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WO2006006569A1 - Phenylpyridine derivative or salt thereof, herbicide containing the same as active ingredient, and method of use thereof - Google Patents

Phenylpyridine derivative or salt thereof, herbicide containing the same as active ingredient, and method of use thereof Download PDF

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Publication number
WO2006006569A1
WO2006006569A1 PCT/JP2005/012781 JP2005012781W WO2006006569A1 WO 2006006569 A1 WO2006006569 A1 WO 2006006569A1 JP 2005012781 W JP2005012781 W JP 2005012781W WO 2006006569 A1 WO2006006569 A1 WO 2006006569A1
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Prior art keywords
group
halo
alkyl
alkoxy
alkyl group
Prior art date
Application number
PCT/JP2005/012781
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French (fr)
Japanese (ja)
Inventor
Eiji Takizawa
Shuji Kumata
Takahiro Kiyokawa
Original Assignee
Nihon Nohyaku Co., Ltd.
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Publication of WO2006006569A1 publication Critical patent/WO2006006569A1/en

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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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to novel phenyl pyridines or salts thereof, herbicides containing these as active ingredients, and methods of using the same.
  • pyridine derivatives have herbicidal activity and plant growth-regulating action (see, for example, Patent Documents 1 to 6).
  • a pyridine carboxylate having a structure similar to that of the present invention.
  • acid amides are known to have pharmaceutical activity (e.g., see Patent Document 7-9.) with 0 tooth force
  • a benzene ring and pyridine ring directly bonded at specific positions Hue Dirubiridine carboxylic acid amides and their herbicidal activity are known to date.
  • Patent Document 1 European Patent Application Publication No. 0955300
  • Patent Document 2 Pamphlet of International Publication No. 98Z04550
  • Patent Document 3 European Patent Application Publication No. 0955292
  • Patent Document 4 Pamphlet of International Publication No.OOZ75112
  • Patent Document 5 Pamphlet of International Publication No. 01Z00580
  • Patent Document 6 Pamphlet of International Publication No.99Z28301
  • Patent Document 7 International Publication No.04Z14844 Pamphlet
  • Patent Document 8 International Publication No.04Z02948 Pamphlet
  • Patent Document 9 US Patent Application Publication No. 2004Z0077853
  • a stable supply of food is indispensable for the elimination of the food crisis accompanying the expected increase in the world population in the near future.
  • a stable food supply requires economical and efficient killing or control of weeds, which are obstacles to crop cultivation and harvesting.
  • the development of LV, herbicides and plant growth regulators is becoming increasingly important.
  • the present inventors have excellent herbicidal activity that the group of compounds having a phenol pyridine skeleton represented by the general formula (I) or salts thereof can solve the above problems. As a result, the present invention has been completed.
  • R 1 is a C-C alkyl group, a halo C-C alkyl group, a C-C alkyl group, a halo C-
  • Di-C-C alkylamino group that can be selected A substituted group having 1 to 5 substituents selected Enore group,
  • Di-C-C alkylamino group power which may be different is selected 1- to 5-substituent substituted heterocyclic C-C alkyl group or halogen atom, cyan group which may be the same or different,
  • R 2 is a hydrogen atom, C-C alkyl group, C-C alkenyl group, C-C alkynyl group, C-
  • R 1 8 2 8 1 8 Indicates a alkoxycarbonyl group.
  • R 1 and R 2 together can form a 3- to 8-membered ring containing at least one heteroatom selected from oxygen atom, sulfur atom, and nitrogen atom.
  • R 3 is a halogen atom, cyano group, nitro group, hydroxyl group, pentafluorosulfur group (one SF), C-C alkyl group, halo C-C alkyl group, C-C alkenyl group, halo C -C
  • PC-C alkoxy group C-C alkoxy carbo group, C-C alkylthio group, C-C
  • they may be the same or different.
  • R 4 is a halogen atom, a C-C alkyl group, a halo C-C alkyl group, a C-C alkenyl group.
  • PC-C alkyl sulfo group C-C alkyl carbo group, C-C alkoxy car
  • Si group, hydroxyl group, formyl group, cyano group, nitro group which may be the same or different
  • R 5 and R 6 may be the same or different hydrogen atom, C-C alkyl group or halo C- C represents an alkyl group. ) Is represented. However, R 4 is the same when there are multiple
  • two adjacent R 4 groups together can be C-C alkylene.
  • a dioxy group or a halo c -c alkylenedioxy group can be indicated.
  • X represents an oxygen atom, a sulfur atom, a group represented by NH 3 or a single bond
  • Y represents an oxygen atom or a sulfur atom
  • m represents an integer of 0 to 3
  • n represents an integer of 1 to 5
  • p represents 0 or 1;
  • halogen atom means a chlorine atom, a bromine atom, an iodine atom or a fluorine atom.
  • C 1 -C alkyl group means a straight chain having 1 to 8 carbon atoms, 3 carbon atoms
  • 18 represents 8 to 8 branched or alicyclic alkyl groups, for example, methyl group, ethyl group, normal propyl group, isopropyl group, cyclopropyl group, 1-methylcyclopropyl group, 2-methylsilane Chloropropyl group, normal butyl group, isobutyl group, secondary butyl group, tertiary butyl group, 1,2-dimethylbutyl group, cyclobutyl group, 1-methylcyclobutyl group, cyclopropylmethyl group, normal pentyl group, neopentyl group, A cyclopentyl group,
  • Examples include 1-methylcyclopentyl group, 2-methylcyclopentyl group, normal hexyl group, cyclohexyl group, 1-methylcyclohexyl group, n-octyl group and the like.
  • halo C 1 -C alkyl group is the same or different and may be one or more halogen atoms
  • the "C 1 -C alkenyl group” is a straight chain having 2 to 8 carbon atoms and having 3 to 8 carbon atoms.
  • C 2 -C alkynyl group means a straight chain having 2 to 8 carbon atoms and having 5 to 8 carbon atoms.
  • a branched or alicyclic alkyl group is exemplified, and examples thereof include an ethur group, 2-propynyl group, 2-buturyl group, 1-methyl-2-propynyl group, 2-cyclohexynyl group and the like.
  • C 1 -C alkoxy group means a straight alkoxy group having 1 to 8 carbon atoms, 3 carbon atoms
  • ⁇ 8 branched or alicyclic alkoxy groups for example, methoxy group, ethoxy group, normal propoxy group, isopropoxy group, cyclopropoxy group, normal butoxy group, secondary butoxy group, tertiary butoxy group, normal Examples thereof include a pentyloxy group, an isobenzyloxy group, a neopentyloxy group, a cyclopentyloxy group, a normal hexyloxy group, and a normal octyloxy group.
  • Halo C-C alkoxy group refers to one or more halogen atoms which may be the same or different.
  • a group having 3 to 6 branched or alicyclic alkyl groups bonded to a sulfur atom for example, methylthio group, ethylthio group, normal propylthio group, isopropylthio group, cyclopropylpropyl group, normal butylthio group Secondary butylthio group, tertiary butylthio group, normal pentylthio group, isopentylthio group, neopentylthio group, cyclopentylthio group, normal hexylthio group, normaloctylthio group and the like.
  • C 1 -C alkylsulfier group means a straight alkyl group having 1 to 6 carbon atoms, carbon
  • a sulfinyl group such as a methylsulfuryl group, an ethylsulfuryl group, a normalpropylsulfuryl group, or an isopropylsulfuryl group.
  • C 1 -C alkylsulfonyl group means a linear alkyl group having 1 to 6 carbon atoms, carbon
  • Amino group substituted with 1 to 6 alkyl groups which may be the same or different, such as dimethylamino group, jetylamino group, methylethylamino group, methylnormalpropylamino group, ethylisopropyl.
  • Amino group dinormal propylamino group, diisopropylamino group, dinormal butylamino group, normal propyl normal butylamino group, methyl normal butylamino group, diisobutylamino group, disecondary butyl amino group, ditertiary butyl An amino group, an ethyl normal pentyl amino group, a di n-pentyl alumino group, an ethyl n-hexyl alumino group, a di n-hexyl alumino group, etc.
  • alkyl group an amino group, an ethyl normal pentyl amino group, a di n-pentyl alumino group, an ethyl n-hexyl alumino group, a di n-hexyl alumino group, etc.
  • a substituted carbocyclic group for example, a methyl carbo yl group, an ethyl carbo ol group, a normal propyl carbo ol group, an isopropyl carbo ol group, a normal butyl carbonyl group, an isobutyl carbo ol group, a secondary butyl carbo ol; Group, tertiary chinorecanol boninole group, nonolemanole pentinorecanoreboninore group, nonolemanolehexinorecanolevonole group and the like.
  • heterocyclic group refers to a 3- to 8-membered heterocyclic group having at least one heteroatom selected from an oxygen atom, a sulfur atom, or nitrogen atom, and includes, for example, an oxsilane ring, oxetane ring, furan ring, dihydro Furan ring, tetrahydrofuran ring, thiophene ring, dihydrothiophene ring, tetrahydrothiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, pyran ring, dihydran pyran ring, tetrahydropyran ring, thiane ring, oxazole ring, isoxazole ring, thi A group having an azole ring, isothiazole ring, imidazole ring, triazole ring, pyrazole ring, pyridine ring, pyrimidine ring,
  • C 1 -C and the like indicate a range of carbon numbers such as 1 to 5 and 1 to 6 carbon atoms.
  • scale 1 and R 2 together are oxygen atom, sulfur atom, nitrogen atomic energy 3 to 8 membered ring containing at least one hetero atom selected” means, for example, pyrroline ring, pyrrolidine ring, Examples include a virazoline ring, a virazolidine ring, an oxazoline ring, an oxazolidine ring, an isoxazoline ring, an isoxazolidine ring, a thiazoline ring, a thiazolidine ring, an isothiazoline ring, an isothiazolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.
  • R 1 is preferably C-C alkyl.
  • halogen atom which may be different, a C-C alkyl group, a halo C-C alkyl group, C
  • a phenyl group having the above substituent more preferably a C-C alkyl group, halo C-C
  • a halo C-C alkoxy group force is a selected phenyl group having one or more substituents.
  • R 2 is preferably a hydrogen atom, a C-C alkyl group, C-C alkoxy C-C alkyl
  • 1 8 2 8 group more preferably a hydrogen atom, a C 1 -C alkyl group or a C 1 -C alkyl carbo-
  • R 3 is preferably a C-C alkyl group, a halo C-C alkyl group, a C-C alkyl group,
  • alkyl group halo C-C alkyl group, C-C alkoxy group or halo C-C alkoxy group
  • substitution position of R 3 is the 4-position of the pyridine ring.
  • R 4 is preferably a C-C alkyl group, a halo C-C alkyl group, a C-C alkoxy C-
  • halo C-C alkyl group More preferably a halo C-C alkyl group, a halo C-C alkoxy C-C alkyl
  • X is preferably an oxygen atom or a single bond
  • Y is preferably an oxygen atom
  • m is preferably 1
  • n is preferably 1 or 2.
  • Examples of the salts of the phenylpyrrolidines represented by the general formula (I) include acetate, propionate, butyrate, oxalate, adipate, dodecanedioate, laurate, stearate, trifluoro Acetate, fumarate, maleate, benzoate, phthalate, etc.
  • Examples thereof include sulfonates such as salts; inorganic acid salts such as hydrochlorides, sulfates, nitrates and carbonates.
  • the pyrrolidines or salts thereof of the present invention represented by the general formula (I) are novel compounds and can be produced, for example, according to the following production method.
  • W is a halogen atom, a trifluoromethylsulfo-oxy group, a methanesulfo-oxy group, p— Indicates a leaving group such as a toluenesulfonyloxy group.
  • the inert solvent that can be used in this reaction is not particularly limited as long as it does not directly participate in this reaction.
  • alcohols such as methanol, ethanol, and isopropyl alcohol
  • aromatic carbonization such as benzene, toluene, and xylene.
  • Ketones such as ruketone and methyl isobutyl ketone; halogenated hydrocarbons such as chloroform and dichloromethane; water; esters such as methyl acetate and ethyl acetate; ethers such as jetyl ether, tetrahydrofuran and dioxane;
  • Examples include polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and pyridine. These inert solvents can be used alone or in admixture of two or more. I'll do it.
  • Examples of the base that can be used in this reaction include alkali metal hydrides such as sodium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate. Inorganic salts such as potassium fluoride; organic bases such as pyridine and triethylamine, etc., and the amount used is in the range of equimolar to excess molar relative to the phenylboronic acid represented by the general formula (VII).
  • the reaction can be carried out by appropriately selecting in step 2 and preferably 2 moles are used.
  • Transition metal catalysts that can be used in this reaction include palladium on carbon, palladium acetate, dichlorobis (triphosphine) palladium, tetrakis (triphenylphosphine) paradium. And palladium compounds such as tris (dibenzylacetone) palladium, bis (triphenylphosphine) nickel chloride and tetrakis (triphenylphosphine) nickel-like compounds.
  • the amount used may be appropriately selected from the range of 0.0001 mole to equimolar to the pyridine represented by the general formula (II), and the reaction is preferably performed. It is good to use double mole.
  • phosphine ligands such as triphenylphosphine, tritolylphosphine, tri-t-butylphosphine, etc.
  • the amount used is 0.5 times that of the transition metal catalyst. It is preferable to select appropriately in the range of mol to 100 times mol, preferably in the range of equimolar to 10 times mol. It is also possible to carry out the reaction without using a ligand.
  • the reaction temperature is suitably in the range of 50 ° C to the boiling point of the inert solvent used, and preferably in the range of room temperature to 120 ° C.
  • the reaction time is not constant depending on the scale of the reaction and the reaction temperature, but is in the range of several minutes to 48 hours.
  • the solvent is distilled off under reduced pressure, water is added, Insoluble in benzene, toluene, xylene, etc .; halogenated hydrocarbons such as chloroform, dichloromethane, etc .; extracted with esters such as ethyl acetate, washed with saturated saline, and then anhydrous sodium sulfate And drying with a drying agent such as anhydrous magnesium sulfate, and the solvent may be distilled off under reduced pressure. If a solvent insoluble in water is used, water is added to the reaction mixture, and the mixture is separated.
  • the organic layer is washed with saturated Japanese saline, dried with a drying agent such as anhydrous sodium sulfate or anhydrous magnesium sulfate, and reduced pressure. And the solvent may be distilled off. If the residue obtained after distilling off the solvent is purified by recrystallization, suspension washing, column chromatography or the like, the compound represented by the general formula (I), which is the target product, can be obtained.
  • a drying agent such as anhydrous sodium sulfate or anhydrous magnesium sulfate
  • a general reaction is achieved by reacting the carboxylic acid represented by the general formula (III) and the amine represented by the general formula (IV) in the presence of a base and a condensing agent in the presence or absence of an inert solvent.
  • a compound represented by the formula (I) can be produced.
  • the inert solvent that can be used in this reaction is not particularly limited as long as it does not directly participate in this reaction.
  • aromatic hydrocarbons such as benzene, toluene, xylene, etc .
  • acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone
  • Halogenated hydrocarbons such as chloroform and dichloromethane
  • Water Esters such as methyl acetate and ethyl acetate
  • Ethers such as diethyl ether, tetrahydrofuran and dioxane
  • polar solvents such as dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and pyridine.
  • Examples of the base that can be used in this reaction include alkali metal hydrides such as sodium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate. Inorganic salts such as potassium fluoride; organic bases such as pyridine, DBU, triethylamine and the like. The amount used is equimolar to excess molar relative to the amine represented by the general formula (IV). The reaction may be performed by selecting appropriately within the range.
  • Examples of the condensing agent that can be used in this reaction include carbonyldiimidazole, dicyclohexylcarbodiimide, 2-iodine chloride, 1-methylpyridium, and the use amount thereof is represented by the general formula (III).
  • the reaction may be carried out by appropriately selecting in the range of equimolar to excess molar relative to the carboxylic acid.
  • the carboxylic acid represented by the general formula (III) and the amine represented by the general formula (IV) may be used in an equimolar amount.
  • the amine represented by IV) should be used in excess.
  • the reaction temperature is suitably in the range of 50 ° C to the boiling point of the inert solvent used, and preferably in the range of room temperature to 120 ° C.
  • the reaction time is not constant depending on the scale of the reaction and the reaction temperature, but is in the range of several minutes to 48 hours.
  • the target compound of the general formula (I) can be isolated by the same method as in Production Method 1.
  • Production method 3 Production by reaction of acid halides with amines
  • the acid represented by the general formula (V) is reacted with the amine represented by the general formula (IV) in the presence or absence of an inert solvent and a base.
  • the compounds represented can be produced.
  • the inert solvent and the base that can be used in this reaction are the same as those in Production Method 2, and the amount of the base used is generally equimolar to excess molar relative to the acid or halide represented by the formula (V). You can select the reaction within the range of and perform the reaction.
  • reaction temperature is preferably in the range of 50 ° C to the boiling point of the inert solvent used, and preferably in the range of 0 ° C to 80 ° C. Reaction time is constant depending on reaction scale and reaction temperature Not, it ranges from a few minutes to 48 hours.
  • Production method 4 Production by reaction of carbonyl compound and oxiamines
  • the carbonyl compound represented by general formula (la) is reacted with oxyamines or acid addition salts thereof represented by general formula (VI) in the presence or absence of an inert solvent and a base. As a result, a compound represented by the general formula (lb) can be produced.
  • the base that can be used in this reaction is the same as in Production Method 2, and the amount used is generally appropriately selected within the range of equimolar to excess molar with respect to the oxiamines represented by formula (VI). Just do it.
  • the reaction temperature is suitably in the range of 50 ° C to the boiling point of the inert solvent used, and preferably in the range of room temperature to 80 ° C.
  • the reaction time is not constant depending on the scale of the reaction and the reaction temperature, but is in the range of several minutes to 48 hours.
  • the target compound of the general formula (lb) can be isolated by the same method as in Production Method 1.
  • the inert solvent and base that can be used in this reaction are the same as in Production Method 2, and the amount of the base used is in the range of equimolar to excess molar relative to the compound represented by the general formula (VIII). If you select and respond appropriately.
  • the reaction temperature is preferably in the range of 50 ° C to the boiling point of the inert solvent used, and is preferably in the range of 0 ° C to 100 ° C.
  • the reaction time is not constant depending on the scale of the reaction and the reaction temperature, but is in the range of several minutes to 48 hours.
  • the target compound of the general formula (I) can be isolated by the same method as in Production Method 1.
  • the pyrrolidines represented by the general formula (Id) and an oxidant in the presence or absence of an inert solvent By reacting in the presence, the compound represented by the general formula (Ie) can be produced.
  • the inert solvent that can be used in this reaction is not particularly limited as long as it is not directly involved in this reaction.
  • aromatic hydrocarbons such as benzene, toluene, xylene, etc .
  • Ketones such as ethyl ketone and methyl isobutyl ketone
  • Halogenated hydrocarbons such as chloroform and dichloromethane
  • Water Esters such as methyl acetate and ethyl acetate
  • Ethers such as diethyl ether, tetrahydrofuran and dioxane
  • Acetonitrile And polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
  • oxidizing agent examples include m-peroxybenzoic acid, hydrogen peroxide, and peracetic acid.
  • the reaction temperature is preferably in the range of 50 ° C to the boiling point of the inert solvent used, and preferably in the range of 0 ° C to 25 ° C.
  • the reaction time is not constant depending on the scale of the reaction and the reaction temperature, but ranges from a few minutes to 48 hours.
  • the production method 1 may be used.
  • the compound represented by the general formula (II) as an intermediate is, for example, a method described in International Publication No. 00Z175112, European Patent Application Publication No. 0053011 or European Patent Application Publication No. 447004. It can be manufactured according to
  • the compound represented by the general formula (III) as an intermediate can be produced, for example, according to the method described in International Publication No. 04Z014844 pamphlet or International Publication No. 04Z002948 pamphlet.
  • the intermediate compound represented by the general formula (IV) is commercially available and may be used.
  • the compound represented by the general formula (V), which is an intermediate, is obtained from the corresponding compound (III). It can be produced by halogenation by a conventional method using a catalyst.
  • the salts of the phenylpyrrolidines of the present invention can be produced by the following method.
  • R 2 , R 3 , R 4 , X, Y, m, n and p are the same as described above, and A represents an inorganic acid or an organic acid.
  • the salt represented by the general formula (If) is obtained by reacting the phenylpyrrolidine represented by the general formula (I) with an inorganic acid or an organic acid in the presence or absence of an inert solvent. It can be manufactured.
  • an organic acid or an inorganic acid can be used as an acid that can be used in this reaction.
  • an organic acid acetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, dodecanedioic acid, lauric acid, stearic acid, Carboxylic acids such as trifluoroacetic acid, fumaric acid, maleic acid, benzoic acid, phthalic acid; sulfonic acids such as methanesulfonic acid, 1,3 propanedisulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, etc. Can do.
  • inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and carbonic acid.
  • the inert solvent that can be used in this reaction is the same as in Production Method 6.
  • this reaction is an equimolar reaction, it is sufficient to use equimolar amounts of the phenylpyridines represented by the general formula (I) and the inorganic acid or organic acid, but any of the reactants can be used in excess.
  • the inorganic acid or organic acid is preferably used in excess.
  • the reaction temperature is preferably in the range of 50 ° C to the boiling point of the inert solvent used, and preferably in the range of 0 ° C to 25 ° C.
  • the reaction time is not constant depending on the scale of the reaction and the reaction temperature, but ranges from a few minutes to 48 hours.
  • the solvent is distilled off under reduced pressure, and the crystals are separated by filtration to produce inorganic acid salts and organic acid salts. This is sufficient, but if you want to further purify, wash with the above inert solvent. By doing so, high-purity phenyluridine acid addition salts can be produced.
  • Dissolving, separating, suspending, mixing, impregnating, adsorbing or adhering to appropriate dosage forms such as suspensions, milk suspensions, emulsions, solutions, wettable powders, granules, powders, tablets, jumbo drugs,
  • appropriate dosage forms such as suspensions, milk suspensions, emulsions, solutions, wettable powders, granules, powders, tablets, jumbo drugs.
  • the preparation may be used as a knocking agent.
  • Examples of the inert carrier that can be used in the present invention can be either solid or liquid.
  • Examples of the material that can be a solid carrier include vegetable powders (for example, soybean powder, cereal flour, wood flour, husk) Powder, sawdust, tobacco stem powder, walnut shell powder, bran, fiber powder, residues after extraction of plant extracts), synthetic polymers such as pulverized synthetic resin, clays (e.g.
  • silica eg diatomaceous earth, silica sand, mica, white carbon (hydrous finely divided silicon, hydrous silicic acid, synthetic high-dispersion silicic acid that contains calcium silicate as the main component) ;
  • Activated carbon natural minerals (such as yow powder, pumice, calcined diatomaceous earth, attapulgite and zeolite), brick ground, fly ash, sand, plastic Examples include mineral carriers such as polyethylene, polypropylene, and polysalt vinylidene, inorganic mineral powders such as calcium carbonate and calcium phosphate, chemical fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and ammonium chloride, compost, etc.
  • the material that can be used as a liquid carrier is selected from those having solvent ability itself and those capable of dispersing the active ingredient compound with the aid of an auxiliary agent without having solvent ability.
  • the following carriers can be exemplified as representative examples, and these are used alone or in the form of a mixture of two or more, such as water, alcohols (for example, methanol, ethanol, isopropanol, butanol, ethylene).
  • ketones eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, etc.
  • ethers eg, ethyl ether, dioxane, cellosolve, dipropyl ether, tetrahydrofuran, etc.
  • aliphatic carbonization Hydrogens e.g. kerosene, mineral oil, etc.
  • aromatic hydrocarbons e.g.
  • esters eg, ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, etc.
  • amides eg, dimethylformamide, ethylformamide, dimethylacetamide) Etc.
  • nitriles eg, acetonitrile
  • adjuvants typical adjuvants exemplified below can be mentioned, and these adjuvants are used depending on the purpose and are used alone, in some cases, in combination with two or more kinds of adjuvants, In some cases it is also possible to use no adjuvants.
  • Surfactants are used for emulsification, dispersion, solubilization and Z or wetting purposes of the active ingredient compounds, such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene higher fatty acid esters, polyoxy Interfaces such as ethylene succinate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkylaryl sulfonate, naphthalene sulfonic acid condensate, lignosulfonate, and higher alcohol sulfate An activator can be exemplified.
  • auxiliaries such as casein, gelatin, starch, methylcellulose, carboxymethylcellulose, Adjuvants such as xanthan gum, gum arabic, polyvinyl alcohol, pine oil, coconut oil, bentonite, and lignite sulfonate can also be used.
  • adjuvants such as wax, stearate, alkyl phosphate and the like may be used.
  • auxiliary agents such as naphthalene sulfonic acid condensate and condensed phosphate can be used.
  • an antifoaming agent for example, an auxiliary agent such as silicone oil can be used.
  • the compounding ratio of the active ingredient compound can be adjusted as necessary and is not particularly limited.
  • the compounding ratio is about 0.001 to 90% by weight.
  • the compounding ratio of the active ingredient compound is preferably about 0.01 to 50% by weight, more preferably about 0.1 to 10% by weight.
  • the compounding ratio of the active ingredient compound is preferably about 0.01 to 90% by weight, more preferably about 0.1 to 60% by weight. is there.
  • a preparation containing a pyrrolidine or a salt thereof represented by the general formula (I) of the present invention is diluted with water and applied, the adhesiveness and spreadability are improved, and the herbicidal effect is improved.
  • an auxiliary agent such as a spreading agent may be added to the spray liquid.
  • Adjuvants such as spreading agents used include surfactants (the above-mentioned nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants), paraffin, Examples include butyl acetate, polyacrylate, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, crop oil (mineral oil, animal and vegetable oils), and liquid fertilizer.
  • adjuncts such as spreading agents
  • the amount of adjuncts such as spreading agents varies depending on the type. Usually, it is appropriate to add 0.01 to 5% by weight to the spray liquid. Depending on the type of the adjuvant, it is possible to add it as a component in the preparation in advance.
  • the application rate of the herbicide containing as an active ingredient the fur-rubiridines or salts thereof represented by the general formula (I) of the present invention is the structure of the compound, the target weed, the treatment time, the treatment method, the properties of the soil, etc.
  • the force varies depending on the conditions.
  • the amount of active ingredient per hectare is 2 to 2000 g, preferably 5 to LOOOg.
  • the target weeds of the herbicide of the present invention include, for example, Shiroza, Akaza, Inutade, Harutade, Inubu, Aaubu, Jacobe, Hotokenoza, Ichibi, Onamomi, Maruasaagao, Datura, Seiokarasana, Yaemdara Broadleaf weeds such as Seythmus mille, Oro shagiku, Kosendandasa, Meishiba, Ohishiba, Inubie, Enokorogusa, etc. Narrow-leaved weeds.
  • broad-leaved weeds such as Kakashidasa, Azena, Konogi, Abnomé, Mizono-kobe, Heramodaka, Omodaka and Urica-koji
  • narrow-leaved weeds such as Tainubie, Tamagayari, Inuhotarui and Mizugayari.
  • the herbicide of the present invention can control the above weeds in upland fields and paddy fields by any treatment method of soil treatment, foliage treatment or flooding treatment.
  • crops to which the herbicide of the present invention is applied include corn, wheat, barley, rice, soybean, and the like, and these crops have little effect in both soil treatment and foliage treatment. It can be used as a selective herbicide in crop cultivation.
  • the herbicide of the present invention for example, in the soil treatment and foliage treatment for crops that have been improved in genetic traits such as corn, wheat, barley, rice, soybean, etc. and imparted drug resistance etc. However, it can be used as a selective herbicide in the cultivation of these crops.
  • the herbicide of the present invention can be mixed and applied with other pesticides such as insecticides, fungicides, plant growth regulators, and fertilizers used in the same field. In addition, in order to further stabilize the herbicidal effect, it can be mixed with other herbicides.
  • both preparations may be mixed at the time of application, but they may be applied in advance as preparations containing both.
  • herbicides that can be suitably mixed and applied for the above purpose include the following.
  • Glyphosate and its salts Darifosinate and its salts, Bialafos and its salts, Organic phosphorus herbicides such as butamifos, arlofos, benzulide, sulfarate, diarates, triarates, EPTC, butyrate, esprocalp, thiobencalp (benchocarb), molly Carbamate herbicides such as Nate, Isopolynate, Dimepiperate, Pyributicalp, FenMedifam, Chlorprofam, Ashram, etc.
  • Organic phosphorus herbicides such as butamifos, arlofos, benzulide, sulfarate, diarates, triarates, EPTC, butyrate, esprocalp, thiobencalp (benchocarb), molly Carbamate herbicides such as Nate, Isopolynate, Dimepiperate, Pyribut
  • Urea herbicides metazachlor, araclos monore, butacronore, pretila clonore, acetoclonole, metolacronore, tenino Amide herbicides such as recral, diethyl, dimethenamide, propanil, diflufen-can, mefenacet, flue naset, bromobutide, isoxaben (benzamizole), triflura Di-tro-phosphorus herbicides such as phosphorus, benfluralin, prodamine, oryzalin, butralin, pendimethalin,
  • Diphenyl ether herbicides such as chloro-trophene, chloromethoxyl, oxyfluorfen, biphenox, acifluolfen and salts thereof, fluoroglycophene, lactofen, fomesafen, acrophene, and amides Sulfuron, Chlorimlonethyl, Sulfomethylon methinole, Primisnorephron, Benzenoreflon methinore, Ethoxysulfuron, Cyclosnole Famron, Chlorsulfuron, Metosulfuronmethyl, Tribenuron methyl, Triasulfuron, Sinosulfuron, Etamethsulfuron Methyl, triflusulfuron methyl, prosulfuron, thifensulfuron methyl, pyrazosulfuronethyl, halosulfuron methyl, frazasulfuron, rimsulfuron, nico
  • herbicides include indanofan, funoleridone, funole mouth chloridone, flurtamone, norefnorrazon, caffen stranol, fentrazamide, snolefentrazone , Force norefentra zonethyl, pentoxazone, oxadiazone, oxadialgyl, pyraflufenethyl, isopropazole, flupoxam, cromazone, isoxaflutol, isoxachlortol, dithiopyr, thiazopyr, pirithiovac and its salts, pyriminoback methyl, bispiri Bags and salts thereof, bromacil, terbacil, lenacyl, fluprobasil, oxadichrome mehon, symmetrine, chlorphthalim, full microlac pentyl, full Oxazine, cinidoneethyl, azafenidin
  • 6-n- (4-fluorophenol) -4-methylpyridine-2-force Ruboxamide (0.30 g, 1.13 mmol)
  • 3 rifluoromethoxyphenyl-poronic acid (0.28 g, 1. 36 mmol)
  • 2M aqueous sodium carbonate solution 1.5 ml, 3.0 mmol
  • toluene (3.0 ml)
  • tetrakistriphenylphosphine palladium (0.10 g 0.087 mmol
  • the above is uniformly mixed and pulverized to obtain a powder.
  • the above is uniformly mixed, kneaded with an appropriate amount of water, granulated and dried to obtain granules.
  • the above is uniformly mixed and ground to obtain a wettable powder.
  • Test Example 1 Herbicidal effect test on paddy weeds before emergence
  • Test Example 2 Herbicidal effect test on paddy field weeds after emergence.
  • a 75 cm 2 plastic pot is filled with soil (Pyongyang soil), seeds of Inubie and Yinhotarui, which are paddy field weeds, are sown and covered with 75 cm 3 of soil mixed with Azena and Mizojakobe seeds, then 5 cm deep It was flooded and raised in a greenhouse.
  • soil Pulongyang soil
  • seeds of Inubie and Yinhotarui which are paddy field weeds
  • 75 cm 3 of soil mixed with Azena and Mizojakobe seeds then 5 cm deep It was flooded and raised in a greenhouse.
  • the drug containing the compound of the present invention as an active ingredient was treated as a chemical solution having a predetermined effective dose (gZha).
  • gZha predetermined effective dose
  • security with respect to an important crop, and the useful compound used for it can be obtained.

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Abstract

A phenylpyridine derivative represented by the general formula (I) wherein R1 represents C1-8 alkyl, etc. and R2 represents hydrogen, etc., provided that R1 and R2 in combination may form a 3- to 8-membered ring containing at least one heteroatom selected among oxygen, sulfur, and nitrogen; R3 represents halogeno, etc.; R4 represents halo(C1-8 alkyl), etc., provided that two adjacent R4's may be bonded to each other to represent C1-4 alkylenedioxy or halo(C1-4 alkylenedioxy); X represents oxygen, sulfur, -NH-, or a single bond; Y represents oxygen or sulfur; m is an integer of 0-3; n is an integer of 1-5; and p is 0 or 1.

Description

フエ二ルビリジン類又はその塩類、これらを有効成分とする除草剤及びそ の使用方法  Fenrubiridines or salts thereof, herbicides containing these as active ingredients, and methods of use thereof
技術分野  Technical field
[0001] 本発明は、新規なフエ二ルビリジン類又はその塩類、これらを有効成分として含有 する除草剤及びその使用方法に関する。  [0001] The present invention relates to novel phenyl pyridines or salts thereof, herbicides containing these as active ingredients, and methods of using the same.
背景技術  Background art
[0002] 従来、ピリジン誘導体が除草活性及び植物成長調節作用を有することは知られて いる（例えば、特許文献 1乃至 6参照。 )0又、本発明と類似の構造を有するフエ-ル ピリジンカルボン酸アミド類が医薬活性を有することが知られている（例えば、特許文 献 7乃至 9参照。 )0し力しながら、本発明による、特定の位置でベンゼン環とピリジン 環とが直結したフエ二ルビリジンカルボン酸アミド類及びその除草活性については、 これまで知られて ヽな 、。 [0002] Conventionally, it has been known that pyridine derivatives have herbicidal activity and plant growth-regulating action (see, for example, Patent Documents 1 to 6). 0 Also, a pyridine carboxylate having a structure similar to that of the present invention. acid amides are known to have pharmaceutical activity (e.g., see Patent Document 7-9.) with 0 tooth force, according to the present invention, a benzene ring and pyridine ring directly bonded at specific positions Hue Dirubiridine carboxylic acid amides and their herbicidal activity are known to date.
[0003] 特許文献 1：欧州特許出願公開第 0955300号明細書  [0003] Patent Document 1: European Patent Application Publication No. 0955300
特許文献 2：国際公開第 98Z04550号パンフレット  Patent Document 2: Pamphlet of International Publication No. 98Z04550
特許文献 3：欧州特許出願公開第 0955292号明細書  Patent Document 3: European Patent Application Publication No. 0955292
特許文献 4 :国際公開第 OOZ75112号パンフレット Patent Document 4 : Pamphlet of International Publication No.OOZ75112
[0004] 特許文献 5：国際公開第 01Z00580号パンフレット  [0004] Patent Document 5: Pamphlet of International Publication No. 01Z00580
特許文献 6 :国際公開第 99Z28301号パンフレット  Patent Document 6: Pamphlet of International Publication No.99Z28301
特許文献 7 :国際公開第 04Z14844号パンフレット  Patent Document 7: International Publication No.04Z14844 Pamphlet
特許文献 8 :国際公開第 04Z02948号パンフレット  Patent Document 8: International Publication No.04Z02948 Pamphlet
特許文献 9：米国特許出願公開第 2004Z0077853号明細書  Patent Document 9: US Patent Application Publication No. 2004Z0077853
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0005] 近い将来予想される世界人口増加に伴う食糧危機の解消には、食糧の安定供給 が必要不可欠である。安定した食糧の供給には、作物栽培及び収穫時に障害となる 雑草の経済的かつ効率の良い枯殺あるいは防除が必要であり、その解決策となる新 LV、除草剤や植物成長調節剤の開発がますます重要となって 、る。 [0005] A stable supply of food is indispensable for the elimination of the food crisis accompanying the expected increase in the world population in the near future. A stable food supply requires economical and efficient killing or control of weeds, which are obstacles to crop cultivation and harvesting. The development of LV, herbicides and plant growth regulators is becoming increasingly important.
本発明は、このような社会の要請に答えるベぐ作物に対する高い安全性と雑草に 対する優れた殺草活性を併せ持つ新規な除草剤を提供することを課題とするもので ある。  It is an object of the present invention to provide a novel herbicide having both high safety for vine crops that respond to such social demands and excellent herbicidal activity against weeds.
課題を解決するための手段 Means for solving the problem
本発明者等は上記の課題を解決すべく鋭意検討した結果一般式 (I)で表されるフエ -ルピリジン骨格を有する化合物群又はその塩類が上記の課題を解決し得る、優れ た除草活性を有することを見出し、本発明を完成するに至った。  As a result of intensive studies to solve the above-mentioned problems, the present inventors have excellent herbicidal activity that the group of compounds having a phenol pyridine skeleton represented by the general formula (I) or salts thereof can solve the above problems. As a result, the present invention has been completed.
即ち、本発明は、下記一般式 (I)：  That is, the present invention provides the following general formula (I):
一般式 (I)  Formula (I)
[化 1] [Chemical 1]
Figure imgf000004_0001
Figure imgf000004_0001
(式中、 R1は C - Cアルキル基、ハロ C - Cアルキル基、 C - Cァルケ-ル基、ハロ C -Wherein R 1 is a C-C alkyl group, a halo C-C alkyl group, a C-C alkyl group, a halo C-
1 8 1 8 2 8 21 8 1 8 2 8 2
Cァルケ-ル基、 C - Cアルキ-ル基、ハロ C - Cアルキ-ル基、 C - Cアルコキシ CC alkyl group, C-C alkyl group, halo C-C alkyl group, C-C alkoxy C
8 2 8 2 8 1 6 18 2 8 2 8 1 6 1
- Cアルキル基、 C - Cアルキルチオ C - Cアルキル基、 C - Cアルキルスルフィエル-C alkyl group, C-C alkylthio C-C alkyl group, C-C alkyl sulfier
6 1 6 1 6 1 6 6 1 6 1 6 1 6
C - Cアルキル基、 C - Cアルキルスルホニル C - Cアルキル基、モノ C - Cアルキル C-C alkyl group, C-C alkylsulfonyl C-C alkyl group, mono C-C alkyl
1 6 1 6 1 6 1 6 アミノ基、同一又は異なっても良いジ C - Cアルキルアミノ基、フエ-ル基、同一又は 1 6 1 6 1 6 1 6 Amino group, same or different di-C-C alkylamino group, phenyl group, same or different
1 6  1 6
異なっても良ぐハロゲン原子、シァノ基、ニトロ基、水酸基、アミノ基、 SH基、 C -C Different halogen atoms, cyan groups, nitro groups, hydroxyl groups, amino groups, SH groups, C -C
1 6 アルキル基、ハロ c - Cアルキル基、 C - Cアルケニル基、ハロ C - Cアルケニル基、  1 6 alkyl group, halo c-C alkyl group, C-C alkenyl group, halo C-C alkenyl group,
1 6 2 6 2 6  1 6 2 6 2 6
C - Cアルキニル基、ハロ C - Cアルキニル基、 C - Cアルコキシ基、ハロ C - Cアルコ C-C alkynyl, halo C-C alkynyl, C-C alkoxy, halo C-C alk
2 6 2 6 1 6 1 6 キシ基、 C - Cアルキルチオ基、ハロ C - Cアルキルチオ基、 C - Cアルケニルチオ基 2 6 2 6 1 6 1 6 Xoxy group, C-C alkylthio group, halo C-C alkylthio group, C-C alkenylthio group
1 6 1 6 2 6  1 6 1 6 2 6
、ハロ C - Cアルケニルチオ基、 C - Cアルキルスルフィニル基、ハロ C - Cアルキル Halo C-C alkenylthio group, C-C alkylsulfinyl group, halo C-C alkyl
2 6 1 6 1 6 スルフィニル基、 c - Cアルキルスルホニル基、ハロ C - Cアルキルスルホニル基、 C 2 6 1 6 1 6 Sulfinyl group, c-C alkylsulfonyl group, halo C-C alkylsulfonyl group, C
1 6 1 6 1 1 6 1 6 1
- cアルキルカルボニル基、ハロ c -cアルキルカルボニル基、フヱニルカルボニル-c alkylcarbonyl group, halo c-c alkylcarbonyl group, phenylcarbonyl
6 1 6 6 1 6
基、 C - Cアルコキシカルボニル基、モノ C - Cアルキルアミノ基又は同一若しくは異Group, C-C alkoxycarbonyl group, mono C-C alkylamino group, or the same or different
1 6 1 6 1 6 1 6
なって良いジ C - Cアルキルアミノ基力 選択される 1〜5個の置換基を有する置換フ ェ-ノレ基、 Di-C-C alkylamino group that can be selected A substituted group having 1 to 5 substituents selected Enore group,
フエ-ル C - Cアルキル基、同一又は異なっても良ぐハロゲン原子、シァノ基、ニトロ Phenyl C-C alkyl group, halogen atom which may be the same or different, cyan group, nitro
1 8  1 8
基、水酸基、アミノ基、 SH基、 C - Cアルキル基、ハロ C - Cアルキル基、 C - Cアル Group, hydroxyl group, amino group, SH group, C-C alkyl group, halo C-C alkyl group, C-C al
1 6 1 6 2 6 ケ-ル基、ハロ C - Cァルケ-ル基、 C - Cアルキ-ル基、ハロ C - Cアルキ-ル基、  1 6 1 6 2 6 Kale group, halo C-C alkyl group, C-C alkyl group, halo C-C alkyl group,
2 6 2 6 2 6 2 6 2 6 2 6
C - Cアルコキシ基、ハロ C - Cアルコキシ基、 C - Cアルキルチオ基、ハロ C - CアルC-C alkoxy group, halo C-C alkoxy group, C-C alkylthio group, halo C-C al
1 6 1 6 1 6 1 6 キルチオ基、 C - Cァルケ-ルチオ基、ハロ C - Cァルケ-ルチオ基、 C - Cアルキル 1 6 1 6 1 6 1 6 Kirthio group, C-C alkyl thio group, halo C-C alkyl thio group, C-C alkyl
2 6 2 6 1 6 スルフィエル基、ハロ C - Cアルキルスルフィエル基、 C - Cアルキルスルホ-ル基、  2 6 2 6 1 6 Sulfiel group, halo C-C alkyl sulfier group, C-C alkyl sulfonyl group,
1 6 1 6  1 6 1 6
ハロ C - Cアルキルスルホ-ル基、 C - Cアルキルカルボ-ル基、ハロ C - CアルキルHalo C-C alkylsulfol group, C-C alkylcarbol group, halo C-C alkyl
1 6 1 6 1 6 カルボ-ル基、フエ-ルカルポ-ル基、 C - Cアルコキシカルボ-ル基、モノ C - Cァ 1 6 1 6 1 6 Carbon group, phenol group, C-C alkoxy group, mono C-C group
1 6 1 6 ルキルアミノ基又は同一若しくは異なって良いジ C - Cアルキルアミノ基力 選択され  1 6 1 6 alkylamino group or di-C-C alkylamino group which may be the same or different
1 6  1 6
る 1〜5個の置換基を環上に有する置換フエニル C - Cアルキル基、複素環基、同一 Substituted phenyl C 1 -C alkyl group, heterocyclic group having the same 1 to 5 substituents on the ring, the same
1 8  1 8
又は異なっても良ぐハロゲン原子、シァノ基、ニトロ基、水酸基、アミノ基、 SH基、 C Or a halogen atom, cyano group, nitro group, hydroxyl group, amino group, SH group, C which may be different
1 1
- Cアルキル基、ハロ C - Cアルキル基、 C - Cアルケニル基、ハロ C - Cアルケニル-C alkyl group, halo C-C alkyl group, C-C alkenyl group, halo C-C alkenyl
6 1 6 2 6 2 6 6 1 6 2 6 2 6
基、 C - Cアルキニル基、ハロ C - Cアルキニル基、 C - Cアルコキシ基、ハロ C - CァGroup, C-C alkynyl group, halo C-C alkynyl group, C-C alkoxy group, halo C-C
2 6 2 6 1 6 1 6 ルコキシ基、 c - Cアルキルチオ基、ハロ C - Cアルキルチオ基、 C - Cアルケニルチ 2 6 2 6 1 6 1 6 Lucoxy group, c-C alkylthio group, halo C-C alkylthio group, C-C alkenyl group
1 6 1 6 2 6 ォ基、ハロ c - Cアルケニルチオ基、 C - Cアルキルスルフィニル基、ハロ C - Cアル  1 6 1 6 2 6o group, halo c-C alkenylthio group, C-C alkylsulfinyl group, halo C-C al
2 6 1 6 1 6 キルスルフィニル基、 C - Cアルキルスルホニル基、ハロ C - Cアルキルスルホニル基  2 6 1 6 1 6 Kill sulfinyl group, C-C alkylsulfonyl group, halo C-C alkylsulfonyl group
1 6 1 6 1 6 1 6
、 C - Cアルキルカルボニル基、ハロ C - Cアルキルカルボニル基、フエニルカルボ二, C-C alkylcarbonyl group, halo C-C alkylcarbonyl group, phenylcarbonyl
1 6 1 6 1 6 1 6
ル基、 c - Cアルコキシカルボニル基、モノ C - Cアルキルアミノ基又は同一若しくはGroup, c-C alkoxycarbonyl group, mono C-C alkylamino group, or the same or
1 6 1 6 1 6 1 6
異なって良いジ C - Cアルキルアミノ基力 選択される 1〜5個の置換基を有する置 複素環 C - Cアルキル基又は同一若しくは異なっても良ぐハロゲン原子、シァノ基、 Di-C-C alkylamino group power which may be different is selected 1- to 5-substituent substituted heterocyclic C-C alkyl group or halogen atom, cyan group which may be the same or different,
8  8
ニトロ基、水酸基、アミノ基、 SH基、 C - Cアルキル基、ハロ C - Cアルキル基、 C - C Nitro group, hydroxyl group, amino group, SH group, C-C alkyl group, halo C-C alkyl group, C-C
1 6 1 6 2 6 アルケニル基、ハロ c - Cアルケニル基、 C - Cアルキニル基、ハロ C - Cアルキニル  1 6 1 6 2 6 Alkenyl group, halo c-C alkenyl group, C-C alkynyl group, halo C-C alkynyl
2 6 2 6 2 6  2 6 2 6 2 6
基、 C - Cアルコキシ基、ハロ C - Cアルコキシ基、 C - Cアルキルチオ基、ハロ C - CGroup, C-C alkoxy group, halo C-C alkoxy group, C-C alkylthio group, halo C-C
1 6 1 6 1 6 1 6 アルキルチオ基、 C - Cアルケニルチオ基、ハロ C - Cアルケニルチオ基、 C - Cアル 1 6 1 6 1 6 1 6 Alkylthio group, C-C alkenylthio group, halo C-C alkenylthio group, C-C al
2 6 2 6 1 6 キルスルフィニル基、ハロ C - Cアルキルスルフィニル基、 C - Cアルキルスルホニル  2 6 2 6 1 6 Kill sulfinyl group, halo C-C alkylsulfinyl group, C-C alkylsulfonyl
1 6 1 6  1 6 1 6
基、ハロ C - Cアルキルスルホニル基、 C - Cアルキルカルボニル基、ハロ C - Cアル キルカルボ-ル基、フヱ-ルカルボ-ル基、 C - Cアルコキシカルボ-ル基、モノ C -Group, halo C-C alkylsulfonyl group, C-C alkylcarbonyl group, halo C-C al Kill carbo group, full carbo group, C-C alkoxy carbo group, mono C-
1 6 11 6 1
Cアルキルアミノ基又は同一若しくは異なって良いジ C - Cアルキルアミノ基から選択Selected from C alkylamino groups or di-C-C alkylamino groups which may be the same or different
6 1 6 6 1 6
される 1〜5個の置換基を環上に有する置換複素環 C -Cアルキル基を示す。  And a substituted heterocyclic C 1 -C alkyl group having 1 to 5 substituents on the ring.
1 8  1 8
[0009] R2は水素原子、 C - Cアルキル基、 C - Cアルケニル基、 C - Cアルキニル基、 C -[0009] R 2 is a hydrogen atom, C-C alkyl group, C-C alkenyl group, C-C alkynyl group, C-
1 8 2 8 2 8 11 8 2 8 2 8 1
Cアルコキシ C - Cアルキル基、シァノ C - Cアルキル基、 C - CアルキルカルボニルC alkoxy C-C alkyl group, cyan C-C alkyl group, C-C alkylcarbonyl
8 1 8 1 8 1 8 8 1 8 1 8 1 8
基、ハロ C - Cアルキルカルボニル基、 C - Cアルケニルカルボニル基又は C - Cァ  Group, halo C-C alkylcarbonyl group, C-C alkenylcarbonyl group or C-C
1 8 2 8 1 8 ルコキシカルボ二ル基を示す。又、 R1と R2は一緒になつて酸素原子、硫黄原子、窒 素原子力 選択される少なくとも 1つのへテロ原子を含む 3〜8員環を形成することが できる。 1 8 2 8 1 8 Indicates a alkoxycarbonyl group. R 1 and R 2 together can form a 3- to 8-membered ring containing at least one heteroatom selected from oxygen atom, sulfur atom, and nitrogen atom.
R3はハロゲン原子、シァノ基、ニトロ基、水酸基、ペンタフルォロサルファ-ル基（一 SF )、 C - Cアルキル基、ハロ C - Cアルキル基、 C - Cァルケ-ル基、ハロ C - CァR 3 is a halogen atom, cyano group, nitro group, hydroxyl group, pentafluorosulfur group (one SF), C-C alkyl group, halo C-C alkyl group, C-C alkenyl group, halo C -C
5 1 8 1 8 2 8 2 8 ルケ-ル基、 C - Cアルキ-ル基、ハロ C - Cアルキ-ル基、 C - Cアルコキシ基、ノヽ 5 1 8 1 8 2 8 2 8 Luke group, C-C alkyl group, halo C-C alkyl group, C-C alkoxy group, no
2 8 2 8 1 8  2 8 2 8 1 8
PC - Cアルコキシ基、 C - Cアルコキシカルボ-ル基、 C - Cアルキルチオ基、 C - C PC-C alkoxy group, C-C alkoxy carbo group, C-C alkylthio group, C-C
1 8 1 8 1 8 1 8 アルキルスルフィエル基、 C - Cアルキルスルホ-ル基、 C - Cアルキルアミノ基又は 1 8 1 8 1 8 1 8 Alkylsulfier group, C-C alkylsulfol group, C-C alkylamino group or
1 8 1 8  1 8 1 8
同一若しくは異なっても良いジ C - Cアルキルアミノ基を示す。ただし、 R3は、複数の Di C 1 -C alkylamino groups which may be the same or different are shown. However, R 3 is more than one
1 8  1 8
場合には、同一又は異なっても良い。  In some cases, they may be the same or different.
[0010] R4はハロゲン原子、 C - Cアルキル基、ハロ C - Cアルキル基、 C - Cアルケニル基 [0010] R 4 is a halogen atom, a C-C alkyl group, a halo C-C alkyl group, a C-C alkenyl group.
1 8 1 8 2 8  1 8 1 8 2 8
、ハロ C - Cァルケ-ル基、 C - Cアルキ-ル基、ハロ C - Cアルキ-ル基、 C - Cアル Halo C-C alkyl group, C-C alkyl group, halo C-C alkyl group, C-C alkyl
2 8 2 8 2 8 1 8 コキシ基、ハロ C - Cアルコキシ基、 C - Cアルコキシ C - Cアルキル基、ハロ C - Cァ 2 8 2 8 2 8 1 8 Coxy group, halo C-C alkoxy group, C-C alkoxy C-C alkyl group, halo C-C
1 8 1 8 1 8 1 8 ルコキシ C - Cアルキル基、 C - Cアルコキシ C - Cアルコキシ基、ハロ C - Cアルコキ  1 8 1 8 1 8 1 8 Lucoxy C-C alkyl group, C-C alkoxy C-C alkoxy group, halo C-C alkoxy
1 8 1 8 1 8 1 8 シ C - Cアルコキシ基、 C - Cアルキルスルホ -ルァミノ基、ハロ C - Cアルキルスルホ 1 8 1 8 1 8 1 8 Si C-C alkoxy group, C-C alkyl sulfo-lumino group, halo C-C alkyl sulfo group
1 8 1 8 1 8 1 8 1 8 1 8
-ルァミノ基、 C - Cアルキルチオ基、ハロ C - Cアルキルチオ基、 C - Cアルキルス  -Luamino group, C-C alkylthio group, halo C-C alkylthio group, C-C alkyls
1 8 1 8 1 8  1 8 1 8 1 8
ルフィ-ル基、ハロ C - Cアルキルスルフィエル基、 C - Cアルキルスルホ-ル基、ノヽ  Rufyl group, halo C-C alkyl sulfiel group, C-C alkyl sulfol group, no
1 8 1 8  1 8 1 8
PC - Cアルキルスルホ-ル基、 C - Cアルキルカルボ-ル基、 C - Cアルコキシカル PC-C alkyl sulfo group, C-C alkyl carbo group, C-C alkoxy car
1 8 1 8 1 8 1 8 1 8 1 8
ボ-ル基、 C - Cアルキルカルボ-ルォキシ基、ハロ C - Cアルキルカルボ-ルォキ  Bor group, C-C alkyl carboloxy group, halo C-C alkyl carboloxy group
1 8 1 8  1 8 1 8
シ基、水酸基、ホルミル基、シァノ基、ニトロ基、同一又は異なっても良いトリ C - C了  Si group, hydroxyl group, formyl group, cyano group, nitro group, which may be the same or different
1 8 ルキルシリル基、ペンタフルォロサルファニル基（― SF )又は— C (R5) =NOR6 (式 1 8 alkylsilyl group, pentafluorosulfanyl group (—SF 3) or — C (R 5 ) = NOR 6 (formula
5  Five
中、 R5及び R6は同一又は異なっても良ぐ水素原子、 C - Cアルキル基又はハロ C - Cアルキル基を示す。）で表される基を示す。ただし、 R4は、複数の場合には、同一R 5 and R 6 may be the same or different hydrogen atom, C-C alkyl group or halo C- C represents an alkyl group. ) Is represented. However, R 4 is the same when there are multiple
5 Five
又は異なっても良い。又、 2つの隣接する R4は互いに一緒になつて C - Cアルキレン Or it may be different. Also, two adjacent R 4 groups together can be C-C alkylene.
1 4  14
ジォキシ基又はハロ c -cアルキレンジォキシ基を示すことができる。  A dioxy group or a halo c -c alkylenedioxy group can be indicated.
1 4  14
Xは酸素原子、硫黄原子、 NH で表される基又は単結合を示し、 Yは酸素原子 又は硫黄原子を示し、 mは 0〜3の整数を示し、 nは 1〜5の整数を示し、 pは 0又は 1 を示す。 )で表されるフエ-ルビリジン類又はその塩類及び該化合物を含有する除草 剤並びにその使用方法に関する。  X represents an oxygen atom, a sulfur atom, a group represented by NH 3 or a single bond, Y represents an oxygen atom or a sulfur atom, m represents an integer of 0 to 3, n represents an integer of 1 to 5, p represents 0 or 1; ) Or a salt thereof, a herbicide containing the compound and a method of using the same.
発明の効果  The invention's effect
[0011] 本発明によれば、高い除草効果を示し、かつ、重要作物に対して十分な安全性を 示す除草剤及びそれに用いられる有用な化合物を得ることが出来る。 発明を実施するための最良の形態  [0011] According to the present invention, it is possible to obtain a herbicide exhibiting a high herbicidal effect and sufficient safety for important crops, and a useful compound used therein. BEST MODE FOR CARRYING OUT THE INVENTION
[0012] 以下本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の一般式 (I)で表されるフエ-ルビリジン類又はその塩類の定義において、「 ハロゲン原子」とは塩素原子、臭素原子、沃素原子又はフッ素原子を示す。  In the definition of the pyrrolidines or salts thereof represented by the general formula (I) of the present invention, the “halogen atom” means a chlorine atom, a bromine atom, an iodine atom or a fluorine atom.
「C -Cアルキル基」とは、炭素原子数 1〜8個の直鎖状、炭素原子数 3  “C 1 -C alkyl group” means a straight chain having 1 to 8 carbon atoms, 3 carbon atoms
1 8 〜8個の分 岐鎖状又は脂環式のアルキル基を示し、例えば、メチル基、ェチル基、ノルマルプロ ピル基、イソプロピル基、シクロプロピル基、 1ーメチルシクロプロピル基、 2—メチルシ クロプロピル基、ノルマルブチル基、イソブチル基、セカンダリーブチル基、ターシャリ 一ブチル基、 1, 2—ジメチルブチル基、シクロブチル基、 1ーメチルシクロブチル基、 シクロプロピルメチル基、ノルマルペンチル基、ネオペンチル基、シクロペンチル基、 18 represents 8 to 8 branched or alicyclic alkyl groups, for example, methyl group, ethyl group, normal propyl group, isopropyl group, cyclopropyl group, 1-methylcyclopropyl group, 2-methylsilane Chloropropyl group, normal butyl group, isobutyl group, secondary butyl group, tertiary butyl group, 1,2-dimethylbutyl group, cyclobutyl group, 1-methylcyclobutyl group, cyclopropylmethyl group, normal pentyl group, neopentyl group, A cyclopentyl group,
1ーメチルシクロペンチル基、 2—メチルシクロペンチル基、ノルマルへキシル基、シク 口へキシル基、 1ーメチルシクロへキシル基、 n—ォクチル基等が挙げられる。 Examples include 1-methylcyclopentyl group, 2-methylcyclopentyl group, normal hexyl group, cyclohexyl group, 1-methylcyclohexyl group, n-octyl group and the like.
[0013] 「ハロ C - Cアルキル基」とは、同一又は異なっても良い 1以上のハロゲン原子により The “halo C 1 -C alkyl group” is the same or different and may be one or more halogen atoms
1 8  1 8
置換された炭素原子数 1〜8個の直鎖状、炭素原子数 3〜8個の分岐鎖状又は脂環 式のアルキル基を示し、例えばクロロメチル基、トリフルォロメチル基、 2—クロロェチ ル基、 2—フルォロェチル基、 2, 2—ジフルォロェチル基、 2,2,2—トリフルォロェチ ル基、 2,2,2 トリクロ口ェチル基、 3 クロ口プロピル基、 3 ブロモプロピル基、 3,3, 3 トリフルォロプロピル基、 2,2,3,3—テトラフルォロプロピル基、 2,2,3,3,3 ペン タフルォロプロピル基、 1ーメチルー 2,2,2—トリフルォロェチル基、 2,2,2—トリフル オロー 1 （トリフルォロメチル）ェチル基、 1ーメチルー 2,2,3,3,3 ペンタフルォロ プロピル基、 3 クロ口プロピル基、 3 ブロモプロピル基、 1—フルォロシクロプロピ ル基、 2—フルォロシクロプロピル基、 2—トリフルォロメチルシクロプロピル基、 2—メ チルー 2—トリフルォロメチルシクロプロピル基、 2—トリフルォロメチルシクロプロピル メチル基、 2—メチルー 2 トリフルォロメチルシクロプロピルメチル基、 4 クロロブチ ル基、 4,4,4 トリフルォロブチル基、 2,2,3, 3,4,4,4 ヘプタフルォロブチル基、 5, 5, 5—トリフルォロペンチル基、 6, 6, 6—トリフルォ口へキシル基、 7—フルォロヘプ チル基、 8 クロロォクチル基、 2, 2 ジフルォロシクロプロピル基、（2, 2 ジフルォ ロシクロプロピノレ）メチノレ基、 2, 2—ジクロロシクロプロピノレ基、 (2, 2—ジクロロシクロ プロピル)メチル基、パーフルォロォクチル基等が挙げられる。 A substituted or straight-chain alkyl group having 1 to 8 carbon atoms, a branched or alicyclic alkyl group having 3 to 8 carbon atoms, such as chloromethyl group, trifluoromethyl group, 2-chloroethyl Group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2,2,2 trichloroethyl group, 3 cyclopropyl group, 3 bromopropyl group, 3,3, 3 Trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3 pen Tafluoropropyl group, 1-methyl-2,2,2-trifluoroethyl group, 2,2,2-trifluoro 1 (trifluoromethyl) ethyl group, 1-methyl-2,2,3,3,3 pentafluoro group Propyl group, 3-chloropropyl group, 3-bromopropyl group, 1-fluorocyclopropyl group, 2-fluorocyclopropyl group, 2-trifluoromethylcyclopropyl group, 2-methyl-2-trifluoro Fluoromethylcyclopropyl group, 2-trifluoromethylcyclopropylmethyl group, 2-methyl-2 trifluoromethylcyclopropylmethyl group, 4 chlorobutyl group, 4,4,4 trifluorobutyl group, 2,2 , 3,3,4,4,4 Heptafluorobutyl group, 5, 5, 5-trifluoropentyl group, 6, 6, 6-trifluorohexyl group, 7-fluoroheptyl group, 8 chlorooctyl group 2, 2 Difluorocyclopropi Group, (2, 2 Jifuruo b cyclopropylcarbamoyl Honoré) Mechinore group, 2, 2-dichloro-cyclopropyl Honoré group, (2, 2-dichloro-cyclopropyl) methyl group, per full O Roo lipped group, and the like.
[0014] 「C -Cアルケニル基」とは、炭素原子数 2〜8個の直鎖状、炭素原子数 3〜8個の [0014] The "C 1 -C alkenyl group" is a straight chain having 2 to 8 carbon atoms and having 3 to 8 carbon atoms.
2 8  2 8
分岐鎖状又は脂環式のアルケニル基を示し、例えば、ビュル基、ァリル基、 2—ブテ -ル基、 2—メチルー 2—プロぺ-ル基、 1ーメチルー 2—プロぺ-ル基、 1 メチル 2—ブテュル基、 2—メチルー 2—ブテュル、 2—ペンテ-ル基、 2—へキセ -ル基 、 2—シクロへキセ -ル基等が挙げられる。  Represents a branched or alicyclic alkenyl group, such as a bur group, a allyl group, a 2-butene group, a 2-methyl-2-propyl group, a 1-methyl-2-propyl group, Examples include 1-methyl 2-butur group, 2-methyl-2-butur, 2-pentyl group, 2-hexyl group, 2-cyclohexyl group and the like.
「C -Cアルキニル基」とは、炭素原子数 2〜8個の直鎖状、炭素原子数 5〜8個の “C 2 -C alkynyl group” means a straight chain having 2 to 8 carbon atoms and having 5 to 8 carbon atoms.
2 8 2 8
分岐鎖状又は脂環式のアルキ-ル基を示し、例えば、ェチュル基、 2—プロピニル 基、 2—ブチュル基、 1ーメチルー 2—プロピニル基、 2—シクロへキシニル基等が挙 げられる。  A branched or alicyclic alkyl group is exemplified, and examples thereof include an ethur group, 2-propynyl group, 2-buturyl group, 1-methyl-2-propynyl group, 2-cyclohexynyl group and the like.
「C -Cアルコキシ基」とは、炭素原子数 1〜8個の直鎖アルコキシ基、炭素原子数 3 “C 1 -C alkoxy group” means a straight alkoxy group having 1 to 8 carbon atoms, 3 carbon atoms
1 8 1 8
〜8個の分岐鎖状又は脂環式アルコキシ基を示し、例えば、メトキシ基、エトキシ基、 ノルマルプロポキシ基、イソプロポキシ基、シクロプロポキシ基、ノルマルブトキシ基、 セカンダリーブトキシ基、ターシャリーブトキシ基、ノルマルペンチルォキシ基、イソべ ンチルォキシ基、ネオペンチルォキシ基、シクロペンチルォキシ基、ノルマルへキシ ルォキシ基、ノルマルォクチルォキシ基等が挙げられる。  ~ 8 branched or alicyclic alkoxy groups, for example, methoxy group, ethoxy group, normal propoxy group, isopropoxy group, cyclopropoxy group, normal butoxy group, secondary butoxy group, tertiary butoxy group, normal Examples thereof include a pentyloxy group, an isobenzyloxy group, a neopentyloxy group, a cyclopentyloxy group, a normal hexyloxy group, and a normal octyloxy group.
[0015] 「ハロ C - Cアルコキシ基」とは、同一又は異なっても良い 1以上のハロゲン原子によ [0015] "Halo C-C alkoxy group" refers to one or more halogen atoms which may be the same or different.
1 8  1 8
り置換された炭素原子数 1〜8個の直鎖アルコキシ基、炭素原子数 3〜8個の分岐鎖 状又は脂環式アルコキシ基を示し、例えば、クロロメトキシ基、フルォロメトキシ基、トリ フルォロメトキシ基、 2—クロ口エトキシ基、 2—フルォロエトキシ基、 2,2—ジフルォロ エトキシ基、 2,2,2 トリフルォロエトキシ基、 2,2,2 トリクロ口エトキシ基、 3 クロ口 プロポキシ基、 3 ブロモプロポキシ基、 3, 3, 3 トリフルォロプロポキシ基、 2,2,3,3 ーテトラフルォロプロポキシ基、 2,2,3,3,3 ペンタフルォロプロポキシ基、 2, 2 ジ フルォロシクロプロポキシ基、 2, 2—ジクロロシクロプロポキシ基、 1—メチル 2,2,2 —トリフルォロエトキシ基、 2,2,2—トリフルォロ— 1— (トリフルォロメチル）エトキシ基、 1ーメチルー 2,2,3, 3, 3 ペンタフルォロプロポキシ基、 3 クロ口プロポキシ基、 3— ブロモプロポキシ基、 4 クロロブトキシ基、 4,4,4 トリフルォロブトキシ基、 5, 5, 5 トリフルォロペンチルォキシ基、 6, 6, 6—トリフルォ口へキシルォキシ基等を示す。 「C -Cアルキルチオ基」とは、炭素原子数 1〜6個の直鎖アルキル基、炭素原子数Substituted straight chain alkoxy group having 1 to 8 carbon atoms, branched chain having 3 to 8 carbon atoms Or a cycloaliphatic alkoxy group, for example, chloromethoxy group, fluoromethoxy group, trifluoromethoxy group, 2-chloroethoxy group, 2-fluoroethoxy group, 2,2-difluoroethoxy group, 2,2,2 trifluoro group Loethoxy group, 2,2,2 Trichlorodioxy group, 3-Dichloropropoxy group, 3 Bromopropoxy group, 3, 3, 3 Trifluoropropoxy group, 2,2,3,3-Tetrafluoropropoxy group 2,2,3,3,3 pentafluoropropoxy group, 2,2 difluorocyclopropoxy group, 2,2-dichlorocyclopropoxy group, 1-methyl 2,2,2 -trifluoroethoxy 1,2,2,2-trifluoro-1- (trifluoromethyl) ethoxy group, 1-methyl-2,2,3,3,3 pentafluoropropoxy group, 3-propoxy group, 3-bromopropoxy group 4 Chlorobutoxy group 4,4,4 Tri Ruorobutokishi group, 5, 5, 5 triflumizole Ruo b pliers Ruo alkoxy group, a 6, 6, Kishiruokishi group to 6-Torifuruo port. “C 1 -C alkylthio group” means a linear alkyl group having 1 to 6 carbon atoms, carbon atoms
1 6 1 6
3〜6個の分岐鎖状又は脂環式アルキル基が硫黄原子に結合した基を示し、例えば 、メチルチオ基、ェチルチオ基、ノルマルプロピルチオ基、イソプロピルチオ基、シク 口プロピルチオ基、ノルマルブチルチオ基、セカンダリーブチルチオ基、ターシャリー ブチルチオ基、ノルマルペンチルチオ基、イソペンチルチオ基、ネオペンチルチオ基 、シクロペンチルチオ基、ノルマルへキシルチオ基、ノルマルォクチルチオ基等が挙 げられる。  A group having 3 to 6 branched or alicyclic alkyl groups bonded to a sulfur atom, for example, methylthio group, ethylthio group, normal propylthio group, isopropylthio group, cyclopropylpropyl group, normal butylthio group Secondary butylthio group, tertiary butylthio group, normal pentylthio group, isopentylthio group, neopentylthio group, cyclopentylthio group, normal hexylthio group, normaloctylthio group and the like.
「C -Cアルキルスルフィエル基」とは、炭素原子数 1〜6個の直鎖アルキル基、炭 “C 1 -C alkylsulfier group” means a straight alkyl group having 1 to 6 carbon atoms, carbon
1 6 1 6
素原子数 3〜6個の分岐鎖状又は脂環式アルキル基がスルフィニル基に結合した基 を示し、例えば、メチルスルフィエル基、ェチルスルフィ-ル基、ノルマルプロピルス ルフィ-ル基、イソプロピルスルフィエル基、シクロプロピルスルフィエル基、ノルマル ブチルスルフィ-ル基、セカンダリーブチルスルフィ-ル基、ターシャリーブチルスル フィエル基、ノルマルペンチルスルフィ-ル基、イソペンチルスルフィ-ル基、ネオペ ンチルスルフィ-ル基、シクロペンチルスルフィ-ル基、ノルマルへキシルスルフィ二 ル基、ノルマルォクチルスルフィエル基等が挙げられる。 A group in which a branched or alicyclic alkyl group having 3 to 6 elemental atoms is bonded to a sulfinyl group, such as a methylsulfuryl group, an ethylsulfuryl group, a normalpropylsulfuryl group, or an isopropylsulfuryl group. Group, cyclopropylsulfuryl group, normal butylsulfuryl group, secondary butylsulfuryl group, tertiary butylsulfuryl group, normalpentylsulfuryl group, isopentylsulfuryl group, neopentylsulfuryl group And cyclopentylsulfyl group, normal hexylsulfyl group, and normaloctylsulfel group.
「C -Cアルキルスルホニル基」とは、炭素原子数 1〜6個の直鎖アルキル基、炭素 “C 1 -C alkylsulfonyl group” means a linear alkyl group having 1 to 6 carbon atoms, carbon
1 6 1 6
原子数 3〜6個の分岐鎖状又は脂環式アルキル基がスルホニル基に結合した基を示 し、例えば、メチルスルホ -ル基、ェチルスルホ -ル基、ノルマルプロピルスルホ-ル 基、イソプロピルスルホ-ル基、シクロプロピルスルホ-ル基、ノルマルブチルスルホ ニル基、セカンダリーブチルスルホ -ル基、ターシャリーブチルスルホ-ル基、ノルマ ルペンチルスルホ -ル基、イソペンチルスルホ -ル基、ネオペンチルスルホ -ル基、 シクロペンチルスルホ -ル基、ノルマルへキシルスルホ -ル基、ノルマルォクチルス ルホニル基等が挙げられる。 A group in which a branched or alicyclic alkyl group having 3 to 6 atoms is bonded to a sulfonyl group, such as a methylsulfol group, an ethylsulfol group, or a normalpropylsulfol group. Group, isopropylsulfol group, cyclopropylsulfol group, normal butylsulfonyl group, secondary butylsulfol group, tertiary butylsulfol group, normal pentylsulfol group, isopentylsulfol group And neopentylsulfol group, cyclopentylsulfol group, normal hexylsulfol group, normaloctylsulfonyl group and the like.
「モノ C -Cアルキルアミノ基」とは、 1個の炭素原子数 1〜6個のアルキル基で置換 “Mono C 1 -C alkylamino” is substituted with 1 to 6 carbon atoms
1 6 1 6
されたアミノ基を示し、例えばメチルァミノ基、ェチルァミノ基、ノルマルプロピルアミノ 基、イソプロピルアミノ基、ノルマルブチルァミノ基、イソブチルァミノ基、セカンダリー ブチルァミノ基、ターシャリーブチルァミノ基、ノルマルペンチルァミノ基、ノルマルへ キシルアミノ基等を示し、「同一又は異なっても良いジ C - Cアルキルアミノ基」とは 2 For example, methylamino group, ethylamino group, normal propylamino group, isopropylamino group, normal butylamino group, isobutylamino group, secondary butylamino group, tertiary butylamino group, normal pentylamino group , A normal hexylamino group, etc., and “a di-C-C alkylamino group which may be the same or different” is 2
1 6  1 6
個の同一又は異なっても良い炭素原子数 1〜6個のアルキル基で置換されたァミノ 基を示し、例えばジメチルァミノ基、ジェチルァミノ基、メチルェチルァミノ基、メチルノ ルマルプロピルアミノ基、ェチルイソプロピルアミノ基、ジノルマルプロピルアミノ基、ジ イソプロピルアミノ基、ジノルマルブチルァミノ基、ノルマルプロピルノルマルブチルァ ミノ基、メチルノルマルブチルァミノ基、ジイソブチルァミノ基、ジセカンダリーブチル アミノ基、ジターシャリーブチルァミノ基、ェチルノルマルペンチルァミノ基、ジノルマ ルペンチルァミノ基、ェチルノルマルへキシルァミノ基、ジノルマルへキシルァミノ基 等を示し、「C - Cアルキルカルボ-ル基」とは、炭素原子数 1〜6個のアルキル基で Amino group substituted with 1 to 6 alkyl groups which may be the same or different, such as dimethylamino group, jetylamino group, methylethylamino group, methylnormalpropylamino group, ethylisopropyl. Amino group, dinormal propylamino group, diisopropylamino group, dinormal butylamino group, normal propyl normal butylamino group, methyl normal butylamino group, diisobutylamino group, disecondary butyl amino group, ditertiary butyl An amino group, an ethyl normal pentyl amino group, a di n-pentyl alumino group, an ethyl n-hexyl alumino group, a di n-hexyl alumino group, etc. With alkyl group
1 6  1 6
置換されたカルボ-ル基を示し、例えばメチルカルボ-ル基、ェチルカルボ-ル基、 ノルマルプロピルカルボ-ル基、イソプロピルカルボ-ル基、ノルマルブチルカルボ ニル基、イソブチルカルボ-ル基、セカンダリーブチルカルボ-ル基、ターシャリーブ チノレカノレボニノレ基、ノノレマノレペンチノレカノレボニノレ基、ノノレマノレへキシノレカノレボニノレ 基等を示す。 A substituted carbocyclic group, for example, a methyl carbo yl group, an ethyl carbo ol group, a normal propyl carbo ol group, an isopropyl carbo ol group, a normal butyl carbonyl group, an isobutyl carbo ol group, a secondary butyl carbo ol; Group, tertiary chinorecanol boninole group, nonolemanole pentinorecanoreboninore group, nonolemanolehexinorecanolevonole group and the like.
「複素環基」とは、酸素原子、硫黄原子又は窒素原子力 選択される少なくとも 1つ のへテロ原子を有する 3〜8員複素環基を示し、例えば、ォキシラン環、ォキセタン環 、フラン環、ジヒドロフラン環、テトラヒドロフラン環、チォフェン環、ジヒドロチォフェン 環、テトラヒドロチォフェン環、ピロール環、ピロリン環、ピロリジン環、ピラン環、ジヒド 口ピラン環、テトラヒドロピラン環、チアン環、ォキサゾール環、イソォキサゾール環、チ ァゾール環、イソチアゾール環、イミダゾール環、トリァゾール環、ピラゾール環、ピリ ジン環、ピリミジン環、ピリダジン環、ピぺリジン環、ピぺラジン環、モルホリン環又は 1, 3—ォキサジン環を有する基等が挙げられる。 The term “heterocyclic group” refers to a 3- to 8-membered heterocyclic group having at least one heteroatom selected from an oxygen atom, a sulfur atom, or nitrogen atom, and includes, for example, an oxsilane ring, oxetane ring, furan ring, dihydro Furan ring, tetrahydrofuran ring, thiophene ring, dihydrothiophene ring, tetrahydrothiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, pyran ring, dihydran pyran ring, tetrahydropyran ring, thiane ring, oxazole ring, isoxazole ring, thi A group having an azole ring, isothiazole ring, imidazole ring, triazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, piperidine ring, piperazine ring, morpholine ring or 1,3-oxazine ring, etc. Can be mentioned.
これらの基が「C - Cアルキル」、「ハロ C - Cアルキル」、「ハロ C - Cアルコキシ」、「  These groups are “C-C alkyl”, “halo C-C alkyl”, “halo C-C alkoxy”, “
1 8 1 8 1 8 複素環」等として部分を示す場合も上記「C -Cアルキル基」、「ハロ C -Cアルキル基  1 8 1 8 1 8 Heterocycle "and the like also indicate the above" C 1 -C alkyl group "," halo C 1 -C alkyl group "
1 8 1 8 1 8 1 8
」、「ハロ C -Cアルコキシ基」、「複素環基」等と同じ意味の部分を示す。又、「C -c」 ”,“ Halo C 1 -C alkoxy group ”,“ heterocyclic group ”and the like. "C -c"
1 8 1 5 1 8 1 5
、「C -C」等は炭素数 1〜5、 1〜6のように炭素数の範囲を示す。 , “C 1 -C” and the like indicate a range of carbon numbers such as 1 to 5 and 1 to 6 carbon atoms.
1 6  1 6
又、「尺1と R2は一緒になつて酸素原子、硫黄原子、窒素原子力 選択される少なく とも 1つのへテロ原子を含む 3〜8員環」とは、例えば、ピロリン環、ピロリジン環、ビラ ゾリン環、ビラゾリジン環、ォキサゾリン環、ォキサゾリジン環、イソォキサゾリン環、イソ ォキサゾリジン環、チアゾリン環、チアゾリジン環、イソチアゾリン環、イソチアゾリジン 環、ピぺリジン環、ピぺラジン環、モルホリン環等が挙げられる。 In addition, “scale 1 and R 2 together are oxygen atom, sulfur atom, nitrogen atomic energy 3 to 8 membered ring containing at least one hetero atom selected” means, for example, pyrroline ring, pyrrolidine ring, Examples include a virazoline ring, a virazolidine ring, an oxazoline ring, an oxazolidine ring, an isoxazoline ring, an isoxazolidine ring, a thiazoline ring, a thiazolidine ring, an isothiazoline ring, an isothiazolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.
一般式 (I)で表されるフエ-ルビリジン類において、 R1として好ましくは C - Cアルキ In the ferroviridines represented by the general formula (I), R 1 is preferably C-C alkyl.
1 8 ル基、ハロ C - Cアルキル基、 C - Cァルケ-ル基、ハロ C - Cァルケ-ル基又は同一  1 8 group, halo C -C alkyl group, C -C alk group, halo C -C alk group or the same
1 8 2 8 2 8  1 8 2 8 2 8
若しくは異なっても良ぐハロゲン原子、 C - Cアルキル基、ハロ C - Cアルキル基、 C Or a halogen atom which may be different, a C-C alkyl group, a halo C-C alkyl group, C
1 6 1 6 1 1 6 1 6 1
- Cアルコキシ基、ハロ C - Cアルコキシ基、シァノ基又は-トロ基力 選択される 1以-C alkoxy group, halo C-C alkoxy group, cyano group or -tro group force selected 1 or more
6 1 6 6 1 6
上の置換基を有するフエ-ル基であり、更に好ましくは、 C - Cアルキル基、ハロ C - C A phenyl group having the above substituent, more preferably a C-C alkyl group, halo C-C
1 5 1 アルキル基又は同一若しくは異なっても良ぐハロゲン原子、ハロ C - Cアルキル基 1 5 1 alkyl group or halogen atom which may be the same or different, halo C -C alkyl group
5 1 5 5 1 5
又はハロ C - Cアルコキシ基力 選択される 1以上の置換基を有するフエ-ル基であ Or a halo C-C alkoxy group force is a selected phenyl group having one or more substituents.
1 5  1 5
る。 The
R2として好ましくは水素原子、 C - Cアルキル基、 C - Cアルコキシ C - Cアルキル R 2 is preferably a hydrogen atom, a C-C alkyl group, C-C alkoxy C-C alkyl
1 8 1 8 1 8 基、シァノ C - Cアルキル基、 C - Cァルケ-ル基、 C - Cアルキ-ル基、 C - Cアルキ  1 8 1 8 1 8 group, cyan C-C alkyl group, C-C alkyl group, C-C alkyl group, C-C alkyl group
1 8 2 8 2 8 1 8 ルカルボ-ル基、ハロ C - Cアルキルカルボ-ル基又は C - Cァルケ-ルカルポ-ル  1 8 2 8 2 8 1 8 Lucol group, halo C-C alkyl carbol group or C-C alkenyl carpol
1 8 2 8 基であり、更に好ましくは水素原子、 C - Cアルキル基又は C - Cアルキルカルボ- 1 8 2 8 group, more preferably a hydrogen atom, a C 1 -C alkyl group or a C 1 -C alkyl carbo-
1 8 1 8 1 8 1 8
ル基である。 Group.
R3として好ましくは C - Cアルキル基、ハロ C - Cアルキル基、 C - Cァルケ-ル基、 R 3 is preferably a C-C alkyl group, a halo C-C alkyl group, a C-C alkyl group,
1 8 1 8 2 8  1 8 1 8 2 8
ハロ C - Cァルケ-ル基、 C - Cアルキ-ル基、ハロ C - Cアルキ-ル基、 C - CアルHalo C-C alkyl group, C-C alkyl group, Halo C-C alkyl group, C-C alkyl
2 8 2 8 2 8 1 8 コキシ基、ハロ C - Cアルコキシ基、ペンタフルォロサルファ-ル基（— SF；)、 C - Cァ ルキルチオ基、 C - Cアルキルスルフィエル基、 C - Cアルキルスルホ-ル基、モノ C 2 8 2 8 2 8 1 8 Coxy group, halo C-C alkoxy group, pentafluorosulfur group (—SF;), C-C Alkylthio group, C-C alkyl sulfier group, C-C alkyl sulfo group, mono C
1 8 1 8 1 1 8 1 8 1
- Cアルキルアミノ基又はジ C - Cアルキルアミノ基であり、更に好ましくは、 C - Cァ-C alkylamino group or di-C-C alkylamino group, more preferably C-C
8 1 8 1 5 ルキル基、ハロ C - Cアルキル基、 C - Cアルコキシ基又はハロ C - Cアルコキシ基で 8 1 8 1 5 In alkyl group, halo C-C alkyl group, C-C alkoxy group or halo C-C alkoxy group
1 5 1 5 1 5  1 5 1 5 1 5
あり、好まし ヽ R3の置換位置はピリジン環 4位である。 Yes, preferably the substitution position of R 3 is the 4-position of the pyridine ring.
[0019] R4として好ましくは C - Cアルキル基、ハロ C - Cアルキル基、 C - Cアルコキシ C -[0019] R 4 is preferably a C-C alkyl group, a halo C-C alkyl group, a C-C alkoxy C-
1 8 1 8 1 8 11 8 1 8 1 8 1
Cアルキル基、ハロ C - Cアルコキシ C - Cアルキル基、 C - Cァルケ-ル基、ハロ CC alkyl group, halo C-C alkoxy C-C alkyl group, C-C alkyl group, halo C
8 1 8 1 8 2 8 28 1 8 1 8 2 8 2
- Cァルケ-ル基、 C - Cアルキ-ル基、ハロ C - Cアルキ-ル基、 C - Cアルコキシ-Calkell group, C-C alkyl group, halo C-C alkyl group, C-C alkoxy
8 2 8 2 8 1 8 基、ハロ C - Cアルコキシ基、 C - Cアルコキシ C - Cアルコキシ基、ハロ C - Cアルコ 8 2 8 2 8 1 8 group, halo C-C alkoxy group, C-C alkoxy C-C alkoxy group, halo C-C alcohol
1 8 1 8 1 8 1 8 キシ C - Cアルコキシ基、ペンタフルォロサルファ-ル基（— SF )、トリメチルシリル基 1 8 1 8 1 8 1 8 Xoxy C-C alkoxy group, pentafluorosulfur group (—SF), trimethylsilyl group
1 8 5 1 8 5
、 C - Cアルキルカルボ-ルォキシ基、ハロ C - Cアルキルカルボ-ルォキシ基、 C - , C-C alkylcarbo-loxy group, halo C-C alkylcarbo-loxy group, C-
1 8 1 8 11 8 1 8 1
Cアルキルスルホ -ルァミノ基、ハロ C - Cアルキルスルホ -ルァミノ基、 C - CアルキC alkylsulfo-lumino group, halo C-C alkylsulfo-lamino group, C-C alkyl
8 1 8 1 8 ルカルボニル基、 C - Cアルコキシカルボ-ル基又はハロ C - Cアルキレンジォキシ 8 1 8 1 8 rucarbonyl group, C-C alkoxycarbonyl group or halo C-C alkylenedioxy
1 8 1 4  1 8 1 4
基であり、更に好ましくはハロ C - Cアルキル基、ハロ C - Cアルコキシ C - Cアルキル  More preferably a halo C-C alkyl group, a halo C-C alkoxy C-C alkyl
1 8 1 8 1 8 基、ハロ C - Cアルコキシ基又はジフルォロメチレンジォキシ基（一 OCF O—）である  1 8 1 8 1 8 group, halo C-C alkoxy group or difluoromethylenedioxy group (one OCF O—)
1 8 2  1 8 2
Xとして好ましくは酸素原子又は単結合であり、 Yとして好ましくは酸素原子であり、 mとして好ましくは 1であり、 nとして好ましくは 1又は 2である。 X is preferably an oxygen atom or a single bond, Y is preferably an oxygen atom, m is preferably 1, and n is preferably 1 or 2.
一般式 (I)で表されるフエ二ルビリジン類の塩類としては、酢酸塩、プロピオン酸塩、 酪酸塩、シユウ酸塩、アジピン酸塩、ドデカン二酸塩、ラウリン酸塩、ステアリン酸塩、 トリフルォロ酢酸塩、フマール酸塩、マレイン酸塩、安息香酸塩、フタル酸塩等の力 ルボン酸塩類;メタンスルホン酸塩、 1, 3—プロパンジスルホン酸塩、 p—トルエンス ルホン酸塩、ドデシルベンゼンスルホン酸塩等のスルホン酸塩類；塩酸塩、硫酸塩、 硝酸塩、炭酸塩等の無機酸塩類等が例示できる。  Examples of the salts of the phenylpyrrolidines represented by the general formula (I) include acetate, propionate, butyrate, oxalate, adipate, dodecanedioate, laurate, stearate, trifluoro Acetate, fumarate, maleate, benzoate, phthalate, etc. Lubonates; methanesulfonate, 1,3-propanedisulfonate, p-toluenesulfonate, dodecylbenzenesulfonate Examples thereof include sulfonates such as salts; inorganic acid salts such as hydrochlorides, sulfates, nitrates and carbonates.
[0020] 一般式 (I)で示される本発明のフエ-ルビリジン類又はその塩類は新規ィ匕合物であ り、例えば以下の製造方法に従って製造することができる。 [0020] The pyrrolidines or salts thereof of the present invention represented by the general formula (I) are novel compounds and can be produced, for example, according to the following production method.
製造方法 1. スズキカップリング反応による製造  Manufacturing method 1. Manufacturing by Suzuki coupling reaction
[化 2] Xノ[Chemical 2] X
Figure imgf000013_0001
Figure imgf000013_0001
(II)  (II)
(式中、 R R2、 R3、 R4、 X、 Y、 m、 n及び pは前記に同じくし、 Wはハロゲン原子、トリ フルォロメチルスルホ-ルォキシ基、メタンスルホ-ルォキシ基、 p—トルエンスルホニ ルォキシ基等の脱離基を示す。 ) (Wherein RR 2 , R 3 , R 4 , X, Y, m, n and p are the same as above, W is a halogen atom, a trifluoromethylsulfo-oxy group, a methanesulfo-oxy group, p— Indicates a leaving group such as a toluenesulfonyloxy group.)
[0021] 一般式 (II)で表されるピリジン類と一般式 (VII)で表されるフエ-ルポロン酸類とを 塩基及び遷移金属触媒の存在下、配位子又は不活性溶媒の存在下若しくは非存在 下に反応させることにより一般式 (I)で表される化合物を製造することができる。 [0021] A pyridine represented by the general formula (II) and a ferropolonic acid represented by the general formula (VII) in the presence of a base and a transition metal catalyst, in the presence of a ligand or an inert solvent, or By reacting in the absence, the compound represented by the general formula (I) can be produced.
本反応で使用できる不活性溶媒としては、本反応に直接関与しないものであれば 特に限定されず、例えばメタノール、エタノール、イソプロピルアルコール等のアルコ ール類；ベンゼン、トルエン、キシレン等の芳香族炭化水素類；アセトン、メチルェチ o ：T "  The inert solvent that can be used in this reaction is not particularly limited as long as it does not directly participate in this reaction. For example, alcohols such as methanol, ethanol, and isopropyl alcohol; aromatic carbonization such as benzene, toluene, and xylene. Hydrogen; acetone, methyl ester o: T "
ルケトン、メチルイソブチルケトン等のケトン類；クロ口ホルム、ジクロロメタン等のハロ ゲン化炭化水素類；水；酢酸メチル、酢酸ェチル等のエステル類；ジェチルエーテル 、テトラヒドロフラン、ジォキサン等のエーテル類；ァセトニトリル、 N, N—ジメチルホル ムアミド、 N—メチルピロリドン、ジメチルスルホキシド、ピリジン等の極性溶媒等を挙 げることができ、これらの不活性溶媒は単独で又は 2種類以上を混合して使用するこ とがでさる。  Ketones such as ruketone and methyl isobutyl ketone; halogenated hydrocarbons such as chloroform and dichloromethane; water; esters such as methyl acetate and ethyl acetate; ethers such as jetyl ether, tetrahydrofuran and dioxane; Examples include polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and pyridine. These inert solvents can be used alone or in admixture of two or more. I'll do it.
本反応で使用できる塩基としては、例えば水素化ナトリウム等のアルカリ金属水素 化物；水酸化ナトリウム、水酸ィ匕カリウム等のアルカリ金属水酸ィ匕物;炭酸ナトリウム、 炭酸カリウム等のアルカリ金属炭酸塩;弗化カリウム等の無機塩類;ピリジン、トリェチ ルァミン等の有機塩基類等を挙げることができ、その使用量は一般式 (VII)で表され るフエニルボロン酸類に対して等モル〜過剰モルの範囲で適宜選択して反応を行え ば良ぐ好ましくは 2倍モル用いるのが良い。  Examples of the base that can be used in this reaction include alkali metal hydrides such as sodium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate. Inorganic salts such as potassium fluoride; organic bases such as pyridine and triethylamine, etc., and the amount used is in the range of equimolar to excess molar relative to the phenylboronic acid represented by the general formula (VII). The reaction can be carried out by appropriately selecting in step 2 and preferably 2 moles are used.
[0022] 本反応で使用できる遷移金属触媒としてはパラジウム炭素、酢酸パラジウム、ジクロ 口ビス（トリフエ-ルホスフィン)パラジウム、テトラキス（トリフエ-ルホスフィン)パラジゥ ム、トリス（ジベンジルアセトン)パラジウム等のパラジウム化合物類、ビス（トリフエ-ル ホスフィン）ニッケルクロリド及びテトラキス（トリフエ-ルホスフィン）ニッケル等の-ッケ ルイ匕合物等を挙げることができ、その使用量は一般式 (II)で表されるピリジン類に対 して 0. 0001倍モル〜等モルの範囲で適宜選択して反応を行えば良ぐ好ましくは 0 . 0001倍モル〜 0. 2倍モル用いるのが良い。 [0022] Transition metal catalysts that can be used in this reaction include palladium on carbon, palladium acetate, dichlorobis (triphosphine) palladium, tetrakis (triphenylphosphine) paradium. And palladium compounds such as tris (dibenzylacetone) palladium, bis (triphenylphosphine) nickel chloride and tetrakis (triphenylphosphine) nickel-like compounds. The amount used may be appropriately selected from the range of 0.0001 mole to equimolar to the pyridine represented by the general formula (II), and the reaction is preferably performed. It is good to use double mole.
本反応で使用できる配位子としてはトリフエ-ルホスフィン、トリトリルホスフィン、トリ t ブチルホスフィン等のホスフィン配位子等を挙げることができ、その使用量は遷移 金属触媒に対して 0. 5倍モル〜 100倍モルの範囲で適宜選択すれば良ぐ好ましく は等モル〜 10倍モルの範囲である。又、配位子を使用しないで反応させることもでき る。  Examples of ligands that can be used in this reaction include phosphine ligands such as triphenylphosphine, tritolylphosphine, tri-t-butylphosphine, etc., and the amount used is 0.5 times that of the transition metal catalyst. It is preferable to select appropriately in the range of mol to 100 times mol, preferably in the range of equimolar to 10 times mol. It is also possible to carry out the reaction without using a ligand.
本反応は等モル反応であるので一般式 (Π)で表されるピリジン類及び一般式 (VII) で表されるフエ-ルポロン酸類を等モル使用すれば良 、が、 V、ずれかの反応剤を過 剰に使用することもでき、好ましくは一般式 (VII)で表されるフエ-ルポロン酸類を過 剰に使用するのが良い。  Since this reaction is an equimolar reaction, it is sufficient to use equimolar amounts of the pyridines represented by the general formula (Π) and the ferropolonic acids represented by the general formula (VII). The agent can be used in excess, and it is preferable to use the phenolic acid represented by the general formula (VII) in excess.
反応温度は 50°C〜使用する不活性溶媒の沸点域の範囲で適宜行えば良ぐ好 ましくは室温〜 120°Cの範囲である。反応時間は反応の規模及び反応温度により一 定しないが、数分〜 48時間の範囲である。  The reaction temperature is suitably in the range of 50 ° C to the boiling point of the inert solvent used, and preferably in the range of room temperature to 120 ° C. The reaction time is not constant depending on the scale of the reaction and the reaction temperature, but is in the range of several minutes to 48 hours.
[0023] 反応後、目的物である一般式 (I)の化合物を単離するには、水に溶解する溶媒を 用いた場合は、減圧下溶媒を留去し、水を加えた後、水に不溶のベンゼン、トルエン 、キシレン等の芳香族炭化水素；クロ口ホルム、ジクロロメタン等のハロゲンィ匕炭化水 素類;酢酸ェチル等のエステル類で抽出し、飽和食塩水で洗浄後、無水硫酸ナトリウ ム、無水硫酸マグネシウム等の乾燥剤で乾燥し、減圧下で溶媒を留去すれば良い。 水に不溶の溶媒を用いた場合は、反応混合物に水を加えた後分液し、有機層を飽 和食塩水で洗浄後、無水硫酸ナトリウム、無水硫酸マグネシウム等の乾燥剤で乾燥 し、減圧下で溶媒を留去すれば良い。溶媒留去後得られた残渣を、再結晶、懸濁洗 浄、カラムクロマトグラフィー等で精製すれば目的物である一般式 (I)で表される化合 物が得られる。 [0023] After the reaction, in order to isolate the target compound of the general formula (I), when a solvent that dissolves in water is used, the solvent is distilled off under reduced pressure, water is added, Insoluble in benzene, toluene, xylene, etc .; halogenated hydrocarbons such as chloroform, dichloromethane, etc .; extracted with esters such as ethyl acetate, washed with saturated saline, and then anhydrous sodium sulfate And drying with a drying agent such as anhydrous magnesium sulfate, and the solvent may be distilled off under reduced pressure. If a solvent insoluble in water is used, water is added to the reaction mixture, and the mixture is separated. The organic layer is washed with saturated Japanese saline, dried with a drying agent such as anhydrous sodium sulfate or anhydrous magnesium sulfate, and reduced pressure. And the solvent may be distilled off. If the residue obtained after distilling off the solvent is purified by recrystallization, suspension washing, column chromatography or the like, the compound represented by the general formula (I), which is the target product, can be obtained.
[0024] 製造方法 2. カルボン酸類とァミン類との反応による製造 [化 3] [0024] Production Method 2. Production by Reaction of Carboxylic Acids with Amines [Chemical 3]
Figure imgf000015_0001
Figure imgf000015_0001
(ΠΙ) ( I )  (ΠΙ) (I)
(式中、
Figure imgf000015_0002
R2、 R3、 R4、 X、 Y、 m、 n及び pは前記に同じ。 ) (Where
Figure imgf000015_0002
R 2 , R 3 , R 4 , X, Y, m, n and p are the same as above. )
一般式 (III)で表されるカルボン酸と一般式 (IV)で表されるァミン類とを塩基及び縮 合剤の存在下、不活性溶媒の存在下又は非存在下に反応させることにより一般式 (I )で表される化合物を製造することができる。  A general reaction is achieved by reacting the carboxylic acid represented by the general formula (III) and the amine represented by the general formula (IV) in the presence of a base and a condensing agent in the presence or absence of an inert solvent. A compound represented by the formula (I) can be produced.
本反応で使用できる不活性溶媒としては、本反応に直接関与しないものであれば 特に限定されず、例えばベンゼン、トルエン、キシレン等の芳香族炭化水素類;ァセ トン、メチルェチルケトン、メチルイソブチルケトン等のケトン類；クロ口ホルム、ジクロロ メタン等のハロゲンィ匕炭化水素類；水；酢酸メチル、酢酸ェチル等のエステル類；ジェ チルエーテル、テトラヒドロフラン、ジォキサン等のエーテル類；ァセトニトリル、 N, N ージメチルホルムアミド、 N—メチルピロリドン、ジメチルスルホキシド、ピリジン等の極 性溶媒等を挙げることができ、これらの不活性溶媒は単独で又は 2種類以上を混合 して使用することができる。  The inert solvent that can be used in this reaction is not particularly limited as long as it does not directly participate in this reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, etc .; acetone, methyl ethyl ketone, methyl Ketones such as isobutyl ketone; Halogenated hydrocarbons such as chloroform and dichloromethane; Water; Esters such as methyl acetate and ethyl acetate; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Acetonitrile, N, N Examples include polar solvents such as dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and pyridine. These inert solvents can be used alone or in admixture of two or more.
本反応で使用できる塩基としては、例えば水素化ナトリウム等のアルカリ金属水素 化物；水酸化ナトリウム、水酸ィ匕カリウム等のアルカリ金属水酸ィ匕物;炭酸ナトリウム、 炭酸カリウム等のアルカリ金属炭酸塩；弗化カリウム等の無機塩類;ピリジン、 DBU、ト リエチルァミン等の有機塩基類等を挙げることができ、その使用量は一般式 (IV)で 表されるアミン類に対して等モル〜過剰モルの範囲で適宜選択して反応を行えば良 い。  Examples of the base that can be used in this reaction include alkali metal hydrides such as sodium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate. Inorganic salts such as potassium fluoride; organic bases such as pyridine, DBU, triethylamine and the like. The amount used is equimolar to excess molar relative to the amine represented by the general formula (IV). The reaction may be performed by selecting appropriately within the range.
本反応で使用できる縮合剤としてはカルボニルジイミダゾール、ジシクロへキシルカ ルボジイミド、ヨウ化 2—クロ口一 1—メチルピリジ-ゥム等を挙げることができ、その使 用量は一般式 (III)で表されるカルボン酸に対して等モル〜過剰モルの範囲で適宜 選択して反応を行えば良 、。 [0026] 本反応は等モル反応であるので一般式 (III)で表されるカルボン酸及び一般式 (IV )で表されるアミン類を等モル使用すれば良 、が、好ましくは一般式 (IV)で表される アミン類を過剰に使用するのが良い。 Examples of the condensing agent that can be used in this reaction include carbonyldiimidazole, dicyclohexylcarbodiimide, 2-iodine chloride, 1-methylpyridium, and the use amount thereof is represented by the general formula (III). The reaction may be carried out by appropriately selecting in the range of equimolar to excess molar relative to the carboxylic acid. [0026] Since this reaction is an equimolar reaction, the carboxylic acid represented by the general formula (III) and the amine represented by the general formula (IV) may be used in an equimolar amount. The amine represented by IV) should be used in excess.
反応温度は 50°C〜使用する不活性溶媒の沸点域の範囲で適宜行えば良ぐ好 ましくは室温〜 120°Cの範囲である。反応時間は反応の規模及び反応温度により一 定しないが、数分〜 48時間の範囲である。  The reaction temperature is suitably in the range of 50 ° C to the boiling point of the inert solvent used, and preferably in the range of room temperature to 120 ° C. The reaction time is not constant depending on the scale of the reaction and the reaction temperature, but is in the range of several minutes to 48 hours.
反応後、目的物である一般式 (I)の化合物を単離するには、製造方法 1に同じくす れば良い。  After the reaction, the target compound of the general formula (I) can be isolated by the same method as in Production Method 1.
[0027] 製造方法 3. 酸ハライド類とアミン類との反応による製造  [0027] Production method 3. Production by reaction of acid halides with amines
[化 4]  [Chemical 4]
Figure imgf000016_0001
Figure imgf000016_0001
(V) ( I )  (V) (I)
(式中、
Figure imgf000016_0002
R2、 R3、 R4、 X、 Y、 m、 n及び pは前記に同じくし、 Zはハロゲン原子を示 す。） (Where
Figure imgf000016_0002
R 2 , R 3 , R 4 , X, Y, m, n and p are the same as above, and Z is a halogen atom. )
一般式 (V)で表される酸ノ、ライドと一般式 (IV)で表されるァミン類とを不活性溶媒 及び塩基の存在下又は非存在下に反応させることにより一般式 (I)で表される化合 物を製造することができる。  In the general formula (I), the acid represented by the general formula (V) is reacted with the amine represented by the general formula (IV) in the presence or absence of an inert solvent and a base. The compounds represented can be produced.
[0028] 本反応で使用できる不活性溶媒及び塩基としては、製造方法 2に同じであり、塩基 の使用量は一般に式 (V)で表される酸ノ、ライドに対して等モル〜過剰モルの範囲で 適宜選択して反応を行えば良 、。 [0028] The inert solvent and the base that can be used in this reaction are the same as those in Production Method 2, and the amount of the base used is generally equimolar to excess molar relative to the acid or halide represented by the formula (V). You can select the reaction within the range of and perform the reaction.
本反応は等モル反応であるので一般式 (V)で表される酸ハライド及び一般式 (IV) で表されるアミン類を等モル使用すれば良いが、いずれかの反応剤を過剰に使用す ることもでき、好ましくは一般式 (IV)で表されるアミン類を過剰に使用するのが良い。 反応温度は 50°C〜使用する不活性溶媒の沸点域の範囲で適宜行えば良ぐ好 ましくは 0°C〜80°Cの範囲である。反応時間は反応の規模及び反応温度により一定 しないが、数分〜 48時間の範囲である。 Since this reaction is an equimolar reaction, the acid halide represented by the general formula (V) and the amine represented by the general formula (IV) may be used in an equimolar amount, but any one of the reactants is used in excess. It is also possible to use an excess of the amine represented by the general formula (IV). The reaction temperature is preferably in the range of 50 ° C to the boiling point of the inert solvent used, and preferably in the range of 0 ° C to 80 ° C. Reaction time is constant depending on reaction scale and reaction temperature Not, it ranges from a few minutes to 48 hours.
反応後、目的物である一般式 (I)で表される化合物を単離するには、製造方法 1 同じくすれば良い。  After the reaction, in order to isolate the compound represented by the general formula (I) as the target product, the same production method 1 may be used.
[0029] 製造方法 4. カルボニル化合物とォキシァミン類との反応による製造  [0029] Production method 4. Production by reaction of carbonyl compound and oxiamines
[化 5]  [Chemical 5]
Figure imgf000017_0001
(式中、 R2、 R3、 R5、 R6、 X、 m及び pは前記に同じ。 )
Figure imgf000017_0001
(Wherein R 2 , R 3 , R 5 , R 6 , X, m and p are the same as above.)
一般式 (la)で表されるカルボ二ルイ匕合物と一般式 (VI)で表されるォキシアミン類又 はその酸付加塩類とを不活性溶媒及び塩基の存在下又は非存在下に反応させるこ とにより一般式 (lb)で表される化合物を製造することができる。  The carbonyl compound represented by general formula (la) is reacted with oxyamines or acid addition salts thereof represented by general formula (VI) in the presence or absence of an inert solvent and a base. As a result, a compound represented by the general formula (lb) can be produced.
[0030] 本反応で使用できる不活性溶媒としては、製造方法 1に同じである。 [0030] The inert solvent that can be used in this reaction is the same as in Production Method 1.
本反応で使用できる塩基としては、製造方法 2に同じくし、その使用量は一般に式 ( VI)で表されるォキシァミン類に対して等モル〜過剰モルの範囲で適宜選択して反 応を行えば良い。  The base that can be used in this reaction is the same as in Production Method 2, and the amount used is generally appropriately selected within the range of equimolar to excess molar with respect to the oxiamines represented by formula (VI). Just do it.
本反応は等モル反応であるので一般式 (la)で表されるカルボ二ルイ匕合物及び一 般式 (VI)で表されるォキシアミン類を等モル使用すれば良 、が、 V、ずれかの反応剤 を過剰に使用することもでき、好ましくは一般式 (VI)で表されるォキシアミン類を過剰 に使用するのが良い。  Since this reaction is an equimolar reaction, it is sufficient to use equimolar amounts of the carbonyl compound represented by the general formula (la) and the oxyamine represented by the general formula (VI). These reactants can be used in excess, and preferably the oxyamines represented by the general formula (VI) are used in excess.
反応温度は 50°C〜使用する不活性溶媒の沸点域の範囲で適宜行えば良ぐ好 ましくは室温〜 80°Cの範囲である。反応時間は反応の規模及び反応温度により一 定しないが、数分〜 48時間の範囲である。  The reaction temperature is suitably in the range of 50 ° C to the boiling point of the inert solvent used, and preferably in the range of room temperature to 80 ° C. The reaction time is not constant depending on the scale of the reaction and the reaction temperature, but is in the range of several minutes to 48 hours.
反応後、目的物である一般式 (lb)の化合物を単離するには、製造方法 1に同じく すれば良い。  After the reaction, the target compound of the general formula (lb) can be isolated by the same method as in Production Method 1.
[0031] 製造方法 5. フエ-ルビリジン類の窒素原子上の水素原子置換反応による製造 [化 6]
Figure imgf000018_0001
[0031] Production method 5. Production of pyrrolidines by hydrogen atom substitution reaction on the nitrogen atom [Chemical 6]
Figure imgf000018_0001
(Ic) ( I )  (Ic) (I)
(式中、 R R2、 R3、 R4、 W、 X、 Y、 m、 n及び pは前記に同じ。 ) (Wherein, RR 2, R 3, R 4, W, X, Y, m, n and p are as defined above.)
一般式 (Ic)で表されるフエ-ルビリジン類と一般式 (VIII)で表される化合物とを不 活性溶媒及び塩基の存在下又は非存在下に反応させることにより一般式 (I)で表さ れる化合物を製造することができる。  It is represented by the general formula (I) by reacting the ferroviridines represented by the general formula (Ic) with the compound represented by the general formula (VIII) in the presence or absence of an inert solvent and a base. Can be produced.
[0032] 本反応で使用できる不活性溶媒及び塩基としては、製造方法 2に同じであり、塩基 の使用量は一般式 (VIII)で表される化合物に対して等モル〜過剰モルの範囲で適 宜選択して反応を行えば良 、。 [0032] The inert solvent and base that can be used in this reaction are the same as in Production Method 2, and the amount of the base used is in the range of equimolar to excess molar relative to the compound represented by the general formula (VIII). If you select and respond appropriately.
本反応は等モル反応であるので一般式 (Ic)で表されるフエ-ルビリジン類及び一 般式 (VIII)で表される化合物を等モル使用すれば良!ヽが、 Vヽずれかの反応剤を過 剰に使用することもでき、好ましくは式 (VIII)で表される化合物を過剰に使用するの が良い。  Since this reaction is an equimolar reaction, it is sufficient to use equimolar amounts of the pyrrolidines represented by the general formula (Ic) and the compounds represented by the general formula (VIII). The reactant can be used in excess, and preferably the compound represented by formula (VIII) is used in excess.
反応温度は 50°C〜使用する不活性溶媒の沸点域の範囲で適宜行えば良ぐ好 ましくは 0°C〜100°Cの範囲である。反応時間は反応の規模及び反応温度により一 定しないが、数分〜 48時間の範囲である。  The reaction temperature is preferably in the range of 50 ° C to the boiling point of the inert solvent used, and is preferably in the range of 0 ° C to 100 ° C. The reaction time is not constant depending on the scale of the reaction and the reaction temperature, but is in the range of several minutes to 48 hours.
反応後、目的物である一般式 (I)の化合物を単離するには、製造方法 1に同じくす れば良い。  After the reaction, the target compound of the general formula (I) can be isolated by the same method as in Production Method 1.
[0033] 製造方法 6. ピリジン類の酸化反応による製造  [0033] Production method 6. Production of pyridines by oxidation reaction
[化 7]
Figure imgf000018_0002
[Chemical 7]
Figure imgf000018_0002
(1め (Ie)  (First (Ie)
(式中、
Figure imgf000018_0003
R2、 R3、 R4、 X、 Y、 m、及び nは前記に同じ。 ) (Where
Figure imgf000018_0003
R 2 , R 3 , R 4 , X, Y, m, and n are the same as above. )
一般式 (Id)で表されるフエ-ルビリジン類と酸化剤とを不活性溶媒存在下又は非 存在下に反応させることにより一般式 (Ie)で表される化合物を製造することができる。 The pyrrolidines represented by the general formula (Id) and an oxidant in the presence or absence of an inert solvent. By reacting in the presence, the compound represented by the general formula (Ie) can be produced.
[0034] 本反応で使用できる不活性溶媒としては、本反応に直接関与しな ヽものであれば 特に限定されず、例えばベンゼン、トルエン、キシレン等の芳香族炭化水素類;ァセ トン、メチルェチルケトン、メチルイソブチルケトン等のケトン類；クロ口ホルム、ジクロロ メタン等のハロゲンィ匕炭化水素類；水；酢酸メチル、酢酸ェチル等のエステル類；ジェ チルエーテル、テトラヒドロフラン、ジォキサン等のエーテル類；ァセトニトリル、 N, N —ジメチルホルムアミド、 N—メチルピロリドン、ジメチルスルホキシド等の極性溶媒等 を挙げることができ、これらの不活性溶媒は単独で又は 2種類以上を混合して使用す ることがでさる。 [0034] The inert solvent that can be used in this reaction is not particularly limited as long as it is not directly involved in this reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, etc .; Ketones such as ethyl ketone and methyl isobutyl ketone; Halogenated hydrocarbons such as chloroform and dichloromethane; Water; Esters such as methyl acetate and ethyl acetate; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Acetonitrile And polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide. These inert solvents can be used alone or in admixture of two or more.
本反応で使用できる酸化剤としては m クロ口過安息香酸、過酸化水素、過酢酸 等を挙げることができる。  Examples of the oxidizing agent that can be used in this reaction include m-peroxybenzoic acid, hydrogen peroxide, and peracetic acid.
本反応は等モル反応であるので一般式 (Id)で表されるフエ-ルビリジン類及び酸 ィ匕剤を等モル使用すれば良いが、いずれかの反応剤を過剰に使用することもでき、 好ましくは酸化剤を過剰に使用するのが良い。  Since this reaction is an equimolar reaction, it is only necessary to use equimolar amounts of the pyrrolidines represented by the general formula (Id) and the acidic agent, but any of the reactants can be used in excess. It is preferable to use an oxidizing agent in excess.
反応温度は 50°C〜使用する不活性溶媒の沸点域の範囲で適宜行えば良ぐ好 ましくは 0°C〜25°Cの範囲である。反応時間は反応の規模及び反応温度により一定 しないが、数分〜 48時間の範囲である。  The reaction temperature is preferably in the range of 50 ° C to the boiling point of the inert solvent used, and preferably in the range of 0 ° C to 25 ° C. The reaction time is not constant depending on the scale of the reaction and the reaction temperature, but ranges from a few minutes to 48 hours.
反応後、目的物である一般式 (Ie)で表される化合物を単離するには、製造方法 1 に同じくすれば良い。  After the reaction, in order to isolate the compound represented by the general formula (Ie), which is the target product, the production method 1 may be used.
[0035] 中間体である一般式 (II)で表される化合物は、例えば、国際公開第 00Z175112 号パンフレット、欧州特許出願公開第 0053011号明細書又は欧州特許出願公開第 447004号明細書記載の方法に準じて製造できる。  [0035] The compound represented by the general formula (II) as an intermediate is, for example, a method described in International Publication No. 00Z175112, European Patent Application Publication No. 0053011 or European Patent Application Publication No. 447004. It can be manufactured according to
中間体である一般式 (III)で表される化合物は、例えば、国際公開第 04Z014844 号パンフレット又は国際公開第 04Z002948号パンフレット記載の方法に準じて製 造できる。  The compound represented by the general formula (III) as an intermediate can be produced, for example, according to the method described in International Publication No. 04Z014844 pamphlet or International Publication No. 04Z002948 pamphlet.
中間体である一般式 (IV)で表される化合物は、市販されて 、るものを用いれば良 い。  The intermediate compound represented by the general formula (IV) is commercially available and may be used.
中間体である一般式 (V)で表される化合物は、対応する化合物 (III)より塩ィ匕チォニ ル等を用いる常法によりハロゲンィ匕して製造できる。 The compound represented by the general formula (V), which is an intermediate, is obtained from the corresponding compound (III). It can be produced by halogenation by a conventional method using a catalyst.
[0036] さらに、本発明のフエ二ルビリジン類の塩類は以下の方法で製造することができる。  [0036] Further, the salts of the phenylpyrrolidines of the present invention can be produced by the following method.
製造方法 7.  Manufacturing method 7.
[化 8]  [Chemical 8]
Figure imgf000020_0001
Figure imgf000020_0001
(式中、
Figure imgf000020_0002
R2、 R3、 R4、 X、 Y、 m、 n及び pは前記に同じくし、 Aは無機酸又は有機 酸を示す。 ) (Where
Figure imgf000020_0002
R 2 , R 3 , R 4 , X, Y, m, n and p are the same as described above, and A represents an inorganic acid or an organic acid. )
即ち、一般式 (I)で表されるフエ二ルビリジン類と無機酸又は有機酸とを、不活性溶 媒存在下又は非存在下に反応させることにより一般式 (If)で表される塩類を製造す ることがでさる。  That is, the salt represented by the general formula (If) is obtained by reacting the phenylpyrrolidine represented by the general formula (I) with an inorganic acid or an organic acid in the presence or absence of an inert solvent. It can be manufactured.
[0037] 本反応で使用できる酸としては有機酸、無機酸を用いることが出来、有機酸として は酢酸、プロピオン酸、酪酸、シユウ酸、アジピン酸、ドデカン二酸、ラウリン酸、ステ アリン酸、トリフルォロ酢酸、フマール酸、マレイン酸、安息香酸、フタル酸等のカルボ ン酸類；メタンスルホン酸、 1, 3 プロパンジスルホン酸、 p—トルエンスルホン酸、ド デシルベンゼンスルホン酸等のスルホン酸類等を挙げることができる。無機酸として は塩酸、硫酸、硝酸、炭酸等を挙げることができる。  [0037] As an acid that can be used in this reaction, an organic acid or an inorganic acid can be used. As an organic acid, acetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, dodecanedioic acid, lauric acid, stearic acid, Carboxylic acids such as trifluoroacetic acid, fumaric acid, maleic acid, benzoic acid, phthalic acid; sulfonic acids such as methanesulfonic acid, 1,3 propanedisulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, etc. Can do. Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and carbonic acid.
本反応で使用できる不活性溶媒としては、製造方法 6に同じである。  The inert solvent that can be used in this reaction is the same as in Production Method 6.
本反応は等モル反応であるので一般式 (I)で表されるフエ二ルビリジン類及び無機 酸又は有機酸を等モル使用すれば良いが、いずれかの反応剤を過剰に使用するこ ともでき、好ましくは無機酸又は有機酸を過剰に使用するのが良い。  Since this reaction is an equimolar reaction, it is sufficient to use equimolar amounts of the phenylpyridines represented by the general formula (I) and the inorganic acid or organic acid, but any of the reactants can be used in excess. The inorganic acid or organic acid is preferably used in excess.
反応温度は 50°C〜使用する不活性溶媒の沸点域の範囲で適宜行えば良ぐ好 ましくは 0°C〜25°Cの範囲である。反応時間は反応の規模及び反応温度により一定 しないが、数分〜 48時間の範囲である。  The reaction temperature is preferably in the range of 50 ° C to the boiling point of the inert solvent used, and preferably in the range of 0 ° C to 25 ° C. The reaction time is not constant depending on the scale of the reaction and the reaction temperature, but ranges from a few minutes to 48 hours.
反応後溶媒を減圧留去し、結晶をろ別し、無機酸塩、有機酸塩を製造することが出 来る。このままでも十分であるが、更に精製したい場合は上記の不活性溶媒で洗浄 することにより高純度のフエ二ルビリジン酸付加塩類を製造することが出来る。 After the reaction, the solvent is distilled off under reduced pressure, and the crystals are separated by filtration to produce inorganic acid salts and organic acid salts. This is sufficient, but if you want to further purify, wash with the above inert solvent. By doing so, high-purity phenyluridine acid addition salts can be produced.
[0038] 上記の製造方法に従って製造できる一般式 (I)で表される本発明化合物を第 1表 に例示する力 本発明はこれらに限定されるものではない。尚、表中、「n—」はノルマ ルを、「i―」はイソを、「c―」はシクロを、「一」は単結合を、「*」は無置換であることを 示す。  [0038] The ability to exemplify the compounds of the present invention represented by the general formula (I) that can be produced according to the above production method in Table 1. The present invention is not limited to these. In the table, “n-” represents normal, “i-” represents iso, “c-” represents cyclo, “one” represents a single bond, and “*” represents unsubstituted.
[0039] [表 1] [0039] [Table 1]
一般式 (I)Formula (I)
Figure imgf000022_0001
Figure imgf000022_0001
第 1表 （R2 = H、 p = 0)
Figure imgf000022_0002
Table 1 (R 2 = H, p = 0)
Figure imgf000022_0002
2]
Figure imgf000023_0001
] 第 1表 き) 2]
Figure imgf000023_0001
] (Table 1)
Figure imgf000024_0001
]
Figure imgf000025_0001
]
Figure imgf000026_0001
] 第 1表 （^き)
Figure imgf000024_0001
]
Figure imgf000025_0001
]
Figure imgf000026_0001
] Table 1 (^)
Figure imgf000027_0001
Figure imgf000027_0001
[0045] [表 7]  [0045] [Table 7]
第 2表 （R4=3- 0CF3、 Y=0、 p = 0) Table 2 (R 4 = 3- 0CF 3 , Y = 0, p = 0)
Figure imgf000027_0002
Figure imgf000027_0002
[0046] [表 8]
Figure imgf000028_0001
本発明の一般式 (I)で表されるフエ-ルビリジン類又はその塩類を除草剤として使 用する場合、農薬製剤上の常法に従い、使用上都合の良い形状に製剤して使用す るのが一般的である。即ち、本発明の一般式 (I)で表されるフエ二ルビリジン類又はそ の塩類は、これらを適当な不活性担体に、又は必要に応じて補助剤と一緒に、適当 な割合に配合して溶解、分離、懸濁、混合、含浸、吸着若しくは付着させ、適宜の剤 形、例えば懸濁剤、乳懸濁剤、乳剤、液剤、水和剤、粒剤、粉剤、錠剤、ジャンボ剤 、ノック剤等に製剤して使用すれば良い。 [0046] [Table 8]
Figure imgf000028_0001
When using the pyrrolidines or salts thereof represented by the general formula (I) of the present invention as herbicides, they should be formulated in a convenient form according to conventional methods for agricultural chemical formulations. Is common. That is, the phenylpyrrolidines or salts thereof represented by the general formula (I) of the present invention are blended in an appropriate ratio together with an appropriate inert carrier or, if necessary, an adjuvant. Dissolving, separating, suspending, mixing, impregnating, adsorbing or adhering to appropriate dosage forms such as suspensions, milk suspensions, emulsions, solutions, wettable powders, granules, powders, tablets, jumbo drugs, The preparation may be used as a knocking agent.
本発明で使用できる不活性担体としては固体又は液体の何れであっても良ぐ固 体の担体になり得る材料としては、例えば植物質粉末類 (例えばダイズ粉、穀物粉、 木粉、榭皮粉、鋸粉、タバコ茎粉、タルミ殻粉、ふすま、繊維素粉末、植物エキス抽 出後の残渣等)、粉砕合成樹脂等の合成重合体、粘土類 (例えばカオリン、ベントナ イト、酸性白土等）、タルク類 {例えばタルク、ピロフィライト等 }、シリカ類 (例えば珪藻 土、珪砂、雲母、ホワイトカーボン (含水微粉珪素、含水珪酸ともいわれる合成高分 散珪酸で、製品により珪酸カルシウムを主成分として含むものもある。；)）、活性炭、天 然鉱物質類 (例えばィォゥ粉末、軽石、焼成珪藻土、ァタパルジャイトおよびゼォライ ト等）、レンガ粉砕物、フライアッシュ、砂、プラスチック担体等 (例えばポリエチレン、 ポリプロピレン、ポリ塩ィ匕ビユリデン等）、炭酸カルシウム、燐酸カルシウム等の無機鉱 物性粉末、硫安、燐安、硝安、尿素、塩安等の化学肥料、堆肥等を挙げることができ 、これらは単独で若しくは二種以上の混合物の形で使用される。 [0048] 液体の担体になり得る材料としては、それ自体溶媒能を有するものの他、溶媒能を 有さずとも補助剤の助けにより有効成分ィヒ合物を分散させ得ることとなるものから選 択され、例えば代表例として次に挙げる担体を例示できるが、これらは単独で若しく は 2種以上の混合物の形で使用され、例えば水、アルコール類 (例えばメタノール、 エタノール、イソプロパノール、ブタノール、エチレングリコール等）、ケトン類（例えば アセトン、メチルェチルケトン、メチルイソブチルケトン、ジイソプチルケトン、シクロへ キサノン等）、エーテル類（例えばェチルエーテル、ジォキサン、セロソルブ、ジプロピ ルエーテル、テトラヒドロフラン等)、脂肪族炭化水素類 (例えばケロシン、鉱油等)、 芳香族炭化水素類 (例えばベンゼン、トルエン、キシレン、ソルベントナフサ、アルキ ルナフタレン等）、エステル類（例えば酢酸ェチル、ジイソプピルフタレート、ジブチル フタレート、ジォクチルフタレート等）、アミド類（例えばジメチルホルムアミド、ジェチ ルホルムアミド、ジメチルァセトアミド等）、二トリル類 (例えばァセトニトリル等）、ジメチ ルスルホキシド類等を挙げることができる。 Examples of the inert carrier that can be used in the present invention can be either solid or liquid. Examples of the material that can be a solid carrier include vegetable powders (for example, soybean powder, cereal flour, wood flour, husk) Powder, sawdust, tobacco stem powder, walnut shell powder, bran, fiber powder, residues after extraction of plant extracts), synthetic polymers such as pulverized synthetic resin, clays (e.g. kaolin, bentonite, acid clay) ), Talc {eg talc, pyrophyllite, etc.}, silica (eg diatomaceous earth, silica sand, mica, white carbon (hydrous finely divided silicon, hydrous silicic acid, synthetic high-dispersion silicic acid that contains calcium silicate as the main component) ;)), Activated carbon, natural minerals (such as yow powder, pumice, calcined diatomaceous earth, attapulgite and zeolite), brick ground, fly ash, sand, plastic Examples include mineral carriers such as polyethylene, polypropylene, and polysalt vinylidene, inorganic mineral powders such as calcium carbonate and calcium phosphate, chemical fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and ammonium chloride, compost, etc. These can be used alone or in the form of a mixture of two or more. [0048] The material that can be used as a liquid carrier is selected from those having solvent ability itself and those capable of dispersing the active ingredient compound with the aid of an auxiliary agent without having solvent ability. For example, the following carriers can be exemplified as representative examples, and these are used alone or in the form of a mixture of two or more, such as water, alcohols (for example, methanol, ethanol, isopropanol, butanol, ethylene). Glycol, etc.), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, etc.), ethers (eg, ethyl ether, dioxane, cellosolve, dipropyl ether, tetrahydrofuran, etc.), aliphatic carbonization Hydrogens (e.g. kerosene, mineral oil, etc.), aromatic hydrocarbons (e.g. benzene, Toluene, xylene, solvent naphtha, alkylnaphthalene, etc.), esters (eg, ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, etc.), amides (eg, dimethylformamide, ethylformamide, dimethylacetamide) Etc.), nitriles (eg, acetonitrile), dimethyl sulfoxides and the like.
他の補助剤としては次に例示する代表的な補助剤を挙げることができ、これらの補 助剤は目的に応じて使用され、単独で、ある場合は二種以上の補助剤を併用し、又 ある場合には全く補助剤を使用しないことも可能である。有効成分化合物の乳化、分 散、可溶化及び Z又は湿潤の目的のために界面活性剤が使用され、例えばポリオキ シエチレンアルキルエーテル、ポリオキシエチレンアルキルァリールエーテル、ポリオ キシエチレン高級脂肪酸エステル、ポリオキシエチレン榭脂酸エステル、ポリオキシ エチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノォレエート、アル キルァリールスルホン酸塩、ナフタレンスルホン酸縮合物、リグ-ンスルホン酸塩、高 級アルコール硫酸エステル等の界面活性剤を例示することができる。  As other adjuvants, typical adjuvants exemplified below can be mentioned, and these adjuvants are used depending on the purpose and are used alone, in some cases, in combination with two or more kinds of adjuvants, In some cases it is also possible to use no adjuvants. Surfactants are used for emulsification, dispersion, solubilization and Z or wetting purposes of the active ingredient compounds, such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene higher fatty acid esters, polyoxy Interfaces such as ethylene succinate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkylaryl sulfonate, naphthalene sulfonic acid condensate, lignosulfonate, and higher alcohol sulfate An activator can be exemplified.
[0049] 又、有効成分化合物の分散安定化、粘着及び Z又は結合の目的のために、次に 例示する補助剤を使用することもでき、例えばカゼイン、ゼラチン、澱粉、メチルセル ロース、カルボキシメチルセルロース、キサンタンガム、アラビアゴム、ポリビニルアル コール、松根油、糠油、ベントナイト、リグ-ンスルホン酸塩等の補助剤を使用するこ ともできる。固体製品の流動性改良のために次に挙げる補助剤を使用することもでき 、例えばワックス、ステアリン酸塩、燐酸アルキルエステル等の補助剤を使用できる。 懸濁性製品の解こう剤として、例えばナフタレンスルホン酸縮合物、縮合燐酸塩等の 補助剤を使用することもできる。消泡剤としては、例えばシリコーン油等の補助剤を使 用することちでさる。 [0049] For the purpose of stabilizing the dispersion of the active ingredient compound, sticking and Z or binding, the following auxiliaries can be used, such as casein, gelatin, starch, methylcellulose, carboxymethylcellulose, Adjuvants such as xanthan gum, gum arabic, polyvinyl alcohol, pine oil, coconut oil, bentonite, and lignite sulfonate can also be used. In order to improve the fluidity of the solid product, the following adjuvants may be used. For example, adjuvants such as wax, stearate, alkyl phosphate and the like may be used. As a peptizer for suspension products, for example, auxiliary agents such as naphthalene sulfonic acid condensate and condensed phosphate can be used. As an antifoaming agent, for example, an auxiliary agent such as silicone oil can be used.
有効成分化合物の配合割合は必要に応じて加減することができ特に制限されない 力 その配合割合は 0. 001〜90重量％程度である。例えば、粉剤或いは粒剤とす る場合の有効成分化合物の配合割合は 0. 01〜50重量％程度が好ましぐより好ま しくは 0. 1〜10重量％程度である。また、乳剤、水和剤或いは顆粒水和剤等とする 場合の有効成分化合物の配合割合は 0. 01〜90重量％程度が好ましぐより好まし くは 0. 1〜60重量％程度である。  The compounding ratio of the active ingredient compound can be adjusted as necessary and is not particularly limited. The compounding ratio is about 0.001 to 90% by weight. For example, when it is used as a powder or granule, the compounding ratio of the active ingredient compound is preferably about 0.01 to 50% by weight, more preferably about 0.1 to 10% by weight. In the case of emulsions, wettable powders or granulated wettable powders, the compounding ratio of the active ingredient compound is preferably about 0.01 to 90% by weight, more preferably about 0.1 to 60% by weight. is there.
[0050] 本発明の一般式 (I)で表されるフエ-ルビリジン類又はその塩類を含有する製剤を 水で希釈して施用する場合、付着性ゃ拡展性等を向上させ、除草効果を高めるため に、散布液中に展着剤等の補助剤を添加しても良い。使用される展着剤等の補助剤 としては、界面活性剤 (前記の非イオン系界面活性剤、カチオン系界面活性剤、ァニ オン系界面活性剤、両性系界面活性剤）、パラフィン、ポリ酢酸ビュル、ポリアクリル 酸塩、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピ レンダリコール、クロップオイル (鉱物油、動植物油等）、液体肥料等が挙げられる。こ れらの補助剤は、必要に応じて 2種以上を同時に使用しても良い。展着剤等の補助 剤の使用量は、その種類によって異なる力 通常、散布液中に 0. 01〜5重量％を添 加するのが適当である。又、補助剤の種類によっては、製剤中の成分としてあらかじ め添カ卩しておくことも可能である。  [0050] When a preparation containing a pyrrolidine or a salt thereof represented by the general formula (I) of the present invention is diluted with water and applied, the adhesiveness and spreadability are improved, and the herbicidal effect is improved. In order to increase it, an auxiliary agent such as a spreading agent may be added to the spray liquid. Adjuvants such as spreading agents used include surfactants (the above-mentioned nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants), paraffin, Examples include butyl acetate, polyacrylate, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, crop oil (mineral oil, animal and vegetable oils), and liquid fertilizer. Two or more of these adjuvants may be used simultaneously as necessary. The amount of adjuncts such as spreading agents varies depending on the type. Usually, it is appropriate to add 0.01 to 5% by weight to the spray liquid. Depending on the type of the adjuvant, it is possible to add it as a component in the preparation in advance.
本発明の一般式 (I)で表されるフヱ-ルビリジン類又はその塩類を有効成分とする 除草剤の施用量は、化合物の構造や対象雑草、処理時期、処理方法、土壌の性質 等の条件によって異なる力 通常、 1ヘクタール当りの有効成分量としては 2〜2000 g、好ましくは 5〜： LOOOgの範囲が適当である。  The application rate of the herbicide containing as an active ingredient the fur-rubiridines or salts thereof represented by the general formula (I) of the present invention is the structure of the compound, the target weed, the treatment time, the treatment method, the properties of the soil, etc. The force varies depending on the conditions. Usually, the amount of active ingredient per hectare is 2 to 2000 g, preferably 5 to LOOOg.
[0051] 本発明の除草剤の対象雑草としては、畑地においては、例えば、シロザ、ァカザ、 ィヌタデ、ハルタデ、ィヌビュ、ァオビュ、ハコべ、ホトケノザ、ィチビ、ォナモミ、マル バアサガオ、チョウセンアサガオ、セィヨウカラシナ、ヤエムダラ、セィョウスミレ、ォロ シャギク、コセンダンダサ等の広葉雑草、メヒシバ、ォヒシバ、ィヌビエ、ェノコログサ等 の狭葉雑草が挙げられる。又、水田においては、例えば、キカシダサ、ァゼナ、コナ ギ、アブノメ、ミゾノヽコベ、ヘラォモダカ、ォモダカ、ゥリカヮ等の広葉雑草、タイヌビエ 、タマガヤッリ、ィヌホタルイ、ミズガヤッリ等の狭葉雑草が挙げられる。本発明の除草 剤は、畑地および水田において、土壌処理、茎葉処理又は湛水処理のいずれの処 理方法によっても上記雑草を防除することが可能である。 [0051] The target weeds of the herbicide of the present invention include, for example, Shiroza, Akaza, Inutade, Harutade, Inubu, Aaubu, Jacobe, Hotokenoza, Ichibi, Onamomi, Maruasaagao, Datura, Seiokarasana, Yaemdara Broadleaf weeds such as Seythmus mille, Oro shagiku, Kosendandasa, Meishiba, Ohishiba, Inubie, Enokorogusa, etc. Narrow-leaved weeds. In paddy fields, for example, broad-leaved weeds such as Kakashidasa, Azena, Konogi, Abnomé, Mizono-kobe, Heramodaka, Omodaka and Urica-koji, and narrow-leaved weeds such as Tainubie, Tamagayari, Inuhotarui and Mizugayari. The herbicide of the present invention can control the above weeds in upland fields and paddy fields by any treatment method of soil treatment, foliage treatment or flooding treatment.
本発明の除草剤の適用作物としては、例えば、トウモロコシ、コムギ、ォォムギ、イネ 、ダイズ等が挙げられ、これらの作物に対し、土壌処理および茎葉処理のいずれに おいても影響が少なぐこれらの作物の栽培において選択的除草剤として使用するこ とが可能である。又、本発明の除草剤は、例えば、トウモロコシ、コムギ、ォォムギ、ィ ネ、ダイズ等の遺伝形質を改良し薬剤耐性等を付与した作物に対し、土壌処理及び 茎葉処理の 、ずれにお!、ても影響が少なく、これらの作物の栽培にぉ 、て選択的除 草剤として使用することが可能である。  Examples of crops to which the herbicide of the present invention is applied include corn, wheat, barley, rice, soybean, and the like, and these crops have little effect in both soil treatment and foliage treatment. It can be used as a selective herbicide in crop cultivation. In addition, the herbicide of the present invention, for example, in the soil treatment and foliage treatment for crops that have been improved in genetic traits such as corn, wheat, barley, rice, soybean, etc. and imparted drug resistance etc. However, it can be used as a selective herbicide in the cultivation of these crops.
本発明の除草剤は、同一分野に用いる殺虫剤、殺菌剤、植物成長調節剤等の他 の農薬、及び肥料等と混合施用することができる。又、除草効果をより安定化させる ために他の除草剤と混合施用することもできる。本発明の一般式 (I)で表されるフエ The herbicide of the present invention can be mixed and applied with other pesticides such as insecticides, fungicides, plant growth regulators, and fertilizers used in the same field. In addition, in order to further stabilize the herbicidal effect, it can be mixed with other herbicides. The feather represented by the general formula (I) of the present invention
-ルピリジン類と他の除草剤を混合施用する場合、両者の各々の製剤を施用時に混 合しても良いが、あらかじめ両者を含有する製剤として施用しても良い。上記目的で 好適に混合施用することができる除草剤としては、例えば以下のものが挙げられる。 グリホサート及びその塩、ダリホシネート及びその塩、ビアラホス及びその塩、ブタミ ホス、ァ-ロホス、ベンスリド等の有機リン系除草剤、スルファレート、ジァレート、トリア レート、 EPTC、ブチレート、エスプロカルプ、チォベンカルプ（ベンチォカーブ）、モリ ネート、イソポリネート、ジメピぺレート、ピリブチカルプ、フェンメディファム、クロルプロ ファム、ァシュラム等のカーバメート系除草剤、ジゥロン、リニュロン、フルオメッロン、 ジフエノキスロン、ダイムロン、イソプロッロン、イソゥロン、テブチウロン、メタべンズチ ァズロン、メトベンズロン、クロロトルロン等のウレァ系除草剤、メタザクロール、ァラクロ 一ノレ、ブタクローノレ、プレチラクローノレ、ァセトクローノレ、メトラクローノレ、テニノレクロー ル、ジエタチル、ジメテナミド、プロパニル、ジフルフエ-カン、メフエナセット、フルフエ ナセット、ブロモブチド、イソキサベン (ベンザミゾール)等のアミド系除草剤、トリフルラ リン、ベンフルラリン、プロジァミン、オリザリン、ブトラリン、ペンディメタリン等のジ-ト ロア-リン系除草剤、 -When rupyridines and other herbicides are mixed and applied, both preparations may be mixed at the time of application, but they may be applied in advance as preparations containing both. Examples of herbicides that can be suitably mixed and applied for the above purpose include the following. Glyphosate and its salts, Darifosinate and its salts, Bialafos and its salts, Organic phosphorus herbicides such as butamifos, arlofos, benzulide, sulfarate, diarates, triarates, EPTC, butyrate, esprocalp, thiobencalp (benchocarb), molly Carbamate herbicides such as Nate, Isopolynate, Dimepiperate, Pyributicalp, FenMedifam, Chlorprofam, Ashram, etc. Urea herbicides, metazachlor, araclos monore, butacronore, pretila clonore, acetoclonole, metolacronore, tenino Amide herbicides such as recral, diethyl, dimethenamide, propanil, diflufen-can, mefenacet, flue naset, bromobutide, isoxaben (benzamizole), triflura Di-tro-phosphorus herbicides such as phosphorus, benfluralin, prodamine, oryzalin, butralin, pendimethalin,
[0053] 2, 4 D及びその誘導体、 2, 4, 5— T及びその誘導体、 MCPA及びその誘導体、 ジクロプロップ及びその誘導体、メコプロップ及びその誘導体、 MCPB及びその誘導 体、ジカンパ及びその誘導体、 2, 3, 6— TBA及びその誘導体、キンク口ラック及び その誘導体、キンメラック及びその誘導体、クロビラリド及びその誘導体、ピクロラム及 びその誘導体、トリクロピル及びその誘導体、フルロキシピル及びその誘導体、べナ ゾリン及びその誘導体、ジクロホップ及びその誘導体、フルアジホップ及びその誘導 体、ハロキシホップ及びその誘導体、フエノキサプロップ及びその誘導体、キザロホッ プ及びその誘導体、クロジナホップ及びその誘導体、シハロホップ及びその誘導体 等のカルボン酸系除草剤、ブロモキシ-ル及びその誘導体、アイォキシニル及びそ の誘導体、ジノテルブ及びその誘導体等のフエノール系除草剤、ァロキシジム及び その塩、セトキシジム、シクロキシジム、トラノレコキシジム、ブトロキシジム、クレトジム、 テプラロキシジム、スルコトリオン、メソトリオン、ベンゾビシクロン等のシクロへキサンジ オン系除草剤、  [0053] 2, 4 D and derivatives thereof, 2, 4, 5—T and derivatives thereof, MCPA and derivatives thereof, dicloprop and derivatives thereof, mecoprop and derivatives thereof, MCPB and derivatives thereof, dicampa and derivatives thereof, 2 , 3, 6- TBA and its derivatives, kink mouth rack and its derivatives, quinmerac and its derivatives, cloviralide and its derivatives, picloram and its derivatives, triclopyr and its derivatives, fluroxypyr and its derivatives, benazoline and its derivatives, Carboxylic acid herbicides such as diclohop and derivatives thereof, fluazifop and derivatives thereof, haloxyhop and derivatives thereof, phenoxaprop and derivatives thereof, quizalop and derivatives thereof, clodinafop and derivatives thereof, cyhalohop and derivatives thereof, bromoxyl And its derivatives, ioxy And its derivatives, phenolic herbicides such as dinoterb and its derivatives, aroxidim and its salts, Hexanedione herbicides,
[0054] クロル-トロフェン、クロメトキシ -ル、ォキシフルオルフエン、ビフエノックス、アシフル オルフエン及びその塩、フルォログリコフェン、ラクトフェン、ホメサフェン、ァクロ-フエ ン等のジフエ-ルエーテル系除草剤、アミドスルフロン、クロリムロンェチル、スルホメ ッロンメチノレ、プリミスノレフロン、ベンスノレフロンメチノレ、ェトキシスルフロン、シクロスノレ ファムロン、クロルスルフロン、メトスルフロンメチル、トリべニュロンメチル、トリアスルフ ロン、シノスルフロン、ェタメトスルフロンメチル、トリフルスルフロンメチル、プロスルフ ロン、チフェンスルフロンメチル、ピラゾスルフロンェチル、ハロスルフロンメチル、フラ ザスルフロン、リムスルフロン、ニコスルフロン、フルピルスルフロン及びその塩、イマ ゾスノレフロン、スノレホスノレフロン、ョードスノレフロン、トリトスノレフロン、メソスノレフロン等 のスルホ -ルゥレア系除草剤、パラコート、ジクワット等のビビリジ-ゥム系除草剤、ピ ラゾレート、ビラゾキシフェン、ベンゾフエナップ等のピラゾール系除草剤、シマジン、 アトラジン、シアナジン、シメトリン、ジメタメトリン、トリアジフラム、メトリブジン等のトリア ジン系除草剤、イマザメタべンズ、イマザピル及びその塩、イマザキン及びその塩、ィ マゼタピル及びその塩、イマザモッタス及びその塩等のイミダゾリノン系除草剤、 [0055] その他の除草剤として、インダノフアン、フノレリドン、フノレ口クロリドン、フルルタモン、ノ ノレフノレラゾン、カフエンストローノレ、フェントラザミド、スノレフェントラゾン、力ノレフェントラ ゾンェチル、ペントキサゾン、ォキサジァゾン、ォキサジアルギル、ピラフルフェンェチ ル、イソプロパゾール、フルポキサム、クロマゾン、イソキサフルトール、イソキサクロル トール、ジチォピル、チアゾピル、ピリチォバック及びその塩、ピリミノバックメチル、ビ スピリバック及びその塩、ブロマシル、ターバシル、レナシル、フルプロバシル、ォキ サジクロメホン、シンメチリン、クロルフタリム、フルミクロラックペンチル、フルミオキサ ジン、シニドンェチル、ァザフエ二ジン、フルチアセットメチル、フルメッラム、メトスラム 、クロランスラムメチル、ベンフレセート、エトフメセート、ベンタゾン、ピラクロ-ル、ベ フルブタミド、ピコリナフェン、フロラスラム、プロポキシ力ルバゾン、フル力ルバゾン及 びその塩、シ-ドンェチル、ピノキサベン等が挙げられる。 [0054] Diphenyl ether herbicides such as chloro-trophene, chloromethoxyl, oxyfluorfen, biphenox, acifluolfen and salts thereof, fluoroglycophene, lactofen, fomesafen, acrophene, and amides Sulfuron, Chlorimlonethyl, Sulfomethylon methinole, Primisnorephron, Benzenoreflon methinore, Ethoxysulfuron, Cyclosnole Famron, Chlorsulfuron, Metosulfuronmethyl, Tribenuron methyl, Triasulfuron, Sinosulfuron, Etamethsulfuron Methyl, triflusulfuron methyl, prosulfuron, thifensulfuron methyl, pyrazosulfuronethyl, halosulfuron methyl, frazasulfuron, rimsulfuron, nicosulfuron, flupirsulfuron and Its salts, sulfo-lurea herbicides such as imazosnoreflon, snolefosnorephron, odosnoreflon, tritosnoreflon, and mesosus noreflon, bibilidium herbicides such as paraquat and diquat, pyrazolate, birazoxifene, benzo Pyrazole herbicides such as fenap, triazine herbicides such as simazine, atrazine, cyananadine, cimethrin, dimetamethrin, triadifram, metribudine, imazametabens, imazapyr and its salt, imazaquin and its salt, i Imidazolinone herbicides such as mazetapill and salts thereof, imazamotas and salts thereof, etc. [0055] Other herbicides include indanofan, funoleridone, funole mouth chloridone, flurtamone, norefnorrazon, caffen stranol, fentrazamide, snolefentrazone , Force norefentra zonethyl, pentoxazone, oxadiazone, oxadialgyl, pyraflufenethyl, isopropazole, flupoxam, cromazone, isoxaflutol, isoxachlortol, dithiopyr, thiazopyr, pirithiovac and its salts, pyriminoback methyl, bispiri Bags and salts thereof, bromacil, terbacil, lenacyl, fluprobasil, oxadichrome mehon, symmetrine, chlorphthalim, full microlac pentyl, full Oxazine, cinidoneethyl, azafenidin, fluthiaset methyl, flumeram, methotram, chloransrammethyl, benfrecetate, etofumesate, bentazone, pyrachlor, beflubutamide, picolinafene, florasulam, propoxyrvazone, full force rubazone and its salts, Cidonethyl, pinoxaben and the like.
実施例  Example
[0056] 以下本発明を実施例、製造例及び試験例によりさらに具体的に説明するが本発明 はその要旨を超えない限りこれらの実施例、製造例ならびに試験例に限定されること はない。  [0056] The present invention will be described more specifically with reference to examples, production examples, and test examples. However, the present invention is not limited to these examples, production examples, and test examples as long as the gist thereof is not exceeded.
実施例 1. N— (4 フルオロフェ -ル）—4—メチル—6— (3 トリフルォロメトキシ フエニル)ピリジン 2 カルボキサミド (化合物 No. 1— 3)の製造  Example 1. Preparation of N— (4 fluorophenyl) —4-methyl-6- (3 trifluoromethoxyphenyl) pyridine 2 carboxamide (Compound No. 1-3)
窒素気流下、 6 クロ口— N— (4 フルオロフェ -ル）—4—メチルピリジン— 2—力 ルボキサミド（0. 30g、 1. 13ミリモル）、 3 卜リフルォロメ卜キシフエ-ルポロン酸（0. 28g、 1. 36ミリモル）、 2M炭酸ナトリウム水溶液（1. 5ml、 3. 0ミリモル）とトルエン（3 . Oml)の混合物を 70°Cに昇温後、テトラキストリフエ-ルホスフィンパラジウム（0. 10 g、 0. 087ミリモル)をカ卩え、加熱還流下で 3時間撹拌した。反応混合物に水（20ml) を加え、酢酸ェチルで抽出後、飽和食塩水で洗浄、無水硫酸ナトリウムで乾燥した。 溶媒を減圧流去後、シリカゲルカラムクロマトグラフィーで精製した後、得られた結晶 をへキサンで洗净し、 目的物 0. 31gを得た。  Under nitrogen flow, 6-n- (4-fluorophenol) -4-methylpyridine-2-force Ruboxamide (0.30 g, 1.13 mmol), 3 rifluoromethoxyphenyl-poronic acid (0.28 g, 1. 36 mmol), 2M aqueous sodium carbonate solution (1.5 ml, 3.0 mmol) and toluene (3.0 ml) were heated to 70 ° C, and tetrakistriphenylphosphine palladium (0.10 g 0.087 mmol), and the mixture was stirred for 3 hours under heating to reflux. Water (20 ml) was added to the reaction mixture, extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography, and the obtained crystals were washed with hexane to obtain 0.31 g of the desired product.
収率： 70. 3%  Yield: 70.3%
物性:融点 93〜95°C 以下に本発明の代表的な製剤例及び試験例を示すが、本発明はこれらに限定さ れるものではない。尚、製剤例中、部とあるのは重量部を示す。 Physical property: Melting point 93-95 ° C The following are typical preparation examples and test examples of the present invention, but the present invention is not limited thereto. In the preparation examples, “parts” means “parts by weight”.
製剤例 1.  Formulation example 1.
本発明化合物 10部  Compound of the present invention 10 parts
キシレン 70部  70 parts of xylene
N—メチノレピロリドン 10部  N-Methylolpyrrolidone 10 parts
ポリオキシエチレンノニルフエニルエーテルと  With polyoxyethylene nonyl phenyl ether
アルキルベンゼンスルホン酸カルシウムとの混合物 10部  Mixture with calcium alkylbenzenesulfonate 10 parts
以上を均一に混合溶解して乳剤とする。  The above is mixed and dissolved uniformly to obtain an emulsion.
製剤例 2.  Formulation example 2.
本発明化合物 3部  Compound of the present invention 3 parts
クレー粉末 82部  82 parts of clay powder
珪藻土粉末 15部  Diatomaceous earth powder 15 parts
以上を均一に混合粉砕して粉剤とする。  The above is uniformly mixed and pulverized to obtain a powder.
[0058] 製剤例 3. [0058] Formulation Example 3.
本発明化合物 5部  Compound of the present invention 5 parts
ベントナイトとクレーの混合粉末 90部  90 parts of mixed powder of bentonite and clay
リグ-ンスルホン酸カルシウム 5部  5 parts calcium sulfonate sulfonate
以上を均一に混合し、適量の水を加えて混練し、造粒、乾燥して粒剤とする。  The above is uniformly mixed, kneaded with an appropriate amount of water, granulated and dried to obtain granules.
製剤例 4.  Formulation example 4.
本発明化合物 20部  20 parts of the present compound
カオリンと合成高分散珪酸 75部  Kaolin and synthetic highly dispersed silicic acid 75 parts
ポリオキシエチレンノニルフエニルエーテルと  With polyoxyethylene nonyl phenyl ether
アルキルベンゼンスルホン酸カルシウムとの混合物 5部  5 parts mixture with calcium alkylbenzenesulfonate
以上を均一に混合粉砕して水和剤とする。  The above is uniformly mixed and ground to obtain a wettable powder.
[0059] 試験例 1. 出芽前の水田雑草に対する除草効果試験 [0059] Test Example 1. Herbicidal effect test on paddy weeds before emergence
75cm2のプラスチックポットに土壌 (埴壌土）を充填し、水田雑草であるィヌホタルイ の種子を播種し、コナギ、ァゼナ、ミゾノヽコベの種子を混和した土壌 75cm3で覆土し た後、水深 5cmの状態に湛水した。翌日に、製剤例 1〜4に準じて調製した本発明 化合物を有効成分とする薬剤の所定有効薬量 (gZha)を水で希釈し水面に滴下処 理をした。ついで、温室内で育成し、処理 28日後に除草効果を調査し、無処理と比 較して下記の基準に従って除草効果を評価した。 Fill a 75cm 2 plastic pot with soil (Korean soil), seed seeds of paddy weed, Inuhotarui, and cover with 75cm 3 of soil mixed with Konagi, Azena and Mizono Kobe seeds. After that, it was submerged to a depth of 5 cm. On the next day, a predetermined effective dose (gZha) of a drug comprising the compound of the present invention prepared according to Formulation Examples 1 to 4 as an active ingredient was diluted with water and dropped onto the water surface. Next, the plants were grown in a greenhouse, the herbicidal effect was investigated 28 days after the treatment, and compared with no treatment, the herbicidal effect was evaluated according to the following criteria.
除草効果の判定基準 Criteria for evaluating herbicidal effect
0···0%の除草効果  0 ... 0% weeding effect
1···1%〜39%の除草効果  1 ... 1% to 39% herbicidal effect
2· · ·40%〜69%の除草効果  2.40% to 69% herbicidal effect
3··· 70%〜89%の除草効果  3.70% to 89% weeding effect
4··· 90%以上の除草効果  4 ... 90% or more herbicidal effect
結果を第 4表に示す。尚、表中「一」は試験未実施を表す。 The results are shown in Table 4. In the table, “one” indicates that the test was not performed.
[表 9] [Table 9]
第 4表 Table 4
化合物 ィヌホタルイ ァセ"ナ コ†T ミソ、、ハコへCompound Inho firefly "Nako † T Miso, to Jaco
N o . (g/ha) N o. (G / ha)
1-1 1000 1 4 4 4 1-1 1000 1 4 4 4
1-2 1000 1 4 4 41-2 1000 1 4 4 4
1-3 1000 2 4 4 41-3 1000 2 4 4 4
1-4 1000 4 4 4 41-4 1000 4 4 4 4
1-5 1000 4 4 4 41-5 1000 4 4 4 4
1-6 1000 4 4 4 41-6 1000 4 4 4 4
1-7 1000 1 4 4 41-7 1000 1 4 4 4
1-8 1000 2 4 4 41-8 1000 2 4 4 4
1-9 1000 4 4 4 41-9 1000 4 4 4 4
1-10 1000 4 4 4 41-10 1000 4 4 4 4
1-11 1000 1 4 4 41-11 1000 1 4 4 4
1-12 1000 1 4 4 41-12 1000 1 4 4 4
1-13 1000 3 4 4 41-13 1000 3 4 4 4
1-14 1000 4 2 4 41-14 1000 4 2 4 4
1-15 1000 2 4 4 41-15 1000 2 4 4 4
1-16 1000 1 2 4 41-16 1000 1 2 4 4
1-17 1000 2 4 4 41-17 1000 2 4 4 4
1-18 1000 1 4 4 41-18 1000 1 4 4 4
1-19 1000 - - - -1-19 1000----
1-20 1000 1 4 4 41-20 1000 1 4 4 4
1-21 1000 4 4 4 41-21 1000 4 4 4 4
1-22 1000 3 4 4 41-22 1000 3 4 4 4
1-23 1000 3 4 4 41-23 1000 3 4 4 4
1-24 1000 2 4 4 41-24 1000 2 4 4 4
1-25 1000 4 4 4 41-25 1000 4 4 4 4
1-26 1000 4 4 4 41-26 1000 4 4 4 4
1-27 1000 - - - -1-27 1000----
1-28 1000 4 4 4 41-28 1000 4 4 4 4
1-29 1000 - - - -1-29 1000----
1-30 1000 - - - -1-30 1000----
1-31 1000 4 4 4 41-31 1000 4 4 4 4
1-32 1000 3 4 4 4 第 4表 き 1-32 1000 3 4 4 4 Table 4
化合物 ィヌホタルイ ァセ"ナ コ†T ミソ、 'ハコへ、、Compound: Inho firefly "Nako † T Miso, 'To Jaco,
N o . (g/ha) N o. (G / ha)
1-33 1000 一 - - - 1-33 1000 One---
1-34 1000 4 4 4 41-34 1000 4 4 4 4
1-35 1000 4 4 4 41-35 1000 4 4 4 4
1-36 1000 ― - - -1-36 1000 ―---
1-37 1000 - - - -1-37 1000----
1-38 1000 - - - -1-38 1000----
1-39 1000 - - - -1-39 1000----
1-40 1000 - - - -1-40 1000----
1-41 1000 - - - -1-41 1000----
1-42 1000 - ― 一 -1-42 1000----
1-43 1000 4 4 4 41-43 1000 4 4 4 4
1-44 1000 - 一 - -1-44 1000-One--
1-45 1000 - 一 - 一1-45 1000-One-One
1-46 1000 ― - - 一1-46 1000 ―--One
1-47 1000 4 4 4 41-47 1000 4 4 4 4
1-48 1000 - - - -1-48 1000----
1-49 1000 - - - -1-49 1000----
1-50 1000 2 4 4 41-50 1000 2 4 4 4
1-51 1000 1 4 4 41-51 1000 1 4 4 4
1-52 1000 - - - -1-52 1000----
1-53 1000 4 4 4 41-53 1000 4 4 4 4
1-54 1000 - - 一 -1-54 1000--One-
1-55 1000 - - - -1-55 1000----
1-56 1000 1 1 4 41-56 1000 1 1 4 4
1-57 1000 一 - - 一1-57 1000 One--One
1-58 1000 - - 一 -1-58 1000--One-
1-59 1000 - - - -1-59 1000----
1-60 1000 一 - - 一1-60 1000 One--One
1-61 1000 - - 一 -1-61 1000--One-
1-62 1000 - - - -1-62 1000----
1-63 1000 - - - ―1-63 1000---―
1-64 1000 3 4 4 4 第 4表 き) 1-64 1000 3 4 4 4 (Table 4)
化合物 ィヌホタルイ ァセ"ナ コ†T ミソ、、ハコへCompound Inho firefly "Nako † T Miso, to Jaco
N o . (g/ha) N o. (G / ha)
1-65 1000 4 4 4 4 1-65 1000 4 4 4 4
1-66 1000 4 3 4 41-66 1000 4 3 4 4
1-67 1000 3 4 4 41-67 1000 3 4 4 4
1-68 300 4 4 4 41-68 300 4 4 4 4
1-69 1000 - - 一 -1-69 1000--One-
1-70 300 1 4 4 41-70 300 1 4 4 4
1-71 300 1 4 4 41-71 300 1 4 4 4
1-72 1000 - - 一 -1-72 1000--One-
1-73 1000 - - - -1-73 1000----
1-74 1000 - 一 - -1-74 1000-One--
1-75 1000 - - - -1-75 1000----
1-76 1000 4 4 4 41-76 1000 4 4 4 4
1-77 1000 4 4 4 41-77 1000 4 4 4 4
1-78 1000 4 4 4 41-78 1000 4 4 4 4
1-79 1000 4 4 4 41-79 1000 4 4 4 4
1-80 1000 4 4 4 41-80 1000 4 4 4 4
1-81 1000 4 4 4 41-81 1000 4 4 4 4
1-82 1000 4 4 4 41-82 1000 4 4 4 4
1-83 1000 4 4 4 41-83 1000 4 4 4 4
1-84 1000 - ― - -1-84 1000----
1-85 1000 - - - 一1-85 1000---
1-86 1000 - ― - -1-86 1000----
1-87 300 2 4 4 41-87 300 2 4 4 4
1-88 300 1 4 4 41-88 300 1 4 4 4
1-89 1000 - - - -1-89 1000----
1-90 1000 - 一 - -1-90 1000-One--
1-91 1000 - - 一 -1-91 1000--One-
1-92 1000 - - - -1-92 1000----
1-93 1000 - - - 一1-93 1000---One
1-94 1000 - - - -1-94 1000----
1-95 1000 - - - -1-95 1000----
1-96 1000 - - - - 第 4表 き) 1-96 1000---- (Table 4)
Figure imgf000039_0001
試験例 2. 出芽後の水田雑草に対する除草効果試験。
Figure imgf000039_0001
Test Example 2. Herbicidal effect test on paddy field weeds after emergence.
75cm2のプラスチックポットに土壌 (埴壌土)を充填し、水田雑草であるィヌビエ、ィ ヌホタルイの種子を播種しァゼナ、ミゾハコべの種子を混和した土壌 75cm3で覆土し た後、水深 5cmの状態に湛水し、温室内で育成した。供試植物が子葉期から一葉期 の時期に、本発明化合物を有効成分とする薬剤を所定有効薬量 (gZha)の薬液とし て処理をした。ついで、温室内で育成し、処理 28曰後に除草効果を調査し、試験例 1の基準に従って除草効果を評価した。結果を第 5表に示す。 [0065] [表 13] A 75 cm 2 plastic pot is filled with soil (Pyongyang soil), seeds of Inubie and Yinhotarui, which are paddy field weeds, are sown and covered with 75 cm 3 of soil mixed with Azena and Mizojakobe seeds, then 5 cm deep It was flooded and raised in a greenhouse. When the test plant was from the cotyledon stage to the first leaf stage, the drug containing the compound of the present invention as an active ingredient was treated as a chemical solution having a predetermined effective dose (gZha). Next, it was grown in a greenhouse, and after 28 weeks of treatment, the herbicidal effect was investigated, and the herbicidal effect was evaluated according to the criteria of Test Example 1. The results are shown in Table 5. [0065] [Table 13]
第 5表
Figure imgf000040_0001
Table 5
Figure imgf000040_0001
[0066] [表 14] 第 5表 き) [0066] [Table 14] (Table 5)
化合物 薬量 ィヌビエ ィヌホタルイ ァセ、、ナ ミソ、、ハコへCompound Dosage Innuvie Inholyaase, Namiso, Jaco
N o . (g/ha) N o. (G / ha)
1-33 1000 - - - - 1-33 1000----
1-34 1000 4 4 4 41-34 1000 4 4 4 4
1-35 1000 4 3 3 41-35 1000 4 3 3 4
1-36 1000 ― - 一 -1-36 1000 ― ― One ―
1-37 1000 - - - -1-37 1000----
1-38 1000 - - - -1-38 1000----
1-39 1000 - - - -1-39 1000----
1-40 1000 - - - -1-40 1000----
1-41 1000 - - - -1-41 1000----
1-42 1000 - - - -1-42 1000----
1-43 1000 4 4 4 41-43 1000 4 4 4 4
1-44 1000 - 一 - 一1-44 1000-One-One
1-45 1000 一 一 ― -1-45 1000
1-46 1000 - - - -1-46 1000----
1-47 1000 4 3 4 41-47 1000 4 3 4 4
1-48 1000 - - - -1-48 1000----
1-49 1000 一 一 -1-49 1000
1-50 1000 4 4 4 41-50 1000 4 4 4 4
1-51 1000 4 2 2 41-51 1000 4 2 2 4
1-52 1000 - - - 一1-52 1000---One
1-53 1000 4 4 4 41-53 1000 4 4 4 4
1-54 1000 - - - -1-54 1000----
1-55 1000 - - - -1-55 1000----
1-56 1000 2 2 2 41-56 1000 2 2 2 4
1-57 1000 ― ― - -1-57 1000 ― ―--
1-58 1000 - - - 一1-58 1000---One
1-59 1000 - - - -1-59 1000----
1-60 1000 - - - -1-60 1000----
1-61 1000 - - - -1-61 1000----
1-62 1000 - - - -1-62 1000----
1-63 1000 - - ― -1-63 1000----
1-64 1000 4 2 4 4 第 5表 き) 1-64 1000 4 2 4 4 (Table 5)
化 ィヌビエ ィヌホタルイ ァセ"ナ ミソ"ハコへ、'Kaininubie Inufiretalase "Na Miso"
N o . (g/ha) N o. (G / ha)
1-65 1000 - 4 4 4 1-65 1000-4 4 4
1-66 1000 - 2 2 41-66 1000-2 2 4
1-67 1000 - 3 3 41-67 1000-3 3 4
1-68 300 4 4 4 41-68 300 4 4 4 4
1-69 1000 - - - -1-69 1000----
1-70 300 3 2 4 41-70 300 3 2 4 4
1-71 1000 2 2 1 41-71 1000 2 2 1 4
1-72 1000 - - - -1-72 1000----
1-73 1000 - 一 - -1-73 1000-One--
1-74 1000 - ― - -1-74 1000----
1-75 1000 一 - -1-75 1000 One--
1-76 1000 4 4 4 41-76 1000 4 4 4 4
1-77 1000 4 4 4 41-77 1000 4 4 4 4
1-78 1000 4 4 4 41-78 1000 4 4 4 4
1-79 1000 4 4 4 41-79 1000 4 4 4 4
1-80 300 2 3 4 41-80 300 2 3 4 4
1-81 300 4 2 4 41-81 300 4 2 4 4
1-82 1000 4 4 4 41-82 1000 4 4 4 4
1-83 1000 4 4 4 41-83 1000 4 4 4 4
1-84 1000 - - - -1-84 1000----
1-85 1000 - - 一 一1-85 1000--One
1-86 1000 - ― - -1-86 1000----
1-87 300 - 2 4 41-87 300-2 4 4
1-88 300 - 1 4 41-88 300-1 4 4
1-89 1000 - - - -1-89 1000----
1-90 1000 - ― ― -1-90 1000----
1-91 1000 一 - - -1-91 1000 One---
1-92 1000 - - 一 一1-92 1000--One
1-93 1000 - ― - -1-93 1000----
1-94 1000 一 - - -1-94 1000 One---
1-95 1000 - - - -1-95 1000----
1-96 1000 - - - - 第 5表 （^き) 1-96 1000---- Table 5 (^)
Figure imgf000043_0001
試験例 3.畑地茎葉処理試験
Figure imgf000043_0001
Test example 3. Upland field foliage treatment test
面積 200cm2の榭脂製バットに洪積性埴壌土の畑土壌を充填し、施肥後、ハコべ、 スミレ、ィヌカミツレ、ヤエムダラ及びコムギを播種し、均一に覆土を行った。その後、 温室で栽培管理を続け、供試雑草の生育葉令力 Sl.0〜2.0葉期に達した時、本発明 化合物を有効成分とする薬剤を、有効成分量の処理薬量が 1アール当たり lgとなる ように均一に噴霧処理した。その後、温室内で栽培管理を続け、薬剤処理後 21日目 に除草効果又は薬害について調査を行った。結果を第 6表に示した。 尚、除草効果又は薬害の評価は下記数式により除草率を求め、下記の基準による 除草効果係数又は薬害係数で表した。 Filled with 200 cm 2 of greaves vat with field soil of pelagic clay loam, fertilized, seeded with octopus, violet, inukamite, yaemdara and wheat, and uniformly covered with soil. Thereafter, the cultivation management was continued in the greenhouse, and when the growth weeds of the test weeds reached the leaf stage Sl. 0 to 2.0, a drug containing the compound of the present invention as an active ingredient was treated with an active ingredient amount of 1 lg per are. The spray was uniformly applied so that Thereafter, cultivation management was continued in the greenhouse, and the herbicidal effect or phytotoxicity was investigated on the 21st day after chemical treatment. The results are shown in Table 6. The herbicidal effect or phytotoxicity was evaluated by calculating the herbicidal rate using the following formula and expressing it as a herbicidal effect factor or phytotoxicity factor according to the following criteria.
[0070] [数 1] 処理区における雑草の地上部生体重  [0070] [Equation 1] Overweight weight of weeds in treatment area
除草率又は薬害率 (o/0) = (1 ) x i o o Weeding rate or chemical damage rate (o / 0 ) = (1) xioo
無処理区における雑草の地上部生体重 [0071] 除草効果係数又は薬害係数 除草率又は薬害率(％)  Live weight of above-ground weeds in untreated area [0071] Herbicidal effect factor or phytotoxicity factor
0 0〜20  0 0-20
1 21〜39  1 21-39
2 40〜69  2 40-69
3 70〜89  3 70-89
4 90〜99  4 90-99
5 100  5 100
[0072] [表 17] [0072] [Table 17]
第 6表 Table 6
除草効果 ic f 化合物 N o .  Herbicidal effect ic f Compound No.
ハコぺ スミレ ィヌカミツレ ャ ク "ラ コムキ、、 Hakope Sumire Inukamitsuku "La Komuki,
1-1 - - - - -1-1-----
1-2 - ― - - -1-2------
1-3 4 5 5 5 01-3 4 5 5 5 0
1-4 3 4 2 2 01-4 3 4 2 2 0
1-5 3 4 1 4 01-5 3 4 1 4 0
1-6 3 4 1 4 01-6 3 4 1 4 0
1-7 3 4 3 3 01-7 3 4 3 3 0
1-8 3 4 1 4 01-8 3 4 1 4 0
1-9 4 4 2 4 01-9 4 4 2 4 0
1-10 4 5 3 4 11-10 4 5 3 4 1
1-11 3 3 1 2 01-11 3 3 1 2 0
1-12 3 4 1 3 01-12 3 4 1 3 0
1-13 2 3 1 3 01-13 2 3 1 3 0
1-14 2 3 1 2 01-14 2 3 1 2 0
1-15 2 2 1 2 01-15 2 2 1 2 0
1-16 - - - - -1-16-----
1-17 1 2 1 0 01-17 1 2 1 0 0
1-18 2 3 1 1 01-18 2 3 1 1 0
1-19 - - - - -1-19-----
1-20 3 4 2 3 01-20 3 4 2 3 0
1-21 4 4 3 4 11-21 4 4 3 4 1
1-22 4 4 4 4 11-22 4 4 4 4 1
1-23 3 4 1 2 01-23 3 4 1 2 0
1-24 2 3 1 2 01-24 2 3 1 2 0
1-25 3 4 1 4 01-25 3 4 1 4 0
1-26 2 4 2 4 11-26 2 4 2 4 1
1-27 2 4 1 2 01-27 2 4 1 2 0
1-28 2 4 1 2 01-28 2 4 1 2 0
1-29 2 4 1 2 01-29 2 4 1 2 0
1-30 3 4 4 4 11-30 3 4 4 4 1
1-31 2 4 2 4 11-31 2 4 2 4 1
1-32 3 4 3 4 0 第 6表 き) 1-32 3 4 3 4 0 (Table 6)
除草効果 口 化合物 N o .  Herbicidal effect Mouth compound No.
ハコ Λ スミレ ィヌカミツレ ャ ク ラ コムキ、、 Hako Λ Sumire Inukamitsura Kura Koki,
1-33 3 4 3 3 01-33 3 4 3 3 0
1-34 4 4 1 4 11-34 4 4 1 4 1
1-35 3 4 2 2 01-35 3 4 2 2 0
1-36 3 4 3 4 11-36 3 4 3 4 1
1-37 - - ― - -1-37-----
1-38 2 2 1 2 01-38 2 2 1 2 0
1-39 2 4 1 4 01-39 2 4 1 4 0
1 - 40 3 4 1 4 11-40 3 4 1 4 1
1-41 2 4 1 3 01-41 2 4 1 3 0
1-42 2 3 0 2 01-42 2 3 0 2 0
1-43 2 5 1 3 11-43 2 5 1 3 1
1-44 - - - - ―1-44----―
1-45 - - - - 一1-45----One
1 - 46 - - - - -1-46-----
1-47 2 3 2 4 01-47 2 3 2 4 0
1 - 48 2 5 0 2 01-48 2 5 0 2 0
1-49 - - - - -1-49-----
1-50 3 3 2 4 11-50 3 3 2 4 1
1-51 2 4 2 2 11-51 2 4 2 2 1
1-52 2 4 1 1 01-52 2 4 1 1 0
1-53 3 4 3 4 11-53 3 4 3 4 1
1-54 3 4 2 4 11-54 3 4 2 4 1
1-55 - 一 - - -1-55-One---
1-56 - - - - -1-56-----
1-57 - - - - 一1-57----One
1-58 - 一 一 - -1-58-Ichiichi--
1-59 - - - - -1-59-----
1-60 - - - 一 -1-60---One-
1-61 - ― - - -1-61-―---
1-62 - - - - -1-62-----
1-63 - - - 一 -1-63---One-
1-64 3 5 2 3 0 第 6表 き) 1-64 3 5 2 3 0 (Table 6)
除草効果  Weeding effect
化合物 N o .  Compound No.
ハコ Λ、' スミレ ィヌカミツレ ャ ダ'ラ コムキ、、 Hako Λ, 'Sumireinukamitsura Da' La Komuki,
1-65 3 4 1 3 01-65 3 4 1 3 0
1-66 2 4 0 0 01-66 2 4 0 0 0
1-67 2 4 0 1 01-67 2 4 0 1 0
1-68 3 5 2 4 11-68 3 5 2 4 1
1-69 4 4 0 4 01-69 4 4 0 4 0
1-70 3 4 0 2 01-70 3 4 0 2 0
1-71 3 4 0 2 01-71 3 4 0 2 0
1-72 - - ― - -1-72--―--
1-73 - - - - -1-73-----
1-74 - - - - -1-74-----
1-75 - - - - -1-75-----
1-76 - - - - -1-76-----
1-77 一 一 - - -1-77 one one---
1-78 2 3 1 4 01-78 2 3 1 4 0
1-79 3 3 0 4 01-79 3 3 0 4 0
1-80 - 一 - - 一1-80-One--One
1-81 - - - - -1-81-----
1-82 - - - - -1-82-----
1-83 - - - - -1-83-----
1-84 1 4 2 1 01-84 1 4 2 1 0
1-85 1 3 2 1 01-85 1 3 2 1 0
1-86 - - - - -1-86-----
1-87 3 4 0 3 01-87 3 4 0 3 0
1-88 2 2 1 2 01-88 2 2 1 2 0
1-89 2 3 2 3 01-89 2 3 2 3 0
1-90 5 4 2 4 01-90 5 4 2 4 0
1-91 5 4 3 4 11-91 5 4 3 4 1
1-92 5 4 2 4 01-92 5 4 2 4 0
1-93 - - - - -1-93-----
1-94 一 - ― ―1-94 1---
1-95 一 - - - ―1-95 1----
1-96 一 - - - - 第 6表 （^き) 1-96 One---- Table 6 (^)
Figure imgf000048_0001
Figure imgf000048_0001
試験例 4.畑地土壌処理試験  Test example 4. Upland soil treatment test
面積 200cm2の榭脂製バットに洪積性埴壌土の畑土壌を充填し、施肥後、ノスズメ ノテツボウ、ハコべ、スミレ、ィヌカミツレ、及びコムギを播種し、均一に覆土を行った。 本発明化合物を有効成分とする薬剤を、有効成分量の処理薬量が 1アール当たり 3 gとなるように土壌表面に均一に噴霧処理した。その後、温室内で栽培管理を続け、 薬剤処理後 21日目に除草効果について調査を行い、試験例 3と同様にして除草効 果係数及び薬害係数を求めた。その結果を第 7表に示した。 [0077] [表 21] 第 7表
Figure imgf000049_0001
Filled with 200 cm2 of greaves vat with field soil of pelagic clay loam, fertilized, and seeded with sparrow rotundula, chickweed, violet, wilt, and wheat, and uniformly covered the soil. The agent containing the compound of the present invention as an active ingredient was sprayed uniformly on the soil surface so that the amount of the active ingredient was 3 g per are. Thereafter, cultivation management was continued in the greenhouse, and the herbicidal effect was investigated on the 21st day after the chemical treatment, and the herbicidal efficacy coefficient and the phytotoxicity coefficient were determined in the same manner as in Test Example 3. The results are shown in Table 7. [0077] [Table 21] Table 7
Figure imgf000049_0001
[0078] [表 22] 第 7表 き) [0078] [Table 22] (Table 7)
除駭カ果  Pruning fruit
化合物 N o . ノスス"メノ ハコへ スミレ ィヌカミツレ コムキ、' テツホゥ  Compound No. Noss "Menohako" Sumire Inukamitsuru Komuki, 'Tetsuhou
1-32 4 5 5 5 1 1-32 4 5 5 5 1
1-33 1 2 1 3 01-33 1 2 1 3 0
1-34 4 5 4 3 01-34 4 5 4 3 0
1-35 2 5 4 4 01-35 2 5 4 4 0
1-36 3 5 3 5 01-36 3 5 3 5 0
1-37 - - - - 一1-37----One
1-38 2 5 5 3 01-38 2 5 5 3 0
1-39 4 5 5 4 01-39 4 5 5 4 0
1-40 4 5 5 4 11-40 4 5 5 4 1
1-41 4 5 5 3 01-41 4 5 5 3 0
1-42 2 5 5 4 01-42 2 5 5 4 0
1-43 4 5 5 5 21-43 4 5 5 5 2
1-44 - - - - -1-44-----
1-45 - - - - -1-45-----
1-46 - - - - -1-46-----
1-47 4 5 4 3 01-47 4 5 4 3 0
1-48 1 2 2 2 01-48 1 2 2 2 0
1-49 - - - - -1-49-----
1-50 4 4 5 3 01-50 4 4 5 3 0
1-51 3 5 4 3 01-51 3 5 4 3 0
1-52 3 5 4 2 01-52 3 5 4 2 0
1-53 5 5 5 5 01-53 5 5 5 5 0
1-54 5 5 5 5 01-54 5 5 5 5 0
1-55 - - - - -1-55-----
1-56 一 一 - ― 一1-56 1-1
1-57 一 - - - 一1-57 1---1
1-58 - - - - -1-58-----
1-59 - - 一 - -1-59--One--
1-60 ― - - - 一1-60 ―---One
1-61 - - - - -1-61-----
1-62 - - ― - - 第 7表 （続き) 1-62--―-- Table 7 (continued)
Figure imgf000051_0001
] 第 7表 き)
Figure imgf000051_0001
] (Table 7)
Figure imgf000052_0001
Figure imgf000052_0001
本発明を特定の態様を参照して詳細に説明した力 s、本発明の精神と範囲を離れる ことなく様々な変更および修正が可能であることは、当業者にとって明らかである。 なお、本出願は、 2004年 7月 12日付けで出願された日本特許出願 (特願 2004— 204466)に基づいており、その全体が引用により援用される。 産業上の利用可能性 It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention as described in detail with reference to specific embodiments. This application is based on a Japanese patent application (Japanese Patent Application No. 2004-204466) filed on July 12, 2004, which is incorporated by reference in its entirety. Industrial applicability
本発明によれば、高い除草効果を示し、かつ、重要作物に対して十分な安全性を 示す除草剤及びそれに用いられる有用な化合物を得ることが出来る。  ADVANTAGE OF THE INVENTION According to this invention, the herbicide which shows the high herbicidal effect and shows sufficient safety | security with respect to an important crop, and the useful compound used for it can be obtained.

Claims

請求の範囲 [1] 一般式 (I) Claim [1] General formula (I)
[化 1]  [Chemical 1]
Figure imgf000054_0001
Figure imgf000054_0001
(式中、 R1は C - Cアルキル基、ハロ C - Cアルキル基、 C - Cァルケ-ル基、ハロ C -Wherein R 1 is a C-C alkyl group, a halo C-C alkyl group, a C-C alkyl group, a halo C-
1 8 1 8 2 8 21 8 1 8 2 8 2
Cァルケ-ル基、 C - Cアルキ-ル基、ハロ C - Cアルキ-ル基、 C - Cアルコキシ CC alkyl group, C-C alkyl group, halo C-C alkyl group, C-C alkoxy C
8 2 8 2 8 1 6 18 2 8 2 8 1 6 1
- Cアルキル基、 C - Cアルキルチオ C - Cアルキル基、 C - Cアルキルスルフィエル-C alkyl group, C-C alkylthio C-C alkyl group, C-C alkyl sulfier
6 1 6 1 6 1 6 6 1 6 1 6 1 6
C - Cアルキル基、 C - Cアルキルスルホニル C - Cアルキル基、モノ C - Cアルキル C-C alkyl group, C-C alkylsulfonyl C-C alkyl group, mono C-C alkyl
1 6 1 6 1 6 1 6 アミノ基、同一又は異なっても良いジ C - Cアルキルアミノ基、フエ-ル基、同一又は 1 6 1 6 1 6 1 6 Amino group, same or different di-C-C alkylamino group, phenyl group, same or different
1 6  1 6
異なっても良ぐハロゲン原子、シァノ基、ニトロ基、水酸基、アミノ基、 SH基、 C -C  Different halogen atoms, cyan groups, nitro groups, hydroxyl groups, amino groups, SH groups, C -C
1 6 アルキル基、ハロ c - Cアルキル基、 C - Cアルケニル基、ハロ C - Cアルケニル基、  1 6 alkyl group, halo c-C alkyl group, C-C alkenyl group, halo C-C alkenyl group,
1 6 2 6 2 6  1 6 2 6 2 6
C - Cアルキニル基、ハロ C - Cアルキニル基、 C - Cアルコキシ基、ハロ C - Cアルコ C-C alkynyl, halo C-C alkynyl, C-C alkoxy, halo C-C alk
2 6 2 6 1 6 1 6 キシ基、 c -cアルキルチオ基、ハロ c -cアルキルチオ基、 c -cアルケニルチオ基 2 6 2 6 1 6 1 6 Xoxy group, c-c alkylthio group, halo c-c alkylthio group, c-c alkenylthio group
1 6 1 6 2 6 1 6 1 6 2 6
、ハロ C - Cアルケニルチオ基、 C - Cアルキルスルフィニル基、ハロ C - CアルキルHalo C-C alkenylthio group, C-C alkylsulfinyl group, halo C-C alkyl
2 6 1 6 1 6 スルフィニル基、 c - Cアルキルスルホニル基、ハロ C - Cアルキルスルホニル基、 C 2 6 1 6 1 6 Sulfinyl group, c-C alkylsulfonyl group, halo C-C alkylsulfonyl group, C
1 6 1 6 1 1 6 1 6 1
- cアルキルカルボニル基、ハロ c -cアルキルカルボニル基、フヱニルカルボニル-c alkylcarbonyl group, halo c-c alkylcarbonyl group, phenylcarbonyl
6 1 6 6 1 6
基、 C - Cアルコキシカルボニル基、モノ C - Cアルキルアミノ基又は同一若しくは異 Group, C-C alkoxycarbonyl group, mono C-C alkylamino group, or the same or different
1 6 1 6 1 6 1 6
なって良いジ C - Cアルキルアミノ基力 選択される 1〜5個の置換基を有する置換フ  Di-C-C alkylamino group that can be selected A substituted group having 1 to 5 substituents selected
1 6  1 6
ェニル基、フエニル C - Cアルキル基、同一又は異なっても良ぐハロゲン原子、シァ  Phenyl group, phenyl C-C alkyl group, halogen atom which may be the same or different,
1 8  1 8
ノ基、ニトロ基、水酸基、アミノ基、 SH基、 C - Cアルキル基、ハロ C - Cアルキル基、  Group, nitro group, hydroxyl group, amino group, SH group, C-C alkyl group, halo C-C alkyl group,
1 6 1 6  1 6 1 6
C - Cアルケニル基、ハロ C - Cアルケニル基、 C - Cアルキニル基、ハロ C - Cアル C-C alkenyl group, halo C-C alkenyl group, C-C alkynyl group, halo C-C ar
2 6 2 6 2 6 2 6 キニル基、 c - Cアルコキシ基、ハロ C - Cアルコキシ基、 C - Cアルキルチオ基、ハロ 2 6 2 6 2 6 2 6 quinyl group, c-C alkoxy group, halo C-C alkoxy group, C-C alkylthio group, halo
1 6 1 6 1 6  1 6 1 6 1 6
C -Cアルキルチオ基、 C -Cアルケニルチオ基、ハロ C -Cアルケニルチオ基、 C - C -C alkylthio group, C -C alkenylthio group, halo C -C alkenylthio group, C-
1 6 2 6 2 6 11 6 2 6 2 6 1
Cアルキルスルフィニル基、ハロ C - Cアルキルスルフィニル基、 C - Cアルキルスル ホ-ル基、ハロ C - Cアルキルスルホ-ル基、 C - Cアルキルカルボ-ル基、ハロ C -C alkylsulfinyl group, halo C-C alkylsulfinyl group, C-C alkylsulfuric group Hole group, halo C-C alkyl sulfol group, C-C alkyl carbo ol group, halo C-
1 6 1 6 11 6 1 6 1
Cアルキルカルボ-ル基、フヱ-ルカルボ-ル基、 C - Cアルコキシカルボ-ル基、C alkyl carbo group, full carbon carbo group, C-C alkoxy carbo group,
6 1 6 6 1 6
モノ C - Cアルキルアミノ基又は同一若しくは異なって良いジ C - Cアルキルアミノ基Mono C-C alkylamino group or di-C-C alkylamino group which may be the same or different
1 6 1 6 1 6 1 6
力 選択される 1〜5個の置換基を環上に有する置換フエ-ル C - Cアルキル基、複 A substituted file C-C alkyl group having 1 to 5 selected substituents on the ring;
1 8  1 8
素環基、同一又は異なっても良ぐハロゲン原子、シァノ基、ニトロ基、水酸基、ァミノ 基、 SH基、 C - Cアルキル基、ハロ C - Cアルキル基、 C - Cァルケ-ル基、ハロ C -Heterocyclic group, halogen atom which may be the same or different, cyan group, nitro group, hydroxyl group, amino group, SH group, C-C alkyl group, halo C-C alkyl group, C-C alkyl group, halo C-
1 6 1 6 2 6 21 6 1 6 2 6 2
Cァルケ-ル基、 C - Cアルキ-ル基、ハロ C - Cアルキ-ル基、 C - Cアルコキシ基C-alkyl group, C-C alkyl group, halo C-C alkyl group, C-C alkoxy group
6 2 6 2 6 1 6 6 2 6 2 6 1 6
、ハロ C - Cアルコキシ基、 C - Cアルキルチオ基、ハロ C - Cアルキルチオ基、 C - C Halo C-C alkoxy group, C-C alkylthio group, halo C-C alkylthio group, C-C
1 6 1 6 1 6 2 6 ァルケ-ルチオ基、ハロ C - Cァルケ-ルチオ基、 C - Cアルキルスルフィエル基、ハ 1 6 1 6 1 6 2 6 Alkenylthio group, halo C-Calkarylthio group, C-C alkylsulfier group, C
2 6 1 6  2 6 1 6
PC - Cアルキルスルフィエル基、 C - Cアルキルスルホ-ル基、ハロ C - Cアルキル PC-C alkylsulfier group, C-C alkylsulfol group, halo C-C alkyl
1 6 1 6 1 6 スルホ-ル基、 C - Cアルキルカルボ-ル基、ハロ C - Cアルキルカルボ-ル基、フエ 1 6 1 6 1 6 Sulfol group, C-C alkyl carbo group, halo C-C alkyl carbo group,
1 6 1 6  1 6 1 6
-ルカルボ-ル基、 C - Cアルコキシカルボ-ル基、モノ C - Cアルキルアミノ基又は  -Lucarbol group, C-C alkoxycarbol group, mono C-C alkylamino group or
1 6 1 6 同一若しくは異なって良いジ C - Cアルキルアミノ基カも選択される 1〜5個の置換基  1 6 1 6 Di-C-C-alkylamino group, which may be the same or different, is also selected 1-5 substituents
1 6  1 6
を有する置換複素環基、複素環 C -Cアルキル基又は同一若しくは異なっても良ぐ Substituted heterocyclic groups, heterocyclic C 1 -C alkyl groups, or the same or different
1 8  1 8
ハロゲン原子、シァノ基、ニトロ基、水酸基、アミノ基、 SH基、 C - Cアルキル基、ハロ Halogen atom, cyano group, nitro group, hydroxyl group, amino group, SH group, C-C alkyl group, halo
1 6  1 6
C - Cアルキル基、 C - Cアルケニル基、ハロ C - Cアルケニル基、 C - Cアルキニル C-C alkyl group, C-C alkenyl group, halo C-C alkenyl group, C-C alkynyl group
1 6 2 6 2 6 2 6 1 6 2 6 2 6 2 6
基、ハロ C - Cアルキニル基、 C - Cアルコキシ基、ハロ C - Cアルコキシ基、 C - Cァ Group, halo C-C alkynyl group, C-C alkoxy group, halo C-C alkoxy group, C-C
2 6 1 6 1 6 1 6 ルキルチオ基、ハロ c -cアルキルチオ基、 c -cアルケニルチオ基、ハロ c -cアル  2 6 1 6 1 6 1 6 alkylthio group, halo c -c alkylthio group, c -c alkenylthio group, halo c -c al
1 6 2 6 2 6 ケニルチオ基、 c - Cアルキルスルフィニル基、ハロ C - Cアルキルスルフィニル基、  1 6 2 6 2 6 Kenylthio group, c-C alkylsulfinyl group, halo C-C alkylsulfinyl group,
1 6 1 6  1 6 1 6
C - Cアルキルスルホニル基、ハロ C - Cアルキルスルホニル基、 C - Cアルキルカル C-C alkylsulfonyl group, halo C-C alkylsulfonyl group, C-C alkylcal
1 6 1 6 1 6 1 6 1 6 1 6
ボニル基、ハロ c - Cアルキルカルボニル基、フエニルカルボニル基、 C - Cアルコキ Bonyl group, halo c-C alkylcarbonyl group, phenylcarbonyl group, C-C alkoxy
1 6 1 6 シカルボニル基、モノ C - Cアルキルアミノ基又は同一若しくは異なって良いジ C - C  1 6 1 6 Sicarbonyl group, mono C-C alkylamino group or di-C-C which may be the same or different
1 6 1 6 アルキルアミノ基力 選択される 1〜5個の置換基を環上に有する置換複素環 C -C  1 6 1 6 Alkylamino group power A substituted heterocycle having 1 to 5 selected substituents on the ring C 1 -C
1 8 アルキル基を示す。 R2は水素原子、 C - Cアルキル基、 C - Cアルケニル基、 C - C 1 8 represents an alkyl group. R 2 is a hydrogen atom, a C-C alkyl group, a C-C alkenyl group, C-C
1 8 2 8 2 8 アルキニル基、 c - Cアルコキシ C - Cアルキル基、シァノ C - Cアルキル基、 C - Cァ  1 8 2 8 2 8 Alkynyl group, c-C alkoxy C-C alkyl group, Cyano C-C alkyl group, C-Ca
1 8 1 8 1 8 1 8 ルキルカルボニル基、ハロ C - Cアルキルカルボニル基、 C - Cアルケニルカルボ二  1 8 1 8 1 8 1 8 alkylcarbonyl group, halo C-C alkylcarbonyl group, C-C alkenylcarbonyl
1 8 2 8  1 8 2 8
ル基又は C - Cアルコキシカルボ二ル基を示す。又、 R1と R2は一緒になつて酸素原 Or a C 1 -C alkoxycarbonyl group. R 1 and R 2 are joined together
1 8  1 8
子、硫黄原子、窒素原子から選択される少なくとも 1つのへテロ原子を含む 3〜8員環 を形成することができる。 R3はハロゲン原子、シァノ基、ニトロ基、水酸基、ペンタフ ルォロサルファ-ル基（ SF ), C -Cアルキル基、ハロ C - Cアルキル基、 C - Cァ 3- to 8-membered ring containing at least one heteroatom selected from a child, a sulfur atom and a nitrogen atom Can be formed. R 3 is a halogen atom, cyano group, nitro group, hydroxyl group, pentafluorosulfur group (SF), C 1 -C alkyl group, halo C 1 -C alkyl group, C 1 -C 1
5 1 8 1 8 2 8 ルケ-ル基、ハロ C - Cァルケ-ル基、 C - Cアルキ-ル基、ハロ C - Cアルキ-ル基  5 1 8 1 8 2 8 Luke group, halo C-C alkyl group, C-C alkyl group, halo C-C alkyl group
2 8 2 8 2 8  2 8 2 8 2 8
、 C - Cアルコキシ基、ハロ C - Cアルコキシ基、 C - Cアルコキシカルボ-ル基、 C - C-C alkoxy group, halo C-C alkoxy group, C-C alkoxycarbo group, C-
1 8 1 8 1 8 11 8 1 8 1 8 1
Cアルキルチオ基、 C - Cアルキルスルフィエル基、 C - Cアルキルスルホ-ル基、 CC alkylthio group, C-C alkylsulfier group, C-C alkylsulfol group, C
8 1 8 1 8 18 1 8 1 8 1
-Cアルキルアミノ基又は同一若しくは異なっても良いジ C - Cアルキルアミノ基を示-C alkylamino group or diC-C alkylamino group which may be the same or different
8 1 8 8 1 8
す。ただし、 R3は、複数の場合には、同一又は異なっても良い。 R4はハロゲン原子 、 C - Cアルキル基、ハロ C - Cアルキル基、 C - Cァルケ-ル基、ハロ C - Cァルケ-The However, R 3 may be the same or different when there are a plurality of R 3 . R 4 is a halogen atom, a C-C alkyl group, a halo C-C alkyl group, a C-C alkyl group, a halo C-C alkyl group
1 8 1 8 2 8 2 8 ル基、 C - Cアルキ-ル基、ハロ C - Cアルキ-ル基、 C - C 1 8 1 8 2 8 2 8 group, C-C alkyl group, halo C-C alkyl group, C-C
2 8 2 8 1 8  2 8 2 8 1 8
アルコキシ基、ハロ c - Cアルコキシ基、 C - Cアルコキシ C - Cアルキル基、ハロ C -Alkoxy group, halo c-C alkoxy group, C-C alkoxy C-C alkyl group, halo C-
1 8 1 8 1 8 11 8 1 8 1 8 1
Cアルコキシ C - Cアルキル基、 C - Cアルコキシ C - Cアルコキシ基、ハロ C - CァC alkoxy C-C alkyl group, C-C alkoxy C-C alkoxy group, halo C-C
8 1 8 1 8 1 8 1 8 ルコキシ c - Cアルコキシ基、 C - Cアルキルスルホ -ルァミノ基、ハロ C - Cアルキル 8 1 8 1 8 1 8 1 8 Lucoxy c-C alkoxy group, C-C alkyl sulfo-lamino group, halo C-C alkyl
1 8 1 8 1 8 スルホ -ルァミノ基、 C - Cアルキルチオ基、ハロ C - Cアルキルチオ基、 C - Cアル  1 8 1 8 1 8 Sulfo-lumino group, C-C alkylthio group, halo C-C alkylthio group, C-C al
1 8 1 8 1 8 キルスルフィエル基、ハロ C - Cアルキルスルフィエル基、 C - Cアルキルスルホ-ル  1 8 1 8 1 8 Kill sulfier group, halo C-C alkyl sulfier group, C-C alkyl sulfole
1 8 1 8  1 8 1 8
基、ハロ C - Cアルキルスルホ-ル基、 C - Cアルキルカルボ-ル基、 C - Cアルコキ Group, halo C-C alkylsulfol group, C-C alkyl carbonyl group, C-C alkoxy group
1 8 1 8 1 8 シカルボニル基、 C - Cアルキルカルボ-ルォキシ基、ハロ C - Cアルキルカルボ- 1 8 1 8 1 8 Sicarbonyl group, C-C alkylcarbo-oxy group, halo C-C alkylcarbo-
1 8 1 8 ルォキシ基、水酸基、ホルミル基、シァノ基、ニトロ基、同一又は異なっても良いトリ C 1 8 1 8 Roxy group, hydroxyl group, formyl group, cyano group, nitro group, same or different tri C
1 1
- Cアルキルシリル基、ペンタフルォロサルファニル基（ SF )又は C(R5) =NOR- C alkylsilyl group, penta full O b Sulfur sulfonyl group (SF) or C (R 5) = NOR
8 5 8 5
6(式中、 R5及び R6は同一又は異なっても良ぐ水素原子、 C -Cアルキル基又はハ 6 (wherein R 5 and R 6 may be the same or different, a hydrogen atom, a C 1 -C alkyl group or
1 5  1 5
PC - Cアルキル基を示す。）で表される基を示す。ただし、 R4は、複数の場合には、PC-C represents an alkyl group. ) Is represented. However, R 4 is
1 5 1 5
同一又は異なっても良い。又、 2つの隣接する R4は互いに一緒になつて C - Cアルキ It may be the same or different. Also, two adjacent connexion R 4 are together a mutually C - C alkyl
1 4 レンジォキシ基又はハロ C - Cアルキレンジォキシ基を示すことができる。 Xは酸素  1 4 may represent a dioxy group or a halo C-C alkylene dioxy group. X is oxygen
1 4  14
原子、硫黄原子、 NH で表される基又は単結合を示し、 Yは酸素原子又は硫黄 原子を示し、 mは 0〜3の整数を示し、 nは 1〜5の整数を示し、 pは 0又は 1を示す。 ) で表されるフエ二ルビリジン類又はその塩類。 An atom, a sulfur atom, a group represented by NH 3 or a single bond, Y represents an oxygen atom or a sulfur atom, m represents an integer of 0 to 3, n represents an integer of 1 to 5, and p represents 0. Or 1 ) Or a salt thereof.
R1が C - Cアルキル基、ハロ C - Cアルキル基、モノ C - Cアルキルアミノ基、同一又R 1 is a C-C alkyl group, a halo C-C alkyl group, a mono C-C alkylamino group,
1 8 1 8 1 6 1 8 1 8 1 6
は異なっても良いジ C - Cアルキルアミノ基、フエニル基又は同一若しくは異なっても May be different di C-C alkylamino groups, phenyl groups or the same or different
1 6  1 6
良ぐハロゲン原子、 C - Cアルキル基、ハロ C - Cアルキル基、 C - Cアルコキシ基、 ハロ C - Cアルコキシ基力 選択される 1〜5個の置環基で置換された置換フエ-ルGood halogen atom, C-C alkyl group, halo C-C alkyl group, C-C alkoxy group, Halo C-C alkoxy group force Substituted phenyl substituted with 1 to 5 selected ring substituents
1 6 1 6
基であり、 R2が水素原子、 C - Cアルキル基、 C - Cアルコキシカルボ-ル基又は C -R 2 is a hydrogen atom, a C-C alkyl group, a C-C alkoxycarbo group or a C-
1 8 1 8 11 8 1 8 1
Cアルキルカルボ-ル基であり、 R3が C - Cアルキル基又は C - Cアルコキシ基であA C alkyl carbonyl group, and R 3 is a C-C alkyl group or a C-C alkoxy group.
8 1 8 1 8 8 1 8 1 8
り、 R4が C - Cアルキル基、ハロ C - Cアルキル基、 C - Cアルコキシ基、ハロ C R 4 is a C-C alkyl group, a halo C-C alkyl group, a C-C alkoxy group, a halo C
1 8 1 8 1 8 1 1 8 1 8 1 8 1
- Cアルコキシ基、シァノ基、ジフルォロメチレンジォキシ基（一 OCF O—）又はテトラ-C alkoxy group, cyano group, difluoromethylenedioxy group (one OCF O—) or tetra
8 2 8 2
フルォロエチレンジォキシ基（一 OCF CF O—）であり、 Yが酸素原子である請求項  A fluoroethylenedioxy group (one OCF CF 2 O—), wherein Y is an oxygen atom.
2 2  twenty two
1記載のフエ-ルビリジン類又はその塩類。  2. The pyrrolidine or salt thereof according to 1.
[3] mが 1である請求項 1又は 2いずれか 1項記載のフエ-ルビリジン類又はその塩類。 [3] The pyrrolidine or salt thereof according to any one of claims 1 and 2, wherein m is 1.
[4] R4がノヽロ C - Cアルキル基、ハロ C - Cアルコキシ基又はジフルォロメチレンジォキシ [4] R 4 is a nano C-C alkyl group, a halo C-C alkoxy group or difluoromethylenedioxy
1 5 1 5  1 5 1 5
基（一 OCF O—）である請求項 1乃至 3いずれか 1項記載のフエ-ルビリジン類又は  The pyrrolidines according to any one of claims 1 to 3, or a group (one OCF O-)
2  2
その塩類。  Its salts.
[5] 請求項 1乃至 4いずれか 1項記載のフエ二ルビリジン類又はその塩類を有効成分とし て含有する除草剤。  [5] A herbicide containing as an active ingredient the phenylrubiridines or salts thereof according to any one of claims 1 to 4.
[6] 請求項 5記載の除草剤の有効量を土壌又は植物に処理することを特徴とする除草剤 の使用方法。  [6] A method of using the herbicide, characterized by treating an effective amount of the herbicide according to claim 5 with soil or plants.
PCT/JP2005/012781 2004-07-12 2005-07-11 Phenylpyridine derivative or salt thereof, herbicide containing the same as active ingredient, and method of use thereof WO2006006569A1 (en)

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