WO2004011445A1 - Aminosalicylamide derivative, process for producing the same and agri-horticultural pesticide - Google Patents

Abstract

An aminosalicylamide compound represented by the formula: (1) wherein R1 represents a hydrogen atom, etc; R2 represents a hydrogen atom, etc; R3 represents a hydrogen atom, etc; R4 represents a C1-12 alkyl group, a substituted or unsubstituted phenyl group, etc.; and A represents a group of the formula: (2) (3) wherein X represents an oxygen atom or a sulfur atom; and B represents a substituted or unsubstituted phenyl group, a C1-16 alkyl group, etc., or a salt of the aminosalicylamide compound. There is further an agri-horticultural pesticide comprising at least one thereof as an active ingredient.

Description

 Aminosalicylic acid amide derivative, manufacturing method and fungicide for agricultural and horticultural use

 The present invention relates to a novel aminosalicylic acid derivative and a fungicide for agricultural and horticultural use containing the compound as an active ingredient.

Background art

 In the cultivation of agricultural and horticultural crops, a number of control agents are used for crop diseases.However, their control efficacy is insufficient, and their use is limited by the emergence of drug-resistant pathogens. From the viewpoint of causing phytotoxicity and contamination of plants, toxicity to humans and fishes, and environmental impact, there are many cases that are not necessarily satisfactory control agents. Therefore, there is a strong demand for a drug that can be used safely with few such disadvantages.

また、 B i o chem. Β i ο ρ h y s. Ac t a 1222 (2) 149— 154， 1995. J. o f B i o c em. 246 (23) 7125-30, 1971 等 には、類似の化学構造を有するアンチマイシンの抗真菌活性について記載されている。 発明の開示 Aminosalicylic acid amide compounds similar to the compounds of the present invention are disclosed in WO 97/08135 as having insecticidal and fungicidal activity. However, their biological activities are not always practically sufficient. Further, compounds represented by the following formulas (A) and (B) are exemplified, but neither physical constants nor biological activity data are described.

In addition, Bio chem. Β i ορ hys. Acta 1222 (2) 149—154, 1995. J. of Biom. 246 (23) 7125-30, 1971 The antifungal activity of antimycin is described. Disclosure of the invention

 An object of the present invention is to provide an aminosalicylic acid amide compound which can be industrially advantageously synthesized, has a certain effect, and can be used safely as a fungicide for agricultural and horticultural use. The present invention firstly provides a formula (1)

H 0R ₂ 0 R ₃

^R 1 丫¹

 0 W¾A

Η ^κ 4

 (1)

Wherein the hydrogen atom or represents an _alkyl group _c R ₂ is a hydrogen atom, C i _ ₆ alkoxycarbonyl group, - represents an alkyl group, or, optionally substituted by G Fuweniru C i _ ₈ alkyl group.

 R 3 represents a hydrogen atom or a —6 alkyl group.

R ₄ is C _{1 2} alkyl group, C ₂ - ₈ alkenyl group, C ₂ - ₈ alkynyl group, C i-s Haroaru kill group may Fuweniru group optionally substituted by G, or may be substituted with G Represents a phenyl C 8 alkyl group.

A represents _n representing a heterocyclic ring represented by the formula (2) or the formula (3)

 (2)

(3)

(Wherein, X represents an oxygen atom or a sulfur atom, B is optionally Fuweniru group optionally substituted by G, 6 alkyl group, C ₂ - _{1 6} alkenyl group, an _alkynyl group.)

G is a halogen atom, Ji alkyl group, Ji ₆ alkoxy groups, C i -s alkylthio group, - 6 haloalkyl group or an C IS haloalkoxy group, 5 of two of these G is identical or different phases, It may be replaced. ]

And a salt thereof, and a fungicide for agricultural and horticultural use containing one or more of such compounds as an active ingredient.

Embodiment of the Invention

 In the definition of the above formula (1),

Represents a hydrogen atom or a _6- alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutynole, t-butyl, pentyl, isopentylene, neopentinole, t-pentyl, hexyl, isohexyl, etc. .

R ₂ is a C i _ ₆ alkoxycarbonyl group such as hydrogen atom, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl; methylcarbonyl, ethylcarbonyl, propylcarbonyl, isopropylcarbonyl , C Bok ₆ alkyl Rukaruponiru group such butylcarbonyl, t one butylcarbonyl; represents optionally substituted by G benzyl, 2-Fuweniruechiru, 3 Fuweniru propyl, phenyl C alkyl group such as 4-phenylbutyl.

R ₃ represents a hydrogen atom or an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutynole, t-butyl, pentyl, isopentinole, neopentyl, t-pentyl, hexyl, and isohexyl. Express. R ₄ is d- such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isoptyl, t-butyl, pentyl, isopentyl, neopentyl, t-pentinole, hexyl, isohexyl, heptyl, decyl, pendecyl, etc. ₂ alkyl group; Eteniru, 1 one propenyl, 2 _ propenyl, 1 Buteniru, 2-butenyl, C ₂ one ₈ alkenyl group of the 2-pentenyl and the like; Echiniru, 1 one-propynyl, 2-propynyl, 1-heptynyl , 2-heptynyl, 3-heptynyl, 1-methyl-2-propynyl, 4 one C ₂ _ ₈ § Rukiniru group pentynyl and the like; chloromethyl, Furuoromechiru, Promo methyl, dichloromethyl, difluoromethyl Oromechiru, jib port Momechinore, trichloromethyl, Trifolometinole, tripromethyl, trichloroethyl, trifluore G in optionally substituted Fuweniru group optionally; Le, pentaerythritol full O Roe C haloalkyl group chill like benzyl which may be substituted by G, 2-Fuweniruechiru, 3 Fuwenirupuropiru, such as 4 Fuwenirupuchiru Fuweniru C i _ ₈ Represents an alkyl group.

 A represents a heterocyclic ring represented by the formula (2) or (3).

In the definition of equation (2) or (3),

X represents an oxygen atom or a sulfur atom.

B is a phenyl group which may be substituted with G; methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, t-pentyl, hexyl, iso hexyl, heptyl, decyl, etc. Undeshiru C - _{1 6} alkyl group; Eteniru, 1 _ propenyl, 2-propenyl, 1-butenyl, 2 - heptenyl, C ₂ _ ₁₆ alkenyl group of the 2-pentenyl and the like; Echiniru, 1 one propynyl, 2 - represents a ₁₆ alkynyl group - propynyl, 1 one heptynyl, 2-heptynyl, 3-heptynyl, 1-methyl-2-propyl sulfonyl, C ₂ etc. 4 one pentynyl.

G is a halogen atom such as fluorine, chlorine, bromine and iodine; a 6-alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl and t-butyl; methoxy, ethoxy, propoxy, isopropoxy, C ₆ alkoxy groups such as butoxy, sec-butoxy, isobutoxy, and t-butoxy; alkylthio groups such as methylthio, ethylthio, n-propylthio, iso-propylthio, n-butylthio, is 0-butylthio, sec-butylthio, and t-butylthio C ^ haloalkyl groups such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tripromomethyl, trichloroethyl, trifluoroethyl, pentafluoroethyl and the like; Chloromethane butoxy, Furuoro main butoxy, Puromome butoxy, Jikurorome butoxy, Jifuruorome butoxy, Jiburomome butoxy, trichloroacetic main butoxy, Torifuruorome butoxy, Toripuromome butoxy, Torikuroroe butoxy, triflumizole Ruo b ethoxy, penta full O b C 1 _-6 halo ethoxy Represents an alkoxy group, and these Gs may be the same or different and may be substituted with 2 to 5 Gs. Next, the production method of the compound of the present invention will be described _c

了) ( Manufacturing method Wind

End) (

 (4) (1)

(In the formula, R ₂ , R ₃ , R ₄ and A represent the same meaning as described above, and Z represents a leaving group such as a halogen atom, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, and 11-imidazole. The compound (7) is reacted with the amino derivative (8) to produce the ditrosalicylic acid amide derivative (6), and further reduced to the aminosalicylic acid amide derivative (4). The compound (I) of the present invention is prepared by the acylation reaction.

 That is, the compound (7) and the compound (8) are reacted in a suitable organic solvent at —20 ° C. to: I at 20 ° C. using an appropriate condensing agent for 1 to several tens of hours to obtain a corresponding compound. Produce nitrosalicylic acid amide derivative (6). Solvents that can be used include hydrocarbons such as benzene and toluene, ethers such as dimethyl ether and THF, halogenated hydrocarbons such as chloroform and dichloromethane, DMF, DMS0, and acetonitrile. . Examples of the condensing agent include acid anhydride agents such as methyl chloroformate, ethyl chloroformate, and diethoxyphosphonyl cyanide; dicyclohexylcarpoimide; 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride. Examples include carpoimides such as salts, and 1,1-carbonylbis-1H-imidazole.

 Next, the compound (6) is reduced in a suitable organic solvent at 0 ° C to 40 ° C with a suitable heterogeneous transition metal catalyst under normal pressure or under pressure under a hydrogen atmosphere to respond. Aminosalicylic acid amide derivative (4) can be obtained. Examples of the solvent that can be used for the reaction include water, alcohols such as methanol and ethanol, hydrocarbons such as benzene and toluene, ethers such as ether and THF, and ethyl acetate.

Examples of the catalyst include a nickel catalyst such as Raney nickel, a palladium catalyst such as palladium-carbon, a cobalt catalyst, a ruthenium catalyst, a rhodium catalyst, and a platinum catalyst. Next, the compound (4) is reacted in an appropriate organic solvent at −20 ° C. to 120 ° C. for 1 to several tens of hours using the acylating agent (5) to obtain the corresponding compound of the present invention, acylamino salicyl. The acid amide derivative (1) can be obtained. Solvents that can be used include hydrocarbons such as benzene and toluene, ethers such as getyl ether and THF, carbon halides such as chloroform and dichloromethane, DMF, DMSO, and acetonitrile. .

(Agricultural and horticultural fungicides)

 The compound of the present invention (the compound represented by the formula (1) or a salt thereof) includes a wide variety of filamentous fungi such as algae (Oomy cetes :), ascomycetes (capsules), It has excellent bactericidal activity against bacteria belonging to incomplete fungi (Deuter omy cetes) and basidiomycetes (Basidi omy cetes). The composition containing the compound of the present invention as an active ingredient is used for controlling various diseases that occur during the cultivation of agricultural and horticultural crops including flowers, turf and grass, by seed treatment, foliage application, soil application or water application. be able to. For example,

Tensa Leaf spot (Cercosporabeetticola

Lackasey brown spot (My cos p aer e l l a a r a ch i d i s)

 Black Shibu (My c o s p a e r e 1 l a b e rk e l e y i) Kiyuri powdery mildew (Spha e r o t h e c a f u l i g i ne a)

 Vine withered (My c spha e r e 1 1 a me l on is)

 Sclerotia (Scl erotiniiniasclelerotiorum) Gray rot (Botry tiisciinerae)

 Scab (C l a do s po r i um cu cume r i num) Tomato Gray mold (Botry t i s c i n e r e a)

 Leaf mold (C l a do s po r i um f u 1 v urn)

Eggplant gray rot (Botry t i s c i n e r e a)

 Black Death (Coryne s pora a me long ena e)

 Powdery mildew (Ery s i p h e c i c o r a c e a r um) Strawberry Gray mold (Bo t r t i s c i n e r e a)

 Powdery mildew (Soh ae r o t h e c a u mu 1 i)

Onion gray rot (Botry t i s a 1 1 i i)

 Gray mold (Botry t i s c i n e r e a)

Singen sclerotium (Scl erotiniiascl erotiorum)

 Gray mold (Botry t i s c i n e r e a)

 Phosphorus powdery mildew (Pod 0 s p h ae r a l e u c o t r i cha)

Scab (Venturiai na e qua lis) Monilia disease (Mon ilinia ma 1 i)

Oyster powdery mildew (Phy 1 1 a c t i n i a k a k i c o 1 a)

 Ash rot (G l o e o s p o r i um k a k ϊ)

 Horn spot leaf disease (Cercosporakaki)

Peach oat to rot (Mo ni 1 ini a f ru c t i c o l a)

Grape Gray mold (Botry t i s c i n e r e a)

 Powdery mildew (Unc i nu l a n e c a t or)

 晚 rot 两 (G l ome r e l l a c i ngu l a t a)

Pear Scab (Ven tu r i a na s h i c o l a)

 Gymno s porang i um a s i a t i cum;

 Black spot (A l t e rna r i a k i ku c i ana)

Cha rot (Pe st a l o t i a t e a e)

 Anthracnose (Coll e t o t r i c um t he a e— s i n ens i s) Sick sickness (E l s i no e f awc e t t i)

 Blue mold (Pen i c i 1 1 i um i t a 1 i c um)

 Green Power, Blight (Pen i c i 1 1 i um d i g i t a tum

 Gray mold (Botry t i s c i ne r e a)

Ery s i ph e g rami n i s f. S p. Ho r d e i) Naked smut (Us t i l a go n u d a)

 Fusarium head blight of wheat (G i b b e r e 1 l az e a e)

 Leaf rust (Pu c c i n i a r e c ond i t a)

 Spot disease (Co ch l i ob o l u s s a t i vu s)

 Eye spot disease (Ps eudo c e r c o s p o r e l l a he r p o t r i c o i d e s)

 Fusarium wilt (Lep t os pha e r i a no d o r u m)

 Powdery mildew (Erysiphegramininisf.sp.triticci)

 Red snow rot (Mi c r on e c t r i e l l a n i va l i s)

Rice blast (Py r i cu l a r i a o ry z a e

 Sheath blight (Rh i z o c t on i a s o l an i)

 Stupid seedling disease (Gibb e r e l l a f u j i ku r o i),

 Sesame leaf blight (Co ch l i ob hi l u s n i y ab e anu s) ヽ sclerotium rot (S c l e ro o t i n i a s c l e r o t i o rum)

 Powdery mildew (Ery s i p h e c i cho r a c e a rum)

 Tulip gray mold (Botry t i s c i n e r e a)

Bentgrass snow rot bacterial sclerotium (S clerotiniaborealis), Powdered powdery mildew (E rysipegr ami nis),

Soybean purpura (Cercosporarakikikuchii),

Potato tomato blight (Phytophophora ainfestans), Yayuribe and (Ps eudop e r ono spora cuben sis), Grape bee and (Pla smop ara avi t i co1a;

 It can be used for pest control.

 In recent years, various pathogens have developed resistance to benzimidazole fungicides ゃ dicarboximide fungicides, etc., resulting in insufficient efficacy of these drugs, and effective drugs for resistant bacteria have been desired. . The compound of the present invention is a drug having an excellent bactericidal effect not only on pathogenic bacteria sensitive to such drugs but also on resistant bacteria.

 For example, gray mold fungus (Botrytiscinerea), sugar beet brown spot (Cercosporabeticola), and apple scab (Venturlai nae qualis) resistant to benzimidazole fungicides such as thiophanate methyl, benomyl, and carbendazim. No pear? The compound of the present invention is also effective against bacterium (Venturianasashco1a) as well as susceptible bacteria.

 Furthermore, the compound of the present invention is also effective against gray mold fungi (Botry ti cs i n e r e a) that are resistant to dicarboximide fungicides (eg, vinclozolin, procymidone, iprodione), as well as the susceptible bacteria.

 Diseases more preferably applied include brown spot of sugar beet, powdery mildew of wheat, blast of rice, apple scab, gray mold of cucumber, brown spot of laccasei, and the like. The compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to underwater contact substances such as ship bottoms and fish nets.

 Some of the compounds of the present invention exhibit insecticidal and acaricidal activity.

 The fungicide of the present invention contains one or more of the compounds of the present invention as an active ingredient.

 When the compound of the present invention is actually applied, it can be used in a pure form without adding other components, and can be in the form of a general pesticide for use as a pesticide, that is, a wettable powder, a granule, a powder, It can also be used in the form of emulsions, aqueous solvents, suspensions, wettable powders and the like.

 Additives and carriers that can be added to the pesticide formulation include, for solid preparations, plant powders such as soy flour and flour, diatomaceous earth, apatite, gypsum, talc, bentonite, and pyrophyll. Organic and inorganic compounds such as mineral fine powder such as light and clay, sodium benzoate, urea and sodium sulfate are used.

 When a liquid dosage form is intended, kerosene, xylene and petroleum-based aromatic hydrocarbons, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, trichlorethylene, Methyl isobutyl ketone, mineral oil, vegetable oil, water, etc. can be used as the solvent.

Furthermore, in order to obtain a uniform and stable form in these preparations, surfactant A sexual agent can also be added. The surfactant that can be added is not particularly limited, and examples thereof include an alkylphenyl ether to which polyoxyethylene is added, an alkyl ether to which polyoxyethylene is added, and a higher fatty acid ester to which polyoxyethylene is added. Non-ionic surfactants such as terbitol, sorbitan higher fatty acid ester to which polyoxetylene is added, and tristyrylphenyl ether to which polyoxetylene is added, sulfate salts of alkylphenyl ether to which polyoxyethylene is added, Alkyl benzene sulfonate, higher alcohol sulfate, alkyl naphthalene sulfonate, polycarboxylate, lignin sulfonate, formaldehyde condensate of alkyl naphthalene sulfonate, copolymer of isoptylene maleic anhydride, etc. Is raised I can do it.

 The wettable powder, emulsion, floor pull, 7] solvent and granule wettable powder thus obtained are diluted with water to a specified concentration to obtain a solution, suspension or emulsion, which is used as a powder or granule. The agent is used by spraying it on the plant.

 The amount of the active ingredient is usually preferably from 0.01 to 90% by weight, more preferably from 0.05 to 85% by weight, based on the whole composition (formulation).

 The formulated fungicide composition of the present invention is applied to a plant, a seed, a water surface or soil as it is or after being diluted with water or the like. The application rate varies depending on the weather conditions, formulation, application magnetism, application method, application location, target disease, target crop, etc., but is usually 1-1,000 g in terms of the amount of active compound per hectare. , Preferably from 10 to L 0 g.

 When applying wettable powders, emulsions, suspensions, aqueous solvents, granule wettable powders, etc. with water, the application concentration is 1 to 100 ppm, preferably 10 to 250 ppm. In the case of granules and powders, apply as is without dilution.

It goes without saying that the compound of the present invention alone is sufficiently effective, but it can also be used in combination with one or more of various fungicides, insecticides and acaricides, or synergists. Typical examples of fungicides, insecticides, acaricides, and plant growth regulators that can be used by mixing with the compound of the present invention are shown below. Fungicide:

 Kyabutane, Folpet, Thiuram, Ziram, Zineb, Maneb, Mancozeb, Provineb, Polycarbamate, Chlorothalonil, Quintonesen, Captahor, Eve Logion, Procymidone, Vinclozolin, Fluoromid, Thimoxanil, Mepronil, Flutronil, Flutronil , Oxycarboxin, josetyl aluminum, propamocarb, triadimefon, triadimenol

, Propiconazolone, diclobutrazole, bitertanol, hexaconazole, myclobutanil, flusilazole, metconazole, etaconazole, flutrimazole, cyproconazole, epoxyconazole, flutriafene, benconazole, diniconazole, sainiconazole Proconazos, fenarimol, triflumizole, prochlora S, imazalil, ゾ furazoate, tridemorph, fenpropimorph, triforine, zuthiobate, pyrifenox, anilazine, polyoxin, metalaxyl, oxadixyl, furalaxyl, isoprothiolane, probenazole, pyrrolnitrin, sulphacin gazin Dihydrostreptomycin sulfate, benomyl, carbendazim, thiophanate methyl, hymexazole, basic copper chloride, basic copper sulfate, pentinacetate, hydroxylamine triphenyltin, dietophenecap, metasulfocap, quinomethionate, binapacryl , Lecithin, baking soda, dithianon, dinocap, phenaminosulf, diclomedine, guazatine, dozine, IBP, edifonphos, Mepanipyrim, Fermzone, Triclamide, Metasulfocarp ', Fluazinam, Etoquinolak, Dimethomorph, Pyroquilon, Tecmouth Phthalam, Fusalide, Phenazinoxide, Thiabendazol, Tricyclazonole, Vinclozolin, Simoxanil, Cyclobutanil Guazatine, propamocalp hydrochloride, oxolinic acid, hydroxyisoxazole, iminoctadine diacid salt and the like. Insecticide · Acaricide:

Organophosphorus and carbamate pesticides:

 Phanthion, Pnitrothion, Diazinon, Chlorpyrifos, ESP, Nomidothione, Fentate, Dimethate, Formothione, Marathon, Trichlorfon, Thiometone, Phosmet, Dichlorvos, Phacephate, EPBP, Methylparathion, Thionexion, Thionixion , Isoxathion, pyridafenthion, hosalon, metidathion, sulprophos, chlorfenvinphos, tetrachlorvinphos, dimethylvinphos, propaphos, isofenphos, ethylthiomethone, propofinophos, pyraclophos, monocrotophos, azidinphosmethyl, aldicarburubino, thiodiamine , Carbosulfan, Benfracarb, Frachoka Flop ', Purobokisuru, B P M C, MTM C, M I P C, carbaryl, Pirimi curve, E Chio Fen Culp, full hackberry deer Norev, E D D P and the like.

 Pyrethroid insecticides:

 Permethrin, Cypermethrin, Deltamethrin, Fumbrelet, Phumbreth / Printhrin, Pyrethrin, Aresulin, Tetramethrin, Resmethrin, Dimethrin, Propasulin, Phenothrin, Prothrin, Fulvalinate, Cyfluthrin, Cyhalothrin, Flucitrinate, Ethofritol AMPPROX, Cycloprothrin, Trollamethrin, Sirafluofen, Propfenprox, Acrinasulin, etc.

Benzoylurea and other insecticides:

Difluvenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetravenzuron, flufenoxuron, flucycloxuron, buprofidine, pyriproxyfen, methoprene, benzepin, diafentiuron, acetamiprid, imimidulone Daclopride, ditenviram, fipronil, kazole tap, thiocyclam, bensultap, nicotine sulfate, rotenone, methaldehyde, machine oil, microbial pesticides such as BT and insect pathogenic viruses. Nematicide:

 Fenamiphos, phosthiazate, etc. Acaricide:

 Chlorbenzylate, phenisobromolate, dicophor, amitraz, BPPS, benzomate, hexithiax, fenbutatin oxide, polynactin, quinomethionate, CPCBS, tetradihon, avermectin, milbemectin, clofentezine, cihexatin, pyridaben, Fenpyroximate, tebufenvirad, pyrimidiphene, pentochalp, dienochlor and the like. Plant growth regulator:

 Gibberellins (eg Gibberellin A3, Gibberellin A4, Gibberellin A7) I AA, NAA. BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be described in more detail with reference to examples. Example 1

 Method for producing N- (1- (5-phenyloxazol-2-yl) -2,2-dimethylpropyl) -3-formamide-2-hydroxybenzamide (Compound No. 2-13)

G-α- (5-Phenyloxazole-2-yl) -2,2-dimethylpropyl) -2-hydroxy-3-nitrobenzamide 0.5 g (2.5 mmo 1) in acetic acid This was dissolved in 1 mL of ethyl acetate, and 0.1 g of 10% palladium-carbon was added to the catalyst. Place the mixture under a hydrogen atmosphere For 1 hour. The reaction mixture was filtered, and the solvent was distilled off under reduced pressure. Next, the residue was dissolved in 10 ml of dichloromethane, 5 ml of a dichloromethane solution of N-formylimidazole (2.5 mmol) was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was poured into ice water, neutralized with 1N diluted hydrochloric acid, extracted with dichloromethane, and the organic layer was washed with brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (solvent hexane-monoethyl acetate = 4: 1) to obtain 0.15 g of the desired product. Yield 30% Reference Example 1

 Production of N- (l- (5-phenyloxazole-2-yl) -2,2-dimethylpropyl) -2-hydroxy-3-nitrobenzamide

Dissolve 0.5 g (2.2 mmo 1) of 1- (5-phenyloxazole-2-yl) -2,2-dimethylpropylamine in 20 ml of benzene, and add 0.5 g of 3-nitrosalicylic chloride. g (2.2 mmo 1) of benzene solution (5 ml) was added. Next, 0.45 ml (4.4 mmo 1) of triethylamine was added to the mixture, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into ice water, neutralized with 1N diluted hydrochloric acid, extracted with dichloromethane, and the organic layer was washed with brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (solvent hexane-monoethyl acetate = 4: 1) to obtain 0.6 g of the desired product. Yield 68% Reference Example 2

 Preparation of 1- (5-phenyloxazole-2-yl) -2,2-dimethylpropylamine

Dissolve 1.0 g (2.8 mmo 1) of N- [l- (5-phenyloxazole-2-yl) -2,2-dimethylpropyl] phthalimid in 30 ml of ethanol and add hydrazine 0.42 g (8.4 mmo 1) of 7_K hydrate was added, and the mixture was heated under reflux. After 4 hours, allow to cool and precipitate phthalhydra The zide was filtered off, the filtrate was concentrated under reduced pressure, redissolved in ethyl acetate, washed with saturated saline, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. As a result, 0.5 g of the desired product was obtained. 79% yield. Reference example 3

 Production of N- [1- (5-phenyloxazo-2-yl) -2,2-dimethylpropyl] phthalimid

2.0 g (9.3 mmo 1) of N-phthaloyltetraleucine was dissolved in 30 ml of benzene, and 1.9 g (9.3 mmo 1) of phosphorus pentachloride was added, followed by stirring at room temperature for 30 minutes. The solvent was distilled off from the reaction solution under reduced pressure, and the obtained crystals were dissolved in 30 ml of toluene, and 1.5 g (9.3 mmo 1) of α-azidoacetopentanone and 2.4 g of triphenylphosphine (9. 3mmo 1) was added, and the mixture was heated under reflux for 2 hours. The reaction mixture was poured into ice water, neutralized with 1N diluted hydrochloric acid, extracted with dichloromethane, and the organic layer was washed with saturated saline, dried by adding magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (solvent hexane / monoethyl acetate = 4: 1) to obtain 1.Og of the desired product. Yield 30% Tables 1 and 2 show typical examples of the compound of the present invention including the above Examples.

Table 1

600 / C00Zdf / X3d contract OOZ OAV 91

6 £ 9600 / e003df / XDd ooz OAV HHHS

 O dimension C

 Dimension D I * -38 CH3 H BB H -39 H MOM BB H -40 H Ac H S

 * -41 H Bn H S -42 H H F F H S One -43 H H burble H S

H H H S

H H H S -46 H H H S -47 H H H S

 * Abbreviations in the table are each

 MOM: methoxymethyl

 Ac: acetyl

 Bn: benzyl

 Boc: t-butoxycarbonyl

Represents LI

g, *

6 £ 9600 / C00Zdf / X3d 00 OAV Si

6C9600 / C00Zdf / 13d Contract 00Z ΟΛ \ 61

C9600 / £ 00ZdT / X3d S iO / t "OOZ OAV

个 〇 HH

Individual

0 H ^ο ν H 39-3 pieces

0 H ΙΛΙΟΙΑΙ H L9-S pieces

0 H H ”d! 09-2 pieces

*

 0 H H SHOSHO

 Individual

 *

0 Bok ^S dLU ® 0 HH 817-3

 D C

0 H

 Individual H SHO L -Z

0 H H H 917-3

*

 0 H H H S17-S

 U

0 ₀ 66-86duJ ヽ₀ 0 HHH

0 HHH C9600 / C00Zdf / X3d contract OOZ OAV zz

6C9600 / C00Zdf / X3d Contract OOZ OAV

-°

Next, some examples of the germicidal composition of the present invention will be described. However, the additives and the addition ratio are not limited to these examples, but can be changed in a wide range.

 Parts in Formulation Examples are parts by weight. Formulation Example 1 wettable powder

 Compound of the present invention 40 parts

 Clay 4 8 parts

 Dioctyl sulfosuccinate sodium salt 4 parts

 Lignin sulfonic acid sodium salt 8 parts

By uniformly mixing the above and pulverizing finely, a wettable powder with an active ingredient of 40% is obtained ₍ Formulation Example 2 Emulsion

 Compound of the present invention 10 parts

 Solbesso 2 0 0 5 3 parts

 Cyclohexanone 2 6 parts

 Dodecylbenzenesulfonic acid calcium salt 53 ο 411 ο 1 part

 咅 咅

 Polyoxyethylene alkylaryl ether 10 parts

 By mixing and dissolving the above, an emulsion containing 10% of the active ingredient is obtained. Formulation Example 3 Powder

 Compound of the present invention 10 parts

 Clay 90 parts

 If the above are uniformly mixed and finely pulverized, a powder containing 10% of the active ingredient is obtained. Formulation execution 4 granules

 Compound of the present invention

 Crewe

Bentonite

 Dioctyl sulfosuccinate sodium salt

 Potassium phosphate

 The above components are crushed and mixed well, water is added, and the mixture is kneaded well. Formulation Example 5 Suspension

 Compound of the present invention

Polyoxetylene alkylaryl Sodium polycarboxylate 2 parts

 Glycerin 10 parts

 Xanthan gum 0.2 parts

 Water 73. 8 parts

 The above ingredients are mixed and wet-pulverized until the particle size becomes 3 μm or less to obtain a 10% active ingredient suspension. Formulation Example 6 Granule wettable powder

 Compound of the present invention 40 parts

 Clay 36 parts

 Potassium chloride 10 parts

 Alkylbenzenesulfonic acid sodium salt 1 part

 Lignin sulfonic acid sodium salt 8 parts

 Alkylbenzenesulfonic acid sodium salt

 5 parts formaldehyde condensate

 The above components are uniformly mixed, finely ground, and then added with an appropriate amount of water and kneaded to form a clay. If the clay is granulated and dried, a wettable powder with an active ingredient of 40% is obtained. . The invention's effect

 Next, Test Examples show that the compound of the present invention is useful as an active ingredient of various plant disease controlling agents. Test example 1 Apple scab control test

 Emulsions of the compound of the present invention of Example 4 were sprayed onto apple seedlings (variety “Kunimitsu”, 3-4 leaf stage) grown in unglazed pots at a concentration of 200 ppm of the active ingredient. After air-drying at room temperature, conidia of the apple scab (Venturia ianaequalis) were inoculated, and the cells were kept in a room at 20 ° C and a high humidity, where the light and darkness were repeated every 12 hours, for 2 weeks. As a result of comparing the appearance of lesions on the leaves with that of no treatment and determining the control effect, the following compounds showed excellent control values of 75% or more.

1-1, 1, 23, 2-1, 2-3, 2-5, 2-8, 2-9, 2-10, 2-11, 2-13, 2-25, 2-26, 2- 27, 2-28, 2-29, 2-34, 2-35, 2-37, 2-39, 2-43, 2-63, 2-64, 2-65, 2-67 Test Example 2 Green Bean Mold control test The flowers of the kidney beans (variety “Nagauzura”) cultivated in the seedling raising bat were excised, and the emulsion of the compound of the present invention was immersed in a medicinal solution prepared with an active ingredient of 200 ppm. After immersion, the mixture was air-dried and spray-inoculated with Botrytiscinerea. The inoculated flowers were placed on untreated bean leaves and kept in a constant temperature room (20.C) for 7 days. The lesion diameter on the leaves was compared with that of untreated leaves, and the control value was determined. As a result, did the following compounds show a control value of 75% or more?

2-44 Test Example 3 Budobe and disease control test

 Grape seedlings (variety “Kaiji”, 2 leaf stage) grown in unglazed pots were sprayed with the emulsion of the present invention compound of Example 4 at a concentration of 200 ppm of the active ingredient. After spraying, air-dry at room temperature, spray inoculate a suspension of zoospores of grape downy mildew (Pla smop araviticola), and repeat the light and dark every 12 hours. High humidity constant temperature room (20 ° C) For 10 days. The appearance of lesions on the leaves was compared with that of no treatment, and the control effect was determined. As a result, the following compounds showed excellent control values of 75% or more.

1-1, 1-23, 2-3, 2-5, 2-8, 2-9, 2 10, 2-11,

2- 13, 2-25, 2-26, 2—27, 2—28, 229, 2-32, 2—34, 2-35, 2—38, 2-39, 2—40, 243, 2-63, 2-65, 2-67 Test Example 4 Tomato disease control test

 Tomato seedlings (variety “Regina”, 4-5 leaf stage) cultivated in an unglazed pot were sprayed with the emulsion of the compound of the present invention of Example 4 at a concentration of 200 ppm of the active ingredient. After spraying, air-dry at room temperature, spray inoculate with a suspension of zoospores of Phytophthora rainfestans, and repeat the light and dark every 12 hours. For 4 days. The appearance of lesions on the leaves was compared with that of no treatment, and the control effect was determined. As a result, the following compounds showed excellent control values of 75% or more.

2-3, 2-8, 2-10, 2-13, 2-27, 2-28, 2-29, 2-34,

 2-37, 2-39, 2-40, 2-65

Claims

The scope of the claims  1. Equation (1)

 (1) [In the formula, represents a hydrogen atom or a C i-s alkyl group. R ₂ represents a hydrogen atom, a C i_ ₆ alkoxycarbonyl group, an alkylcarbonyl group, or a phenyl C ₁₈ alkyl group which may be substituted with G. R ₃ represents a hydrogen atom or a C ₆ alkyl group. R ₄ is an alkyl group, C ₂ - represents an ₈ alkynyl group, Haroaru kill group which may be substituted by G Fuweniru group, or, optionally substituted Fuweniru C 8 alkyl group in G - ₈ alkenyl, C ₂ . A represents a heterocyclic ring represented by the formula (2) or the formula (3).

(2)

 (3)  (In the above formula, X represents an oxygen atom or a sulfur atom, B is a phenyl group which may be substituted with G, d-w alkyl group, a C 2 ^ _s alkenyl or C ₂ one _s alkynyl group,. ) G represents a halogen atom, an alkyl group, an alkoxy group, a d- ₆ alkylthio group, a d-6 haloalkyl group, or a C- ₆ haloalkoxy group, wherein G is the same or different and is substituted with 2 to 5 groups; May be. ] An aminosalicylic acid amide compound represented by the formula: or a salt thereof. 2. Equation (1)

(1) (Wherein,, R ₂ , R ₃ , R ₄ and A have the same meaning as in claim 1). One or more of an aminosalicylic acid compound or a salt thereof is represented by the following formula: A fungicide for agricultural and horticultural use characterized by containing as an active ingredient.