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WO1997041105A1 - Nouveaux derives de benzene a substitution heterocycle et herbicides - Google Patents

Nouveaux derives de benzene a substitution heterocycle et herbicides Download PDF

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Publication number
WO1997041105A1
WO1997041105A1 PCT/JP1997/001423 JP9701423W WO9741105A1 WO 1997041105 A1 WO1997041105 A1 WO 1997041105A1 JP 9701423 W JP9701423 W JP 9701423W WO 9741105 A1 WO9741105 A1 WO 9741105A1
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group
methyl
solvent
compound
added
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PCT/JP1997/001423
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English (en)
Japanese (ja)
Inventor
Hiroyuki Adachi
Masao Yamaguchi
Osamu Miyahara
Katsunori Tanaka
Takashi Kawana
Akihiro Takahashi
Masami Koguchi
Hideki Yamagishi
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Nippon Soda Co., Ltd.
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Application filed by Nippon Soda Co., Ltd. filed Critical Nippon Soda Co., Ltd.
Priority to AU24058/97A priority Critical patent/AU2405897A/en
Priority to KR1019980708595A priority patent/KR20000065049A/ko
Publication of WO1997041105A1 publication Critical patent/WO1997041105A1/fr

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    • 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
    • C07D413/10—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 aromatic 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
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms

Definitions

  • the present invention relates to a novel vilapool derivative and a herbicide in which a benzoyl group is substituted at the 4-position of the virazol ring.
  • WO 96/262 06 describes a compound represented by the formula [IV]. These compounds are only given as examples, and their physical properties are not specifically described.
  • An object of the present invention is to provide a herbicide that can be synthesized industrially advantageously, has a lower dose, is effective, has high safety, and has high crop selectivity.
  • the present invention relates to a 4-benzyl virazole compound in which the 3-position of the benzoyl moiety represented by the general formula [I] is substituted with a heterocycle, wherein the enol hydroxyl group of the pyrazoyl ring is protected. It is a herbicide characterized by containing the compound as an active ingredient.
  • the present invention provides a compound represented by the formula (I):
  • R 1 is a halogen atom, alkyl group, Y an alkoxy group, a secondary Bok port group, Shiano group, a haloalkyl group, a haloalkoxy group, c Bok 6 Al Kiruchio group, - (; alkylsulfinyl group or ⁇ alkyl Represents a sulfonyl group.
  • R 2 is a halogen atom, a nitro group, a cyano group, a C, 1 ⁇ alkyl group, a C-alkoxy group, a haloalkyl group, a ⁇ - haloalkoxy group, a 6- alkylthio group, a d-alkylsulfinyl group, or a C-alkylsulfonyl group Represents a group.
  • R 3 is halogen atom, C, - 6 alkyl group, 6 alkoxy group, a nitro group, Shiano group, d-G haloalkyl groups, C WINCH B alkylthio group, 1; alkylsulfanyl Finiru group or C, - e alkyl sulfonyl Represents a hydroxyl group.
  • n 0, 1, and 2.
  • R 3 may be the same or different
  • Het represents a saturated or unsaturated 5-membered heterocyclic group substituted with R 7 and R 8 containing 1 to 3 N, 0 or S atoms, which is bonded to a benzene ring at a carbon atom portion.
  • R 4 represents a hydrogen atom or a d alkyl group.
  • R 5 is a hydrogen atom, de alkyl group, C 2 - 1 - G alkenyl group or C 2; represents a alkynyl group.
  • R 6 is, C 6 alkyl group, C 3 - 8 cycloalkyl group, (Ci-G alkyl group,
  • X is S0 2, represents a (CH 2) mCO, which may be substituted by alkyl C, one 6 alkylene emissions group or a single bond. m represents 0, 1, 2, and 3. ] Or a herbicide containing such a compound.
  • the present invention relates to a pyrazole compound represented by the general formula [I] and a herbicide containing the compound as an active ingredient.
  • R ′ is a halogen atom such as fluorine, chlorine, and bromine; a 6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, and t-butyl; De alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy,
  • C such as nitro group, cyano group, trifluoromethyl and trifluoroethyl; haloalkoxy group such as haloalkyl group and trifluoromethoxy group; C (; alkylthio group such as methylthio, ethylthio, propylthio and isopropylthio;
  • a C alkylsulfinyl group such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, or
  • R 2 is a halogen atom such as fluorine, chlorine, or bromine; a nitro group, a cyano group; a d-alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, or t-butyl;
  • Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, etc .;
  • Cl- ⁇ haloalkyl groups such as trifluoromethyl and trifluoroethyl, haloalkoxy groups such as trifluoromethoxy and trichloromethoxy, C n alkylthio groups such as methylthio, ethylthio, propylthio and isopropylthio;
  • C, -6 alkylsulfinyl group such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, or
  • R 3 is a halogen atom such as fluorine, chlorine, bromine,
  • D-6 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, etc.
  • C-to-haloalkyl groups such as trifluoromethyl and trifluoroethyl
  • Dc alkylthio groups such as menalthio, ethylthio, propylthio, and isopropylthio
  • a C, -o alkylsulfinyl group such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl group, or
  • Het represents a saturated or unsaturated 5-membered heterocyclic group which may have 1 to 4 N, 0 or S atoms and may have substituents R 7 and R 8 .
  • the heterocyclic group is bonded to the benzene ring at a carbon atom.
  • Het includes, for example, 2-furyl, 3-furyl, 4-furyl, 5-furyl, 2-phenyl, 3-phenyl, 4-phenyl, 5-phenyl, 2-pyrrolyl, 3-pyrrolyl, 4-pyrrolyl ,
  • 1,2,4 oxaziazolu 3-yl 1,2,4 oxaziazolu 5-yl, 1,3,4 oxaziazoll-2 -yl, 1,3,4-oxagiazi Zol 5-yl, 1, 2, 4-thia diazo 3 -yl, 1, 2, 4-thia diazo 5-lu, 1, 3, 4-thia diazo 2-yl, 1 , 3,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,2,4-triazo-1-yl-5-yl group and the like.
  • hetero ring is an arbitrary position thereof, a fluorine, chlorine, halogen atom such as bromine, methyl, C etc. Echiru group, - fi alkyl group, main Bok alkoxy, C etc. ethoxy group, - 6 ⁇ alkoxy, Substituents such as C fi haloalkyl groups such as trifluoromethyl group R 7 , R May be provided.
  • Het includes the following heterocyclic groups.
  • R 7 and R 8 each independently represent a hydrogen atom, a 6- alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl group, methoxy, ethoxyquin, propoxy group, etc.
  • d-ci represents a halogen atom such as an alkoxy group, fluorine, chlorine, or bromine, or C, such as a trifluoromethyl group; and a haloalkyl group).
  • IT stands for hydrogen, methyl, ethyl, propyl, isopropyl, butyl
  • Hydroxy d-e alkyl groups such as hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl and hydroxypropyl;
  • Alkoxy such as methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, methoxyxethyl, ethoxyxethyl, ethoxypropyl, methoxypropyl, ethoxypropyl, butoxymethyl, t-butoxymethyl, t-butoxyethyl, etc.
  • ⁇ ! Represents an alkyl group.
  • R 5 is a hydrogen atom, d- 6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl group,
  • alkynyl group - G alkenyl group or Echiniru, C 2 such propargyl group - vinyl, propenyl, crotyl, C 2 etc. Ariru.
  • R 6 is a Cl- ⁇ alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isoptyl, t-butyl, Cyclopropyl, cyclobutyl, cyclopentyl, c 3, such as a cyclohexyl group - 8 cycloalkyl group, or,
  • Alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, etc., ds alkoxy groups such as methoxy, ethoxyquin, propoxy, isopropoxy, butoxy, t-butoxy, etc.
  • alkoxy groups such as methoxy, ethoxyquin, propoxy, isopropoxy, butoxy, t-butoxy, etc.
  • trifluoromethyl trichloro Romethyl, fluoromethyl, chloromethyl, difluromethyl, dichloromethyl
  • Ci haloalkyl groups such as trifluoroethyl and pentafluoroethyl, Ct- 6 haloalkoxy groups such as trifluoromethoxy group, nitro groups or halogen atoms such as fluorine, chlorine and bromine.
  • Ct- 6 haloalkoxy groups such as trifluoromethoxy group
  • nitro groups or halogen atoms such as fluorine, chlorine and bromine.
  • X is, S0 2, (CH 2) mCO (m denotes 0, 1, 2 or 3.), Methyl, which may be methylene substituted by an alkyl group such as Echiru, ethylene, C and propylene group, - represents a ⁇ alkylene group or a single bond.
  • XR e, CH 2 A r, CH 2 COA r and S_ ⁇ 2 A r wherein, Ar is any position of the benzene ring is (methyl, Echiru, propyl, isopropyl, heptyl, Isopuchiru D-6 alkyl group such as tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, butoxy, tert-butoxy, etc.
  • a Cj haloalkyl group such as chloromethyl, dichloromethyl, trifluoroethyl, and penrofluoroethyl, or a halogen atom such as fluorine, chlorine, and bromine).
  • a CH 2 Ar group which may have a substituent.
  • the compound of the present invention can be produced by the following method c
  • R 1 , R 2 , R 3 , R 4 , R 5 , R (l , X, n and Het have the same meaning as described above.
  • Q represents a halogen atom
  • an alkylcarbonyloxy group Represents an alkoxycarbonyloxy group or a benzoyloxy group
  • L represents a halogen atom.
  • Compounds [1 Va) and [IVb) are obtained by adding 1 mol or 1 mol each of compound [VI I] and compound [Va] (Q has the same meaning as described above). It can be obtained by reacting in the presence of a base.
  • the base used in the reaction include alkali metal hydroxides such as sodium chloride, HaOH, alkali metal carbonates such as sodium carbonate and carbonated lime, and alkali metal hydroxides such as calcium hydroxide and magnesium hydroxide.
  • organic bases such as C alkyl) amine and pyridine, and sodium phosphate and the like.
  • solvent water, methylene chloride, chloroform, toluene, ethyl acetate, dimethylformamide (DMF), tetrahydrofuran (THF), dimethoxane (DME), and acetonitrile are used.
  • DMF dimethylformamide
  • THF tetrahydrofuran
  • DME dimethoxane
  • the reaction mixture is stirred at 0 ° C to 50 ° C until the reaction is completed.
  • the reaction can be carried out in a two-phase system using a phase transfer hornworm medium such as a quaternary ammonium salt.
  • compounds [I Va] and [IVb] can be obtained by reacting compound [VII] with compound [Vb] in the presence of a dehydrating condensing agent such as dicyclohexylcarpoimide (DCC). You can also get it.
  • a dehydrating condensing agent such as dicyclohexylcarpoimide (DCC).
  • DCC dicyclohexylcarpoimide
  • the solvent used in the reaction with DCC or the like include methylene chloride, chloroform, toluene, ethyl acetate, dimethylformamide, THF, dimethyl oxyethane, acetonitrile, t-amyl alcohol and the like.
  • Reaction-10T proceeds smoothly at ⁇ 50 ° C, and the reaction mixture is processed by a conventional method.
  • the compounds [I Va] and [I Vb] can be used as a mixture in the next rearrangement reaction.
  • the rearrangement reaction is performed in the presence of a cyano compound and a mild base. That is, 1 mol of the compounds (IVa) and (IVb) is converted from 1 to 4 mol of a base, preferably from 1 to 2 mol of a base and from 0.01 mol to 1.0 mol, preferably from 0.05 mol.
  • the compound represented by [Ia] is obtained by reacting with 0.2 mol of a cyanide compound. Any of the bases described above can be used. Examples of the cyano compound include potassium cyanide, sodium cyanide, and sodium cyanide.
  • Polymers holding tonocyanhydrin, hydrogen cyanide, potassium cyanide and the like can be used.
  • the reaction is completed in a shorter time by adding a small amount of a phase transfer catalyst such as crown ether to the reaction system.
  • the reaction is carried out at a temperature lower than 80 ° C, preferably at room temperature to 40 ° C.
  • the solvent used is 1,2-dichloroethane, toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, methylisobutyl ketone, THF, dimethyloxetane and the like.
  • This rearrangement reaction can also be carried out in an inert solvent in the presence of a base such as lithium carbonate, sodium carbonate, triethylamine, pyridine and the like.
  • a base such as lithium carbonate, sodium carbonate, triethylamine, pyridine and the like.
  • the amount of the base used is 0.5 to 2.0 mol with respect to the compounds [I Va] and [I Vb], and the solvent is THF, dioxane, t-amyl alcohol, t-butyl alcohol, etc. Is used.
  • the reaction temperature is preferably from room temperature to the boiling point of the solvent to be used.
  • the compound (IVa) and (IVb) can also be isolated without using a base together with a dehydrating condensing agent such as DCC without isolation. Ia] can be obtained.
  • the base used is potassium carbonate, sodium carbonate, triethylamine, pyridine or the like, and the amount of the base is 0.5 to 2.0 mol with respect to compound [VII].
  • the solvent include THF, dioxane, t-amyl alcohol, t-butyl alcohol, and the like.
  • the reaction temperature is preferably from room temperature to the boiling point of the solvent used.
  • Compound [I] can be produced by reacting compound [Ia] with R 8 XL (L represents halogen) in the presence of a base.
  • Bases used in this reaction include alkali metal hydroxides such as KOH and HaOH, alkali metal carbonates such as carbonate carbonate and sodium carbonate, and alkaline earth metals such as calcium hydroxide. Mizusani ⁇ , alkaline earth metal carbonates such as calcium carbonate, Toryechi Ruami down, diisopropyl E chill ⁇ Mi down like birds (C preparative 6 alkyl) ⁇ Mi emission, organic bases such as pin lysine, phosphoric acid Natoriumu etc. Can be mentioned.
  • Compound U is a quaternary ammonium It can also be produced by using a phase transfer catalyst such as a pum salt, and reacting with a two-phase system of water and a solvent insoluble in water in the above solvent.
  • 5-Hydroxypyrazoles represented by the general formula [VII] are described in, for example, JP-A-62-234069 or JP-A-3-434375. It can be manufactured according to the method exemplified below.
  • the aldehyde (3) and the carboxylic acid (4) which are synthetic intermediates for the production of the compound of the present invention, can be produced as follows.
  • R ′ and Rz represent the same meaning as described above, R ° represents a hydrogen atom or a lower alkyl group, and W represents a halogen atom.
  • a simple halogen such as chlorine or bromine or a halogenating agent such as N-bromosuccinimide (NBS) or N-chlorosuccinic imide (NCS)
  • NBS N-bromosuccinimide
  • NCS N-chlorosuccinic imide
  • a benzyl halide derivative (2) is obtained by reacting in the presence of a radical reaction initiator such as benzoylperoxide, and then, for example, J. Am. Chem.
  • the aldehyde compound (3) can be produced by the method described in 1767 (1949).
  • the carboxylic acid compound (4) is converted from the toluene derivative (1) by an oxidation reaction such as potassium permanganate, or from the aldehyde compound (3) by the Jones reagent, chromic acid or potassium permanganate. It can be produced by a known method such as an oxidation reaction.
  • R 1Q and R 1 ′ represent a hydrogen atom or a lower alkyl group
  • V represents a halogen atom
  • R 12 represents a lower alkyl group. Represents.
  • the aldoxime (5) can be produced by reacting the aldehyde (3) with hydroxylamine hydrochloride or hydroxylamine sulfate in the presence of a base. Further, by reacting the aldoxime compound (5) with a dehydrating agent such as acetic anhydride, phosphorus pentoxide, and thionyl chloride, a corresponding cyano compound (6) can be produced. Next, the ketone body (8) is produced, for example, by applying the Kn 0 evenage 1 condensation reaction described in Organic Reaction s, Vol. 15, page 254, to produce a nitroolefin body (7). The nitrofluorinated compound (7) can be obtained by reducing with an activated iron-aqueous system or lithium aluminum hydride and then hydrolyzing.
  • the alcohol form (10) is prepared by reacting the aldehyde form (3) with a Grignard reagent to produce an alcohol form (9), and this alcohol form (9) is activated with manganese dioxide, chromic acid, or the like. It can be produced by oxidizing with an oxidizing agent.
  • the vinyl ketone (24) is prepared by reacting the aldehyde (3) and methyl ketone (21) in water in the presence of a catalyst at 0 to 50 ° C for 1 to 50 hours according to a method known in the literature. After obtaining the aldol form (23), the product can be produced by dehydrating this in a suitable solvent in the presence of a catalyst.
  • the catalyst used for producing the aldol compound (23) include metal hydroxides such as sodium hydroxide and barium hydroxide, and organic bases such as piperidine and pyridine.
  • Examples of the catalyst used in the next dehydration reaction include acids such as concentrated sulfuric acid and p-toluenesulfonic acid.
  • acids such as concentrated sulfuric acid and p-toluenesulfonic acid.
  • solvent for the dehydration reaction hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as dichloromethane and chloroform can be used.
  • the vinyl ketone compound (24) is obtained by reacting the aldehyde compound (3) and the phosphorane (22) in a suitable solvent at a temperature between room temperature and the boiling point of the solvent used for 10 minutes to 30 hours. Can also be manufactured.
  • the amide form (12), the hydrazide form (13) and the -diketone form (15) can each be produced as follows.
  • R 1 , R 2 and R 8 represent the same meaning as described above, and R 13 and R ′ ⁇ R 15 each independently represent a lower alkyl group.
  • the carboxylic acid compound (4) is converted into an inert solvent such as hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as methylene chloride and chloroform and the like in a solvent such as phosgene, thionyl chloride and oxalyl chloride.
  • an inert solvent such as hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as methylene chloride and chloroform and the like in a solvent such as phosgene, thionyl chloride and oxalyl chloride.
  • the amide form (12) and the hydrazide form (13) can be produced by a known method of reacting ammonia or hydrazine using the carbonyl chloride form (11).
  • the / 3-diketone (15) is composed of a magnesium salt obtained by reacting magnesium alcohol with the / 3-ketoester (14), and a carbonyl chloride
  • (11) can be produced by reacting Next, a method for synthesizing a heterocyclic intermediate will be exemplified.
  • R 1 , R 2 , and R 3 represent the same meaning as described above, and R 16 corresponds to R 7 or R 8 described above.
  • the oxazole compound represented by the general formula (17) can be obtained, for example, by converting an aldehyde compound (3) and an isonitrile compound (16) in the presence of a base in a suitable solvent from room temperature to the boiling point of the solvent used. It can be produced by reacting at a temperature between ⁇ and 30 hours.
  • a base in this reaction include carbonates such as sodium hydrogencarbonate and potassium carbonate, sodium hydroxide, alkali metal hydroxides such as hydroxide hydroxide, sodium methylate, sodium ethylate, and the like.
  • Organic bases such as metal alcohols, triethylamine, 1,8-diazabicyclo.4.0] pendane-7-cene (DBU) and the like.
  • solvent used in this reaction examples include alcohols such as methanol, ethanol, and isopropanol; hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chloroform; and tetrahydrofuran ( Ethers such as THF) and dioxane; nitriles such as acetonitrile; and N, N-dimethylformamide (DMF).
  • alcohols such as methanol, ethanol, and isopropanol
  • hydrocarbons such as benzene and toluene
  • halogenated hydrocarbons such as dichloromethane and chloroform
  • Ethers such as THF
  • dioxane dioxane
  • nitriles such as acetonitrile
  • R 1 , R 2 , and R ° represent the same meaning as described above, and R 17 is the aforementioned R 7 or Corresponding to R 8.
  • the thiazole form represented by the general formula (20) can be produced from the amide form (12) via the thioamide form (18).
  • the thioamide form (18) is prepared by reacting the amide form (12) with phosphorus pentasulfide or Lawesson's reagent in a solvent or without solvent at a temperature between room temperature and the boiling point of the solvent used. Can be manufactured.
  • the solvent used in this reaction include hydrocarbons such as benzene and toluene, and ethers such as dioxane.
  • thioamide form (18) and ⁇ -haloketone (19) are heated in a suitable solvent without a base or in a suitable solvent without using a base, at a temperature between room temperature and the boiling point of the solvent used.
  • the thiazole compound (20) can be produced by reacting for 1 to 30 hours.
  • Bases used in this reaction include carbonates such as sodium bicarbonate and carbon dioxide, sodium hydroxide, alkaline metal hydroxides such as hydroxide, sodium methylate, sodium ethylate and the like. And organic bases such as triethanolamine, DBU and the like.
  • Examples of the solvent used in this reaction include alcohols such as methanol, ethanol, and isopropanol; hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chloroform; acetone; and methylethyl.
  • Examples include ketones such as ketones, esters such as methyl acetate and ethyl acetate, ethers such as THF and dioxane, nitriles such as acetonitrile, and DMF.
  • R 1 , R 2 , R 8 and R 18 represent the same meaning as described above, and R 19 represents a hydrogen atom or a C, -fi alkyl group.
  • Isoxazole (26a) is obtained by reacting vinylketone (24) with hydroxylamine in a suitable solvent at a temperature between 0 ° C and the boiling point of the solvent used for 0.5 to 5 hours. After obtaining the oxime compound (25), it can be produced by further ring closure and oxidation reaction. In this reaction, hydroxylamine can be reacted in the form of sulfate or hydrochloride without neutralization. The reaction can also be carried out after neutralization using a suitable base.
  • Examples of the base used for neutralization include sodium bicarbonate, carbonates such as carbon dioxide, sodium hydroxide, alkali metal hydroxides such as hydroxide, sodium carboxylate such as sodium acetate, sodium methyla Metal alcoholates such as sodium and sodium ethyl acetate; and organic bases such as triethylamine and pyridine.
  • Examples of the solvent used include alcohols such as methanol, ethanol and isopropanol; hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chloroform; ethers such as THF and dioxane; Examples include nitriles such as tritolytril, DMF, pyridine, acetic acid, water and the like, and a mixed solvent of two or more of these solvents.
  • alcohols such as methanol, ethanol and isopropanol
  • hydrocarbons such as benzene and toluene
  • halogenated hydrocarbons such as dichloromethane and chloroform
  • ethers such as THF and dioxane
  • Examples include nitriles such as tritolytril, DMF, pyridine, acetic acid, water and the like, and a mixed solvent of two or more of these solvents.
  • potassium iodide monoiodide For ring
  • the pyrazole derivative (28a) can be produced in two steps from the vinyl ketone derivative (24). That is, first, the vinylketone compound (24) and the substituted hydrazine are reacted in an appropriate solvent at 0 ° C. at a temperature between the boiling points of the solvents for 0.5 to 5 hours to react with the dihydropyrazole compound (27). ).
  • Solvents used in this reaction include alcohols such as methanol, ethanol and isopropanol, hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, THF, dioxane and the like.
  • Ethers nitriles such as acetate nitrile, DMF, pyridine, acetic acid, water and the like, and a mixed solvent of two or more of these solvents.
  • an oxidizing agent such as dihydropyrazolate (27) and activated manganese dioxide, dicyanodiclo-benzoquinone (DDQ), nickel peroxide, NBS, etc., in an appropriate solvent at room temperature, is used to determine the boiling point of the solvent.
  • the pyrazole compound (28a) can be produced by reacting at a temperature between the two. Examples of the solvent used in this reaction include hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform and carbon tetrachloride, and the like.
  • R 1 , R 2 , and R ° have the same meanings as described above, R 2n has the same meaning as R 7 , R 2 ′ has the same meaning as Ra, and R 22 has the same meaning as R 5 . Represents the same meaning.
  • the isoxazole derivative represented by the general formula (26b) and the pyrazole derivative represented by the general formula (28b) are the same as the / 3-diketone (15) and hydroxylamine and substituted hydrazine, respectively. Can also be produced by reacting These reactions are carried out in an appropriate solvent at a temperature between 0 ° C. and the boiling point of the solvent used. In this reaction, acids such as sulfuric acid and p-toluenesulfonic acid can be used as a catalyst.
  • the solvent examples include alcohols such as methanol, ethanol and isopropanol; hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chloroform; ethers such as THF and dioxane; Examples include nitriles such as trinitrile, DMF, pyridine, acetic acid, water and the like, and a mixed solvent of two or more of these solvents.
  • R 1 , R 2 , and R ° represent the same meaning as described above, and R 23 and R 24 represent the aforementioned R 7
  • the isoxazole compound represented by the general formula (31) is obtained by converting an aldoxime compound (5) with a halogenating agent such as chlorine, bromine, N-chlorozaxinimide (NCS) or NBS, to benzene or toluene. 10 to 50 ° in solvents such as hydrocarbons such as dichloromethane, halogenated hydrocarbons such as dichloromethane and chloroform, ethers such as THF and dioxane, nitriles such as acetonitrile, and DMF.
  • a halogenating agent such as chlorine, bromine, N-chlorozaxinimide (NCS) or NBS
  • solvents such as hydrocarbons such as dichloromethane, halogenated hydrocarbons such as dichloromethane and chloroform, ethers such as THF and dioxane, nitriles such as acetonitrile, and DMF.
  • reaction with C After reaction with C, it is reacted with an organic base such as triethylamine, or a base such as sodium bicarbonate or carbonate such as carbonated lime to form a nitriloxide compound (29), which is then reacted with a vinyl acetate. (30) at a temperature from room temperature to the boiling point of the solvent used.
  • organic base such as triethylamine, or a base such as sodium bicarbonate or carbonate such as carbonated lime
  • an isoxazole compound (31) can be produced by reacting the above-mentioned halide with the above-mentioned base in the presence of vinyl acetate (30) for 2 times.
  • Thousand saziazols (34) can be produced via amidoximes (31).
  • the amide doxime form (31) is produced by reacting the nitrile form (6) with hydroxyamine in a suitable solvent at a temperature between room temperature and the boiling point of the solvent used. Hydroxylamine is obtained by converting sulfate or hydrochloride into a suitable base, for example, sodium hydrogencarbonate, carbonate such as carbonated lime, alkali metal hydroxide such as sodium hydroxide or hydroxylated lime, acetic acid.
  • carboxylate salts such as sodium, metal alcoholates such as sodium methylate and sodium ethylate, and organic bases such as triethylamine and pyridine.
  • organic bases such as triethylamine and pyridine.
  • the solvent used for the reaction include alcohols such as methanol, ethanol, and isopropanol; hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chloroform; ethers such as THF and dioxane; and acetate nitrile. And nitriles such as DMF, pyridine, acetic acid, water and the like, and a mixed solvent of two or more of these solvents.
  • the boiling point of the solvent to be used at 15 ° C in a suitable solvent
  • the oxaziazole compound (34) can be produced.
  • Bases used in this reaction include carbonates such as sodium bicarbonate and carbon dioxide, sodium hydroxide, alkaline metal hydroxides such as hydroxyladium, triethylamine, pyridine and DBU. Organic bases and the like can be mentioned.
  • the solvent examples include hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, ethers such as THF and dioxane, nitriles such as acetonitrile, DMF, and pyridine.
  • hydrocarbons such as benzene and toluene
  • halogenated hydrocarbons such as dichloromethane and chloroform
  • ethers such as THF and dioxane
  • nitriles such as acetonitrile, DMF, and pyridine.
  • R 1 , R 2 , and R fl represent the same meaning as described above, and R 26 corresponds to R 7 described above.
  • R 27 represents a lower alkyl group.
  • the oxaziazol form (37) is composed of the hydrazide form (13) and the orthoester (35) or imidate (36) in a suitable solvent at a temperature between 15 ° C and the boiling point of the solvent used. At temperature! It can be produced by reacting for up to 30 hours.
  • the solvent used in this reaction include hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, ethers such as THF and dioxane, and nitrile such as acetate. , DMF, pyridine, etc.
  • the isoxazole compound represented by the general formula (40) can be produced from the ketone compound (8) via the dimethylaminomethylidene compound (39). That is, the ketone (8) and the dimethyl amide acetal (38) are produced by reacting in a solvent-free or suitable solvent at a temperature from room temperature to 200 ° C or the boiling point of the solvent used. Can be. As the solvent used in this reaction, hydrocarbons such as toluene and xylene are used.
  • the isoxazole compound (40) can be produced in the same manner as in the production of the isoxazole compound (26b).
  • the pyrazole derivative represented by the general formula (41) can also be reacted with the dimethylaminomethylidene derivative (39) and the substituted hydrazine in the same manner as the pyrazole derivative (28b). Can be manufactured. -
  • R ′, R 2 , R a , and R : i have the same meaning as described above, R 32 corresponds to R 7 , and R 33 corresponds to R 5.
  • the oxaziazole compound represented by the general formula (44) can be produced from the amide compound (12) via the amidine compound (43). That is, the amide compound (12) and the dimethyl amido acetal compound (42) are allowed to react with each other without solvent or in a suitable solvent at a temperature of 0 to 200 ° C or the boiling point of the solvent used. To produce an amidine compound (43). As a solvent used in this reaction, hydrocarbons such as toluene and xylene are used. Next, the oxazidazole compound (44) can be produced from the obtained amidine compound (43) and hydroxylamine in the same manner as in the production of the isoxazole compound (26b).
  • the triazole derivative represented by the general formula (45) can be produced in the same manner as the pyrazole derivative (28b) by reacting the amidine derivative (43) with the substituted hydrazine.
  • isoxazole compound represented by the formula (26-3) is converted into a 41C1 compound represented by the formula (26-1) in the presence of a base in the presence of a base represented by R'SH.
  • a 4-SR 'form represented by the formula (26-2) is formed by c
  • R ′, R 9 and Het have the same meanings as described above, and R ′ represents a ⁇ , - ⁇ alkyl group.
  • Examples of the base used in this reaction include sodium hydroxide, alkali metal hydroxide such as hydroxylating lime, metal alkoxide such as sodium methoxide and sodium ethoxide, and carbonate such as sodium carbonate and carbonated lime. And hydrides such as sodium hydride, organic bases such as triethylamine, diisopropylethylamine, diaza-bicyclo [5,4,0] -indene-7-cene (DBU) and pyridine. it can.
  • Examples of the solvent used in the reaction include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran (THF) and 1,2-dimethoxybenzene (DME), and ⁇ , ⁇ -dimethylformamide. Amides (DMF), (F,) -dimethylacetamide (DMA), etc.), DMSO, acetonitrile, benzene, toluene, xylene and the like.
  • the next oxidation reaction is carried out in an inert solvent such as water, an organic acid such as acetic acid, dichloromethane, chloroform, halogenated hydrocarbon such as carbon tetrachloride, hydrogen peroxide, peracetic acid, perbenzoic acid, m
  • an oxidizing agent such as peroxyacid such as peroxybenzoic acid, sodium hypochlorite, hypochlorous acid such as hypochlorite realm.
  • the reaction proceeds smoothly in a temperature range from room temperature to the boiling point of the solvent used.
  • the compound ⁇ a] which is a raw material of the compound [I] of the present invention may exist in a number of tautomeric forms, for example, as shown below.
  • the compound of the present invention, various intermediates, and the like can be obtained by performing a usual post-treatment after the completion of the reaction.
  • Example 1 the compound of the present invention will be described in more detail with reference to Examples, Production Examples and Reference Examples.
  • Example 1 the compound of the present invention will be described in more detail with reference to Examples, Production Examples and Reference Examples.
  • V then 2U5 then 0U2 4-Me- n i n ..
  • 1-ethyl-5-hydroxypyrazole hydrochloride 0.65 g (0.0043 mol) and triethylamine 0.9 g (0.0809 mol) were combined with methylene chloride 20 m1 And dissolved in 1,2-glucose—3— (1,2-isoxazole-3-yl) -1.4-g (1.34 g) (0.043 mol) 5 ml of a methylene chloride solution was added dropwise at room temperature, and the mixture was further stirred at room temperature for 1 hour. The reaction mixture was washed with 1N-hydrochloric acid and then with saturated saline, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • the reaction mixture was washed with 1N hydrochloric acid, 1N aqueous sodium hydroxide solution, and then with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • the residue was dissolved in acetonitrile 2 Om 1, 0.96 g of triethylamine and 0.14 g of acetone cyanohydrin were added, and the mixture was stirred overnight at room temperature.
  • the solvent was distilled off under reduced pressure, the residue was dissolved in benzene, and extracted with an aqueous sodium carbonate solution. To the obtained aqueous layer was added chloroform, and the solution was precipitated with concentrated hydrochloric acid.
  • the reaction mixture was washed with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate and then with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • the residue was dissolved in acetate nitrile (1 Om 1), 0.33 g of triethylamine and 0.04 g of acetone cyanohydrin were added, and the mixture was stirred at room temperature for 1 hour.
  • the solvent was distilled off under reduced pressure, the residue was dissolved in benzene, and extracted twice with 5 Oml of saturated aqueous sodium hydrogen carbonate. To the resulting aqueous layer was added 10 ml of form, and the mixture was acid-precipitated with concentrated hydrochloric acid.
  • aqueous layer is acidified with hydrochloric acid, filtered and washed with water, dried and dried at 8.96 pounds of 3- (1,3-oxazolu-l-5-yl) -1,2,4-dichloromethane I got a benzoic acid. 86% yield
  • Methyl 2,4-dichloro-3- (5-methyl-1,3,4-butadiazole-2-yl) benzoate 2.63 g (0.009 1 mol) and potassium carbonate 1.3 g ( (0.0mol) was dissolved in 20ml of dimethylformamide, and 10ml of dimethylformamide in which 0.65g (0.013mol) of methylthiol was dissolved was added. Stirred overnight at room temperature. The reaction mixture was poured into ice water, extracted with ethyl acetate, washed with brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography, and 2. lg of oily product was obtained as methyl 2-chloro-3- (5-methyl-1,3,4-oxazidazoyl-2-yl) -1,4-methylthiobenzoate. I got a game. Yield 77.3%
  • Methyl 2-chloro-3- (5-methyl-1,3,4-oxadiazol-2-yl) -14-methylthiobenzoate 2.1 (0.0700 mol) was converted to a 20-m1 mouthpiece form. And 3.7 g (0.021 mol) of m-chloroperbenzoic acid was added thereto, followed by stirring at room temperature for 3 hours. The reaction mixture was filtered, and the filtrate was washed with a 1N aqueous sodium hydroxide solution and then with a saturated saline solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • Methyl 2-chloro-4-1-methanesulfonyl 3- (5-methyl-1-1,3,4-oxaziazol-1-yl) benzoate 1.52 g (0.0046 mol) was dissolved in 14 ml of ethyl alcohol, 14 ml of 1N caustic soda was added, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into ice water and acidified with concentrated hydrochloric acid. The precipitated crystals were filtered and washed with water, and the obtained crystals were -dried to obtain 1.3 g of the target compound as white crystals. 90% yield
  • Methyl 2,4-dichloro-3- (5-methyl-1,2,4-lexadiazol-1-yl) benzoate 2.75 g (0.095 mol) and potassium carbonate 1.3 2 g (0.095 mol) was dissolved in 20 ml of dimethylformamide, and 0.7 g (0.014 mol) of methionthiol was dissolved in 10 ml of dimethylformamide. The mixture was stirred overnight at room temperature. The reaction mixture was poured into ice water, extracted with ethyl acetate, washed with saturated saline, and dried over magnesium sulfate.
  • Methyl 2-chloro-1,3- (5-methyl-1,2,4-oxaziazol-1-yl) -1-methylthiobenzoate 2.8 g (0.0084 mol) in 20 ml It was dissolved in mouth form, and 4.95 g (0.028 mol) of m-chloroperbenzoic acid was added, followed by stirring at room temperature for 3 hours. Insolubles were filtered off from the reaction mixture, and the filtrate was washed with a 1N aqueous solution of sodium hydroxide and saturated brine, and then dried over magnesium sulfate.
  • Methyl 2,4-dichloro-1-hydroxyiminomethylbenzoate (11.00 g, 0.0443) was dissolved in dimethylformamide (11 Om1), and N-promosaxin was dissolved.
  • Dimethylformamide (110 ml) in which 3.17 g (0.214 mol) of imide was dissolved was added dropwise at 10 ° C or lower over 1 hour.
  • a solution of 2.167 g (0.214 mol) of triethylamine in 110 ml of dimethylformamide was added dropwise at 10 ° C. or lower over 1 hour. The mixture was further stirred at the same temperature for 1 hour.
  • Methyl 2,4-dichloro-1,3-hydroxyminomethylbenzoate 15.87 g (0.063 9 mol) was dissolved in dimethylformamide 160 ml, and dimethylformamide was dissolved. A solution in which 55.0 g (0.308 mol) of N-prosuccinimide was dissolved in 16 Om1 was added dropwise at 10 ° C or lower over 1 hour. Then, a solution of 31.3 g (0.309 mol) of triethylamine dissolved in 16 Om1 of dimethylformamide was added dropwise at 10 ° C. or lower over 1 hour. After completion, the mixture was further stirred at the same temperature for 1 hour.
  • reaction mixture was poured into ice water, quickly extracted with methylene chloride, washed with cold water, and dried over magnesium sulfate. After filtration, 21.53 g (0.215 mol) of isopropenyl acetate was added to the filtrate, and the mixture was heated under reflux overnight. The reaction mixture was cooled and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to give the title compound 8.57 as crystals.
  • Methyl 2,4-dichloro-3-formylbenzoate 2.478 was dissolved in dry HF 2 O ml, and the mixture was dissolved in methylmagnesium bromide dogetil ether solution (3.0 mo 1/1). ) 4.0 ml was slowly dropped. After the addition, the cooling bath was removed, and the mixture was stirred for 1 hour while the temperature was raised naturally. The reaction mixture was poured into iced water, acidified with dilute hydrochloric acid, and extracted with diethyl ether. The organic layer was washed with water and saturated saline, and then dried over magnesium sulfate.
  • Methyl 2-chloro-1-4-methanesulfonyl 3- (5-methylisoxazo-ru-41-yl) benzoate 0.84 g was dissolved in dioxane 2 Om 1 and concentrated hydrochloric acid 1 Oml was added. After the addition, the mixture was stirred for 16 hours while heating under reflux. After cooling, dioxane was distilled off, extracted with ethyl acetate, and the organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate.
  • Methyl 2,4-dichloro-3- (2-dimethylaminomethylidene-1-oxopropyl) benzoate 7.57 g was dissolved in 30 ml of dioxane and 16 ml of water, and 1.7 mg of hydroxylamine hydrochloride was obtained. Og was added and stirred at room temperature for 17 hours. After evaporating the solvent under reduced pressure, the obtained residue was dissolved in ethyl acetate, washed with brine, and dried over anhydrous magnesium sulfate.
  • the compound of the present invention shows a high herbicidal activity under any conditions of upland crops, soil treatment and foliage treatment. It also contains compounds that have selectivity for barley and other crops, soybeans, ivy and other crops.
  • the compound of the present invention also includes a compound exhibiting a plant growth regulating action for producing growth suppression and the like against useful plants such as crops, ornamental plants and fruit trees.
  • the compound of the present invention has excellent herbicidal activity against rice weeds such as paddy field weeds, such as Nobie, Yumagayari, Omodaka and Houyu, and has selectivity for rice.
  • the compound of the present invention can be applied to the control of weeds in orchards, lawns, track ends, vacant lots and the like.
  • the herbicide of the present invention contains one or more of the compounds of the present invention as an active ingredient.
  • the compound of the present invention can be used in a pure form without adding other components, and can be used in the form of a general pesticide for the purpose of using it as a pesticide, that is, a wettable powder, a granule, a powder, It can also be used in the form of emulsions, aqueous solvents, suspensions, flowables and the like.
  • plant powders such as soybean flour and flour, diatomaceous earth, apatite, gypsum, talc, bentonite, mineral fine powders such as pyrophyllite and clay, and benzoic acid Organic and inorganic compounds such as soda, urea, and sodium sulfate are used.
  • petroleum fractions such as kerosene, xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, trichloroethylene, methylisobutyl ketone,
  • mineral oil, vegetable oil, water, etc. as solvent.
  • Surfactants can be added, if necessary, to obtain a uniform and stable form in these preparations.
  • the concentration of the active ingredient in the herbicide of the present invention varies depending on the form of the preparation described above.
  • the concentration is 5 to 90%, preferably 10 to 8%. 5%: 3 to 70% in the emulsion, preferably 5 to 60%: 0.01 to 50%, preferably 0.05 to 4% in the granule 0% 'concentration is used
  • the wettable powder and emulsion thus obtained are diluted with water to a predetermined concentration to form a suspension or emulsion, and the granules are sprayed or mixed before or after germination of the weeds. Is done. In actually applying the herbicide of the present invention, an appropriate amount of 0.1 g or more of the active ingredient per hectare is applied.
  • the herbicide of the present invention can also be used by mixing with known fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers, and the like.
  • the synergistic effect of the mixed drug can be expected to have a higher effect. In that case, a combination with a plurality of known herbicides is also possible.
  • Suitable agents to be used in combination with the herbicide of the present invention include anilide herbicides such as diflufdican and propanil, and clomouth aceroalide-based herbicides such as arlacrol and pretilachlor, 2, 4-D, 2, 4-Alkyl herbicides such as DB, herbicides such as diclohop-methyl, phenoxaprop-ethyl, etc., herbicides such as oxyphenoxyalkanoic acid, alkamba, pyrithiobac, etc.
  • anilide herbicides such as diflufdican and propanil
  • clomouth aceroalide-based herbicides such as arlacrol and pretilachlor
  • 2, 4-D 2, 4-Alkyl herbicides
  • DB herbicides such as diclohop-methyl, phenoxaprop-ethyl, etc.
  • herbicides such as oxyphenoxyalkanoic acid, alkamba, pyrithiobac, etc.
  • Dinitroaniline herbicides such as trifluralin and pendimethalin; Diphenyl ether herbicides such as phenylene and homesaphene; sulfonylrea herbicides such as benzenesulfuron-methyl and nicosulfuron; triazinon-based herbicides such as methotrazine and metamitrone; and triazines such as atrazine and cyanazine.
  • Herbicides triazopyrimidine herbicides such as flumellam, butoryl herbicides such as promoxinil and dikopenenyl, pyridazinone herbicides such as chloridazone and norflurazon, phosphate-based herbicides such as glyphosate and glufosinetol Quaternary ammonium salt herbicides such as paraquat, difenzoquat, etc .; cyclic imid herbicides such as full microrac cupentyl, fluthiacetomethyl; etc .; Bok Rion, cinmethylin, Jichiopiru, pyrazolate, pyridate, Furupokisamu, bentazone, Benfuruse Ichito, furthermore, sethoxydim, Torarukoki And cyclohexanedione herbicides such as Jim. Vegetable oils and oil concentrates can also be added to these combined products.
  • Compound 20 of the present invention 20 parts White carbon 20 parts Gesso earth 52 parts 8 Sodium alkyl sulfate 8 parts or more uniformly mixed and finely pulverized to obtain a 20% active ingredient wettable powder c
  • Sodium alkyl sulfate 7 parts The above mixture was uniformly mixed and finely pulverized, and then granulated into granules having a diameter of 5 to 1.0 mm to obtain granules having an active ingredient of 5%.
  • the herbicidal effect was investigated according to the following criteria and expressed as a herbicidal index.
  • the numbers 1, 3, 5, 7, and 9 are intermediate values between 0 and 2, 2 and 4, 4 and 6, 6 and 8, and 8 and 10, respectively.
  • the weed kill rate was calculated by the following formula.
  • Herbicidal rate (%) ⁇ -—— ———— ⁇ " ⁇ 100 Test example 1 Upland foliage spraying test
  • IV-6 7 9 1 0 1 0 1 0 1 0 0 0 0 0 0 0
  • Test example 2 Paddy foliage treatment test
  • Pots having a surface area of 100 cm 2 were filled with paddy soil, and after replacement, seeds of Nobie, Hotaru, Konagi and Omodaka were sown, and then the two-leaf rice was transplanted. This was grown in a greenhouse, and when each weed reached the 1- to 1.5-leaf stage, it was submerged at a depth of 3 cm. Was dripped so that the active ingredient was 63 g / ha. Three weeks after the treatment, the herbicidal effect and the degree of phytotoxicity of rice were investigated, and the results are shown in Table 23.
  • composition containing the compound of the present invention is useful as a herbicide.

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Abstract

L'invention concerne des composés représentés par la formule générale (I) dans laquelle R1 représente halogéno, alkyle C¿1?-C6, alcoxy C1-C6 ou analogue; R?2¿ représente halogéno, alkylsulfonyle C¿1?-C6 ou analogue; n représente 0, 1 ou analogue; Het représente un groupe hétérocyclique à 5 éléments saturé ou non saturé, lequel est lié au cycle benzène au niveau d'un atome de carbone et contient un à quatre hétéroatomes sélectionnés parmi N, O et S et est substitué par R?7 et R8; R3¿ représente hydrogène ou analogue; R4 représente hydrogène, alkyle C¿1?-C6 ou analogue; R?5¿ représente alkyle C¿1?-C6 ou analogue; R?6¿ représente phényle facultativement substitué; et X représente SO¿2?, CH2CO, méthylène ou analogue. Les composés précités présentent une excellente activité herbicide de sorte que des compositions les contenant sont utiles en tant qu'herbicides.
PCT/JP1997/001423 1996-04-26 1997-04-24 Nouveaux derives de benzene a substitution heterocycle et herbicides WO1997041105A1 (fr)

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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998028981A1 (fr) * 1996-12-27 1998-07-09 Nippon Soda Co., Ltd. Composition herbicide
EP0891972A1 (fr) * 1996-03-26 1999-01-20 Nippon Soda Co., Ltd. Derives d'acide benzoique a substitution 3-(isoxazol-5-yl) et leur procede de production
WO1999010328A1 (fr) * 1997-08-07 1999-03-04 Basf Aktiengesellschaft 4-benzoyl-pyrazole heterocycliquement substitue comme herbicides
EP0900795A1 (fr) * 1996-04-26 1999-03-10 Nippon Soda Co., Ltd. Derives du benzene substitues par des heterocycles, et herbicides
WO1999021852A1 (fr) * 1997-10-27 1999-05-06 Nippon Soda Co., Ltd. Nouveaux derives de benzoylpyrazole et herbicides
WO1999023094A1 (fr) * 1997-10-30 1999-05-14 Nippon Soda Co., Ltd. Nouveaux composes, produits intermediaires, et desherbants de benzoylpyrazole
WO1999054328A1 (fr) * 1998-04-22 1999-10-28 Nippon Soda Co., Ltd. Nouveau composes de benzoylpyrazole et herbicide
WO2000003993A1 (fr) * 1998-07-16 2000-01-27 Ishihara Sangyo Kaisha Ltd. Composes de type pyrazole, procede de production de ces composes et herbicides contenant lesdits composes
US6165944A (en) * 1997-01-17 2000-12-26 Basf Aktiengesellschaft 4-(3-heterocyclyl-1-benzoyl) pyrazoles and their use as herbicides
JP2002514630A (ja) * 1998-05-11 2002-05-21 ビーエーエスエフ アクチェンゲゼルシャフト イソオキサゾリン−３−イルアシルベンゼンの製造方法
JP2002531562A (ja) * 1998-12-04 2002-09-24 ビーエーエスエフ アクチェンゲゼルシャフト ３−（ヘテロシクリル）−置換ベンゾイルピラゾール類
US6610631B1 (en) 1999-09-30 2003-08-26 Bayer Aktiengesellschaft Substituted aryl ketones
US6746989B1 (en) 1999-03-27 2004-06-08 Bayer Aktiengesellschaft Substituted benzoylpyrazoles as herbicides
US6864219B2 (en) 2000-01-17 2005-03-08 Bayer Aktiengesellschaft Substituted aryl ketones
EP1618098A2 (fr) * 2003-04-11 2006-01-25 PCT Therapeutics Inc. Composes d'acide benzoique 1,2,4-oxadiazole et utilisation de ceux-ci dans la suppression non-sens et le traitement de maladies
US7608564B2 (en) 1997-01-17 2009-10-27 Basf Aktiengesellschaft 3-heterocyclyl-substituted benzoyl derivatives
US8101641B2 (en) 2006-09-25 2012-01-24 Ptc Therapeutics, Inc. Hydroxylated 1,2,4-oxadiazole benzoic acid compounds and compositions thereof
US9873677B2 (en) 2014-03-06 2018-01-23 Ptc Therapeutics, Inc. Pharmaceutical compositions and salts of a 1,2,4-oxadiazole benzoic acid
US10517853B2 (en) 2015-10-30 2019-12-31 Ptc Therapeutics, Inc. Methods for treating epilepsy
WO2021204669A1 (fr) 2020-04-07 2021-10-14 Bayer Aktiengesellschaft Diamides d'acide isophtalique substitués
WO2021204665A1 (fr) 2020-04-07 2021-10-14 Bayer Aktiengesellschaft Diamides d'acide isophtalique substitués
WO2021204667A1 (fr) 2020-04-07 2021-10-14 Bayer Aktiengesellschaft Diamides d'acide isophtalique substitués

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102329277B (zh) * 2011-10-24 2013-08-07 海南霞迪药业有限公司 一种制备帕瑞昔布的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6253971A (ja) * 1985-09-03 1987-03-09 Nissan Chem Ind Ltd ピラゾ−ル誘導体、その製造法および選択性除草剤
JPH02173A (ja) * 1987-03-17 1990-01-05 Nissan Chem Ind Ltd ピラゾール誘導体及び選択性除草剤
WO1996026206A1 (fr) * 1995-02-24 1996-08-29 Basf Aktiengesellschaft Derives de pyrazol-4-yl-benzoyle et leur utilisation comme herbicides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6253971A (ja) * 1985-09-03 1987-03-09 Nissan Chem Ind Ltd ピラゾ−ル誘導体、その製造法および選択性除草剤
JPH02173A (ja) * 1987-03-17 1990-01-05 Nissan Chem Ind Ltd ピラゾール誘導体及び選択性除草剤
WO1996026206A1 (fr) * 1995-02-24 1996-08-29 Basf Aktiengesellschaft Derives de pyrazol-4-yl-benzoyle et leur utilisation comme herbicides

Cited By (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0891972A4 (fr) * 1996-03-26 2000-12-13 Nippon Soda Co Derives d'acide benzoique a substitution 3-(isoxazol-5-yl) et leur procede de production
EP0891972A1 (fr) * 1996-03-26 1999-01-20 Nippon Soda Co., Ltd. Derives d'acide benzoique a substitution 3-(isoxazol-5-yl) et leur procede de production
EP0900795A1 (fr) * 1996-04-26 1999-03-10 Nippon Soda Co., Ltd. Derives du benzene substitues par des heterocycles, et herbicides
EP0900795A4 (fr) * 1996-04-26 2000-12-13 Nippon Soda Co Derives du benzene substitues par des heterocycles, et herbicides
WO1998028981A1 (fr) * 1996-12-27 1998-07-09 Nippon Soda Co., Ltd. Composition herbicide
US6165944A (en) * 1997-01-17 2000-12-26 Basf Aktiengesellschaft 4-(3-heterocyclyl-1-benzoyl) pyrazoles and their use as herbicides
US7608564B2 (en) 1997-01-17 2009-10-27 Basf Aktiengesellschaft 3-heterocyclyl-substituted benzoyl derivatives
US9045465B1 (en) 1997-01-17 2015-06-02 Basf Se 3-heterocyclyl-substituted benzoyl derivatives
US6207618B1 (en) 1997-08-07 2001-03-27 Basf Aktiengesellschaft Heterocyclic substituted 4-benzoyl-pyrazole as herbicides
WO1999010328A1 (fr) * 1997-08-07 1999-03-04 Basf Aktiengesellschaft 4-benzoyl-pyrazole heterocycliquement substitue comme herbicides
WO1999021852A1 (fr) * 1997-10-27 1999-05-06 Nippon Soda Co., Ltd. Nouveaux derives de benzoylpyrazole et herbicides
WO1999023094A1 (fr) * 1997-10-30 1999-05-14 Nippon Soda Co., Ltd. Nouveaux composes, produits intermediaires, et desherbants de benzoylpyrazole
US6147031A (en) * 1997-10-30 2000-11-14 Nippon Soda Co., Ltd. Benzoylpyrazole compounds, intermediate preparing therefor and herbicides
US6245716B1 (en) 1998-04-22 2001-06-12 Nippon Soda Co., Ltd. Benzoylpyrazole compounds and herbicide
WO1999054328A1 (fr) * 1998-04-22 1999-10-28 Nippon Soda Co., Ltd. Nouveau composes de benzoylpyrazole et herbicide
JP2002514630A (ja) * 1998-05-11 2002-05-21 ビーエーエスエフ アクチェンゲゼルシャフト イソオキサゾリン−３−イルアシルベンゼンの製造方法
JP4786032B2 (ja) * 1998-05-11 2011-10-05 ビーエーエスエフ ソシエタス・ヨーロピア イソオキサゾリン−３−イルアシルベンゼンの製造方法
WO2000003993A1 (fr) * 1998-07-16 2000-01-27 Ishihara Sangyo Kaisha Ltd. Composes de type pyrazole, procede de production de ces composes et herbicides contenant lesdits composes
JP2002531562A (ja) * 1998-12-04 2002-09-24 ビーエーエスエフ アクチェンゲゼルシャフト ３−（ヘテロシクリル）−置換ベンゾイルピラゾール類
US6746989B1 (en) 1999-03-27 2004-06-08 Bayer Aktiengesellschaft Substituted benzoylpyrazoles as herbicides
US7279444B2 (en) 1999-03-27 2007-10-09 Bayer Cropscience Gmbh Substituted benzoylpyrazoles
US6610631B1 (en) 1999-09-30 2003-08-26 Bayer Aktiengesellschaft Substituted aryl ketones
US6727206B2 (en) 1999-09-30 2004-04-27 Bayer Aktiengesellschaft Substituted aryl ketones
US6864219B2 (en) 2000-01-17 2005-03-08 Bayer Aktiengesellschaft Substituted aryl ketones
JP4851933B2 (ja) * 2003-04-11 2012-01-11 ピーティーシー セラピューティクス，インコーポレーテッド １，２，４−オキサジアゾール安息香酸化合物ならびにナンセンス抑制及び疾患の治療のためのその使用
US9205088B2 (en) 2003-04-11 2015-12-08 Ptc Therapeutics, Inc. Compositions of 1,2,4-oxadiazol benzoic acid compounds and methods for their use
AU2004229487B9 (en) * 2003-04-11 2010-06-10 Ptc Therapeutics, Inc. 1,2,4-oxadiazole benzoic acid compounds
EP1618098A4 (fr) * 2003-04-11 2008-07-16 Pct Therapeutics Inc Composes d'acide benzoique 1,2,4-oxadiazole et utilisation de ceux-ci dans la suppression non-sens et le traitement de maladies
JP2006522826A (ja) * 2003-04-11 2006-10-05 ピーティーシー セラピューティクス，インコーポレーテッド １，２，４−オキサジアゾール安息香酸化合物ならびにナンセンス抑制及び疾患の治療のためのその使用
EP4101846A1 (fr) * 2003-04-11 2022-12-14 PTC Therapeutics, Inc. Composés d'acide benzoïque 1,2,4-oxadiazole et leur utilisation pour la suppression non-sens et le traitement de maladies
US8129540B2 (en) 2003-04-11 2012-03-06 Ptc Therapeutics, Inc. Methods for the synthesis of 1,2,4-oxadiazole benzoic acid compounds
KR101134188B1 (ko) * 2003-04-11 2012-04-12 피티씨 테라퓨틱스, 인크. 1,2,4-옥사디아졸 벤조산 화합물
US8227494B2 (en) 2003-04-11 2012-07-24 Ptc Therapeutics, Inc. Pharmaceutical compositions of 1,2,4-oxadiazole benzoic acid and their use for the treatment of disease
US8486982B2 (en) 2003-04-11 2013-07-16 Ptc Therapeutics, Inc. 1,2,4-oxadiazole benzoic acids
EP3889142A1 (fr) * 2003-04-11 2021-10-06 PTC Therapeutics, Inc. Composés d'acide benzoïque 1,2,4-oxadiazole et leurs utilisation pour la suppression non-sens et le traitement de maladies
US8796322B2 (en) 2003-04-11 2014-08-05 Ptc Therapeutics, Inc. Methods for using 1,2,4-oxadiazole benzoic acid compounds
US8975287B2 (en) 2003-04-11 2015-03-10 Ptc Therapeutics, Inc. Methods for using 1,2,4-Oxadiazole benzoic acid compounds
EP1618098A2 (fr) * 2003-04-11 2006-01-25 PCT Therapeutics Inc. Composes d'acide benzoique 1,2,4-oxadiazole et utilisation de ceux-ci dans la suppression non-sens et le traitement de maladies
EP2910551A1 (fr) * 2003-04-11 2015-08-26 PTC Therapeutics, Inc. Composes d'acide benzoique 1,2,4-oxadiazole et utilisation de ceux-ci dans la suppression non-sens et le traitement de maladies
AU2004229487B2 (en) * 2003-04-11 2010-05-20 Ptc Therapeutics, Inc. 1,2,4-oxadiazole benzoic acid compounds
EP3103800A1 (fr) * 2003-04-11 2016-12-14 PTC Therapeutics, Inc. Composé d'acide benzoïque 1,2,4-oxadiazole et son utilisation pour la suppression non-sens et le traitement de maladies
EP3178816A1 (fr) * 2003-04-11 2017-06-14 PTC Therapeutics, Inc. Composé d'acide benzoïque 1,2,4-oxadiazole et son utilisation pour la suppression non-sens et le traitement de maladies
US9861617B2 (en) 2003-04-11 2018-01-09 Ptc Therapeutics, Inc. Compositions of 1,2,4-oxadiazole benzoic acid compounds and methods for their use
EP3632902A1 (fr) * 2003-04-11 2020-04-08 PTC Therapeutics, Inc. Composé d'acide benzoïque 1,2,4-oxadiazole et son utilisation pour la suppression non-sens et le traitement de maladies
EP3345895A1 (fr) * 2003-04-11 2018-07-11 PTC Therapeutics, Inc. Composé d'acide benzoïque 1,2,4-oxadiazole et son utilisation pour la suppression non-sens et le traitement de maladies
US10071081B2 (en) 2003-04-11 2018-09-11 Ptc Therapeutics, Inc. Compositions of 1,2,4-oxadiazole benzoic acid compounds and methods for their use
EP3549936A1 (fr) * 2003-04-11 2019-10-09 PTC Therapeutics, Inc. Composé d'acide benzoïque 1,2,4-oxadiazole et son utilisation pour la suppression non-sens et le traitement de maladies
US8691511B2 (en) 2006-09-25 2014-04-08 Ptc Therapeutics, Inc. Hydroxylated 1,2,4-oxadiazole benzoic acid compounds, compositions thereof and their use in bioassays
US8101641B2 (en) 2006-09-25 2012-01-24 Ptc Therapeutics, Inc. Hydroxylated 1,2,4-oxadiazole benzoic acid compounds and compositions thereof
US10233161B2 (en) 2014-03-06 2019-03-19 Ptc Therapeutics, Inc. Pharmaceutical compositions and salts of a 1,2,4-oxadiazole benzoic acid
US9873677B2 (en) 2014-03-06 2018-01-23 Ptc Therapeutics, Inc. Pharmaceutical compositions and salts of a 1,2,4-oxadiazole benzoic acid
US10618877B2 (en) 2014-03-06 2020-04-14 Ptc Therapeutics, Inc. Pharmaceutical compositions and salts of a 1,2,4-oxadiazole benzoic acid
US10517853B2 (en) 2015-10-30 2019-12-31 Ptc Therapeutics, Inc. Methods for treating epilepsy
WO2021204669A1 (fr) 2020-04-07 2021-10-14 Bayer Aktiengesellschaft Diamides d'acide isophtalique substitués
WO2021204665A1 (fr) 2020-04-07 2021-10-14 Bayer Aktiengesellschaft Diamides d'acide isophtalique substitués
WO2021204667A1 (fr) 2020-04-07 2021-10-14 Bayer Aktiengesellschaft Diamides d'acide isophtalique substitués

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