4- [4- (4-fluorophenyl) -2-piperidin-4-yl-thiazol-5-yl] pyrimidin-2-yl} amine (Compound 4), 4- [4- (4-fluorophenyl) -2-piperidin-4-yl-thiazol-5-yl] -2-pyrrolidin-1-yl-pyrimidine (Compound 5), 4- [4- (4-fluorophenyl) -2-piperidin-4-yl-thiazol-5-yl] -2-piperidin-1-yl-pyrimidine (Compound 6), 3-fluorophenyl- {4- [4- (4-fluorophenyl) -2-piperidin-4-yl-thiazol-5-yl] pyrimidin-2-yl} amine (Compound 7), 3-cyanophenyl- {4- [4- (4-fluorophenyl) -2-piperidin-4-yl-thiazol-5-yl] pyrimidin-2-yl} amine (Compound 8), 3-methoxyphenyl- {4- [4- (4-fluorophenyl) -2-piperidin-4-yl-thiazol-5-yl] pyrimidin-2-yl} amine (Compound 9), 3- {4- [4- (4-fluorophenyl) -2-piperidin-4-yl-thiazol-5-yl] pyrimidin-2-yl} benzoic acid methyl ester (Compound 10) , 3-hydroxymethyl-phenyl- {4- [4- (4-fluorophenyl) -2-piperidin-4-yl-thiazol-5-yl] pyrimidin-2-yl} amine (Compound 11 ), 3- (1-hydroxyethyl) phenyl- {4- [4- (4-fluorophenyl) -2-piperidin-4-yl-thiazol-5-yl] pyrimidin-2-yl} amine (Compound 12), 4-fluorophenyl- {4- [4- (4-fluorophenyl) -2-piperidin-4-yl-thiazol-5-yl] pyrimidin-2-yl} amine (Compound 13), Ethyl- {4- [4- (4-fluorophenyl) -2- (1-methylpiperidin-4-yl) thiazol-5-yl] pyrimidin-2-yl} methylamine (Compound 15) , Diethyl- {4- [4- (4-fluorophenyl) -2- (1-methylpiperidin-4-yl) thiazol-5-yl] pyrimidin-2-yl} amine (Compound 17) , 4- [4- (4-fluorophenyl) -2- (1-methylpiperidin-4-yl) thiazol-5-yl] -2-pyrrolidin-1-yl-pyrimidine (Compound 18 ), 4- [4- (4-fluorophenyl) -2- (1-methylpiperidin-4-yl) thiazol-5-yl] -2-piperidin-1-yl-pyrimidine (Compound 19 ), 3-fluorophenyl- {4- [4- (4-fluorophenyl) -2- (1-methylpiperidin-4-yl) thiazol-5-yl] pyrimidin-2-yl} amine ( Compound 21), 3-cyanophenyl- {4- [4- (4-fluorophenyl) -2- (1-methylpiperidin-4-yl) thiazol-5-yl] pyrimidin-2-yl} amine ( Compound 22), 3-methoxyphenyl- {4- [4- (4-fluorophenyl) -2- (1-methylpiperidin-4-yl) thiazol-5-yl] pyrimidin-2-yl} amine ( Compound 23), 3-hydroxymethyl-phenyl- {4- [4- (4-fluorophenyl) -2- (1-methylpiperidin-4-yl) thiazol-5-yl] pyrimidin-2-yl} Amines (compound 24), 4-fluorophenyl- {4- [4- (4-fluorophenyl) -2- (1-methylpiperidin-4-yl) thiazol-5-yl] pyrimidin-2-yl} amine ( Compound 25), Or an agrochemically acceptable salt thereof.