WO2003087056A1 - Nouveau compose oxime o-ether, procede de production, et bactericide agricole ou horticole - Google Patents

Nouveau compose oxime o-ether, procede de production, et bactericide agricole ou horticole Download PDF

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WO2003087056A1
WO2003087056A1 PCT/JP2003/004746 JP0304746W WO03087056A1 WO 2003087056 A1 WO2003087056 A1 WO 2003087056A1 JP 0304746 W JP0304746 W JP 0304746W WO 03087056 A1 WO03087056 A1 WO 03087056A1
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formula
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mmol
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Daisuke Ichinari
Hisashi Tanigawa
Hiroshi Sano
Hiroshi Hamamura
Akira Mitani
Shuichi Ito
Takahiro Ando
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Nippon Soda Co.,Ltd.
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Priority to AU2003235152A priority Critical patent/AU2003235152A1/en
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Publication of WO2003087056A1 publication Critical patent/WO2003087056A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/53—Nitrogen atoms
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N43/80—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 1,2
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring

Definitions

  • Novel oxime 0-ether compound, production method and fungicide for agricultural and horticultural use Novel oxime 0-ether compound, production method and fungicide for agricultural and horticultural use
  • the present invention relates to a novel oxime 0-ether compound, a method for producing the same, and a fungicide for agricultural and horticultural use containing the compound as an active ingredient.
  • Japanese Patent Application Laid-Open No. Hei 9-13047 describes that oxime 0-ether containing a compound represented by the following structural formula is effective as a bactericide.
  • WO 01Z3 458 6 exemplifies a compound in which a pyridine ring portion similar to the compound of the present invention is substituted with a haloalkyl group, but a pyridyl group having a 6-position substituted with a haloalkyl group. Oxime 0-ether compounds containing are not described. Disclosure of the invention
  • An object of the present invention is to provide a novel oxime 0-ether compound which can be synthesized industrially advantageously, is a reliable fungicide, and can be an excellent agricultural and horticultural fungicide.
  • the present inventors have found that in the following formula [I], the oxime ether compound in which the substituent R 2 at the 6-position of the pyridine moiety is an alkyl group has a particularly excellent control effect on agricultural and horticultural crop diseases. And completed the present invention.
  • the present invention firstly comprises the formula (I) [I]
  • R 1 represents an alkyl group, C 2 ⁇ 6 alkenyl group, C 2 ⁇ 6 alkynyl group, C 3 ⁇ 6 consequent opening alkyl group, an alkoxy group, a haloalkyl group, an alkylthio group, an amino group, a mono- or di
  • It represents a ⁇ 6 alkylamino group, a C- 6 alkoxy group, an alkoxyalkyl group, a nitro group, a cyano group, a hydroxy group or a halogen atom.
  • n represents an integer of 0 to 3, and when m is 2 or more, R 1 may be the same or different.
  • R 2 represents a haloalkyl group.
  • R 3 represents a hydrogen atom, an alkyl group, C 3 ⁇ 6 cycloalkyl group.
  • R 4 and R 5 are the same or different and represent a hydrogen atom or an alkyl group.
  • X represents a phenyl group which may be substituted by R 6 or an optionally substituted 5- to 6-membered aromatic heterocyclic group containing 1 to 3 atoms of nitrogen, io and oxygen.
  • R 6 is an alkyl group, C 3-6 Shikuroarukinore group, C 2 ⁇ 6 alkenyl, C 2 - 6 Al Kiniru group, alkoxy group, alkoxy alkyl group, C alkoxy C ⁇ 1-6 alkoxy group, Ji 3-6 cycloalkyl Arukiruokishi group, haloalkoxy group, C 2 ⁇ 6 Al Keniruokishi group, C 2 ⁇ 6 Arukiniruokishi group, an alkylcarbonyl O alkoxy group, a mono- or di-C ⁇ 6 alkyl Scarpa carbamoyl O alkoxy group, C ⁇ 6 alkylsulfonyl Okishi group, and Table C-Bok 6 haloalkylsulfonyl O alkoxy group, Ji Bok 6 haloalkyl group, Ci ⁇ 6 alkylthio group, amino group, mono- or di-alkylamino group, hydroxy group or hal
  • a fungicide for agricultural and horticultural use characterized by containing one or more of the oxime 0-ether compound represented by the formula [I] or a salt thereof as an active ingredient.
  • Embodiment of the invention :
  • R 1 is a C 6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexinole and its isomers,
  • cycloalkynole groups such as cyclopropyl, cyclopentyl and cyclohexyl
  • Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, t-butoxy
  • C-Roalkynole groups such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tripromomethyl, trichloroethyl, trifluoromethyl, pentafluoroethyl, etc., methylthio , Echiruchio, isopropylthio, C WINCH 6 alkylthio groups such Puchiruchio, an amino group,
  • Mono- or di-C alkylamino groups such as methylamino, ethylamino, propylamino, dimethylamino, getylamino, dipropylamino, dibutylamino, ethylisopropylamino,
  • Ci to 6 alkoxy C to 6 alkyl groups such as Ci to 6 acyloxy groups such as acetoxy, propionyloxy and bivaloyloxy, methoxymethinole, methoxethyl, ethoxymethylinole, propoxymethizole and butoxymethyl;
  • R 1 represents an integer of 03.
  • R 1 may be the same or different.
  • R 2 is chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethylinole, dibromomethinole, trichloromethyl, trifrenoleolomethyl, tripromethinole, trichloroethyl, trifluoromethyl, pentafluoroethyl, etc. Represents a C haloalkyl group.
  • R 3 is a hydrogen atom
  • ⁇ 6 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec_butyl, isoptyl, t-butyl, pentyl and its isomers, hexyl and its isomers, C such as cyclopropyl, cyclopentyl and cyclohexyl Represents a 3 to 6 cycloalkyl group.
  • RR 5 is the same or different and is a hydrogen atom
  • Ci- 6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and its isomers.
  • X is a phenyl group which may be substituted by R 6 , or
  • R 6 is a Ci- 6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl and its isomers, hexyl and its isomers,
  • Ci- 6 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, t-butoxy,
  • C 6 alkoxy C ⁇ ⁇ 6 alkoxy groups such as methoxy methoxy, methoxy ethoxy, ethoxy methoxy, propoxy methoxy, butoxy methoxy, etc.
  • a C 3-6 cycloalkyloxy group such as cyclopropyloxy, cyclopentyloxy, cyclohexyloxy,
  • Chloromethane butoxy Furuorome butoxy, Puromome butoxy, Jikurorome butoxy, Jifuruoro main butoxy, Jiburomome butoxy, trichloroacetic main butoxy, Torifuruorome butoxy, tribromo main butoxy, trichloro port ethoxy, torr full O b ethoxy, C WINCH penta full O b ethoxy 6 Haloalkoxy group,
  • Alkylcarbonyloxy groups such as acetoxy, propionyloxy, and bivaloyloxy;
  • Mono- or di-Ci- 6- alkyl rubamoyloxy groups such as methylcarbamoyloxy, dimethylcarbamoyloxy, ethylcarbamoyloxy, t-butylcarbamoyloxy, etc., and carbon atoms such as methylsulfonyloxy and ethylsulfonyloxy 6 alkyl sulfoniroki Group,
  • C ⁇ 6 haloalkylsulfonyloxy groups such as chloromethylsulfonyloxy, fluoromethylsulfonyloxy, and trifluoromethylsulfonyloxy;
  • C 6 haloalkyl groups such as chloromethyl, fluoromethyl, bromomethyl, dichloromethyl, difluoromethyl, dibromomethyl, trichloromethyl, trifluoromethyl, tripromomethyl, trichloroethyl, trifluoromethyl, pentafluoroethyl, methylthio, Ci- 6 alkylthio groups such as ethylthio and isopropylthio,
  • Mono- or dialkylamino groups such as methylamino, ethylamino, propylamino, dimethylamino, getylamino, dipropylamino, dibutylamino, ethylisopropylamino,
  • R 6 when R 6 is 2 to 6 are the same or different, also, two R 6, fused 5 is an alkylene chain 7-membered containing heteroatoms of such as methylene Njiokishi group May be formed.
  • R 6 is - 6 alkyl group, 6 alkoxy group or a compound which is an Ha androgenic atom, or X is a pyridyl group, pyrimidinyl group, furyl group, or is a thienyl group Compounds are preferred.
  • L represents a halogen atom such as chlorine, bromine, iodine, etc., a methanesulfonyloxy group, ⁇ . It represents a leaving group such as a toluenesulfonyloxy group.
  • the compound represented by the formula [I] is prepared by mixing the compound represented by the formula [II] and the compound represented by the formula [III] in the absence of a solvent in the presence of a deoxidizing agent such as a base.
  • a deoxidizing agent such as a base.
  • it can be obtained by stirring in a solvent at a reaction temperature of 0 to 150 ° C for 10 minutes to 24 hours.
  • Solvents that can be used in this reaction include ketones such as acetone and 2-butanone, ethers such as dimethyl ether and tetrahydrofuran, aromatic hydrocarbons such as benzene and toluene, Examples include alcohols such as methanol and ethanol, acetonitrile, N, N-dimethylformamide, dimethylsulfoxide and water. These solvents can also be used as a mixture of two or more solvents.
  • the base examples include inorganic bases such as 7J sodium oxide, hydroxylated lime, carbonated lime, sodium carbonate, sodium hydrogen chloride, alkali metal alcoholates such as sodium methylate, sodium ethylate, pyridine, triethyl And organic bases such as amine and DBU.
  • inorganic bases such as 7J sodium oxide, hydroxylated lime, carbonated lime, sodium carbonate, sodium hydrogen chloride, alkali metal alcoholates such as sodium methylate, sodium ethylate, pyridine, triethyl And organic bases such as amine and DBU.
  • 2-methylpyridines represented by the formula [VI I] are derivatized to pyridine-N-oxide with an oxidizing agent such as hydrogen peroxide and metabenzo-peroxybenzoic acid (mCPBA), followed by anhydrous acetic acid.
  • an oxidizing agent such as hydrogen peroxide and metabenzo-peroxybenzoic acid (mCPBA)
  • mCPBA metabenzo-peroxybenzoic acid
  • 2-acetoxymethylpyridines After hydrolyzing 2-acetoxymethylpyridines and leading to 2-hydroxymethylpyridines, the 2-pyridinecarboxylate represented by the formula [IV-1] is reacted with an oxidizing agent such as manganese diacid.
  • Xyaldehydes can be synthesized.
  • 2-pyridinecarboxyaldoximes represented by the formula [II-1] can be produced by reacting 2-pyridincarboxaldehydes represented by the formula [IV-1] with hydroxylamine. .
  • the 2-pyridinecarboxaldehydes represented by the formula [IV-1] can also be produced by the following method. i-PrMgCI
  • a formyl amide such as DMF Formylation of the 2-position by means of the above can produce a 2-pyridinepyridinecarboxaldehyde represented by the formula [IV-1].
  • a cyanating agent such as copper cyanide is allowed to act on pyridines substituted with a halogen at the 2-position represented by the formula [VI II], or pyridine N unsubstituted at the 2-position represented by the formula [IX] —Oxides are converted to cyanopyridines of the formula [X] by the action of a cyanating agent such as trimethylsilyl cyanide (TMS CN) and then reduced to diisopropylaluminum hydride (DI BAH) Or by conversion to a formyl group with an agent, or after conversion to the alkoxycarbonyl group by hydrolysis after conversion to the 2-position, and hydroxymethylene with a reducing agent such as lithium aluminum hydride (LAH).
  • 2-pyridinecarboxaldehydes represented by the formula [IV-11] can also be converted to a formyl group by an oxidizing agent such as manganese diacid or the like. It can be produced.
  • pyridines substituted with halogen at the 2-position represented by the formula [VI II] are reacted with carbon monoxide in alcohol in the presence of a catalyst such as a palladium complex to form an alkoxycarbonyl compound at the 2-position.
  • the 2-pyridine represented by the formula [IV-1] can also be obtained by directly introducing a group, converting it into a hydroxymethyl group with a reducing agent such as LAH, and then converting it into a formyl group with an oxidizing agent such as manganese dioxide.
  • Carboxaldehydes can be produced.
  • R 2 has the same meaning as described above.
  • R represents a lower alkyl group and PG represents a protecting group.
  • the bromine atom represented by the formula [XI] is substituted and protected at the 2-position.
  • a pyridine compound having a hydroxymethyl group is reacted with carbon monoxide in alcohol in the presence of a catalyst such as a palladium complex to introduce an alkoxyl group, followed by a reducing agent such as LAH to formula [XI I] It leads to the ⁇ dani thing represented by.
  • the hydroxymethyl group is converted to a fluoromethyl group by a fluorinating agent such as getylaminosulfur trifluoride (DAST), and then the protecting group is removed, and the compound is converted to a compound of the formula [IV-la] by oxidation with manganese diacid or the like.
  • a fluorinating agent such as getylaminosulfur trifluoride (DAST)
  • DAST getylaminosulfur trifluoride
  • the compound represented by the formula [IV-1b] wherein m is 1 and R 1 is CHF 2 among the compounds represented by the formula [IV-1] can be produced by the following method.
  • the hydroxymethyl group of the compound represented by the formula [XI I] is derivatized to an aldehyde by an oxidizing agent such as manganese diacid, it is converted to a difluoromethyl group by a fluorinating agent such as DAST. Then, the protective group is removed, and the compound is oxidized again with manganese dioxide or the like, whereby the compound represented by the formula [IV-lb] can be produced.
  • the compound represented by the formula [IV-1c] wherein m is 1 and R 1 is a cyano group among the compounds represented by the formula [IV-1] can be produced as follows. it can.
  • t-Bu-ONO is reacted to induce the methinole group to be an oxime, which is then converted to a cyano group with a dehydrating agent such as acetic anhydride and then deprotected.
  • the compound represented by the formula [IV-lc] can be produced by oxidizing using manganese dioxide or the like.
  • the compound represented by the formula [IV-1d] wherein m is 1 and R 1 is a fluorine atom can be produced as follows.
  • the compound represented by the formula [XI] is reacted with sodium azide, or the compound represented by the formula [XIV] is subjected to catalytic reduction in the presence of a suitable reducing agent or a suitable catalyst.
  • R 3 is C i one 6 Al kill group or C 3 ⁇ 6 cycloalkyl group among the compounds represented by the formula [II] which is a starting material of the production method of the present invention [I 1-2] is It can be manufactured by the following method.
  • L 1 represents a leaving group such as a halogen atom such as chlorine, bromine or iodine.
  • a cyanopyridine represented by the formula [X] is reacted with a Grignard reagent represented by the formula [XVI], thereby deriving to a ketone represented by the formula [IV-2].
  • 2-pyridinylketonoximes represented by the formula [I1-2] can be produced by reacting with a salt thereof.
  • the ketone represented by the above formula [IV-2] can also be produced as follows.
  • the compound represented by [II-1] can be produced as follows.
  • X represents the same meaning as described above.
  • L 2 represents a halogen atom such as chlorine, bromine and iodine.
  • the benzene or heterocyclic compound having a methyl group represented by the formula [XVI I] is irradiated with a halogenated succinimide such as N-chlorosuccinimide, N-prosuccinimide, or N-succinimide under light irradiation.
  • benzene or a heterocyclic compound having a halomethyl group represented by the formula [II1-1] can be synthesized.
  • X and L represent the same meaning as described above.
  • W represents a halogen atom such as chlorine, a hydroxy group, a hydrogen atom, or a lower alkoxy group.
  • the compound represented by the formula [II1-2] can be produced by reacting a sulfonyl halide such as methanesulfonyl chloride to convert the compound into a sulfonyloxy group.
  • L 3 represents a leaving group such as a halogen atom such as chlorine, bromine, or iodine.
  • a benzene or heterocyclic compound having an alkylcarbonyl group or a formyl group represented by the formula [XIX] is reacted with a Grignard reagent represented by the formula [XX] to form a benzene or a heterocyclic compound having a hydroxymethyl group.
  • a Grignard reagent represented by the formula [XX] to form a benzene or a heterocyclic compound having a hydroxymethyl group.
  • a ring conjugate and further substituting a hydroxyl group with a halogen atom using a halogenating agent such as thionyl chloride or reacting with a sulfonyl halide such as methanesulfonyl chloride to obtain a sulfonyloxy group.
  • a compound of the formula [II 1-3] can be produced.
  • Formula invention it ⁇ compounds represented by [I] is, c production method 2 can also be produced by the following
  • the compound represented by the formula [I] is prepared by mixing the compound represented by the formula [VI] and the compound represented by the formula [V] or a salt thereof without a solvent, preferably in a solvent, at a reaction temperature of 0 to It is obtained by stirring at 50 ° C for 10 minutes to 24 hours.
  • Solvents that can be used include alcohols such as ethanol and methanol, ethers such as dimethyl ether, tetrahydrofuran, and dioxane; cellosolves such as methyl sorb and ethyl sorb; aromatic hydrocarbons such as benzene and toluene; Acetic acid, 7j, N, N-dimethylformamide, dimethylsulfoxide and the like.
  • solvents can be used alone or as a mixture of two or more solvents in various mixing ratios.
  • This reaction does not necessarily require the presence of a catalyst, but the addition of an acid or base may significantly accelerate the reaction.
  • the acid include inorganic acids such as sulfuric acid and hydrochloric acid, organic acids such as paratoluenesulfonic acid, and sodium acetate as a base.
  • the oxyamines represented by the formula [V] can be produced as follows.
  • N-hydroxyphthalimid and the N-hydroxyphthalimide represented by the formula [III] are appropriately reacted in the presence of a suitable base.
  • the compound By reacting in an appropriate solvent, the compound can be produced by deriving to a compound represented by the formula [XXII] and further deprotecting with a deprotecting agent such as hydrazine.
  • the compound represented by the formula [XXI I] can be prepared by reacting an alcohol represented by the formula [XXI] in a suitable solvent in the presence of a condensing agent such as getyl azodicarboxylate (DEAD). It can also be produced by reacting with roxyphthalimide.
  • the compound [1-2] in which R 2 is CH 2 F among the compounds represented by the formula [I] can also be produced by the following method.
  • 2-pyridyl ketones or 2-pyridinecarboxaldehydes having a hydroxymethyl group protected at the 6-position represented by the formula [XXI II] are condensed with oxyamines represented by the formula [V], After deprotecting the compound with an appropriate deprotecting agent to remove the protecting group, the compound is derived into the compound represented by the formula [XXIV], and then expressed by the formula [1-2] using a fluorinated compound such as DAST. Can be produced.
  • the conjugate [1-3] wherein R 2 is CHF 2 can also be produced by the following method.
  • the disulfide compound represented by the formula [XXIV] is difluorinated with a fluorinating agent such as DAST, and the formula [I-13] ]
  • a fluorinating agent such as DAST
  • the desired product can be obtained by performing ordinary post-treatment.
  • Various derivatives can also be synthesized by further chemically modifying the obtained product.
  • the chemical modification described here includes functional group conversion typified by induction of an amino group by a reduction reaction of a nitro group, and a functional group recognized as a protecting group in the field of organic synthesis such as a methoxymethyl group. Deprotection of a group, alkylation of a functional group such as a hydroxyl group or an amino group generated thereby Derivation by an acylation or the like, and a leaving group in the field of organic synthesis such as a halogen atom typified by the S on 0 gashira reaction. Induction using a nucleophilic reagent from a functional group recognized as being effective, and the like.
  • the salt of the compound represented by the formula [I] can be obtained by reacting the compound represented by the formula [I] with an inorganic acid or an organic acid in a suitable solvent.
  • Isomers exist in the oxime portion of the compound of the present invention, and these isomers are included in the scope of the present invention.
  • the structure of the compound of the present invention is determined from NMR, mass spectrum and the like.
  • 6-Hydroxymethyl-4-methylpyridine-12-carboxaldehyde 2,6-Dimethoxybenzyloxymide 1.0 g (3.16 mmol) was dissolved in 1 OmL of benzene, and the activated acid was added. 0.82 g (9.43 mmol) was added, and the mixture was heated under reflux for 8 hours. After the reaction solution was cooled to room temperature, 0.51 g (5.87 mmol) of manganese dioxide was added, and the mixture was further heated under reflux for 4 hours.
  • the total amount of the obtained crude product was mixed with 4.52 g (22.1 mmol) of 4-methyl-16-trifluoromethyl-12-pyridinecarboxyaldoxime and 60 ml of N, N-dimethylformamide. Then, 2.99 g (26.8 mmol) of a 50% aqueous potassium hydroxide solution was stirred at 10 ° C. for 1.5 hours. After the reaction mixture was poured into cold water and the reaction was completed, the reaction mixture was extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • Embodiment of the Invention (Agricultural and Horticultural Fungicide):
  • the compound represented by the formula [1] of the present invention or a salt thereof can be used for a wide variety of filamentous fungi such as oomycetes (Oomycetes), ascomycetes ( ⁇ ) fungi (Ascomvcetes), Fungi (D euter omy cetes), belonging to Basidiomycetes (B asidi omy cetes) It has excellent bactericidal activity against bacteria.
  • composition containing the compound of the present invention as an active ingredient is used for controlling various diseases that occur in cultivation of agricultural and horticultural crops including flowers, turf, and grass by seed treatment, foliage application, soil application or water application. Can be used.
  • Kidney bean sclerotium (S c le ro t i n i a s c l e ro t i o r um;
  • Apple powdery mildew (Pod s pha e r a l e u c o t r i c h a)
  • Anthracnose (Colle t o t r i chum t h e ae— s i n en n s i s) Scab scab CE 1 si n o e f awe e t t i)
  • Soybean purpura (Cercosporakikikuchihii)
  • Tomato Blight (Phy t opht o r a i n f e s t an s), Cucumber blight (P s eudop e r ono s po r a c u b e n si s), Grape blight (P la smop a r a v i t i c o l a
  • It can be used for pest control.
  • 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.
  • the dandelion compound of the present invention is effective against the gray mold fungus (B0 trytiscinerea) that is resistant to dicarboximide fungicides (for example, vinclozolin, procymidone, iblodion) as well as the susceptible bacteria. is there.
  • dicarboximide fungicides for example, vinclozolin, procymidone, iblodion
  • 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.
  • the fungicide of the present invention contains one or more of the compounds of the present invention as an active ingredient.
  • the compound of the present invention 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 the purpose of using it as a pesticide, that is, a wettable powder, a granule, a powder , Emulsions, aqueous solvents, suspensions, flowables and the like.
  • a general pesticide for the purpose of using it as a pesticide, that is, a wettable powder, a granule, a powder , Emulsions, aqueous solvents, suspensions, flowables and the like.
  • Additives and carriers that can be added to the pesticide formulation include, for solid formulations, plant powders such as soybean flour and wheat flour, diatomaceous earth, apatite, gypsum, tanolek, bentonite, and pyrophyllite.
  • Organic and inorganic compounds such as mineral fine powders such as clay and clay, sodium benzoate, urea and sodium sulfate are used.
  • petroleum fractions such as kerosene, xylene, and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, Mineral oil, vegetable oil, water, etc. can be used as the solvent.
  • a surfactant may be added as necessary.
  • the surfactant include alkyl phenyl ether to which polyoxyethylene is added, alkyl ether to which polyoxyethylene is added, higher fatty acid ester to which polyoxyethylene is added, sorbitan higher fatty acid ester to which polyoxetylene is added, and polyoxyethylene.
  • Nonionic surfactants such as tristyryl ether added with oxyethylene, sulfates of alkyl phenyl ethers added with polyoxetylene, alkyl benzene sulfonates, sulfates of higher alcohols, alkyls
  • Examples include naphthalene sulfonate, polycarboxylate, lignin sulfonate, formaldehyde condensate of alkyl naphthalene sulfonate, and copolymer of isobutylene monomaleic anhydride.
  • 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 fungicide composition of the present invention thus formulated 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 ⁇ freshener, emulsion and flowable are diluted to a predetermined concentration with water to prepare a suspension or emulsion, and the powder and granules are used as they are applied to plants.
  • the amount of application varies depending on the weather conditions, formulation, application time, application method, application location, target disease, target crop, etc., but it is usually 1 to 100 g, preferably 100 to 100 g of active ingredient compound per hectare. Is from 10 to: L 0 0 g.
  • the application concentration is :! 11 O O O pm, preferably 10 to 25 O pp m.
  • the compound of the present invention is sufficiently effective when used alone, but it can also be used in combination with one or more of various fungicides, insecticides, acaricides, or synergists.
  • Fungicide fungicides, insecticides, acaricides, and plant growth regulating sleeves that can be used by mixing with the compound of the present invention are shown below.
  • Fungicide insecticides, acaricides, and plant growth regulating sleeves that can be used by mixing with the compound of the present invention are shown below.
  • Copper agent basic copper chloride, basic copper sulfate, etc.
  • Sulfur agents Sulfur agents; thiuram, zineb, maneb, mancozeb, ziram, propineb, polycarbonate, etc.
  • Organic phosphorus agents IBP, EDDPP, triclofosmethyl, pyrazophos, Josetyl and the like.
  • Benzimidazole agents thiophanemethyl, benomyl, carbendazim, thiabenzazole and the like.
  • Dicarboximide agents iprodione, procymidone, vinclozolin, fluorimide and the like.
  • Carboxamide agents oxycarboxin, mepronil, flutranil, techmouth phthalam, triclamide, pencyclone and the like.
  • Asylalanine preparations metalaxyl, oxadixyl, furalaxyl and the like.
  • Methoxyacrylates kresoxime methinole, azoxystropine, methinostrobin and the like. '
  • SBI agent Triadimefon, Triadimenol, Vitelenol, Microbutanil, Hexaconazo monol, Propiconazo monol, Trinole Mizonole, Prochloraz, Ephrazolate, Funarimol, Pyrifenox, Triforin, Flucilazonale, Ethazona , Diclobutrazol, fluotrimazole, fenoretriazole, penconazo mono, dinico nasol, imazalil, tridemorph, fenpropimorph, petiobate, epoxyconazole, metconazole.
  • Antibiotics Polyoxin, blasticidin S, kasugamycin, validamycin, Dihydrostreptomycin sulfate and the like.
  • Acaricide Chlorbenzylate, phenisopromolate, dicohonole, amitraz, BPPS, benzomate, hexthiazox, acid ⁇ : fenbutazin, polynactin, quinomethionate, CPCBS, tetradihon, avermectin, milbemectin, clofentezine, cybenxetine, ciheventine Campiroximate, tebufenvirad, pyrimidifene, penothiocalp, dienochlor and the like.
  • Plant growth regulator Plant growth regulator
  • Parts in Formulation Examples are parts by weight. Difficult case 20 wettable powder
  • Example 23 granules 5 parts of the compound of the present invention
  • Example 2 5 wettable powder for granules
  • 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 was determined by visually observing the diseased state of the plant at the time of the survey, that is, the degree of growth of the disease spots on the leaves, stems, etc., and comparing it with that of no treatment.
  • the flowers of the kidney beans (variety “Nagauzura”) cultivated in the seedling raising bat were excised and immersed in an emulsion of the compound of the present invention adjusted to a concentration of 200 ppm of the active ingredient. After immersion, it was air-dried at room temperature and spray-inoculated with green bean fungus (Botry ti s c i n c i n r e a a). The inoculated flowers were placed on untreated bean leaves and kept in a high-humidity constant temperature room (20 ° C) where light was repeated every 12 hours for 7 days. The lesion diameter on leaves was compared with that of untreated leaves, and the control value was determined. As a result, the following compounds showed 100% control value.
  • the compound numbers correspond to the compound numbers in Tables 1 to 3.
  • Compound A used for comparison also showed a control value of 100%.
  • the first true leaf of the kidney beans (variety “Nagauzura”) cultivated in a pot was sprayed with a drug solution prepared by adjusting the emulsion of the compound 1-267 of the present invention or the comparative compound A to a concentration of 200 ppm of the active ingredient. After air-drying, the kidney pot was placed in a glass greenhouse. Seven days later, the first true leaf was cut off, and a kidney vase, which had been inoculated with a green mold fungus (BotrVticecinera) in advance, was placed on the leaf. After keeping in a high humidity constant temperature room (20 ° C) for 5 days, the diameter of lesions formed on the leaves was compared with that of untreated leaves, and the control value was determined. As a result, Compound 1-267 of the present invention exhibited a control value of 100%, whereas Comparative Compound A showed 59%.
  • the compound of the present invention is a compound having significantly better activity in practical use than the known compound.

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  • 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)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

L'invention concerne un composé oxime O-éther représenté par la formule [I]; un procédé permettant de produire ce composé; et un bactéricide agricole ou horticole contenant le composé en tant que principe actif. [I] dans cette formule, R1 représente alkyle C1-6, alcényle C2-6, alkynyle C2-6, cycloalkyle C3-6, alkoxy C1-6, haloalkyle C1-6, alkylthio C1-6, amino, etc.; m représente un entier relatif compris entre 0 et 3; R2 représente haloalkyle C1-6; R3 représente hydrogène, alkyle C1-6, ou cycloalkyle C3-6; R4 et R5 sont identiques ou différents et chacun représente hydrogène ou alkyle C1-6; et X représente un phényl éventuellement substitué ou un groupe hétérocyclique aromatique à 5 ou 6 éléments.
PCT/JP2003/004746 2002-04-15 2003-04-15 Nouveau compose oxime o-ether, procede de production, et bactericide agricole ou horticole WO2003087056A1 (fr)

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AU2003235152A AU2003235152A1 (en) 2002-04-15 2003-04-15 Novel oxime o-ether compound, production process, and agricultural or horticultural bactericide
JP2003584012A JPWO2003087056A1 (ja) 2002-04-15 2003-04-15 新規オキシムｏ−エーテル化合物、製造方法及び農園芸用殺菌剤

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WO2014093591A1 (fr) * 2012-12-13 2014-06-19 Dow Agrosciences Llc Procédés pour la préparation de 4-amino-3-halo-6-(substitués)picolinates et de 4-amino-5-fluoro-3-halo-6 substitués-picolinates
WO2014093588A1 (fr) * 2012-12-13 2014-06-19 Dow Agrosciences Llc Procédé d'élaboration de picolinates (éventuellement substitués) en 4-amino-5-fluoro-3-chloro-6
WO2015199065A1 (fr) * 2014-06-24 2015-12-30 日本曹達株式会社 Compose pyridine et son utilisation
JP2016500060A (ja) * 2012-11-16 2016-01-07 エフ．ホフマン−ラ ロシュ アーゲーＦ． Ｈｏｆｆｍａｎｎ−Ｌａ Ｒｏｃｈｅ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ ２−トリフルオロメチルイソニコチン酸及びエステルの調製方法
WO2016039048A1 (fr) * 2014-09-10 2016-03-17 日本曹達株式会社 Composé de pyridine et son utilisation
WO2019083008A1 (fr) * 2017-10-27 2019-05-02 住友化学株式会社 Composé pyridine, et composition de lutte contre des organismes nuisibles comprenant celui-ci

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WO2002064566A1 (fr) * 2001-02-14 2002-08-22 Nippon Soda Co.,Ltd. Composes d'oxime o-ether et fongicides a usage agricole et horticole
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WO2001034568A1 (fr) * 1999-11-05 2001-05-17 Nippon Soda Co., Ltd. Composes oxime o-ether et fongicides utiles dans l'agriculture et l'horticulture
WO2002064566A1 (fr) * 2001-02-14 2002-08-22 Nippon Soda Co.,Ltd. Composes d'oxime o-ether et fongicides a usage agricole et horticole
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016500060A (ja) * 2012-11-16 2016-01-07 エフ．ホフマン−ラ ロシュ アーゲーＦ． Ｈｏｆｆｍａｎｎ−Ｌａ Ｒｏｃｈｅ Ａｋｔｉｅｎｇｅｓｅｌｌｓｃｈａｆｔ ２−トリフルオロメチルイソニコチン酸及びエステルの調製方法
WO2014093591A1 (fr) * 2012-12-13 2014-06-19 Dow Agrosciences Llc Procédés pour la préparation de 4-amino-3-halo-6-(substitués)picolinates et de 4-amino-5-fluoro-3-halo-6 substitués-picolinates
WO2014093588A1 (fr) * 2012-12-13 2014-06-19 Dow Agrosciences Llc Procédé d'élaboration de picolinates (éventuellement substitués) en 4-amino-5-fluoro-3-chloro-6
AU2013359258B2 (en) * 2012-12-13 2016-02-04 Dow Agrosciences Llc Processes for the preparation of 4-amino-3-halo-6- (substituted)picolinates and 4-amino-5-fluoro-3-halo-6- (substituted)picolinates
CN105407724A (zh) * 2012-12-13 2016-03-16 美国陶氏益农公司 制备4-氨基-3-卤代-6-(取代的)吡啶甲酸酯和4-氨基-5-氟-3-卤代-6-(取代的)吡啶甲酸酯的方法
CN105407724B (zh) * 2012-12-13 2017-06-09 美国陶氏益农公司 制备4‑氨基‑3‑卤代‑6‑(取代的)吡啶甲酸酯和4‑氨基‑5‑氟‑3‑卤代‑6‑(取代的)吡啶甲酸酯的方法
RU2653855C2 (ru) * 2012-12-13 2018-05-15 ДАУ АГРОСАЙЕНСИЗ ЭлЭлСи Способ получения 4-амино-5-фтор-3-хлор-6-(замещенных)пиколинатов
RU2658825C2 (ru) * 2012-12-13 2018-06-25 ДАУ АГРОСАЙЕНСИЗ ЭлЭлСи Способы получения 4-амино-3-галоген-6(замещенных)пиколинатов и 4-амино-5-фтор-3-галоген-6-(замещенных)пиколинатов
WO2015199065A1 (fr) * 2014-06-24 2015-12-30 日本曹達株式会社 Compose pyridine et son utilisation
JPWO2015199065A1 (ja) * 2014-06-24 2017-04-20 日本曹達株式会社 ピリジン化合物およびその用途
WO2016039048A1 (fr) * 2014-09-10 2016-03-17 日本曹達株式会社 Composé de pyridine et son utilisation
WO2019083008A1 (fr) * 2017-10-27 2019-05-02 住友化学株式会社 Composé pyridine, et composition de lutte contre des organismes nuisibles comprenant celui-ci

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