Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
  • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
  • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
  • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
  • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

• the present invention relates to a novel pyridine derivative, a method for producing the same, and a fungicide for agricultural and horticultural use.
• Japanese Patent Application Laid-Open Nos. 54-17070 and 61-37784 disclose compounds similar to the compound of the present invention. Disclosure of the invention:
• An object of the present invention is to provide a novel compound which can be industrially advantageously synthesized, has a certain effect, and can be used as an agricultural and horticultural fungicide which can be used safely.
• the present invention has the general formula (I):
• A represents an optionally substituted aryl group or an optionally substituted heteroaryl group
• B is an oxygen atom, a sulfur atom, a formula —N (R 1 ) — (wherein, R 1 represents a hydrogen atom, a lower alkyl group or an acyl group.),
• r 1 , r 2 , r 3 , r, r 5 , and r 6 are each a hydrogen atom, a halogen atom, a lower alkyl group, a hydroxy group, a cyano group, a phenyl group, and a lower alkylcarbonyloxy group.
• n 0 or 1
• Y is a lower alkyl group, a halogen atom, a lower alkoxy group, an acyloxy group, a benzyloxy group, a lower alkylsulfonyloxy group, an optionally substituted phenylsulfonyloxy group
• a cyano group, a lower alkylthio group, a mono- or di-lower-alkylamino group, a carbamoyloxyalkyl group, a compound represented by the formula: CH-CH—CH CH—, or a lower alkoxy group.
• n 0, 1 or 2;
• the method for producing the compound of the present invention is as follows.
• L represents a leaving group
• A, B, n, R, Y, m, and q have the same meaning as described above.
• Examples of the leaving group for L include a halogen such as bromine and chlorine, a methanesulfonyl group, and a tosyl group.
• solvents that can be used include alcohols such as ethanol, methanol, and n-propanol; ethers such as dioxane, tetrahydrofuran, dimethoxetane, and dimethyl ether; cellsolves such as methylcellsolve and ethylcellsolve; benzene; and toluene.
• examples include hydrocarbons, halogenated hydrocarbons such as carbon tetrachloride, and chloroform, water, DMF, and DMS0.
• the precipitate is filtered from the reaction solution after completion of the reaction to obtain an HL salt or a thiazolylpyridine compound corresponding to the general formula [I] ′.
• it is neutralized, subjected to ordinary post-treatments such as extraction, and, if necessary, subjected to operations such as chromatography and recrystallization to give the desired thiazolylpyridine compound represented by the general formula [I] ′.
• L is a halogen in the pyridine derivative represented by the general formula [III], it can be synthesized by the following route.
• Hal represents a halogen atom
• Y, m, and R have the same meaning as described above.
• a cyano viridine derivative represented by the general formula [IV] obtained by the method described in J. Org. Chem., 48, 1375 (1983) and a Grignard reagent represented by the general formula [V]. Or by reacting with an alkyl lithium represented by the general formula (VI), and further by subjecting the obtained imidium salt to acid hydrolysis.
• a biliyl ketone derivative represented by the general formula [Vi i] is obtained. Further, this ketone derivative is converted to a brominating agent such as pyridinium bromide or bromine, or a chlorinating agent such as sulfuryl chloride or chlorine.
• a haloketone derivative represented by the general formula [ ⁇ ⁇ _1] is obtained.
• the compound of the present invention may have the following (b), (c), (d),
• Se0 oxidizing agent such as 2
• This reaction is carried out in a solvent such as ethers such as dioxane, alcohols such as ethanol, water and mixtures thereof, For 10 minutes to 24 hours. Further, it can also be obtained by using an oxidizing agent such as chromic anhydride, manganese dioxide, and potassium permanganate described in ACS Monograph 186 "Oxidations in Organic Chemistry," 1990, 103-104.
• a solvent such as ethers such as dioxane, alcohols such as ethanol, water and mixtures thereof.
• an oxidizing agent such as chromic anhydride, manganese dioxide, and potassium permanganate described in ACS Monograph 186 "Oxidations in Organic Chemistry," 1990, 103-104.
• R ′ represents an electron-withdrawing group such as nitrile or carboxylate
• L, D, Y, m, q, and A have the same meaning as described above.
• This reaction proceeds in a solvent in the presence of a base at 0 to 150 ° C for 1 to 24 hours.
• the solvent include aromatic hydrocarbons such as DMF, DMSO, benzene, and toluene, ethers such as dioxane, tetrahydrofuran, and getyl ether, and the like, and mixtures thereof.
• Examples of the base include alkali metal hydrides such as sodium hydride, alkyl lithiums such as n-butyl lithium, alkali metal alkoxides such as sodium methoxide, and inorganic bases such as sodium hydroxide. And organic bases such as DBU.
• alkali metal hydrides such as sodium hydride
• alkyl lithiums such as n-butyl lithium
• alkali metal alkoxides such as sodium methoxide
• inorganic bases such as sodium hydroxide.
• organic bases such as DBU.
• B ′ represents an oxygen atom, a sulfur atom, and the formula —NR 1 — (R has the same meaning as described above.), And L, D, Y, m, q, and A have the same meanings as described above. .
• This reaction can be obtained by reacting in the absence of a solvent, preferably in a solvent, in the presence of a base at 0 to 150 for 1 to 24 hours. Wear.
• the solvent examples include aromatic hydrocarbons such as DMF, DMSO, benzene and toluene, ethers such as dioxane and tetrahydrofuran, etc., acetonitril, pyridine, water and the like, and mixtures thereof.
• aromatic hydrocarbons such as DMF, DMSO, benzene and toluene
• ethers such as dioxane and tetrahydrofuran, etc.
• acetonitril pyridine, water and the like, and mixtures thereof.
• the base examples include alkali metal hydrides such as sodium hydride, alkyl lithiums such as n-butyl lithium, alkali metal alkoxides such as sodium methoxide, and carbon dioxide.
• examples include inorganic bases such as lime and sodium hydroxide, and organic bases such as triethylamine and pyridin.
• the substrate is an aniline, it can also serve as a solvent and a base.
• L ′ represents a halogen atom such as chlorine, bromine, iodine or the like or an alkylthio group
• B ⁇ represents the above.
• M represents a Grignard residue of MgC ⁇ , MgBr or Mgl.
• This reaction is carried out in a solvent in the presence of a catalyst.
• catalysts examples include transition metal catalysts typified by nickel chloride diphenylphosphinoethane.
• This reaction is performed by heat treatment in a solvent in the presence of an oxidizing agent.
• a solvent include aromatic hydrocarbons such as benzene and toluene, ethers such as dioxane and tetrahydrofuran, halogenated hydrocarbons such as carbon tetrachloride and the like, and mixtures thereof.
• the oxidizing agent include iodine, bromine, aqueous hydrogen peroxide and the like.
• a 1,2,4-thiadiazole compound of the general formula [I] wherein D is a nitrogen atom is synthesized by a method described in ELSEVIER, Rodd's Chemistry of Carbon Compounds volume WD pl27-130 (1986). can do.
• the desired product after completion of the reaction, the desired product can be obtained by performing ordinary post-treatment.
• the structure of the compound of the present invention was determined from IR, NMR, MASS and the like.
• Example 1 the compound of the present invention will be further described with reference to Examples and Reference Examples.
• Example 1 the compound of the present invention will be further described with reference to Examples and Reference Examples.
• the port-form layer was washed with a 1N aqueous sodium hydroxide solution, further washed with a saturated saline solution, and dried over anhydrous magnesium sulfate.
• a Grignard solution was prepared by stirring 0.57 g of benzene chloride and 0.09 g of magnesium in 5 ml of ether at room temperature for 2 hours.
• Cold water was added to the reaction solution under ice-cooling, and the aqueous layer was further acidified to pH 1 with a 3N hydrochloric acid aqueous solution, followed by stirring at room temperature for 30 minutes.
• T_9 2-C1 // // li> t oDJ
• the compound of the present invention has an excellent bactericidal activity against a wide variety of filamentous fungi, it can be used for controlling various diseases that occur during cultivation of agricultural and horticultural crops including flowers, turf and pasture.
• brown spot of sugar beet (Cercosporabetico 1a)
• brown spot of laccasei (Mycosphaerellaarachidi s)
• P. kuroshibu (Mycosphaerellaberkeley i)
• powdery mildew of cucumber S phaerothecafuligina no.
• benzimidazole fungicides for example, thiophane monomethyl, benomyl, carbendazim), gray mold (B_o try t_is_cinerea), sugar beet brown spot (Cercosporabeticola), and lingos Fungus (Venturiainaequalis)
• the compounds of the present invention are also effective against pear scabs (Venturianashicola) as well as susceptible bacteria.
• the compound of the present invention is similar to bacteria that are resistant to gray mold fungi (B 0 trytiscinerea) that show shochu properties on dicarboximide fungicides (eg, vinclozolin, procymidone, ibrodione). It is valid.
• gray mold fungi B 0 trytiscinerea
• dicarboximide fungicides eg, vinclozolin, procymidone, ibrodione. It is valid.
• the compound of the present invention may not be used as an antifouling agent for preventing aquatic organisms from adhering to aquatic organisms such as ship bottoms and fish nets.
• the thus-obtained compound of the present invention when the thus-obtained compound of the present invention is actually applied, it can be used in an absolute frame without adding other components, and can be in a form that a general pesticide can take for the purpose of being used as a pesticide, that is, It can also be used in the form of wettable powders, granules, powders, emulsions, aqueous solvents, suspensions and the like.
• solid additives are used as additives and carriers, vegetable powders such as soybean flour, flour, etc., diatomaceous earth, limestone, gypsum, talc, ⁇ , etc.
• Mineral fine powders such as irophyllite, clay, mineral oil, and vegetable oil are used.
• kerosene, mineral oil, petroleum, sorbent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetate, mineral oil Use vegetable oil, water, etc. as solvents.
• Surfactants can be added, if necessary, to obtain a uniform and stable form in these preparations.
• Wettable powder, emulsion obtained in this way Is used as a suspension or an emulsion by diluting it to a predetermined concentration with water, and the powder and granules are used as they are sprayed on plants.
• 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.
• Compound of the present invention 40 parts Diatomaceous earth 53 parts Higher alcohol sulfate 4 parts Alkyl naphthalene sulfonate 3 parts By uniformly mixing and pulverizing finely, a wettable powder with an active ingredient of 40% is obtained.
• Compound of the present invention 5 parts Clay 7 3 parts Bentonite 20 parts Dioctyl sulfosuccinate sodium salt 1 part Sodium phosphate 1 part More than pulverize and mix well and add water. After kneading, the mixture is granulated and dried to obtain granules containing 5% of active ingredient.
• Compound of the present invention 10 parts Sodium ligninsulfonate 4 parts Sodium dodecylbenzenesulfonate 1 part Xanthan gum 0.2 parts Water 84.8 parts or more are mixed. If wet grinding is performed, a suspension containing the active ingredient at 10% is obtained.
• fungicides insecticides, pesticides, and plant growth regulators that can be used by mixing with the compound of the present invention are shown below.
• Jibere Li emissions (such Jibere Li down A 3, Jibere Li down A 4, Jibere Li down A 7) I AA, NAA.
• Test Examples show that the compound of the present invention is useful as an active ingredient of various plant disease controlling agents.
• the control effect can be evaluated by visually observing the disease state of the test plant at the time of the survey, that is, the degree of growth of the lesions and fungi appearing on the leaves and stems. j, "4" if about 10% is recognized compared to the untreated area,
• V- 12 // 5 1 0 Table (continued)
• Test example 3 Wheat powdery mildew control test (prevention test)
• a rice blast (variety “Nipponbare j, 3.0 leaf stage”) planted in a plastic pot was sprayed with a chemical solution of a wettable powder of the compound of the present invention at a predetermined concentration, air-dried at room temperature, and cultivated.
• the plants were grown in a constant temperature room at a temperature of 70% or more at a temperature of 70 ° C.
• the disease status was investigated 7 days after the inoculation, and the control effect was determined, and the results are shown in Table 13.
• Test Example 5 Wheat eye spot control test (Treatment test)
• Wheat seedlings grown in plastic pots were spray-inoculated with a suspension of conidiospores of wheat eye spot fungus (Pseudocercosporellaher potrichoides) obtained by culture, and sprayed. After maintaining the high humidity in the dark for 4 days, a chemical solution of a wettable powder of the compound of the present invention was sprayed at a predetermined concentration and air-dried at room temperature. The plants were grown under repeated lighting and darkness under humidity, and 35 days after inoculation, the onset of the disease was investigated, and the control effect was determined, and the results are shown in Table 14.
• a predetermined concentration of a wettable powder of the compound of the present invention was sprayed onto a seedling of Lingo (cultivar “Kunimitsu j, 3-4 leaf stage”) cultivated in an unglazed pot and air-dried. 1 is) and kept in a room at 20 ° C and high humidity for 2 weeks under light (bright and dark), and the control effect was investigated. It is shown in the table.
• Test Example 7 Control test for prevention of gray mold on cucumber (preventive test) To a young cucumber (variety “Four-leaf J, 1.0-leaf stage”) grown in an unbaked pot, a chemical solution of a predetermined concentration of a wettable powder of the compound of the present invention was applied to young seedlings. After spraying, the plants were air-dried at room temperature, and cultivated gray mold (Botrytiscie a_, a bacterium susceptible to benzimidazole and dicarboxymid), and a drug-sensitive bacterium. bacteria resistant to.
• a medicinal solution of a predetermined concentration of a wettable powder of the compound of the present invention was sprayed on young seedlings of laccase (cultivar “Nacateyuta Riki”, 4.0 bileaf stage) raised in unglazed pots. After spraying, the plants are air-dried at room temperature, spray-inoculated with a suspension of the spores of the lactobacillus brown spot disease fungus (CMy cosphaerellaarachidis) obtained by culturing, and kept at 24 to 28 days in high humidity for 1 day. They were grown in a greenhouse at ⁇ 30 ° C for 12 days, their disease status was investigated, and the control effect was determined. The results are shown in Table 17.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Agronomy & Crop Science (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Plural Heterocyclic Compounds (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

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• 1992
  • 1992-03-19 IL IL101291A patent/IL101291A0/xx unknown
  • 1992-03-19 WO PCT/JP1992/000336 patent/WO1992016527A1/ja active Application Filing
  • 1992-03-19 AU AU14223/92A patent/AU1422392A/en not_active Abandoned
  • 1992-03-21 CN CN92102046.5A patent/CN1065268A/zh active Pending
  • 1992-03-21 TW TW081102184A patent/TW199895B/zh active

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