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WO2005068416A1 - Compose d'amide et methode de lutte contre des maladies des plantes au moyen de ce compose - Google Patents

Compose d'amide et methode de lutte contre des maladies des plantes au moyen de ce compose Download PDF

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Publication number
WO2005068416A1
WO2005068416A1 PCT/JP2004/017316 JP2004017316W WO2005068416A1 WO 2005068416 A1 WO2005068416 A1 WO 2005068416A1 JP 2004017316 W JP2004017316 W JP 2004017316W WO 2005068416 A1 WO2005068416 A1 WO 2005068416A1
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group
formula
reaction
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compound
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Japanese (ja)
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Hiroshi Sakaguchi
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/32—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C07C235/34—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/38—Amides of thiocarboxylic acids
    • C07C327/40—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C327/44—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton

Definitions

  • the present invention relates to an amide compound and a method for controlling plant diseases by applying the amide compound to plants or soil where plants grow.
  • the present inventors have conducted intensive studies to find a compound having an excellent plant disease controlling effect, and as a result, have found that the amide compound represented by the following formula (1) has an excellent plant disease controlling effect, and completed the present invention.
  • R 1 is a hydrogen atom, a halogen atom, a CI-C4 alkyl group, a C2-C4 alkenyl group, a C2-C4 alkynyl group, a C1-C4 haloalkyl group, a C1-C4 alkoxy group, a phenyl group or Represents a phenoxy group
  • a plant disease control composition containing the compound of the present invention and a carrier, and a plant to which an effective amount of the compound of the present invention is applied to a plant or soil where the plant grows.
  • a method for controlling a disease is provided.
  • Specific examples of the substituents represented by RR 2 , R 4 and R 5 in the formula (1) include the following groups.
  • halogen atom represented by R 1 examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom,
  • Examples of the C 1 -C 4 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group and a t-tert-butyl group,
  • Examples of the C 2 -C 4 alkenyl group represented by R 1 include a vinyl group, a 1-methylvinyl group, a 1-propenyl group, a 2-propenyl group, a 1-methyl-2-propenyl group, 2-methyl-2-propenyl, 2-butenyl and 3-butenyl groups,
  • Examples of the C 2 _C 4 alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-methyl-2-propynyl group, a 2-butynyl group and a 3-butyl group.
  • Examples of the C 1 -C 4 haloalkyl group represented by R 1 include a fluoromethyl group, a difluoromethyl group and a trifluoromethyl group,
  • Examples of the C 1 -C 4 alkoxy group represented by R 1 include a methoxy group, an ethoxy group, a popoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group and a tert-butoxy group;
  • halogen atom represented by R 2 examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom,
  • Examples of the C 1 -C 3 haloalkyl group represented by R 2 include a fluoromethyl group, a difluoromethyl group and a trifluoromethyl group;
  • C 3 -C 5 alkylene in which R 1 and R 2 are taken together includes trimethylene, tetramethylene and pentamethylene.
  • C 3 -C 4 alkynyl group represented by R 5 there are a 2-propynyl group, Examples include a tyl-2-propynyl group, a 2-butynyl group and a 3-butynyl group.
  • the compounds of the present invention include, for example, compounds of the following embodiments.
  • an amide compound in which R 1 is a C 1 -C 4 alkoxy group an amide compound in which R 1 is a phenyl group or a phenoxy group; in the formula (1), R ′ is chlorine An amide compound that is an atom;
  • an amide compound wherein R 1 is a C 1 -C 4 alkyl group and R 2 is a halogen atom
  • an amide compound in which R 1 is a phenyl group and R 2 is a hydrogen atom In the formula (1), an amide compound in which R 1 is a phenyl group and R 2 is a halogen atom;
  • an amide compound wherein R 1 is a phenyl group and R 2 is a C 1 -C 4 alkyl group;
  • R ′ is a phenoxy group, and R 2 is a C 1 -C 4 alkyl group.
  • an amide compound in which R 1 is a phenyl group and R 2 is a hydrogen atom an amide compound in which R 4 is a methyl group or an ethyl group in the formula (1);
  • R 1 is a halogen atom, a CI—C4 alkyl group, a C 1—C4A alkyl group or a C 1—C4 alkoxy group
  • R 2 is a halogen atom, a C 1—C 3 alkyl group, An amide compound which is a 1 _C 3 haloalkyl group
  • R 1 is a halogen atom, a CI—C4 alkyl group, a C 1—C4 haloalkyl group or a C 1—C4 alkoxy group
  • R 2 is a halogen atom, a C 1—C3 alkyl group.
  • R 1 is a halogen atom, a CI—C4 alkyl group, a C 1—C4 haloalkyl group or a C 1—C4 alkoxy group
  • R 2 is a hydrogen atom
  • X is an oxygen atom.
  • R 1 is a halogen atom, a CI—C4 alkyl group, a C 1—C4 haloalkyl group or a C 1—C4 alkoxy group
  • R 2 is a halogen atom, a C 1—C3 alkyl group.
  • an amide compound which is a C 1 -C 3 haloalkyl group and X is an oxygen atom;
  • R 4 is a methyl group or Echiru group
  • R 5 is 2-propynyl group
  • amide compound is 1-methyl-2 one-propynyl group or a 2-heptynyl group
  • R 4 Is a methyl group or an ethyl group
  • R 5 is a 2-propynyl group.
  • the compound represented by the formula (1-1), wherein X in the formula (1) is an oxygen atom comprises a compound represented by the formula (2) and a compound represented by the formula (3): It can be produced by reacting in the presence of a base.
  • the reaction is usually performed in the presence of a solvent.
  • solvent used in the reaction examples include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and tert-butyl methyl ether; aliphatic hydrocarbons such as hexane, heptane and octane; toluene; Aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile and ptyronitrile, and acid amides such as N, N-dimethylformamide And sulphoxides such as dimethylsulphoxide and mixtures thereof.
  • ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and tert-butyl methyl ether
  • aliphatic hydrocarbons such as hexane,
  • Examples of the base used in the reaction include carbonates such as sodium carbonate and potassium carbonate, triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] pendec-7-ene, Tertiary amines such as 5-diazabicyclo [4.3.0] non-5-ene; and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
  • carbonates such as sodium carbonate and potassium carbonate
  • triethylamine, diisopropylethylamine 1,8-diazabicyclo [5.4.0] pendec-7-ene
  • Tertiary amines such as 5-diazabicyclo [4.3.0] non-5-ene
  • nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
  • 1 to 10 mol of a base and usually 1 to 5 mol of a compound represented by the formula (2) are used per 1 mol of the compound represented by the formula (3).
  • the reaction temperature of the reaction is usually in the range of 20 to 100, and the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction mixture is poured into water and extracted with an organic solvent, and the organic layer is washed with acidic water (dilute hydrochloric acid, etc.) and basic water (sodium hydrogen carbonate aqueous solution, etc.) as necessary. , Drying, concentrating, or (ii) adding a small amount of water to the reaction mixture, concentrating under reduced pressure, and collecting the obtained solid by filtration to obtain a compound represented by the formula (1-1).
  • the indicated compound can be isolated.
  • the isolated compound represented by the formula (111) may be further purified by an operation such as chromatography and recrystallization.
  • the compound represented by the formula (11) wherein X in the formula (1) is an oxygen atom is represented by the compound represented by the formula (2) or a hydrochloride thereof and the formula (4) It can also be produced by reacting a compound with a compound in the presence of a dehydrating condensing agent.
  • the reaction is usually performed in the presence of a solvent.
  • Solvents used in the reaction include, for example, amides such as N, N-dimethylformamide, sulfoxides such as dimethylsulfoxide, pyridine, quinoline and the like. Nitrogen aromatic compounds and mixtures thereof.
  • Examples of the dehydrating condensing agent used in the reaction include carethylimides such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (hereinafter, referred to as WSC) and 1,3-dicyclohexylcarbodiimide. Is raised.
  • the reaction temperature of the reaction is usually in the range of 0 to 140 ° C, and the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction mixture is poured into water and extracted with an organic solvent, and the organic layer is washed with acidic water (dilute hydrochloric acid or the like) and basic water (sodium hydrogen carbonate aqueous solution or the like) as necessary. , Drying, and concentrating, or (ii) adding a small amount of water to the reaction mixture, concentrating under reduced pressure, and collecting the obtained solid by filtration to obtain a compound represented by the formula (1-1).
  • the indicated compound can be isolated.
  • the isolated compound represented by the formula (1-1) may be further purified by a technique such as chromatography and recrystallization.
  • a compound represented by the formula (1-2) in which X in the formula (1) is a sulfur atom is, for example, a compound represented by the formula (1-1) and 2,4-bis (4- (Methoxy phenyl) can be produced by reacting with 1,3-dithia-2,4-diphosphethane-2,4_disulphide (hereinafter referred to as Lawesson's reagent).
  • the reaction is usually performed in the presence of a solvent.
  • solvent used in the reaction examples include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and tert-butyl methyl ether; aliphatic hydrocarbons such as hexane, heptane and octane; And aromatic hydrocarbons such as xylene and xylene; halogenated hydrocarbons such as chlorobenzene; nitriles such as acetonitrile and ptyronitrile; sulfoxides such as dimethylsulfoxide; and mixtures thereof.
  • ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and tert-butyl methyl ether
  • aliphatic hydrocarbons such as hexane, heptane and octane
  • aromatic hydrocarbons such as xylene and xylene
  • halogenated hydrocarbons
  • the reaction temperature of the reaction is usually in the range of 50 to 150, and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound represented by the formula (1-2) is isolated by performing post-treatment operations such as pouring water into the reaction mixture, extracting with an organic solvent, and drying and concentrating the organic layer. Can be.
  • the isolated compound represented by the formula (1_2) can be further purified by an operation such as chromatography, recrystallization and the like. Next, a method for producing the intermediate of the present invention will be described.
  • the compound represented by the formula (3) and the compound represented by the formula (4) can be produced, for example, according to the following scheme.
  • Ri G represents a methyl group, an ethyl group or a propyl group
  • L 1 represents a chlorine atom or a bromine atom
  • L 2 represents a chlorine atom, a bromine atom, a methanesulfonyloxy group or a trifluoromethanesulfonyl group.
  • R 4 and R 5 have the same meanings as described above.
  • the compound represented by the formula (8) can be produced by reacting the compound represented by the formula (6) and the compound represented by the formula (7) in the presence of a base. The reaction can be performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include 1,4-dioxane and tetrahydrofuran.
  • Ethers such as orchid, ethylene glycol dimethyl ether and tert-butyl methyl ether; aliphatic hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as toluene and xylene; halogenated carbons such as benzene
  • Examples include hydrogens, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile and ptyronitrile, acid amides such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, and mixtures thereof.
  • Examples of the base used in the reaction include carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrides such as sodium hydride and potassium hydride, triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5. 4. 0] INDEC-7-ene, 1,5-diazabicyclo [4.3.0]
  • Non-tertiary amines such as 5-ene and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine Group compounds.
  • the reaction temperature of the reaction is usually in the range of 0 to 100, and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound represented by the formula (8) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extracting the organic solvent, and drying and concentrating the organic layer. it can.
  • the isolated compound represented by the formula (8) can be further purified by operations such as chromatography and recrystallization.
  • the compound represented by the formula (10) can be produced by reacting the compound represented by the formula (8) with the compound represented by the formula (9) in the presence of a base. The reaction is usually performed in the presence of a solvent.
  • solvent used in the reaction examples include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and tert-butyl methyl ether; aliphatic hydrocarbons such as hexane, heptane, and octane; toluene; Examples include aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as chlorobenzene, acid amides such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, water, and mixtures thereof.
  • ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and tert-butyl methyl ether
  • aliphatic hydrocarbons such as hexane, heptane, and octane
  • toluene examples include aromatic hydrocarbons such as xylene, halogen
  • Examples of the base used in the reaction include carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrides such as sodium hydride and potassium hydride, sodium methoxide, and sodium ethoxide. And metal alkoxides such as oxide and potassium tertiary butoxide.
  • carbonates such as sodium carbonate and potassium carbonate
  • alkali metal hydrides such as sodium hydride and potassium hydride
  • sodium methoxide sodium ethoxide
  • metal alkoxides such as oxide and potassium tertiary butoxide.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 100 ° C., and the reaction time is usually in the range of 0 :! to 24 hours.
  • the compound represented by the formula (10) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water and extracting the organic solvent, and drying and concentrating the organic layer. .
  • the isolated compound represented by the formula (10) can be further purified by operations such as chromatography and recrystallization.
  • the compound represented by the formula (11) can be produced by reacting the compound represented by the formula (10) with hydrogen in the presence of a hydrogenation catalyst.
  • the reaction is usually performed in the presence of a solvent. Further, the reaction can be performed in the presence of an acid.
  • the solvent used in the reaction include alcohols such as methanol, ethanol, and propanol; esters such as ethyl acetate and butyl acetate; ethers such as tetrahydrofuran and 1,4-dioxane; and mixtures thereof.
  • the hydrogenation catalyst used for the reaction include transition metal compounds such as palladium carbon, palladium hydroxide, Raney nickel, and platinum oxide.
  • Acids used in the reaction include hydrochloric acid and acetic acid.
  • the reaction is usually performed under a hydrogen atmosphere at 1 to 100 atm.
  • the reaction temperature of the reaction is usually in the range of 120 to 10, and the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction mixture was filtered, the filtrate was extracted with an organic solvent, and the obtained organic layer was subjected to post-treatment operations such as drying and concentration, whereby the compound represented by the formula (11) was obtained. Can be released.
  • the isolated compound represented by the formula (11) can be further purified by a procedure such as chromatography and recrystallization.
  • the compound represented by the formula (13) can be produced by reacting the compound represented by the formula (11) and the compound represented by the formula (12) in the presence of a base.
  • the reaction can be performed in the presence of a solvent.
  • solvent used in the reaction examples include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and tert-butyl methyl ether; aliphatic hydrocarbons such as hexane, heptane, and octane; toluene; Aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile and ptyronitrile, and acid amides such as N, N-dimethylformamide And sulphoxides such as dimethylsulphoxide and mixtures thereof.
  • ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and tert-butyl methyl ether
  • aliphatic hydrocarbons such as hex
  • Examples of the base used for the reaction include carbonates such as sodium carbonate and potassium carbonate, triethylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] indene-7-ene, And tertiary amines such as 5,5-diazabicyclo [4.3.0] non-1-ene and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
  • reaction temperature of the reaction is usually in the range of 0 to 100 t, and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound represented by the formula (13) can be isolated by performing post-treatment operations such as adding an organic solvent to the reaction mixture, if necessary, followed by filtration and concentration of the filtrate. .
  • the isolated compound represented by the formula (13) can be further purified by an operation such as distillation, chromatography, and recrystallization.
  • the compound represented by the formula (4) can be produced by reacting the compound represented by the formula (13) with water in the presence of a base.
  • the reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used for the reaction include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and tert-butyl methyl ether, aromatic hydrocarbons such as toluene and xylene, and halogens such as benzene. Hydrocarbons, nitriles such as acetonitrile and ptyronitrile, alcohols such as methanol, ethanol and propanol, and mixtures thereof.
  • Examples of the base used in the reaction include lithium metal hydroxide such as lithium hydroxide, sodium hydroxide, and hydroxylated water. In this reaction, usually 1 to 10 mol of a base and usually 1 to 100 mol of water are used per 1 mol of the compound represented by the formula (13).
  • the reaction temperature of the reaction is usually in the range of 0 to 150 ° C, and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound represented by the formula (4) is isolated by performing post-treatment operations such as adding acidic water (hydrochloric acid, etc.) to the reaction mixture, extracting the organic solvent, and drying and concentrating the organic layer. be able to.
  • the isolated compound represented by the formula (4) can be further purified by chromatography, recrystallization or the like, but can be used as it is in the next step.
  • the compound represented by the formula (3) can be produced by reacting the compound represented by the formula (4) with a chlorinating agent.
  • the reaction can be performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and tert-butyl methyl ether, aliphatic hydrocarbons such as hexane and heptane, toluene, xylene and the like. Aromatic hydrocarbons, halogenated hydrocarbons such as benzene and the like, and mixtures thereof.
  • Examples of the chlorinating agent used in the reaction include, for example, thionyl chloride, oxalyl chloride and phosphorus oxychloride.
  • the reaction temperature of the reaction is usually in the range of 30 to 150 ° C, and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound represented by the formula (3) can be isolated by performing post-treatment operations such as concentration of the reaction mixture as it is.
  • the isolated compound represented by the formula (3) is usually used for the reaction in the next step without purification, but can be purified by distillation or the like, if necessary.
  • the compound represented by the formula (2) can be produced, for example, by reacting the compound represented by the formula (14) with a reducing agent.
  • the reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and tert-butyl methyl ether; aliphatic hydrocarbons such as hexane, heptane, and octane; toluene; Examples include aromatic hydrocarbons such as xylene and mixtures thereof.
  • Examples of the reducing agent used in the reaction include metal hydrides such as lithium aluminum hydride and diisobutyl dimethyl hydride.
  • a reducing agent is usually used in an amount of 0.5 to 5 mol per 1 mol of the compound represented by the formula (14).
  • the reaction mixture is poured into water, extracted with an organic solvent, and the organic layer is washed with basic water (aqueous sodium hydroxide solution or the like) as necessary, followed by drying, concentration, and other post-treatment operations.
  • basic water aqueous sodium hydroxide solution or the like
  • the compound represented by the formula (2) can be isolated.
  • the isolated compound represented by the formula (2) can be further purified by an operation such as distillation or chromatography.
  • the compound represented by the formula (2) can also be produced according to the following scheme.
  • R i and R 2 represent the same meaning as described above, and L 3 represents a chlorine atom, a bromine atom or a mainsulfonyloxy group.
  • the compound represented by the formula (16) can be produced by reacting the compound represented by the formula (15) with potassium phthalimide.
  • the reaction is usually performed in the presence of a solvent.
  • Solvents used in the reaction include 1,4-dioxane, tetrahydrofuran, ethers such as ethylene glycol dimethyl ether and tert-butyl methyl ether, aliphatic hydrocarbons such as hexane, heptane and octane, and toluene.
  • Aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as benzene and the like, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile and butylonitrile, and acids such as N, N-dimethylformamide Examples thereof include amides, sulfoxides such as dimethyl sulfoxide, and mixtures thereof.
  • the reaction temperature of the reaction is usually in the range of 120 to 100 ° C, and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound represented by the formula (16) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and drying and concentrating the organic layer. it can.
  • the isolated compound represented by the formula (16) can be further purified by operations such as chromatography and recrystallization.
  • the compound represented by the formula (2) can be produced by reacting the compound represented by the formula (16) with hydrazine.
  • the reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include alcohols such as methanol, ethanol, and propanol, water, and mixtures thereof.
  • alcohols such as methanol, ethanol, and propanol
  • water and mixtures thereof.
  • hydrazine itself or hydrate of hydrazine is used as hydrazine.
  • the reaction temperature of the reaction is usually in the range of 0 to 150, and the reaction time is usually in the range of 0.1 to 24 hours.
  • the reaction mixture is filtered, water is added to the filtrate, the mixture is extracted with an organic solvent, and the compound represented by the formula (2) is subjected to post-treatment operations such as drying and concentration of the organic layer. Can be released.
  • the isolated compound represented by the formula (2) can be further purified by an operation such as distillation, and mouth chromatography.
  • the compound represented by the formula (2) can also be produced according to the following scheme.
  • the compound represented by the formula (18) is the same as the compound represented by the formula (17) It can be produced by reacting with a min or a salt thereof (for example, hydrochloride).
  • the reaction is usually performed in the presence of a solvent.
  • Solvents used in the reaction include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and tert-butyl methyl ether; aliphatic hydrocarbons such as hexane, heptane and octane; toluene and xylene Aromatic hydrocarbons such as benzene, halogenated hydrocarbons such as chlorobenzene, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile and ptyronitrile, and acid amides such as N, N-dimethylformamide And sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, propanol and isopropanol, water, and mixtures thereof.
  • ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl
  • the reaction temperature of the reaction is usually in the range of 0 to 150, and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound represented by the formula (18) can be isolated by performing post-treatment operations such as pouring the reaction mixture into water, extracting with an organic solvent, and drying and concentrating the organic layer. it can.
  • the isolated compound represented by the formula (18) can be further purified by an operation such as chromatography, recrystallization and the like.
  • the compound represented by the formula (2) can be produced by reacting the compound represented by the formula (18) with hydrogen in the presence of a hydrogenation catalyst.
  • the reaction is usually performed in the presence of a solvent. It can also be carried out in the presence of an acid.
  • Examples of the solvent used for the reaction include alcohols such as methanol, ethanol, and propanol; esters such as ethyl acetate and butyl acetate; ethers such as tetrahydrofuran and 1,4-dioxane; and mixtures thereof.
  • Examples of the hydrogenation catalyst used for the reaction include transition metal compounds such as palladium carbon, palladium hydroxide, Raney nickel, and platinum oxide. Acids used in the reaction include hydrochloric acid and acetic acid.
  • a hydrogenation catalyst is usually used in an amount of 0.000 :! to 0.5 mol per 1 mol of the compound represented by the formula (18).
  • the reaction is usually performed under a hydrogen atmosphere at 1 to 100 atm.
  • the reaction temperature of the reaction is usually in the range of 120 to 100, and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound represented by the formula (2) can be isolated by performing post-treatment operations such as filtering the reaction mixture and concentrating the filtrate.
  • the isolated compound represented by the formula (2) can be further purified by a procedure such as chromatography and recrystallization.
  • Examples of the plant disease having the controlling effect of the compound of the present invention include plant diseases caused by algae, and specific examples include the following diseases.
  • Vegetables downy mildew of radish (Peronospora brassicae), downy mildew of spinach (Peronospora spinaciae, downy mildew of perensis (Peronospora tabacina), downy mildew of cucumber (Pseudoperonospora cubensis), downy mildew Disease (Plas Sir ara vi t icola), apple, strawberry, ginseng plague (Phytophthora cactorum), tomato, gray plague of cucumber (Phytophora capsici), pineapple plague (Phytophthora cinnamomi), potato, infestation of tomato phytothora > Phytophthora nicotianae var.
  • plant disease can be controlled, but usually, a composition containing the compound of the present invention and a carrier, that is, a form of a composition for controlling a plant disease in which the compound of the present invention is supported on an appropriate carrier
  • the compound for controlling plant diseases of the present invention is obtained by mixing the compound of the present invention with a solid carrier, a liquid carrier, a surfactant and other auxiliaries for preparation, and preparing an emulsion, a water-dispersible powder, a water-dispersible granule, and a flowable powder. It is formulated into powders, granules, etc. These formulations usually contain 0.1 to 90% by weight of the compound of the present invention.
  • solid carrier used in the formulation examples include kaolin clay, Atsuya pulgite clay, bentonite, montmorillonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite and other minerals, corn cob powder, walnut shell powder etc Fine powders or granules of synthetic organic substances such as natural organic substances, synthetic organic substances such as urea, salts such as calcium carbonate and ammonium sulfate, and synthetic inorganic substances such as synthetic hydrous silicon oxide.
  • synthetic organic substances such as natural organic substances, synthetic organic substances such as urea, salts such as calcium carbonate and ammonium sulfate, and synthetic inorganic substances such as synthetic hydrous silicon oxide.
  • Aromatic hydrocarbons such as alkylbenzene and methylnaphthylene, alcohols such as 2-propanol, ethylene glycol, propylene glycol, and cellosolve; ketones such as acetone, cyclohexanone, and isophorone; and vegetable oils such as soybean oil and cottonseed oil , Aliphatic hydrocarbons, esters, dimethylsulfoxide, acetonitrile and water.
  • surfactant examples include alkyl sulfates, alkyl aryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphates, lignin sulfonates, and naphthyl sulfonate formaldehyde polycondensates.
  • anionic surfactants such as polyoxyethylene alkylaryl ether, polyoxyethylene alkylpolyoxypropylene block copolymer, and sorbitan fatty acid ester.
  • auxiliaries include, for example, water-soluble polymers such as polyvinyl alcohol and polyvinyl pyrrolidone, gum arabic, alginic acid and salts thereof, polysaccharides such as CMC (potassium oxymethylcellulose), xanthan gum, aluminum magnesium silicate, and the like. And inorganic substances such as alumina sol, preservatives, coloring agents, stabilizers such as PAP (isopropyl isopropyl phosphate) and BHT.
  • water-soluble polymers such as polyvinyl alcohol and polyvinyl pyrrolidone
  • gum arabic such as gum arabic
  • alginic acid and salts thereof polysaccharides
  • CMC potassium oxymethylcellulose
  • xanthan gum xanthan gum
  • aluminum magnesium silicate aluminum magnesium silicate
  • inorganic substances such as alumina sol, preservatives, coloring agents, stabilizers such as PAP (isopropyl isopropyl phosphate) and B
  • the plant disease controlling agent of the present invention is used, for example, for protecting plants from plant diseases by foliar treatment of plants, and for treating plants that grow on the soil by treating the soil with plants. Used to protect against disease.
  • the amount of treatment depends on the type of crop, etc., which is the plant to be controlled, the type of disease to be controlled, It can be varied depending on the occurrence of the disease to be controlled, the form of preparation, the treatment time, the weather conditions, etc., but usually 1 to 500 g, preferably 5 to 1 as the compound of the present invention per 1000 m 2. 0 g.
  • Emulsions, wettable powders, flowables, etc. are usually processed by diluting with water and spraying.
  • the compound of the present invention is usually diluted to a concentration in the range of 0.001 to 3% by weight, preferably 0.0005 to 1% by weight.
  • Dusts, granules, etc. are usually processed without dilution.
  • the plant disease controlling agent of the present invention can be used in a treatment method such as seed disinfection.
  • the seed disinfection method include a method of immersing a plant seed in the plant disease controlling agent of the present invention prepared so that the concentration of the compound of the present invention is 1 to 100 ppm, and a method of dissolving the present invention in a plant seed.
  • the method for controlling plant diseases of the present invention generally comprises treating an effective amount of the agent for controlling plant diseases of the present invention on a plant in which the occurrence of a disease is predicted or a soil in which the plant is grown, and / or confirming the occurrence of the disease. It is carried out by treating the soil where the plant or its animal grows.
  • the plant disease controlling agent of the present invention is generally used as a plant disease controlling agent for agricultural and horticultural use, i.e., a plant disease controlling agent for controlling plant diseases such as fields, paddy fields, orchards, tea fields, pastures, and lawns.
  • a plant disease controlling agent for controlling plant diseases such as fields, paddy fields, orchards, tea fields, pastures, and lawns.
  • the plant disease controlling agent of the present invention can be used together with other plant disease controlling agents, insecticides, acaricides, nematicides, herbicides, plant growth regulators and / or fertilizers.
  • active ingredients of such plant disease controlling agents include closanilonil, fluazinam, diclofluanid, Josetyl-A-cyclic imide derivatives (such as capbutane, captaphor, and phorpet), and dithiocarbamate derivatives (manneb, mancozeb, Thiram, Ziram, Zineb, Propineb, etc.), inorganic or organic copper derivatives (basic copper sulfate, basic copper chloride, copper hydroxide, oxine copper, etc.), and acylylanine derivatives (metalaxyl, furalaxyl, offrace, ciprofran, benalaxil) And oxadixyl), stoline viruline compounds (cresoxime methyl, azoxy
  • N- (3-phenylpentyl) 1-3- ⁇ 3-methoxy-41- (2-propynyloxy) phenyl ⁇ propionamide 799 mg
  • Lawson's reagent 58 Omg
  • tetrahydrofuran (1 Om1)
  • the residue was subjected to silica gel column purification to give N- (3-phenylbenzyl) 13- ⁇ 3-methoxy-4- (2-propynyloxy) phenyl ⁇ thiopropionamide (hereinafter referred to as Compound 11 of the present invention). 405 mg was obtained.
  • a mixture of 7.43 g of naphthalene-1-carbaldehyde oxime, 0.8 g of 10% palladium on carbon, about 9.4 ml of 36% hydrochloric acid and 200 ml of ethanol is mixed with hydrogen.
  • the mixture was stirred under an atmosphere until absorption of hydrogen gas stopped.
  • the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain 7.52 g of (1-naphthalene) methylamine hydrochloride.
  • each of the present compounds 1 to 15 50 parts of each of the present compounds 1 to 15, 3 parts of calcium ligninsulfonate, Each wettable powder is obtained by well pulverizing and mixing 2 parts of magnesium persulfate and 45 parts of synthetic hydrous silicon oxide.
  • Each powder is obtained by thoroughly pulverizing and mixing 2 parts of each of the present compounds 1 to 15, 88 parts of kaolin clay and 10 parts of talc.
  • Each of the emulsions is obtained by thoroughly mixing 5 parts of each of the compounds 1 to 15 of the present invention, 14 parts of polyoxyethylenestyrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 75 parts of xylene.
  • control effect was determined by visually observing the area of the lesion on the plant where the test was conducted at the time of the survey, and comparing the area of the lesion of the plant treated with the compound of the present invention with the area of the lesion of the untreated plant. It was evaluated by:
  • Plastic pots were filled with sandy loam, and tomatoes (variety: Ponterosa) were sown and grown in a greenhouse for 20 days.
  • Compounds of the present invention 1-2 and 4 to 15 were prepared according to Preparation Example 6, diluted to a predetermined concentration (500 ppm) with water, and the diluted solution was applied to the tomato leaf surface. The foliage was sprayed so as to adhere sufficiently.
  • the lesion area on plants treated with the present compounds 1-2 and 4-15 was 10% or less of the lesion area of untreated plants.
  • Plastic pots were filled with sandy loam, sown with grapes (variety: Berry A), and grown in a greenhouse for 40 days.
  • Each of the present compounds 1 to 4 and 7 to 15 was prepared into a preparation according to Preparation Example 6, diluted with water to a predetermined concentration (200 ppm), and the diluted solution was sprayed on foliage so as to sufficiently adhere to the vine leaves. After drying the diluted solution on the leaf surface, spray inoculation with a suspension of zoosporangium of scabs (containing about 10000 zoospores per lm of suspension) is performed. 2 ml). After inoculation, the plants were cultivated for 1 day under conditions of 23 and relative humidity of 90% or more, and then transferred to a greenhouse at 24 during the day and 20 at night for 6 days. After that, the control effect was investigated.
  • the lesion area on plants treated with the present compounds 1 to 4 and 7 to 15 was 10% or less of the lesion area of untreated plants.
  • Plastic pots were filled with sandy loam, sown with grapes (variety: Veri A), and grown in a greenhouse for 40 days.
  • Compound 11 of the present invention was prepared as a preparation according to Preparation Example 6, diluted with water to a predetermined concentration (50 ppm), and the diluted solution was sprayed on the foliage so as to sufficiently adhere to the vine leaves. After drying the diluted solution on the leaf surface, spray inoculation with a suspension of zoosporangia of grape downy mildew (containing about 10,000 zoospores per m1 of suspension) (one plant Per 2m1). 23t after inoculation: 90% or more relative humidity The plants were cultivated for one day under the conditions, then transferred to a greenhouse at 24 ° C during the day and 20 at night, and cultivated for 6 days. After that, the control effect was investigated.
  • the lesion area on the plant treated with the compound 11 of the present invention was 10% or less of the lesion area of the untreated plant.
  • plant diseases can be controlled.

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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)
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Abstract

Le composé d'amide représenté par la formule (I) a une excellente activité contre des maladies des plantes. Dans la formule, R1 représente un atome d'hydrogène, un atome d'halogène, un groupe alcoyle C1-C4, un groupe alcényle C2-C4, un groupe alcynyle C2-C4, un groupe haloalcoyle C1-C4, un groupe alkoxyle C1-C4, un groupe phényle ou un groupe phénoxyle ; R2 représente un atome d'hydrogène, un atome d'halogène, un groupe alcoyle C1-C3, un groupe haloalcoyle C1-C3 ou un groupe phénoxyle, ou alternativement R1 et R2 peuvent s'associer de façon à former un alcylène C3-C5 ou CH=CH-CH=CH ; R4 représente un groupe alcoyle C1-C4 ; R5 représente un groupe alcynyle C3-C4 ; et X représente un atome d'oxygène ou un atome de soufre.
PCT/JP2004/017316 2003-12-12 2004-11-15 Compose d'amide et methode de lutte contre des maladies des plantes au moyen de ce compose Ceased WO2005068416A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08511772A (ja) * 1993-06-16 1996-12-10 ヘキスト・シエーリング・アグレボ・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング アリールアセトアミド類、それらの製造方法、それらを含有する組成物および殺真菌剤としてのそれらの使用
JP2002504536A (ja) * 1998-02-27 2002-02-12 ノバルティス アクチエンゲゼルシャフト Ｎ−スルホニルおよびｎ−スルフィニルフェニルグリシナミド
JP2002220376A (ja) * 2000-07-25 2002-08-09 Sankyo Co Ltd ５−（ｍ−シアノベンジルアミノ）ピラゾール誘導体
JP2002534500A (ja) * 1999-01-15 2002-10-15 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト 新規アルファースルフェンイミノ酸誘導体
JP2003533502A (ja) * 2000-05-17 2003-11-11 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト 新規のフェニル−プロパギルエーテル誘導体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08511772A (ja) * 1993-06-16 1996-12-10 ヘキスト・シエーリング・アグレボ・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング アリールアセトアミド類、それらの製造方法、それらを含有する組成物および殺真菌剤としてのそれらの使用
JP2002504536A (ja) * 1998-02-27 2002-02-12 ノバルティス アクチエンゲゼルシャフト Ｎ−スルホニルおよびｎ−スルフィニルフェニルグリシナミド
JP2002534500A (ja) * 1999-01-15 2002-10-15 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト 新規アルファースルフェンイミノ酸誘導体
JP2003533502A (ja) * 2000-05-17 2003-11-11 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト 新規のフェニル−プロパギルエーテル誘導体
JP2002220376A (ja) * 2000-07-25 2002-08-09 Sankyo Co Ltd ５−（ｍ−シアノベンジルアミノ）ピラゾール誘導体

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