WO1998021187A1 - Nouveaux derives de benzene a substitution heterocyclique, et herbicide - Google Patents

Nouveaux derives de benzene a substitution heterocyclique, et herbicide Download PDF

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Publication number
WO1998021187A1
WO1998021187A1 PCT/JP1997/003736 JP9703736W WO9821187A1 WO 1998021187 A1 WO1998021187 A1 WO 1998021187A1 JP 9703736 W JP9703736 W JP 9703736W WO 9821187 A1 WO9821187 A1 WO 9821187A1
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group
methyl
solvent
added
compound
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PCT/JP1997/003736
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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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Publication of WO1998021187A1 publication Critical patent/WO1998021187A1/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 pyrazolyl derivative and a herbicide in which the benzoyl group is substituted at the 4-position of the virazol ring.
  • An object of the present invention is to provide a herbicide which 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 41-benzoylpyrazole compound represented by the general formula (I) wherein the 3-position of the benzoyl moiety is substituted with a heterocyclic ring, wherein the benzoyl ring is protected with a phenolic hydroxyl group. It is a herbicide characterized by containing the compound as an active ingredient.
  • R 1 is a halogen atom, d-8 alkyl, d-6 alkoxy group, a nitro port group, Shiano group, d haloalkyl group, ⁇ I 6 haloalkoxy group, Ci Al Kiruchio group, C -! 6 Represents an alkylsulfinyl group or a C alkylsulfonyl group.
  • R 2 is a halogen atom, a nitro group, a cyano group, a d-alkyl group, a Ci- 6 alkoxy group, a Ci-haloalkyl group, a haloalkoxy group, a Ci- G alkylthio group, a d-alkylsulfinyl group, or a d-alkylsulfonyl Represents a group.
  • R 3 is halogen atom, C, - 6 alkyl group, C -!
  • 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, C, - represents a 6 alkynyl group - alkyl group, C 2 - 6 alkenyl group or C 2.
  • R G is, C] - 6 alkyl group, C 3 - 8 cycloalkyl group, an alkyl group, Cl alkoxy, Ci haloalkyl, d-(i haloalkoxy group, may be substituted by nitro group or a halogen atom ) Represents a phenyl group.
  • X is S_ ⁇ 2, (CH 2) mCO, which may be substituted by alkyl C, - representing the e 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 1 is a halogen atom such as fluorine, chlorine, or bromine; a Ci alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, or t-butyl; Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy,
  • C i haloalkyl groups such as nitro group, cyano group, trifluoromethyl, trifluoroethyl, etc .
  • haloalkoxy groups such as trifluoromethoxy group
  • C- 6 alkylthio groups such as methylthio, ethylthio, propylthio, isopropylthio, etc .
  • alkylsulfinyl group such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, or
  • R 2 is a halogen atom such as fluorine, chlorine, and bromine; a nitro group, a cyano group; a C i -alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, and t-butyl;
  • D alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy,
  • Cl- 6 alkylsulfinyl group such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, or
  • R 3 is a halogen atom such as fluorine, chlorine, bromine,
  • Alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl,
  • D alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, nitro, cyano,
  • D haloalkyl groups such as trifluoromethyl and trifluoroethyl
  • Ds alkylthio groups such as methylthio, ethylthio, propylthio, and isopropylthio
  • D-6 alkylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, and isopropylsulfinyl groups, or
  • Het represents a saturated or unsaturated 5-membered heterocyclic group containing 1 to 4 N, 0 or S atoms and optionally having substituents R 7 and R 8 .
  • the heterocyclic group is bonded to the benzene ring at a carbon atom.
  • Het examples include 2-furyl, 3-furyl, 4-furyl, 5-furyl, 2-phenyl, 3-phenyl, 4-phenyl, 5-phenyl, 2-pyrrolyl, 3-pyrrolyl, 4-pyrrolyl ,
  • heterocyclic any position, fluorine, chlorine, halogen atom such as bromine, methyl, d one 6 alkyl group such as Echiru group, main butoxy, etc. ethoxy d-e ⁇ alkoxy, Torifuruoro Substituents such as ( ⁇ -6 haloalkyl group such as methyl group R 7 , R May have eight .
  • Het includes the following heterocyclic groups.
  • R 7 and R 8 are each independently a hydrogen atom, a ⁇ - alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl group, methoxy, ethoxy, propoxy group, etc.
  • d- 6 represents a halogen atom such as an alkoxy group, fluorine, chlorine or bromine, or a C i haloalkyl group such as a trifluoromethyl group).
  • R 4 is a hydrogen atom, an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl,
  • Hydroxyalkyl groups such as hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, hydroxypropyl,
  • 6- alkoxy d- such as methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, methoxyxethyl, ethoxyxyl, ethoxyquinpropyl, methoxypropyl, ethoxypropyl, butoxymethyl, t-butoxymethyl, t-butoxymethyl, etc .; Represents an alkyl group.
  • R 5 is a hydrogen atom, d-alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl group,
  • R 6 is methyl, Echiru, propyl, isopropyl, heptyl, Isopuchiru, t - heptyl etc. d - e alkyl group, Cyclopropyl, cyclobutyl, cyclopentyl, c 3, such as a cyclohexyl group - 8 cycloalkyl group, or,
  • X is S ⁇ 2 , (CH 2 ) mCO (m represents 0, 1, 2 or 3), C!
  • methylene, ethylene, and propylene which may be substituted with an alkyl group such as methyl, ethyl and the like.
  • alkyl group such as methyl, ethyl and the like.
  • — Represents a 6- alkylene group or a single bond.
  • XR 6, CH 2 A r, CH 2 COAr and S0 2 A r wherein, Ar is any position of the benzene ring is (methyl, Echiru, propyl, isopropyl, heptyl, Isopuchiru, t alkyl group such as one-butyl, main butoxy, ethoxy, Purobokishi, Isopurobokishi, butoxy, d one e alkoxy group such as t- butoxy, Bok Rifuruoromechiru, trichloromethyl, Furuoromechiru, click port Romechiru, difluoromethyl port Romechiru, dichloromethyl, triflic C, such as chloroethyl and pentachlorofluoroethyl, which may be substituted by a haloalkyl group or a halogen atom such as fluorine, chlorine, or bromine. And more preferably a CH 2 Ar group which may have a substituent
  • the compound of the present invention can be produced by the following method.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X, ⁇ 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, and L represents a halogen atom.
  • Compounds [I Va] and [I Vb] are compound [VII] and compound [Va] (Q has the same meaning as described above).
  • the base used in the reaction includes alkali metal hydroxides such as KOH and HaH, alkali metal carbonates such as sodium carbonate and carbonated lime, and alkaline earth metal such as calcium hydroxide and magnesium hydroxide.
  • alkali metal hydroxides such as KOH and HaH
  • alkali metal carbonates such as sodium carbonate and carbonated lime
  • alkaline earth metal such as calcium hydroxide and magnesium hydroxide.
  • Al force Li earth metal carbonates such as calcium carbonate, Toryechiruami down, Bokuri (C, - 6 alkyl), such as Jie isopropyl E chill ⁇ Mi emissions amines
  • organic such as pyridine bases, phosphoric acid Examples include sodium.
  • solvent examples include water, methylene chloride, chloroform, toluene, ethyl acetate, dimethylformamide (DMF), tetrahydrofuran (THF), dimethylxetane (DME), and acetonitrile.
  • reaction mixture is stirred at 0 ° C to 50 ° C until the reaction is completed. Further, the reaction can be performed in a two-phase system using a phase transfer catalyst such as a quaternary ammonium salt.
  • a phase transfer catalyst 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, dimethoxetane, acetonitrile, t-amyl alcohol and the like.
  • Reaction The reaction proceeds smoothly at 10 ° C. to 50 ° C., and the reaction mixture is processed by a conventional method.
  • 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 (I Va) and (I Vb) is converted into 1 to 4 mol of the base, preferably 1 to 2 mol of the base and 0.01 to 1.0 mol, preferably 0.05 mol.
  • Any of the bases described above can be used.
  • the cyano compounds include potassium cyanide, sodium cyanide, and sodium cyanide.
  • a polymer holding tonocyan hydride, hydrogen cyanide, or potassium cyanide 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, dimethoxetane and the like.
  • This rearrangement reaction can also be carried out in an inert solvent in the presence of a base such as carbon dioxide lime, sodium carbonate, triethylamine and pyridine.
  • the amount of the base used is 0.5 to 2.0 mol with respect to the compounds [IVa] and [IVb], and the solvent is THF, dioxane, t-amyl alcohol, t-butyl alcohol or the like. Is used.
  • the reaction temperature is preferably from room temperature to the boiling point of the solvent used.
  • the compound (I Va) 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 5 to 2.0 mol based on 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 6 XL (L represents a halogen) in the presence of a base.
  • the base used in this reaction include alkali metal hydroxides such as H and Ha a, alkaline metal carbonates such as carbonated carbonate and sodium carbonate, and alkaline earth metals such as calcium hydroxide.
  • metal hydroxides, Al force Li earth metal carbonates such as calcium carbonate, Toryechi Ruami down, birds such as diisopropyl e chill ⁇ Mi emissions (C, - e alkyl) ⁇ Mi emission, organic bases such as pin lysine, phosphoric acid Examples include sodium and the like.
  • Compound [I] is a quaternary ammonium compound. It can also be produced by reacting in a two-phase system of water and a solvent insoluble in water in the above-mentioned solvent, using a phase transfer catalyst such as a pumium salt.
  • 5-Hydroxypyrazoles represented by the general formula [VII] are described in, for example, the following compounds described in JP-A-62-234069 or JP-A-3-44475. It can be manufactured according to the exemplified method.
  • the aldehyde compound (3) and the carboxylic acid compound (4) which are synthetic intermediates for producing the compound of the present invention, can be produced as follows.
  • R 1 and R 2 represent the same meaning as described above, R 9 represents a hydrogen atom or a lower alkyl group, and W represents a halogen atom.
  • a known method for example, a simple halogen such as chlorine or bromine, or a halogenating agent such as N-bromosuccinic acid imide (NBS) or N-chlorosuccinic acid imid (NCS) is converted to light or After reacting in the presence of a radical initiator such as benzoylperoxide to obtain a benzyl halide derivative (2), for example, J. Am. Chem.
  • the aldehyde compound (3) can be produced by the method described in 1949). That is, by reacting an alkali metal salt of a ditroalkane such as 2-dipropane with an alcohol solvent such as methanol or ethanol at a temperature between 0 ° C and the boiling point of the solvent, the aldehyde compound ( 3) can be manufactured.
  • the carboxylic acid (4) is converted from the toluene derivative (1) by an oxidation reaction of permanganate or the like, or from the aldehyde (3) by a J0nes reagent, chromic acid or permanganate. It can be produced by a known method such as an oxidation reaction.
  • R 1 , R 2 , and R 9 represent the same meaning as described above, R 1 () and R 11 represent a hydrogen atom or a lower alkyl group, V represents a halogen atom, and R 12 represents a lower atom. Represents an alkyl group.
  • 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 Knoevenage 1 condensation reaction described in Organic Reaction s, Vol. 15, page 254, to produce the nitroolefin body (7).
  • the nitroolefin compound (7) can be obtained by reducing with an activated iron-water system or lithium aluminum hydride and then hydrolyzing.
  • the acyl form (10) is prepared by reacting the aldehyde form (3) with a Grignard reagent to produce an alcohol form (9), and the 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 compound (24) is prepared by reacting the aldehyde compound (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 aldole compound (23), it can be produced by dehydrating this in a suitable solvent in the presence of a catalyst.
  • the catalyst used for producing the aldol derivative (23) include metal hydroxides such as sodium hydroxide and barium hydroxide, and organic bases such as piperidine and pyridine.
  • the catalyst used in the subsequent dehydration reaction includes 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) can also be 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 be manufactured.
  • the amide (12), the hydrazide (13) and the / 3-diketone (15) can be respectively produced as follows.
  • RR 2 and R 9 represent the same meaning as described above, and R 13 , R ′′, and 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 agent By reacting with an agent, an intermediate carbonyl chloride (11) is produced.
  • the amide (12) and the hydrazide (13) can be produced by a known method of reacting ammonia or hydrazine using the carbonyl chloride (11).
  • the / 3—diketone (15) is composed of a magnesium salt obtained by reacting magnesium alcoholate with a —ketoester (14) and a carbonyl chloride
  • (11) can be produced by reacting Next, a method for synthesizing a heterocyclic intermediate will be illustrated.
  • R 1 , R 2 and R 9 represent the same meaning as described above, and R 16 corresponds to R 7 or R 8 described above.
  • the oxazolyl form represented by the general formula (17) is obtained by, for example, boiling the aldehyde form (3) and the isonitrile form (16) in a suitable solvent in the presence of a base from room temperature.
  • the reaction can be carried out at a temperature between 1 and 30 hours.
  • the base used in this reaction include carbonates such as sodium hydrogencarbonate and potassium carbonate, alkali metal hydroxides such as sodium hydroxide and hydroxide power, sodium methylate, sodium ethylate and the like.
  • Organic bases such as metal alcoholates, triethylamine, 1,8-diazabicyclo [5.4.0] indene-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 (THF). ), Ethers such as 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
  • THF tetrahydrofuran
  • Ethers such as dioxane, nitriles such as acetonitrile, and N, N-dimethylformamide (DMF).
  • R 1 , R 2 , and R 9 represent the same meaning as described above, and R 17 represents 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 obtained by reacting the amide form (12) with phosphorus pentasulfide or a reagent in the presence or absence of a solvent at a temperature between room temperature and the boiling point of the solvent used. It can be manufactured by Examples of the solvent used in this reaction include hydrocarbons such as benzene and toluene, and ethers such as dioxane.
  • thioamide form (18) and ⁇ -ketone (19) are reacted in the presence of a suitable base or in a suitable solvent without using a base at a temperature between room temperature and the boiling point of the solvent to be used. By reacting for 1 to 30 hours, a thiazole compound (20) can be produced.
  • Bases used in this reaction include sodium hydrogen carbonate, carbonates such as carbon dioxide, sodium hydroxide, alkali metal hydroxides such as hydroxide, sodium methylate, sodium ethylate, etc. And organic bases such as triethylamine, 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 9 , and R 18 represent the same meaning as described above, and R 18 represents a hydrogen atom or a C 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 form (25), it can be further produced by ring closure and oxidation reaction. In this reaction, hydroxylamine can be reacted in the form of sulfate or hydrochloride without neutralization, but can also be reacted after neutralization using a suitable base.
  • Examples of the base used for neutralization include carbonates such as sodium bicarbonate and carbon dioxide, alkali metal hydroxides such as sodium hydroxide and hydroxyladium, carboxylate salts such as sodium acetate, sodium methyla Metal alcohols such as sodium ethylate; 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 tonitrile, DMF, pyridine, acetic acid, water and the like, and a mixed solvent of two or more of these solvents.
  • the iodine-potassium iodide, N_promosuccinimide, palladium catalyst system, etc. are used for the ring-closing 'oxidation reaction, iodine potassium monoiodide, and the J. Amer. Chem. Soc., 94, (1972); J. Hetero cycl. Chem., 14, 1289 (1977); Tetrahe dr on Lett. 1977, 5075. It can be manufactured according to the method described above.
  • the pyrazole (28a) can be produced in two steps from the vinyl ketone (24). That is, first, the vinyl ketone compound (24) and the substituted hydrazine are reacted in an appropriate solvent at a temperature between 0 ° C. and the boiling point of the solvent to be used for 0.5 to 5 hours to obtain a 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, ethers such as THF and dioxane.
  • Nitriles such as acetonitrile, DMF, pyridine, acetic acid, water, etc., and a mixed solvent of two or more of these solvents.
  • dihydrovirazole (27) and oxidizing agent such as activated manganese dioxide, dicyanodiclo-benzoquinone (DDQ), nickel peroxide, NBS, etc. are dissolved in a suitable solvent from room temperature.
  • a pyrazole compound (28a) can be produced.
  • 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 9 represent the same meaning as described above, R 2D represents the same meaning as R 7 , R 21 represents the same meaning as R 8, and R 22 represents the same meaning as R 5 Represents the meaning.
  • An isoxazole derivative represented by the general formula (26b) and a pyrazolide derivative represented by the general formula (28b) are obtained by reacting a diketone (15) with hydroxylamine and substituted hydrazine, respectively. It can also be manufactured by performing the above. 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; and acetonitrile. And nitriles, 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
  • acetonitriles 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 9 represent the same meaning as described above, and R 23 and R 24 correspond to R 7 or R 8 described above.
  • the isoxazole compound represented by the general formula (31) is obtained by combining an aldoxime compound (5) with a halogenating agent such as chlorine, bromine, N-chlorosuccinimide (NCS) or NBS, and a carbonizing agent such as benzene or toluene.
  • a halogenating agent such as chlorine, bromine, N-chlorosuccinimide (NCS) or NBS
  • a carbonizing agent such as benzene or toluene.
  • the isoxazole compound (31) can also be produced by reacting the halide with the base in the presence of vinyl acetate (30).
  • the oxaziazole compound (34) can be produced via the amidedoxime compound (31).
  • the amide doxime form (31) is produced by reacting the nitrile form (6) with hydroxylamine 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 bicarbonate, carbonate such as carbonated lime, alkali metal hydroxide such as sodium hydroxide and hydroxylated lime, and the like.
  • carboxylic acid salts such as sodium acid acid, metal alcoholates such as sodium methylate and sodium ethylate, and organic bases such as triethylamine and pyridine.
  • 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.
  • nitriles such as DMF, pyridine, acetic acid, water and the like, and a mixed solvent of two or more of these solvents.
  • a solvent used at a temperature of 15 ° C in a suitable solvent can be produced by reacting at a temperature between the boiling points of 1 to 30 hours.
  • Examples of the base used in this reaction include carbonates such as sodium hydrogencarbonate and carbonated carbonate, alkali metal hydroxides such as sodium hydroxide and hydroxylated phosphate, and organic bases such as triethylamine, pyridine and DBU. And the like.
  • 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. .
  • R 1 , R 2 , and R 8 represent the same meaning as described above, and R 2G corresponds to R 7 described above.
  • R 27 represents a lower alkyl group.
  • the oxazidazole form (37) is obtained by converting the hydrazide form (13) with the orthoester (35) or imide (36) in a suitable solvent at a temperature of 115 ° C. It can be produced by reacting at a temperature between 1 and 30 hours. Solvents used in this reaction 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, Such as pyridine
  • the isoxazole compound represented by the general formula (40) can be produced from the ketone compound (8) via the dimethylaminomethylidene compound (39). That is, ketone body
  • the reaction can be carried out at a temperature from room temperature to 200 ° C. or the boiling point of the solvent used.
  • the solvent used in this reaction hydrocarbons such as toluene and xylene are used.
  • dimethylaminomethylidene compound (39) is reacted with hydroxylamine to form an isoxazole compound (40).
  • the pyrazole derivative represented by the general formula (41) can be produced in the same manner as the pyrazole derivative (28b) by reacting a dimethylaminomethylidene derivative (39) with a substituted hydrazine. Can be.
  • R 1 , R 2 , R 9 , and R 3 ° represent 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.
  • the amidine compound (43) is produced.
  • hydrocarbons such as toluene and xylene are used.
  • an oxazine diazole (44) can be produced from the obtained amidine (43) and hydroxylamine in the same manner as in the production of the isoxazole (26b). .
  • the triazole represented by the general formula (45) can be produced in the same manner as the pyrazole (28b) by reacting the amidine (43) with a substituted hydrazine. Can be.
  • the isoxazole compound represented by the formula (26-3) is obtained by adding a mercaptan represented by R'SH to a 4-C1 compound represented by the formula (26-1) in the presence of a base. To form a 4-SR 'body represented by the formula (26-2) and then oxidize It can be manufactured by doing.
  • R′R 9 Het represents the same meaning as described above, and R ′ represents a d- 6 alkyl group.
  • Bases used in this reaction include alkali metal hydroxides such as sodium hydroxide and hydroxylating metal, metal alkoxides such as sodium methoxide and sodium ethoxide, sodium carbonate and carbonated carbonate such as carbonated lime.
  • alkali metal hydroxides such as sodium hydroxide and hydroxylating metal
  • metal alkoxides such as sodium methoxide and sodium ethoxide
  • sodium carbonate and carbonated carbonate such as carbonated lime.
  • Examples include salts, hydrides such as sodium hydride, organic bases such as triethylamine, diisopropylethylamine, diaza-bicyclo [540] -indene-7-cene (DBU) and pyridine.
  • DBU diaza-bicyclo [540] -indene-7-cene
  • solvent used in the reaction examples include alcohols such as methanol and ethanol, ethers such as tetrahydrofuran (THF) 1,2-dimethoxyethane (DME), and N, N-dimethylformamide (DMF).
  • ethers such as tetrahydrofuran (THF) 1,2-dimethoxyethane (DME), and N, N-dimethylformamide (DMF).
  • Amides such as (N, N-dimethylacetamide (DMA)), DMS D, acetonitrile, benzene, toluene, xylene and the like can be exemplified.
  • 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 -It is carried out by using oxidizing agents such as peracids such as black perbenzoic acid, sodium hypochlorite, and hypochlorous acid such as hypochlorous acid power.
  • the reaction proceeds smoothly in a temperature range from room temperature to the boiling point of the solvent used.
  • JP 73736 The compound [Ia] 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.
  • V 1 V L then 1 then 1 n then il3 n then 0U2 4 Me ril
  • the reaction mixture was washed with 1N hydrochloric acid and then with a saturated saline solution, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • the residue was dissolved in 20 ml of acetonitrile, 0.47 g (0.0047 mol) of trinitylamine and 0.1 g (0.0011 mol) of acetone hydrin were added, and the mixture was stirred overnight at room temperature. .
  • the solvent was distilled off under reduced pressure, the residue was dissolved in ethyl acetate, washed with 1N-hydrochloric acid and then with saturated brine, dried over magnesium sulfate anhydride, and the solvent was distilled off.
  • the residue was purified by silica gel column chromatography to give the title compound (0.73 g) as crystals.
  • the solvent was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate, washed with 1 N hydrochloric acid and then with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off.
  • the residue was purified by silica gel column chromatography to obtain 0.94 g of the title compound as crystals.
  • the reaction mixture was washed with 1 N hydrochloric acid and then with a saturated saline solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • the residue was dissolved in 20 ml of acetonitrile, and 0.41 g (0.00041 mol) of triethylamine and 0.10 g (0.0011 mol) of acetone cyanohydrin were added, followed by stirring at room temperature overnight. did.
  • the solvent was distilled off under reduced pressure, the residue was dissolved in ethyl acetate, washed with 1N-hydrochloric acid and then with a saturated saline solution, dried over magnesium sulfate, and the solvent was distilled off.
  • the residue was purified by silica gel column chromatography to obtain 0.66 g of the title compound as crystals.
  • the solvent was distilled off under reduced pressure, and the residue was dissolved in dityl acetate, washed with 1 N hydrochloric acid and then with saturated saline, dried over magnesium sulfate, and then the solvent was distilled off.
  • the residue was purified by silica gel column chromatography to obtain 0.35 g of the title compound as crystals.
  • 1,3-year-old 5-benzoyl) benzoyl chloride was added at room temperature, and the mixture was stirred at room temperature for 1 hour.
  • the reaction mixture was washed with 1N hydrochloric acid and then with a saturated saline solution, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • the residue was dissolved in acetone (10 ml), triethylamine (0.24 g) and acetone cyanohydrin (0.10 g) were added, and the mixture was stirred at room temperature overnight.
  • 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 10 ml of acetone nitrile, to which 0.6 g of triethylamine and 0.2 g of acetonetonhydrin were added, followed by stirring at room temperature for 1.5 hours.
  • the solvent was distilled off under reduced pressure, the residue was dissolved in benzene, and extracted with aqueous sodium bicarbonate. To the resulting aqueous layer was added chloroform, and the solution was precipitated with concentrated hydrochloric acid.
  • 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 (20 ml), and triethylamine (0.96 g) and acetone cyanohydrin (0.14 g) were added, followed by stirring at room temperature overnight.
  • the solvent was distilled off under reduced pressure, the residue was dissolved in benzene, and extracted with an aqueous sodium carbonate solution. To the resulting aqueous layer was added porphyrin form and acidified out 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 acetonitrile (10 ml), and triethylamine (0.30 g) and acetone cyanohydrin (0.04) were added, followed by stirring at room temperature for one hour.
  • the solvent was distilled off under reduced pressure, the residue was dissolved in benzene, and extracted twice with 50 ml of saturated aqueous sodium hydrogen carbonate. To the obtained aqueous layer was added 100 ml of chloroform, and the mixture was subjected to acid precipitation 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 10 ml of acetonitrile, 0.28 g of triethylamine and 0.03 g of acetonetonhydrin were added, and the mixture was stirred at room temperature overnight.
  • the solvent was distilled off under reduced pressure, the residue was dissolved in benzene, and extracted twice with 40 ml of saturated aqueous sodium bicarbonate and 20 ml of saturated aqueous sodium hydrogen carbonate.
  • 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 5 ml of acetonitrile, 0.22 g of triethylamine and 0.02 g of acetonitrile were added, and the mixture was stirred at room temperature overnight.
  • the solvent was distilled off under reduced pressure, the residue was dissolved in benzene, and extracted twice with 6.0 ml and 40 ml of saturated aqueous sodium hydrogen carbonate. To the obtained aqueous layer was added 100 ml of chloroform, and the solution was acidified with concentrated hydrochloric acid.
  • 1,4-isoxazol-5-yl) benzoic acid 0.39 g and thionyl iodide synthesized according to a conventional method to give 2,4-dicloco-3- (4-methyl-1,2-isoxazolyl) 5-yl) Benzoyl chloride was added at room temperature, and the mixture was stirred at room temperature. The reaction mixture was washed with 1N hydrochloric acid and then with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
  • Methyl 3-aminocarbonyl-1,2,4-dichlorobenzene benzoate 13.32 g (0.053 mol) and phosphorus pentasulfide 3.6 g (0.016 mol) were dissolved in 90 m of solvent. The mixture was dissolved in 1 and stirred at 80 ° C overnight. The reaction mixture was poured into ice water, extracted with ethyl acetate, washed with saturated saline, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 5.43 g of methyl 3-aminothiocarbonyl_2,4-dichlorobenzoate. Yield 38.4%
  • Methyl 2-chloro-1,4-methanesulfonyl 3- (3-methyl_1,2-isoxazoluyl 5-yl) benzoate 8.19 g (0.024 mol) ) was dissolved in 75 ml of ethyl alcohol, 75 ml of a 1N aqueous solution of caustic soda was added, and the mixture was stirred at room temperature overnight. The reaction mixture was poured into ice water, acidified with concentrated hydrochloric acid, and the precipitated crystals were collected by filtration, washed with water, and dried to give 7.49 g of the desired product as white crystals. 96% yield
  • Methyl 2,4-dichloro-3- (5-methyl-1,3,4-oxadiazol-2-yl) benzoate 2.63 g (0.009 1 mol) and potassium carbonate 1.3 g (0.3%) was dissolved in 20 ml of dimethylformamide, and 10 ml of dimethylformamide in which 0.65 g (0.013 mol) of methanethiol was dissolved was added, followed by stirring at room temperature overnight. 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.
  • Methyl 2-chloro-4,1-methanesulfonyl 3- (5-methyl-1,3,4-oxaziazol-2-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 crystal was filtered and washed with water, and the obtained crystal was dried to obtain 1.3 g of a white crystal as a target product. 90% yield
  • Methyl 2,4-dichloro-3- (5-methyl-1,2,4-oxadiazoyl-3-yl) benzoate 2.75 g CO.095 mol) and potassium carbonate 1.32 g (0 0.095 mol) was dissolved in 20 ml of dimethylformamide, and 10 ml of dimethylformamide in which 0.7 g (0.014 mol) of methylthiol was dissolved was added. And stirred overnight. The reaction mixture was poured into ice water, extracted with ethyl acetate, washed with saturated saline, and dried over magnesium sulfate.
  • Methyl 2-methyl-3-3- (5-methyl-1,2,4-oxaziazol-3-yl) 4-methylthiobenzoate 2.8 g (0.0084 mol) in 20 ml It was dissolved in form, m-chloroperbenzoic acid 4.95 g (0.028 mol) was added, and the mixture was stirred 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.
  • 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-3 hydroxyiminomethylbenzoate (15.87 g, 0.039 mol) was dissolved in dimethylformamide (160 ml) and dissolved in dimethylformamide (16 Oml).
  • a solution of 55.00 g (0.308 mol) of Promosuccinimide was added dropwise at 10 ° C or lower over 1 hour.
  • a solution of 31.3 g (0.309 mol) of triethylamine 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 gel chromatography to obtain the title compound 8.57 as crystals.
  • Methyl 2,4-dichloro-3- (2-oxo-1-dimethylaminomethylidenepropyl) benzoate (4.10 g) was added to dioxane (20 ml) and water (10 ml), and hydroxylamine hydrochloride was added. 90 g was added, and the mixture was stirred at room temperature for 17 hours.
  • the reaction solution was poured into ice water, extracted with ethyl acetate, washed with saturated saline, and dried over anhydrous magnesium sulfate. After the solvent was concentrated under reduced pressure, the residue was purified by silica gel chromatography to obtain 1.8 g of the oxime form as a mixture of isomers.
  • reaction solution was poured into ice water, acidified with concentrated hydrochloric acid, and the extracted organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate.
  • the solvent was concentrated under reduced pressure to obtain 34.3 g of methyl 2,4-dichloro-3- (3,3-dimethylmethoxycarbonyl-1-oxopropyl) benzoate as crystals.
  • 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 paddy weeds such as Nobie, Tamagayari, Omodaka and Hotaru, 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 85%. % : 3 to 70%, preferably 5 to 60% in the emulsion: 0.01 to 50%, preferably 0.05 to 40% in the granule % 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.
  • an appropriate amount of the active ingredient of 0.1 g or more 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 action 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 diflupanican and propanil, and closular aceroalide-based herbicides such as arachlor and pretilachlor, 2, 41-D, 2, 4-1-Alkyl herbicides such as DB Acid herbicides such as diclohop-methyl, phenyloxapropenyl, etc. Alioxyphenoxyalkanoic acid herbicides such as dicampa and pyrithiobac Polycarboxylic acid herbicides, imazaquinone, imazethapyr, etc., imidazolinone herbicides, diurone, isoprolone, etc.
  • anilide herbicides such as diflupanican and propanil
  • closular aceroalide-based herbicides such as arachlor and pretilachlor
  • 2, 41-D 2, 4-1-Alkyl herbicides
  • DB Acid herbicides such as di
  • Herbicides dinitroaniline herbicides such as trifluralin and pendimethalin, Ashiflu Diphenyl ether herbicides such as cli and homesaphen; sulfonylurea herbicides such as benzulfuron-methyl and nicosulfuron; triazinon herbicides such as metrifudine and metamitrone; and triazines such as atrazine and cyanazine.
  • Herbicides such as flumellam, nitrile herbicides such as promoxinil and diclobenyl, pyridazinone herbicides such as chloridazone and norflurazon, and phosphoric acid herbicides such as glyphosate and glufosinate Quaternary ammonium salt herbicides such as paraquat and difunzoquat; cyclic imid herbicides such as flumicrolaccopentyl and fluthiacetomethyl; and others, such as isoxaben, ethofumeset, oxaxiazone, kink mouth lac, chromazon, and suzone.
  • the herbicidal effect was investigated according to the following criteria and expressed as a herbicidal index. Killing rate killing 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 (%) X100 Above-ground fresh grass weight in untreated area
  • Test example 1 Upland foliage spraying test
  • Test example 2 Paddy foliage treatment test
  • a pot with a surface area of 100 cm 2 was filled with paddy soil, and after replacement, seeds of Nobie, Hoyu Rui, Konagi and Omodaka were sown, and the rice plants at the two leaf stage were transplanted. This was grown in a greenhouse, and when the weeds reached the 1- to 1.5-leaf stage, they were flooded at a depth of 3 cm. Was dripped so that the active ingredient became 63 g / ha. Three weeks after the treatment, the herbicidal effect and the degree of phytotoxicity of rice were investigated. The results are shown in Table 23.
  • composition containing the compound of the present invention is useful as a herbicide.

Abstract

L'invention concerne un composé de formule générale (I), dans laquelle R1 représente un atome d'halogène, un groupe alkyle en C¿1-6?, un groupe alcoxy en C1-6 ou un groupe similaire; R?2¿ représente un atome d'halogène, un groupe alkylsulfonyle en C¿1-6? ou un groupe similaire; n est 0, 1 ou similaire; Het représente un groupe hétérocyclique à cinq éléments, saturé ou insaturé et substitué par R?7 et R8¿, chacun contenant de un à quatre atomes N, O ou S liés par des atomes de carbone; R3 représente un atome d'hydrogène ou un atome similaire; R4 représente un atome d'hydrogène, un groupe alkyle en C¿1-6? ou un groupe similaire; R?5¿ représente un groupe alkyle en C¿1-6? ou un groupe similaire; R?6¿ représente un groupe phényle facultativement substitué; et X représente SO¿2?, CH2CO ou un groupe méthylène. Les composés décrits ci-dessus présentant une excellente activité herbicide, une composition contenant lesdits composés est utile en tant qu'herbicide.
PCT/JP1997/003736 1996-11-13 1997-10-16 Nouveaux derives de benzene a substitution heterocyclique, et herbicide WO1998021187A1 (fr)

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JP8/317154 1996-11-13
JP31715496 1996-11-13
JP8/356866 1996-12-26
JP35686696 1996-12-26

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000034247A2 (fr) * 1998-12-04 2000-06-15 Basf Aktiengesellschaft Procede de production de derives de pyrazolylbenzoyl et nouveaux derives de pyrazolylbenzoyl
WO2001046182A1 (fr) * 1999-12-22 2001-06-28 Basf Aktiengesellschaft 3-(4,5-dihydroisoxazol-5-yl)benzoylpyrazoles

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 (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000034247A2 (fr) * 1998-12-04 2000-06-15 Basf Aktiengesellschaft Procede de production de derives de pyrazolylbenzoyl et nouveaux derives de pyrazolylbenzoyl
WO2000034247A3 (fr) * 1998-12-04 2000-11-23 Basf Ag Procede de production de derives de pyrazolylbenzoyl et nouveaux derives de pyrazolylbenzoyl
WO2001046182A1 (fr) * 1999-12-22 2001-06-28 Basf Aktiengesellschaft 3-(4,5-dihydroisoxazol-5-yl)benzoylpyrazoles
US7151075B2 (en) 1999-12-22 2006-12-19 Basf Aktiengesellschaft 3-(4,5-Dihydroisoxazole-5-yl)benzoylpyrazole

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