[go: up one dir, main page]

WO2005122763A1 - Composition bactéricide - Google Patents

Composition bactéricide Download PDF

Info

Publication number
WO2005122763A1
WO2005122763A1 PCT/JP2005/011218 JP2005011218W WO2005122763A1 WO 2005122763 A1 WO2005122763 A1 WO 2005122763A1 JP 2005011218 W JP2005011218 W JP 2005011218W WO 2005122763 A1 WO2005122763 A1 WO 2005122763A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
alkyl group
compound represented
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2005/011218
Other languages
English (en)
Japanese (ja)
Inventor
Masato Soma
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Original Assignee
Sumitomo Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Publication of WO2005122763A1 publication Critical patent/WO2005122763A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • A01N37/38—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 having at least one oxygen or sulfur atom attached to an aromatic ring system

Definitions

  • the present invention relates to a bactericidal composition, particularly to a bactericidal composition which is excellent in controlling plant diseases caused by algae (egg fungi).
  • the present invention is a.
  • X represents an oxygen atom or a sulfur atom
  • R 1 is a hydrogen atom, a halogen atom, a 1 to 4 alkyl group, a C 1 -C 4 haloalkyl group, a C 2 -C 4 alkenyl group, a C 2 -C 4 alkynyl group, a C 1 -C 4 alkoxy group, a C 1 -C 1 C represents a haloalkoxy group or a cyano group,
  • R 2 represents a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, a CI—C 4 haloalkyl group, a C 2 —C 4 alkenyl group or a C 2 —C 4 alkynyl group,
  • R 1 and R 2 together represent a C 3—C 5 polymethylene group or a 1,3-butene gen—1,4-diyl group,
  • R 3 represents a hydrogen atom, a C 1 -C 3 alkyl group or a cyano group
  • R 4 represents a C 1 _C 3 alkyl group
  • a bactericidal composition (hereinafter sometimes referred to as the present composition) containing a phthalimide-based bactericidal compound (hereinafter sometimes referred to as compound (II)) as an active ingredient.
  • the present invention provides a method for controlling a plant disease, which comprises applying an effective amount of the compound (I) and the compound (II) to a plant or soil where the plant grows.
  • a method for controlling a plant disease which comprises applying an effective amount of the compound (I) and the compound (II) to a plant or soil where the plant grows.
  • Examples of the halogen atom represented by R 1 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, and a butyl group. Group, isobutyl group, sec-butyl group and tert-butyl group; C1-C2 alkyl group includes methyl group and ethyl group; and C1-C4 haloalkyl group includes, for example, fluoromethyl group. And difluoromethyl and trifluoromethyl groups.
  • Examples of the 2_4alkenyl group include vinyl, 1-methylvinyl, 1-propenyl, 2-propenyl and 1-methyl.
  • Examples of the C2-C4 alkynyl group include ethynyl group, 1-propynyl group.
  • Examples of the C1-C4 alkoxy group include a methoxy group, an ethoxy group, a propoxy group and an isopropoxy group.
  • Examples of the C 1 _C 4 haloalkoxy group include a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, Examples thereof include a 2,2_trifluoroethoxy group, a 1,1,2,2-tetrafluoroethoxy group and a 2-fluoroethoxy group.
  • the halogen atom represented by R 2 includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom
  • the C 1 -C 4 alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, A butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group
  • a C1-C2 alkyl group includes a methyl group and an ethyl group
  • a C1-C4 haloalkyl group includes, for example, fluoromethyl And difluoromethyl and trifluoromethyl groups.
  • Examples of the 2- to 4-alkenyl groups include a vinyl group, a 1-methylvinyl group, a 1-propenyl group,
  • Examples thereof 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-butynyl group.
  • the C 3-C 5 polymethylene group and R 1 and R 2 has decreased together, trimethylene group, and tetramethylene group and a pentamethylene group, the C 3- C 4 Porimechire down, trimethylene and tetramethylene And methylene groups.
  • Examples of the C 1 -C 4 alkyl group represented by R 5 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 tert-butyl group.
  • Examples of the 2 alkyl group include a methyl group and an ethyl group.
  • Examples of the C 3 -C 4 alkenyl group include a 2-propenyl group, a 1-methyl-2-propenyl group, and a 2-methyl_2- A propenyl group; a C 3 alkenyl group; a 2-propenyl group; and a C 3 _C 4 alkynyl group, a 2-propynyl group, a 1-methyl-2-propynyl group Group, 2-butynyl group,
  • Examples of the C 3 alkynyl group include a 3-propynyl group, and examples include a 2-propynyl group.
  • X is an oxygen atom or a sulfur atom
  • R 1 is a halogen atom or a C 1 -C 2 alkyl group
  • R 2 is a hydrogen atom
  • a halogen atom or a C 1 _C 2 alkyl group, or R 1 and R 2 taken together to form a C 3 -C 4 polymethylene group or 1,3-butadiene-1,4-diyl group
  • X is an oxygen atom
  • R 1 is hydrogen atom, a halogen atom or a C 1 one C 2 alkyl group, or R 2 is a hydrogen atom
  • a compound represented by the formula (2-1) wherein X is an oxygen atom and a compound represented by the formula (2-2) wherein X is a sulfur atom are produced, for example, according to the following scheme. can do.
  • R 1 is a hydrogen atom, a halogen atom, a CI-C4 alkyl group, a C1-C4 haloalkyl group, a C2-C4 alkenyl group, a C2-C4 alkynyl group, a CI-C4 alkoxy Represents a C 1 -C 4 haloalkoxy group or a cyano group,
  • R 2 is a hydrogen atom, a halogen atom, C 1-C4 alkyl group, CI- C4 haloalkyl group, or represents a C 2-C 4 alkenyl or C 2-C 4 alkynyl group, or R 1 and R 2 are together Represents a C 3—C 5 polymethylene group or a 1,3-butene gen _1,4-diyl group,
  • R 3 represents a hydrogen atom, a C 1 -C 3 alkyl group or a cyano group
  • R 4 represents a C 1-C 3 alkyl group
  • R 5 represents a C 1 -C 4 alkyl group, a C 3 -C 4 alkenyl group or a C 3 -C 4 alkynyl group,
  • R 6 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 halogen atom
  • the compound represented by the formula (5) can be produced by reacting the compound represented by the formula (3) with the compound represented by the formula (4).
  • the reaction is carried out in the presence or absence of a solvent, usually in the presence of a base.
  • a solvent usually in the presence of a base.
  • the solvent used in the reaction include 1,4-dioxane, tetrahydrofuran, ethers such as ethylene glycol dimethyl ether, tert-butyl methyl ether, aliphatic hydrocarbons such as hexane, heptane, and octane; Aromatic hydrocarbons such as benzene and xylene; halogenated hydrocarbons such as chlorobenzene; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and butylonitrile; N, N-dimethylformamide Acid amides, sulphoxides 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, diisopropyleulamine, 1,8-diazabicyclo [5. 4. 0] Pendeck-1 7-ene, 1,5-diazabicyclo [4. 3. 0] Tertiary amines such as non-5-ene and nitrogen-containing aromatics such as pyridine and 4-dimethylaminopyridine Group compounds.
  • the amount of the reagent used in the reaction is usually 1 to 10 mol of the base and 1 to 5 mol of the compound of the formula (4) per 1 mol of the compound of the formula (3). is there.
  • 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 (5) is isolated by pouring the reaction mixture into water, extracting with an organic solvent, and performing a post-treatment operation such as drying and concentration of the organic layer. Can be.
  • the isolated compound represented by the formula (5) can be further purified by operations such as chromatography and recrystallization. Process ((1)-2)
  • the compound represented by the formula (7) can be produced by reacting the compound represented by the formula (5) with the compound represented by the formula (6).
  • the reaction is performed in the presence of a base in the presence of a solvent.
  • 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, sodium ethoxide, and potassium tert-butoxide. Metal alkoxides.
  • the amount of the reagent used in the reaction is usually a ratio of 1 to 10 mol of the base to 1 mol of the compound of the formula (5), and a ratio of 1 to 5 mol of the compound of the formula (6). It is.
  • the reaction temperature of the reaction is usually in the range of ⁇ 20 to 100 t, and the reaction time is usually in the range of 0.
  • the compound represented by the formula (7) is isolated by pouring the reaction mixture into water, extracting the organic solvent, and performing a post-treatment operation such as drying and concentration of the organic layer. Can be.
  • the isolated compound represented by the formula (7) can be further purified by operations such as chromatography and recrystallization.
  • Process ((1) -3) The compound represented by the formula (8) can be produced by reacting the compound represented by the formula (7) with hydrogen in the presence of a hydrogenation catalyst.
  • the reaction is usually performed in a hydrogen atmosphere, usually in the presence of a solvent.
  • Examples of the solvent used in the reaction include alcohols such as methanol, ethanol, and propanol, esters such as ethyl acetate and butyl acetate, tetrahydrofuran, ethers such as 1,4-dioxane, and mixtures thereof.
  • Examples of the hydrogenation catalyst used in the reaction include transition metal compounds such as palladium carbon, palladium hydroxide, Raney Nickel®, and platinum oxide.
  • the amount of the hydrogenation catalyst used in the reaction is usually 0.001 to 0.5 mol per 1 mol of the compound represented by the formula (7).
  • the reaction is usually performed under a hydrogen atmosphere at 1 to 100 atm.
  • the reaction can be carried out in the presence of an acid (such as hydrochloric acid) if necessary.
  • an acid such as hydrochloric acid
  • the reaction temperature of the reaction is usually in the range of 120 to 100, and the reaction time is usually 0.20.
  • the range is 1-2 hours.
  • the compound represented by the formula (8) can be isolated by performing post-treatment operations such as filtering the reaction mixture and drying and concentrating the filtrate.
  • 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 a compound represented by the formula (8) with a compound represented by the formula (9).
  • reaction is carried out in the presence or absence of a solvent, usually in the presence of a base.
  • solvent used in the reaction examples include 1,4-dioxane, tetrahydrofuran, ethers such as ethylene glycol dimethyl ether and tert-butyl methyl ether, and aliphatic hydrocarbons such as hexane, heptane and octane.
  • Aromatic hydrocarbons such as xylene, toluene, halogenated hydrocarbons such as benzene and the like, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile and ptyronitrile, N, N — Acid amides such as 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, triethylamine, diisopropylethylamine, 1,8-diaza Tertiary amines such as bicyclo [5.4.0] undeck 7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene and pyridine and 4-dimethylaminopyridine And nitrogen aromatic compounds.
  • carbonates such as sodium carbonate and potassium carbonate
  • triethylamine diisopropylethylamine
  • 1,8-diaza Tertiary amines such as bicyclo [5.4.0] undeck 7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene and pyridine and 4-dimethylaminopyridine And nitrogen aromatic compounds.
  • the amount of the reagent used in the reaction is usually 1 to 10 mol of the base and 1 to 5 mol of the compound of the formula (9) per 1 mol of the compound of the formula (8). is there.
  • 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 (10) 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 (10) can be further purified by an operation such as distillation, chromatography, and recrystallization.
  • the compound represented by the formula (11) can be produced by reacting the compound represented by the formula (10) with water in the presence of a base.
  • the reaction is usually performed in the presence of water and an organic solvent.
  • organic solvent used in the reaction examples include ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether, aromatic hydrocarbons such as toluene and xylene, and chlorobenzene.
  • ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, tert-butyl methyl ether
  • aromatic hydrocarbons such as toluene and xylene
  • chlorobenzene examples include halogenated 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 alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide.
  • the amount of the base used in the reaction is usually 1 to 10 mol per 1 mol of the compound represented by the formula (10).
  • 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 (12) can be produced by reacting the compound represented by the formula (11) with a chlorinating agent.
  • the reaction is performed in the presence or absence of a solvent.
  • 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, halogenated hydrocarbons such as benzene, and mixtures thereof.
  • chlorinating agent used in the reaction examples include thionyl chloride, oxalyl chloride and phosphorus oxychloride.
  • the amount of the reagent used in the reaction is such that the chlorinating agent is usually used in a proportion of 1 to 100 mol per 1 mol of the compound represented by the formula (11).
  • the reaction temperature of the reaction is usually in the range of 30 to 15 Ot :, and the reaction time is usually in the range of 0.1 to 24 hours.
  • the compound represented by the formula (12) can be isolated by performing an operation such as concentration of the reaction mixture as it is.
  • the isolated compound represented by the formula (12) is used as it is in the reaction of the next step.
  • the compound represented by the formula (2-1) can be produced by reacting the compound represented by the formula (12) with the compound represented by the formula (13).
  • the reaction is usually performed in the presence of a solvent and in the presence of a base.
  • 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; Aromatic hydrocarbons such as benzene and xylene; halogenated hydrocarbons such as chlorobenzene; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and butylonitrile; N, N-dimethylformamide Acid amides, dimethyls Sulfoxides such as rufoxide 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
  • 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] Tertiary amines such as 5-diazabicyclo [4.3.0] non-1-ene and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine are exemplified.
  • the amount of the reagent used in the reaction is usually 1 to 10 mol of the base to 1 mol of the compound represented by the formula (12), and 1 to 5 mol of the compound represented by the formula (13) usually. It is.
  • 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.
  • reaction mixture After completion of the reaction, (i) 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 / or basic water (aqueous sodium hydrogen carbonate solution or the like) as necessary. And then 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.
  • the compound represented by 1) can be isolated.
  • the isolated compound represented by the formula (2-1) can be further purified by a technique such as chromatography and recrystallization.
  • the compound represented by the formula (2-1) can also be produced by reacting the compound represented by the formula (11) with the compound represented by the formula (13) in the presence of a dehydrating agent. it can.
  • the reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include acid amides such as N, N-dimethylformamide, sulfoxides such as dimethylsulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
  • Examples of the dehydrating agent used in the reaction include carbodiimides such as 1-ethyl-3- (3-dimethylaminopropyl) carbopimide hydrochloride (hereinafter, referred to as WSC) and 1,3-dicyclohexyl carbopimide. .
  • WSC 1-ethyl-3- (3-dimethylaminopropyl) carbopimide hydrochloride
  • 1,3-dicyclohexyl carbopimide 1,3-dicyclohexyl carbopimide.
  • the amount of the reagent used in the reaction is such that the compound represented by the formula (13) is usually in a ratio of 1 to 3 mol per 1 mol of the compound represented by the formula (11), and the dehydrating agent is usually used.
  • the ratio is 1 to 5 mol.
  • the reaction temperature of the reaction is usually in the range of 0 to 14 Ot, 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 / or basic water (sodium hydrogen carbonate aqueous solution or the like) as necessary. And then 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.
  • the compound represented by 1) can be isolated.
  • the isolated compound represented by the formula (2-1) can be further purified by a technique such as chromatography and recrystallization. Process ((0-9)
  • the compound represented by the formula (2-2) is combined with the compound represented by the formula (2-1) and 2,4-bis (4-methoxyphenyl) -1,3-dithia-1,2,4-diphosphethane-2, It can be produced by reacting with 4-disulfide (hereinafter, referred to as Lawson'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, and aliphatic hydrocarbons such as hexane, heptane and octane. , Aromatic hydrocarbons such as toluene, xylene and the like, 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 toluene, xylene
  • the amount of the Lawson reagent used in the reaction is usually 1 to 10 mol per 1 mol of the compound represented by the formula (2_1).
  • the reaction temperature of the reaction is usually in the range of 50 to 15 Ot :, and the reaction time is usually in the range of 0.5 to 24 hours.
  • the compound represented by the formula (2-2) 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 do.
  • the isolated compound represented by the formula (2-2) can be further purified by a procedure such as chromatography and recrystallization.
  • the compound represented by the formula (2-3) can also be produced according to the following scheme.
  • the compound represented by the formula (15) is, for example, a compound described in Tetrahedron on Letters, vol. 25, No. 41, .pp. 4583-4586, 1984, or US Pat. No. US 4041045. Alternatively, it can be produced according to the methods described in these documents.
  • the compound represented by the formula (15) can be used for the reaction of the next step after isolation, but can also be used for the reaction of the next step without isolation.
  • the compound isolated in the form of a hydrochloride of the compound represented by the formula (15) can be used in the reaction of the next step. Process ((2) -2)
  • the compound represented by the formula (2-3) can be produced by reacting the compound represented by the formula (11) with the compound represented by the formula (15) in the presence of a dehydrating agent.
  • the reaction is usually performed in the presence of a solvent.
  • Examples of the solvent used in the reaction include acid amides such as N, N-dimethylformamide, sulfoxides such as dimethylsulfoxide, nitrogen-containing aromatic compounds such as pyridine and quinoline, and mixtures thereof.
  • Examples of the dehydrating agent used in the reaction include carposimides such as WSC and 1,3-dicyclohexylcarpoimide.
  • the amount of the reagent used in the reaction is such that the compound represented by the formula (15) is usually in a ratio of 1 to 3 mol per 1 mol of the compound represented by the formula (11), and the dehydrating agent is usually in the range of 1 to 3 mol. 5 mole ratio.
  • 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 optionally diluted with acidic water (dilute hydrochloric acid or the like) and / or basic water (sodium hydrogen carbonate aqueous solution or the like).
  • acidic water dilute hydrochloric acid or the like
  • basic water sodium hydrogen carbonate aqueous solution or the like.
  • a post-treatment operation such as adding a small amount of water to the reaction mixture, concentrating under reduced pressure, and collecting the obtained solid by filtration, yields the formula (2) —
  • the compound of 3) can be isolated.
  • the isolated compound represented by the formula (2-3) can be further purified by a technique such as chromatography and recrystallization.
  • the compound represented by the formula (2-3) can also be produced by reacting the compound represented by the formula (15) with the compound represented by the formula (12) 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; Aromatic hydrocarbons such as benzene and xylene; halogenated hydrocarbons such as chlorobenzene; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and butylonitrile; N, N-dimethylformamide Acid amides, sulphoxides such as dimethyl sulfoxide, 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
  • Examples of the base used in the reaction include carbonates such as sodium carbonate and potassium carbonate, triethylamine, diisopropylethylamine, 1,8-diaza Tertiary amines such as bicyclo [5.4.0] ndeck-1 7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene and pyridine and 4-dimethylaminopyridine And nitrogen aromatic compounds.
  • carbonates such as sodium carbonate and potassium carbonate
  • triethylamine diisopropylethylamine
  • 1,8-diaza Tertiary amines such as bicyclo [5.4.0] ndeck-1 7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene and pyridine and 4-dimethylaminopyridine And nitrogen aromatic compounds.
  • the amount of the reagent used in the reaction is usually 1 to 10 mol of the base per 1 mol of the compound represented by the formula (12), and 1 to 5 mol of the compound represented by the formula (15) usually. It is.
  • 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 :! to 24 hours.
  • the reaction mixture is poured into water and extracted with an organic solvent, and the organic layer is diluted with acidic water (dilute hydrochloric acid or the like) and Z or basic water (aqueous sodium hydrogen carbonate solution or the like) as necessary.
  • acidic water dilute hydrochloric acid or the like
  • Z or basic water aqueous sodium hydrogen carbonate solution or the like
  • a post-treatment operation such as adding a small amount of water to the reaction mixture, concentrating under reduced pressure, and collecting the obtained solid by filtration, yields the formula (2) —
  • the compound of 3) can be isolated.
  • the isolated compound represented by the formula (2-3) can be further purified by a technique such as chromatography and recrystallization.
  • the compound represented by the formula (13) can be produced, for example, by reacting the compound represented by the formula (16) with cyanide, ammonium salt and ammonia.
  • 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, 2-propanol, water, and mixtures thereof.
  • Examples of the cyanide compound used in the reaction include sodium cyanide and potassium cyanide.
  • ammonium salt used in the reaction examples include ammonium chloride and ammonium bromide.
  • the amount of the reagent used in the reaction is usually 1 to 5 mol of cyanide, 1 to 5 mol of ammonium salt usually, and ammonia is usually 1 mol of 1 mol of the compound represented by the formula (16). The ratio is from 1 mol to a large excess.
  • the reaction temperature of the reaction is usually in the range of 110 to 100, and the reaction time is usually in the range of 1 to 50 hours.
  • the compound represented by the formula (13) can be isolated by performing an operation such as adding an organic solvent to the reaction mixture, extracting the mixture, and concentrating the organic layer.
  • the hydrochloride of the compound represented by the formula (13) can be isolated by collecting crystals formed by adding an organic solvent and hydrochloric acid to the compound represented by the formula (13) by filtration.
  • 3- (4-Hydroxy-3-methoxyphenyl) 50 g of acrylic acid, 0.5 g of 5% palladium carbon, about 0.05 g of 36% hydrochloric acid, 250 ml of ethanol and 100 ml of tetrahydrofuran And stirred under a hydrogen atmosphere. After the absorption of hydrogen gas ceased, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure to obtain 52 g of 3- (4-hydroxy-3-methoxyphenyl) propionic acid.
  • 3- ⁇ 3-Methoxy-14_ (2-propieroxy) phenyl ⁇ propionic acid chloride 200 mg, 4-methylbenzylamine 99 mg, triethylamine 0.45m1 and tetrahydrofuran 5m1 are mixed, and the mixture is mixed at room temperature. Stir for 1 hour. Thereafter, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed sequentially with 5% hydrochloric acid, a saturated aqueous solution of sodium hydrogen carbonate and saturated saline, dried over magnesium sulfate, and concentrated under reduced pressure. The residue is purified by silica gel column chromatography. Thus, 204 mg of N- (4-methylbenzyl) -13- ⁇ 3-methoxy-4_ (2-propynyloxy) phenyl ⁇ propanamide was obtained.
  • N- (4-cyclobenzyl) -3- (3-ethoxy_41- (2-propynyloxy) phenyl ⁇ propanamide (425 mg) is reacted with the oral reagent 33 Omg in the same manner as in Preparation Example 13.
  • the oral reagent 33 Omg is reacted with the oral reagent 33 Omg in the same manner as in Preparation Example 13.
  • 360 mg of N— (4-cyclobenzyl) -3- ⁇ 3-ethoxy-4- (2-propynyloxy) phenyl ⁇ propanethioamide was obtained.
  • 2-Amino-2_ (4-chlorophenyl) acetonitrile hydrochloride 8.Og, 17 ml of diisopropletylamine and 15 Oml of tetrahydrofuran are mixed, and 0 to 5 t: 3- (3-methoxy-methoxy) 4- (2-propynyloxy) phenyl ⁇
  • 3- (3-methoxy-methoxy) 4- (2-propynyloxy) phenyl ⁇ A mixture of 8.3 g of propionate chloride and 30 ml of tetrahydrofuran was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the reaction mixture was concentrated under reduced pressure. Water was added to the residue and extracted with ethyl acetate.
  • the organic layer was washed sequentially with 5% hydrochloric acid, water, a saturated aqueous solution of sodium hydrogencarbonate and saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
  • the residue is purified by silica gel column chromatography, and N- ⁇ 1- (4-chlorophenyl) _1_cyanomethyl ⁇ -3--3- ⁇ 3-methoxy-14_ (2-propynyloxy) phenyl ⁇ propanamide 8. 6 g were obtained.
  • Propanamide 66 Omg and Lawson's reagent 43 5mg were prepared in the same manner as in Example 13. As a result, 463 mg of N- (4-bromobenzyl) -3- (3-methoxy-4- (2-propynyloxy) phenyl ⁇ propane amide was obtained.
  • a mixture of 31 g of aluminum chloride and 15 Oml of methylene chloride was ice-cooled, 30 g of ethyl oxalyl chloride was mixed, and the mixture was stirred for 30 minutes under ice-cooling.
  • the obtained mixture was gradually added to a mixture of 22 g of indane and 200 ml of methylene chloride under ice-cooling, followed by stirring at room temperature for 1 hour.
  • N- (trichloromethylthio) phthalimide generally name: Folpet
  • N- (trichloromethylthio) cyclohex-14-ene-1,2_carboxyimide (generic) Name: captan)
  • N_ (1,1,2,2-tetrachloroethylthio) cyclohex-4-ene-1,2-dicarboximide (generic name: Cap Yu Hall).
  • composition of the present invention include, for example, the following.
  • X is an oxygen atom or a sulfur atom
  • R 1 is a halogen atom or a C 1 -C 2 alkyl group
  • R 2 is a hydrogen atom, a halogen atom or a C 1 -C 2 alkyl Or R 1 and R 2 together form a C 3—C 4 polymer A styrene group or 1,3-butadiene-1,4-diyl group
  • R 3 is a hydrogen atom
  • R 4 is a C 1 _C 2 alkyl group
  • R 5 is a C 3 alkynyl group
  • X is an oxygen atom
  • R 1 is a hydrogen atom, a halogen atom or a C 1 _C 2 alkyl group
  • R 2 is a hydrogen atom or a halogen atom
  • R 1 And R 2 together form a C 3 -C 4 polymethylene group or a 1,3-butadiene-1,4-diyl group
  • R 3 is a cyano group
  • R 4 is a C 1 -C 2 alkyl group
  • R 5 is a C 1 -C 2 alkyl group, a C 3 alkenyl group or a C 3 alkynyl group, wherein (i) or (ii).
  • the amide compound represented by the formula (1) is N— (4_cyclopentyl) -3- (3-methoxy-4- (2-propynyloxy) phenyl ⁇ propanamide (i Or (ii) a bactericidal composition.
  • the composition of the present invention for example, rice blast (Pyricularia oryzae), Gomaha blight (Cochl iobolus miyabeanus) 3 ⁇ 4 sheath blight (Rhizoctonia solani)
  • Gomaha blight Gomaha blight
  • Gomaha blight Chochl iobolus miyabeanus
  • 3 ⁇ 4 sheath blight Rosizoctonia solani
  • Fusarium head blight Gibberel la zeae
  • Rust Pierinia str ii formis
  • Powdery mildew (Erysiphe cichoracearum) , Cruciferous vegetables Black spot (Al ternaria japonic a), White spot (Cercosp orel la brassicae), Ne thousand of rust (Puccinia allii), soybean purpura (Cercospora kikuchii), sphaceloma disease (Elsinoe glycines black spot disease (Diaporthe phaseolorum var.
  • composition of the present invention has an excellent effect on controlling plant diseases caused by algae (egg fungi).
  • the mixing ratio of compound (I) and compound (II) is particularly limited.
  • the compound (II) is usually in the range of 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, based on 1 part by weight of the compound (I). That is, in the composition of the present invention, the mixing ratio of the compound (I) and the compound (II) is usually 10: 1 to 1: 100, preferably 2 ::! To 1:50.
  • the composition of the present invention may be a mixture of the compound (I) and the compound (II) itself, but is usually a solid carrier, a liquid carrier or / and a gaseous carrier, if necessary, a surfactant, a fixing agent, a dispersant, and a stable agent. Formulation into wettable powders, suspensions, granules, drytablets, emulsions, aqueous liquids, oils, smokers, aerosols, microcapsules, etc. .
  • composition of the present invention can be prepared by mixing the formulated compound (I) with the formulated compound (II).
  • Compound (I) and compound (II) can be mixed at the time of application.
  • These preparations usually contain the active ingredient compound in a total amount of 0.1 to 99% by weight, preferably 0.2 to 90% by weight.
  • solid carriers include clays (kaolin clay, diatomaceous earth, synthetic hydrated silicon oxide, agar pulgite clay, bentonite, acid clay, etc.), talc, and other inorganic minerals (sericite, quartz powder, sulfur powder, Examples include fine powders or granular materials such as activated carbon, calcium carbonate, hydrated silica, etc., and chemical fertilizers (ammonium sulfate, phosphorous ammonium, nitrate, urea, salt ammonium, etc.).
  • liquid carrier examples include water, alcohols ( Methanol, ethanol, ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methyl naphthalene, etc.), aliphatic carbons Hydrogens (hexane, kerosene, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, i) Butter ethers (eg, dioxane, diisopropyl ether), acid amides (eg, dimethylformamide, dimethylacetamide), halogenated hydrocarbons (eg, dichloroethane, trichloroethylene, carbon tetrachloride), and the like.
  • alcohols Methanol, ethanol, ketones (acetone, methyl ethyl ketone, cyclo
  • gaseous carrier examples include butane gas, carbon dioxide gas, and fluorocarbon gas.
  • Surfactants include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives And the like.
  • fixatives and dispersants examples include casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone, PAP (isopropyl isopropyl phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert-butyl-4-methoxyphenol) And 3-tert-butyl 4-methoxyphenol), vegetable oils, mineral oils, fatty acids or their esters, and the like.
  • synthetic water-soluble polymers polyvinyl alcohol, polyvinyl pyrrolidone, PAP (isopropyl isopropyl phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert-butyl-4-methoxyphenol) And 3-tert-buty
  • the preparation of the composition of the present invention is applied as it is or diluted with water to a plant or a soil where the plant grows.
  • the formulation is applied to soil, for example, the formulation or its water dilution is sprayed on the soil surface, and the formulation or its water dilution is mixed with the soil.
  • the application rate is determined by the type of the active ingredient compound, the mixing ratio, the weather conditions, the formulation, the application time, the application method, the application place, and the control. It can vary depending on the type of the target disease, the type of the crop to be controlled, etc., but is usually from 0.01 to 1000 g, preferably from 0 to!: 100, in terms of the total amount of the active ingredient compound per 10 Om 2. g.
  • Emulsions, wettable powders, suspensions, and the like are usually diluted with water so that the active ingredient concentration is 0.0001 to 1% by weight, preferably 0.001 to 0.5% by weight. And powders are usually applied as they are.
  • the preparation of the composition of the present invention can also be used in treatment methods such as seed treatment and ULV.
  • the seed treatment method include a seed dressing treatment with the composition of the present invention, a seed immersion treatment in the composition of the present invention, and a seed spraying treatment of the composition of the present invention.
  • the application rate is usually 0.01 to 50 g, preferably 0.01 to 10 g, as a total amount of the active ingredient compound per kg of seed.
  • the composition of the present invention can be used together with other fungicides, insecticides, acaricides, nematicides, herbicides, fertilizers, soil conditioners, and the like.
  • Parts represent parts by weight.
  • Compound (I) of any one of compounds (1-1) to (1-29) (10 parts); 50 parts of phorbet, cap or captanol; 3 parts of calcium lignin sulfonate; 3 parts of sodium lauryl sulfate 2 Parts and 35 parts of synthetic hydrous silicon oxide are thoroughly pulverized and mixed to obtain a wettable powder.
  • test examples show that the composition of the present invention has an excellent effect of controlling plant diseases. Generally, when two given active ingredient compounds are mixed and treated, the expected The long-awaited control effect is obtained by the formula of Co 1 by shown in the following formula.
  • E Expected control value (%) when active ingredient compound A is treated with mppm and active ingredient compound B is treated with nppm (hereinafter referred to as expected control value)
  • a plastic pot was filled with sandy loam and sown with grapes (variety: Berry A). The plant was grown in a greenhouse for 40 days.
  • a test agent prepared as a wettable powder according to Formulation Example 5 was diluted to a predetermined concentration with water, and sprayed with foliage so as to adhere sufficiently to the leaf surface of a grape seedling having three true leaves developed.
  • a suspension of zoosporangia of the grape downy mildew was spray-inoculated to the foliage of the seedling of the grape. After inoculation, the grape seedlings were allowed to stand overnight in a humid environment and grown for 7 days in a greenhouse.
  • composition of the present invention has an excellent effect in controlling plant diseases, and particularly exhibits an excellent effect in controlling plant diseases caused by alga (egg fungi) such as downy mildew and plague.

Landscapes

  • 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)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention décrit une composition bactéricide contenant un composé d’amide représenté par la formule (1) figurant ci-dessous et un composé bactéricide de phtalimide en tant qu’ingrédients actifs. La présente invention décrit également une méthode pour contrôler les maladies végétales dans laquelle le composé d’amide représenté par la formule (1) figurant ci-dessous et le composé bactéricide de phtalimide sont appliqués à une plante ou au sol sur lequel pousse la plante. (1)
PCT/JP2005/011218 2004-06-17 2005-06-14 Composition bactéricide Ceased WO2005122763A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004-179466 2004-06-17
JP2004179466 2004-06-17

Publications (1)

Publication Number Publication Date
WO2005122763A1 true WO2005122763A1 (fr) 2005-12-29

Family

ID=35509345

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/011218 Ceased WO2005122763A1 (fr) 2004-06-17 2005-06-14 Composition bactéricide

Country Status (1)

Country Link
WO (1) WO2005122763A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58140055A (ja) * 1982-02-12 1983-08-19 Sumitomo Chem Co Ltd Ｎ−ベンジル−フエニルアセトアミド誘導体、その製造法およびこれらを有効成分として含有する農園芸用殺菌剤
WO2004058685A1 (fr) * 2002-12-24 2004-07-15 Sumitomo Chemical Company, Limited Amide et procede de lutte contre les maladies des plantes au moyen de ce compose

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58140055A (ja) * 1982-02-12 1983-08-19 Sumitomo Chem Co Ltd Ｎ−ベンジル−フエニルアセトアミド誘導体、その製造法およびこれらを有効成分として含有する農園芸用殺菌剤
WO2004058685A1 (fr) * 2002-12-24 2004-07-15 Sumitomo Chemical Company, Limited Amide et procede de lutte contre les maladies des plantes au moyen de ce compose

Similar Documents

Publication Publication Date Title
CN103781357B (zh) 吡唑酰胺类化合物作为农用杀菌剂的用途
JP5500582B2 (ja) ピラゾ−ル−４−カルボキサミド誘導体、それらの製造方法及びそれらを有効成分とする殺菌剤
JP6895187B2 (ja) 新規ベンジルアミド化合物、その製造方法、及び殺ダニ剤
JPWO2001034568A1 (ja) オキシムｏ−エーテル化合物および農園芸用殺菌剤
CN102464592A (zh) 酰基苄胺类化合物及其应用
CN113045561A (zh) 用作杀真菌剂的二芳胺衍生物
CN103288771B (zh) 异噻唑类化合物及其作为杀菌剂的用途
WO2005122763A1 (fr) Composition bactéricide
JPH01157953A (ja) ３―シアノ―４―フエニル―ピロール誘導体
CN103124726B (zh) 吡唑酰胺类化合物及其用途
WO2005122765A1 (fr) Composition bactéricide
WO2005122761A1 (fr) Composition bactéricide
WO2000018727A1 (fr) Intermediaires dans la production de composes d'oxime-ether
CN105777640B (zh) 一种吡唑环己二醇醚类化合物及其应用
JPH09301974A (ja) 置換チオフェン誘導体およびこれを有効成分とする農園芸用殺菌剤
WO2005122760A1 (fr) Composition bactéricide
JP2006028164A (ja) 殺菌組成物
JP2006028168A (ja) 殺菌組成物
JP2012056945A (ja) ピラゾール−４−カルボキサミド誘導体、その製造方法及びそれを有効成分とする農園芸用殺菌剤
WO2005122764A1 (fr) Composition bactéricide
JP2006028167A (ja) 殺菌組成物
JP2006028163A (ja) 殺菌組成物
RU2167853C2 (ru) Амиды алкоксиминоуксусной кислоты, фунгицидное средство на их основе и способ борьбы с грибковыми заболеваниями растений
WO2005122762A1 (fr) Composition bactéricide
JP2001501943A (ja) ヒドロキシムおよびヒドラゾン基を含有する殺真菌剤

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase