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WO1995025099A1 - Derives de 2-cyano-1,3-dione utiles en tant qu'herbicides - Google Patents

Derives de 2-cyano-1,3-dione utiles en tant qu'herbicides Download PDF

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Publication number
WO1995025099A1
WO1995025099A1 PCT/EP1995/000950 EP9500950W WO9525099A1 WO 1995025099 A1 WO1995025099 A1 WO 1995025099A1 EP 9500950 W EP9500950 W EP 9500950W WO 9525099 A1 WO9525099 A1 WO 9525099A1
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Prior art keywords
cyano
dione
cyclopropyl
formula
ring
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PCT/EP1995/000950
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English (en)
Inventor
Neil Geach
David William Hawkins
Christopher John Pearson
Philip Henry Gaunt Smith
Nicolas White
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Rhone-Poulenc Agriculture Ltd.
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Priority to AU18942/95A priority Critical patent/AU1894295A/en
Publication of WO1995025099A1 publication Critical patent/WO1995025099A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/60—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/64—Oxygen atoms

Definitions

  • TECHNICAL FIELD This invention relates to novel 2-cyano-l,3-dione derivatives, compositions containing them, processes for their preparation and their use as herbicides. BACKGROUND ART
  • European Patent Publication Nos. 0496630 and 0496631 disclose certain l-phenyl-2-cyano-l,3-dione derivatives possessing herbicidal properties.
  • European Patent Publication No 0213892 discloses herbicidally active enols. DESCRIPTION OF THE INVENTION
  • the present invention provides 2-cyano-l,3-dione derivatives of formula I:
  • Ar represents a monocyclic or fused bicyclic heterocyclic system Het having a heterocyclic first ring and an optional second heterocyclic or carbocyclic ring, the second ring when present being fused to the first ring, the first ring having from 1 to 4 hetero ring atoms and from 4 to 7 total ring atoms, the hetero ring atoms preferably being selected from oxygen, nitrogen and sulphur, the first ring being aromatic or non-aromatic and being optionally substituted by from 1 to 4 R ⁇ groups which may be the same or different, the second ring being optionally substituted by from 1 to 4
  • R2 groups which may be the same or different
  • R! represents a cycloalkyl group containing from three to six carbon atoms optionally substituted by one or more groups selected from R 4 , -CO2R 4 , -SR 4 , halogen and -OR 4 ;
  • R 4 represents a straight- or branched- chain alkyl group containing from one to six carbon atoms which is optionally substituted by one or more halogen atoms;
  • R5 represents:- a group R 4 or phenyl optionally substituted by from one to five groups selected from halogen, R 4 , -CO2R 4 , -COR 4 , -OR 4 , nitro, cyano and
  • R6 and R ⁇ which may be the same or different, each represent the hydrogen atom or a straight- or branched- chain alkyl group containing from one to six carbon atoms which is optionally substituted by one or more halogen atoms; m represents an integer from one to three;
  • R8 represents:- the hydrogen atom; a straight- or branched-chain alkyl, alkenyl or alkynyl group containing up to ten carbon atoms which is optionally substituted by one or more halogen atoms;
  • R9 and R ⁇ which may be the same or different, each represents: the hydrogen atom; a straight- or branched-chain alkyl group containing up to 6 carbon atoms which is optionally substituted by one or more halogen atoms; or phenyl optionally substituted by from one to five groups which may be the same or different selected from halogen, R 4 , -C0 2 R 4 , -COR 4 , -OR 4 , nitro, cyano and -0(CH 2 ) m -OR 4 ; p is zero, 1 or 2; t represents an integer from one to three;
  • R 11 represents -COR 4 or -C0 2 R 4 ;
  • Rl2 represents:- the hydrogen atom; a straight- or branched- chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms; or a cycloalkyl group containing from three to six carbon atoms; enolic tautomeric forms thereof, and agriculturally acceptable salts or metal complexes thereof, which possess valuable herbicidal properties.
  • R 5 , R 6 , R 7 » R 8 , R 9 , R!0, R11 and R 12 contribute to optical isomerism and/or stereoisomerism. All such forms are embraced by the present invention.
  • agriculturally acceptable salts salts the cations of which are known and accepted in the art for the formation of salts for agricultural or horticultural use.
  • the salts are water-soluble.
  • Suitable acid addition salts formed by compounds of formula I include salts with inorganic acids, for example hydrochlorides, sulphates, phosphates and nitrates and salts with organic acids, for example acetic acid.
  • metal complexes compounds in which one or both of the oxygen atoms of the 1,3-dione act as chelating agents to a metal cation.
  • examples of such cations include zinc, manganese, cupric, cuprous, ferric, ferrous, titanium and aluminium.
  • Het where the first heterocyclic and/or the second ring contains a sulphur atom in the ring, the sulphur atom may be in the form of a group -SO- or -SO2-.
  • R 2 represents cyclic ketal or cyclic thioketal preferably the ketal or thioketal ring contains 5 or 6 ring members.
  • the group Het include: thienyl, furyl, pyrrolyl and their benzo-fused analogues; oxazinyl, thiazinyl, pyrazinyl, pyrimidinyl, pyridazinyl and their benzo-fused analogues; thiazolyl, oxazolyl, imidazolyl and their benzo-fused analogues; pyrazolyl, isoxazolyl, isothiazolyl and their benzo-fused analogues; oxadiazolyl, thiadiazolyl, triazolyl and, where appropriate, their benzo-fused analogues; pyridinyl, pyranyl, thiinyl and their benzo-fused analogues; oxadiaziny
  • R* represents a cyclopropyl group optionally substituted by a group R 4 (especially where R 4 is alkyl). More preferably R represents 1-methylcyclopropyl or, most preferably, cyclopropyl.
  • Ar represents an optionally substituted fused bicyclic heterocyclic system having a heterocyclic first ring and a second carbocychc ring (e.g. a benzene ring) are preferred.
  • Compounds in which Ar represents optionally substituted 1,3-benzodioxole, benzo[b]thiophene, benzoxazolinone, benzoxazole or benzo[b]furan are particularly preferred.
  • Het is a fused bicyclic heterocyclic system either the heterocyclic first ring or the second ring may be attached to the carbonyl group of the 2-cyano-l,3-dione.
  • Ar represents optionally substituted pyridyl, pyrazolyl or thienyl are also preferred.
  • R 2 represents a halogen atom or a group selected from -SR 5 , -SOR 5 , -S0 R 5 , -CH S(0)pR 5 , -C0 2 R 4 and -OR 5 are also preferred.
  • R 5 represents a straight- or branched- chain alkyl group containing from one to six carbon atoms are also preferred, most preferably methyl.
  • Ar represents a group Het which is optionally substituted by from one to three groups R 2 .
  • Particularly important compounds of formula (I) because of their herbicidal activity include the following:
  • compounds of formula (I) may be prepared by the reaction of a compound of formula(II):
  • R and Ar are as hereinbefore defined and R represents the hydrogen atom or an ester, with a base.
  • R represents the hydrogen atom.
  • Preferred bases include alkali or alkaline earth metal hydroxides or alkoxides such as sodium ethoxide, or organic bases such as triethylamine. The reaction is generally performed at a temperature from room temperature to the reflux temperature of the mixture.
  • compounds of formula (I) may also be prepared by the reaction of an acid chloride of formula (HI):
  • the reaction is generally performed in the presence of a base in a solvent or solvent mixture.
  • bases include metal hydrides, hydroxides or alkoxides (e.g. sodium or Uthium hydride, sodium hydroxide, potassium hydroxide, magnesium ethoxide or magnesium methoxide), and organic bases such as triethylamine.
  • Suitable solvents include for example tetrahydrofuran; hydrocarbons such as toluene; or halogenated hydrocarbons such as dichloromethane.
  • the reaction is generally performed at a temperature from 0°C to reflux temperature.
  • compounds of formula (I) may also be prepared by the reaction of an acid chloride of formula (N):
  • the reaction is generally performed in the presence of a base in a solvent or solvent mixture.
  • bases include metal hydrides, hydroxides or alkoxides (e.g. sodium or lithium hydride, sodium hydroxide, potassium hydroxide, magnesium ethoxide or magnesium methoxide), and organic bases such as triethylamine.
  • Suitable solvents include for example tetrahydrofuran; hydrocarbons such as toluene; or halogenated hydrocarbons such as dichloromethane.
  • the reaction is generally performed at a temperature from 0°C to reflux temperature. Intermediates in the preparation of compounds of formula I may be prepared by the application or adaptation of known methods, for example as described hereinafter.
  • L is a leaving group and Ar and R are as hereinbefore defined, with a salt of hydroxylamine.
  • Hydroxylamine hydrochloride is generally preferred.
  • L is ethoxy or N,N-dimethylamino.
  • the reaction is generally carried out in a solvent such as ethanol or acetonitrile, optionally in the presence of a base or acid acceptor such as trie ⁇ ylamine or sodium acetate.
  • R is an ester and X is a halogen atom. Generally X is chlorine or bromine and P represents N,N-dialkylamino.
  • the reaction is generally performed in an inert solvent such as toluene or dichloromethane either in the presence of a base such as triethylamine or a catalyst such as a 4 Angstrom molecular sieve or fluoride ion.
  • reaction is generally performed in the presence of a Lewis acid catalyst such as aluminium trichloride, in an inert solvent at a temperature from 0°C to the reflux temperature of the mixture.
  • a Lewis acid catalyst such as aluminium trichloride
  • Intermediates of formula (VII) may be prepared by the reaction of the corresponding compound of formula (X) with either a trialkyl orthoformate such as triethyl orthoformate or a dimethylformamide dialkylacetal such as N,N-dimethylformamide dimethyl acetal.
  • a trialkyl orthoformate such as triethyl orthoformate or a dimethylformamide dialkylacetal such as N,N-dimethylformamide dimethyl acetal.
  • the reaction with triethyl orthoformate is generally carried out in the presence of acetic anhydride at the reflux temperature of the mixture and the reaction with N,N-dimethyl formamide dialkyl acetal is carried out optionally in the presence of an inert solvent at a temperature from room temperature to the reflux temperature of the mixture.
  • the reaction is generally carried out in the presence of an organic base such as triethylamine in an inert solvent such as toluene or dichloromethane at a temperature between -20°C and room temperature.
  • RiOCH (XIII) wherein Rl is as hereinbefore defined, followed by reaction of the metal salt thus obtained with an acid chloride of formula (III) as hereinbefore defined.
  • the metallation is generally performed using n-butyl lithium in an inert solvent such as ether or tetrahydrofuran at a temperature from -78°C to 0°C.
  • the subsequent reaction with the acid chloride is carried out in the same solvent at a temperature between -78°C and room temperature.
  • compounds in which R 2 represents -SOR 5 or -S0 R 5 may be prepared by the oxidation of the sulphur atom of the corresponding compound in which R 2 represents -SR 5 or -SOR 5 .
  • compounds of formula (I) in which a ring member of the group Het is -SO- or -S0 2 - may be prepared by the oxidation of the ring sulphur atom of the corresponding compound of formula (I).
  • the oxidation of the sulphur atom is generally carried out using for example 3-chloroperoxy-benzoic acid in an inert solvent such as dichloromethane at a temperature from -
  • Example 1 Sodium methoxide (0.049g) was added to a stirred suspension of 4-(4-chloro-3-methoxybenzo[b]thien-5-oyl)-5-cyclopropylisoxazole (0.2g) in methanol (5 ml) at room temperature. After 4 hours additional sodium methoxide (0.049g) was added and stirring maintained for 18 hours. The mixture was poured onto water, acidified (2N hydrochloric acid) and extracted (ether).
  • 2,2-Difluoro-l,3-benzodioxole-4-carboxylic acid (15.0g) was dissolved in 1,2-dichloroethane and N,N-dimethylformamide and thionyl chloride (10.6g) added. The mixture was heated under reflux for 1 hour and the solvent evaporated in vacuo. The residue was dissolved in toluene and re-evaporated to yield 2,2-difluoro-l,3- benzodioxole-4-carboxylic acid chloride (17.35g).
  • Methanethiol gas (7.9g) was bubbled into a stirred suspension of sodium hydride (60% dispersion in oil; 6.0g) in dry dimethyl formamide with an exotherm of approximately 20°C observed.
  • a solution of methyl 5-nitro-2-pyridinecarboxylate (23.8g) in dry dimethylformamide was added and the resulting suspension was stirred at 100°C for five hours then left to stand at room temperature overnight. The solvent was evaporated. Water was added cautiously to the residue and the resulting solution was neutralised by the addition of hydrochloric acid (2N) and extracted with ethyl acetate. The combined extracts were washed with water, dried (anhydrous sodium sulphate), filtered and evaporated.
  • Diethyl 2-(5-nitropyridin-2-yl)malonate (67.47g) was stirred in water and aqueous sodium hydroxide solution (2N) was added followed by potassium permanganate (42g) causing the reaction temperature to rise to 60°C. Further portions of aqueous sodium hydroxide solution and potassium permanganate were added maintaining the reaction temperature at 60-70°C. After the final addition, the suspension was stirred at 60°C for 1.5 hours. The hot suspension was then filtered through ⁇ yflo Supercel'. The filter cake was washed with aqueous sodium hydroxide solution (2N). On cooling to room temperature, the filtrate was carefully acidified to pH 1-2 with concentrated hydrochloric acid.
  • a purple solid (7.72g) was filtered and dried in a dessicator and shown to be 4-chloro-3- hydroxybenzo[b]thiophene-5-carboxylic acid, NMR (DMSO O ) 6.67 (1H, s), 7.54 (1H, d), 7.87 (1H, d), 10.3 (1H, s), 13.34 (1H, s) and 4.07 (2H, s), 7.63 (1H, d), 7.93 (1H, d), 13.34 (1H, s) (40% in the keto form).
  • a method for controlling the growth of weeds i.e. undesired vegetation
  • a method for controlling the growth of weeds which comprises applying to the locus a herbicidally effective amount of at least one 2-cyano-l,3-dione derivative of formula I or an enolic tautomeric form thereof, or an agriculturally acceptable salt or metal complex thereof.
  • the 2-cyano-l,3-dione derivatives are normally used in the form of herbicidal compositions (i.e. in association with compatible diluents or carriers and/or surface active agents suitable for use in herbicidal compositions), for example as hereinafter described.
  • the compounds of formula I show herbicidal activity against dicotyledonous (i.e. broad-leafed) and monocotyledonous (e.g. grass) weeds by pre- and/or, post-emergence application.
  • pre-emergence application is meant application to the soil in which the weed seeds or seedlings are present before emergence of the weeds above the surface of the soil.
  • post-emergence application is meant application to the aerial or exposed portions of the weeds which have emerged above the surface of the soil.
  • the compounds of formula I may be used to control the growth of
  • weeds for example, Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Galium aparine, Ipomoea spp. e.g. Ipomoea purpurea, Sesbania exaltata, Sinapis arvensis, Solanum nigrum and Xanthium strumarium, and
  • grass weeds for example Alopecurus myosuroides, Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Eleusine indica and Setaria spp, e.g. Setaria faberii or Setaria viridis, and
  • the amounts of compounds of formula I applied vary with the nature of the weeds, the compositions used, the time of application, the climatic and edaphic conditions and (when used to control the growth of weeds in crop-growing areas) the nature of the crops.
  • the compounds of formula I may be used to control selectively the growth of weeds, for example to control the growth of those species hereinbefore mentioned, by pre- or post-emergence application in a directional or non-directional fashion, e.g. by directional or non-directional spraying, to a locus of weed infestation which is an area used, or to be used, for growing crops, for example cereals, e.g. wheat, barley, oats, maize and rice, soya beans, field and dwarf beans, peas, lucerne, cotton, peanuts, flax, onions, carrots, cabbage, oilseed rape, sunflower, sugar beet, and permanent or sown grassland before or after sowing of the crop or before or after emergence of the crop.
  • cereals e.g. wheat, barley, oats, maize and rice, soya beans, field and dwarf beans, peas, lucerne, cotton, peanuts, flax, onions, carrots, cabbage, oilseed rape, sunflower,
  • the compounds of formula I may also be used to control the growth of weeds, especially those indicated above, by pre- or post-emergence application in established orchards and other tree-growing areas, for example forests, woods and parks, and plantations, e.g. sugar cane, oil palm and rubber plantations.
  • plantations e.g. sugar cane, oil palm and rubber plantations.
  • they may be applied in a directional or non- directional fashion (e.g. by directional or non-directional spraying) to the weeds or to the soil in which they are expected to appear, before or after planting of the trees or plantations at appUcation rates between 0.25 kg and 5 kg, and preferably between 0.5 kg and 4 kg of active material per hectare.
  • the compounds of formula I may also be used to control the growth of weeds, especially those indicated above, at loci which are not crop-growing areas but in which the control of weeds is nevertheless desirable.
  • non-crop-growing areas examples include airfields, industrial sites, railways, roadside verges, the verges of rivers, irrigation and other waterways, scrublands and faUow or uncultivated land, in particular where it is desired to control the growth of weeds in order to reduce fire risks.
  • the active compounds When used for such purposes in which a total herbicidal effect is frequently desired, the active compounds are normally applied at dosage rates higher than those used in crop-growing areas as hereinbefore described. The precise dosage will depend upon the nature of the vegetation treated and the effect sought.
  • the compounds of formula I When used to control the growth of weeds by pre-emergence application, the compounds of formula I may be incorporated into the soil in which the weeds are expected to emerge. It will be appreciated that when the compounds of formula I are used to control the growth of weeds by post-emergence appUcation, i.e. by application to the aerial or exposed portions of emerged weeds, the compounds of formula I wiU also normally come into contact with the soil and may also then exercise a pre-emergence control on later-germinating weeds in the soil.
  • compositions suitable for herbicidal use comprising one or more of the 2-cyano-l,3-dione derivatives of formula I or enolic tautomeric forms thereof, or agriculturaUy acceptable salts or metal complexes thereof in association with, and preferably homogeneously dispersed in, one or more compatible herbicidaUy- acceptable diluents or carriers and/or surface active agents [i.e. diluents or carriers and/or surface active agents of the type generally accepted in the art as being suitable for use in herbicidal compositions and which are compatible with compounds of formula I].
  • compositions in which the compounds of formula I are dissolved in other components.
  • herbicide compositions is used in a broad sense to include not only compositions which are ready for use as herbicides but also concentrates which must be diluted before use.
  • the compositions contain from 0.05 to 90% by weight of one or more compounds of formula I.
  • the herbicidal compositions may contain both a diluent or carrier and surface-active (e.g. wetting, dispersing, or emulsifying) agent.
  • Surface-active agents which may be present in herbicidal compositions of the present invention may be of the ionic or non-ionic types, for example sulphoricinoleates, quaternary ammonium derivatives, products based on condensates of ethylene oxide with alkyl and polyaryl phenols, e.g.
  • nonyl- or octyl-phenols or carboxylic acid esters of anhydrosorbitols which have been rendered soluble by etherification of the free hydroxy groups by condensation with ethylene oxide, alkali and alkaline earth metal salts of sulphuric acid esters and sulphonic acids such as dinonyl- and dioctyl-sodium sulphonosuccinates and alkali and alkaline earth metal salts of high molecular weight sulphonic acid derivatives such as sodium and calcium lignosulphonates and sodium and calcium alkylbenzene sulphonates.
  • the herbicidal compositions according to the present invention may comprise up to 10% by weight, e.g. from 0.05% to
  • herbicidal compositions according to the present invention may comprise higher proportions of surface-active agent, for example up to 15% by weight in Uquid emulsifiable suspension concentrates and up to 25% by weight in Uquid water soluble concentrates.
  • soUd diluents or carriers examples include aluminium silicate, talc, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, adsorbent carbon black and clays such as kaolin and bentonite.
  • the solid compositions (which may take the form of dusts, granules or wettable powders) are preferably prepared by grinding the compounds of formula I with solid diluents or by impregnating the solid diluents or carriers with solutions of the compounds of formula I in volatile solvents, evaporating the solvents and, if necessary, grinding the products so as to obtain powders.
  • Granular formulations may be prepared by absorbing the compounds of formula I (dissolved in suitable solvents, which may, if desired, be volatile) onto the solid diluents or carriers in granular form and, if desired, evaporating the solvents, or by granulating compositions in powder form obtained as described above.
  • Solid herbicidal compositions, particularly wettable powders and granules may contain wetting or dispersing agents (for example of the types described above), which may also, when solid, serve as diluents or carriers.
  • Liquid compositions according to the invention may take the form of aqueous, organic or aqueous-organic solutions, suspensions and emulsions which may incorporate a surface-active agent.
  • Suitable Uquid diluents for incorporation in the liquid compositions include water, glycols, tetrahydrofurfuryl alcohol, acetophenone, cyclohexanone, isophorone, toluene, xylene, mineral, animal and vegetable oils and Ught aromatic and naphthenic fractions of petroleum (and mixtures of these diluents).
  • Surface-active agents, which may be present in the Uquid compositions may be ionic or non-ionic (for example of the types described above) and may, when Uquid, also serve as diluents or carriers.
  • Powders, dispersible granules and liquid compositions in the form of concentrates may be dUuted with water or other suitable diluents, for example mineral or vegetable oils, particularly in the case of Uquid concentrates in which the diluent or carrier is an oil, to give compositions ready for use.
  • suitable diluents for example mineral or vegetable oils, particularly in the case of Uquid concentrates in which the diluent or carrier is an oil, to give compositions ready for use.
  • liquid compositions of the compound of formula I may be used in the form of self-emulsifying concentrates containing the active substances dissolved in the emulsifying agents or in solvents containing emulsifying agents compatible with the active substances, the simple addition of water to such concentrates producing compositions ready for use.
  • Liquid concentrates in which the diluent or carrier is an oil may be used without further dilution using the electrostatic spray technique.
  • Herbicidal compositions according to the present invention may also contain, if desired, conventional adjuvants such as adhesives, protective colloids, thickeners, penetrating agents, stabilisers, sequestering agents, anti-caking agents, colouring agents and corrosion inhibitors. These adjuvants may also serve as carriers or diluents. Unless otherwise specified, the following percentages are by weight. Preferred herbicidal compositions according to the present invention are
  • aqueous suspension concentrates which comprise from 10 to 70% of one or more compounds of formula I, from 2 to 10% of surface-active agent, from 0.1 to 5% of thickener and from 15 to 87.9% of water,
  • wettable powders which comprise from 10 to 90% of one or more compounds of formula I, from 2 to 10% of surface-active agent and from 8 to 88% of solid diluent or carrier,
  • liquid water soluble concentrates which comprise from 5 to 50%, e.g. 10 to 30%, of one or more compounds of formula I, from 5 to 25% of surface-active agent and from 25 to 90%, e.g. 45 to 85%, of water miscible solvent, e.g. dimethylformamide, or a mixture of water-miscible solvent and water,
  • Uquid emulsifiable suspension concentrates which comprise from 10 to 70% of one or more compounds of formula I, from 5 to 15% of surface-active agent, from 0.1 to 5% of thickener and from 10 to 84.9% of organic solvent
  • * granules which comprise from 1 to 90%, e.g. 2 to 10% of one or more compounds of formula I, from 0.5 to 7%, e.g. 0.5 to 2%, of surface-active agent and from 3 to 98.5%, e.g. 88 to 97.5%, of granular carrier and,
  • emulsifiable concentrates which comprise 0.05 to 90%, and preferably from 1 to 60% of one or more compounds of formula I, from 0.01 to 10%, and preferably from 1 to 10%, of surface-active agent and from 9.99 to 99.94%, and preferably from 39 to 98.99%, of organic solvent.
  • Herbicidal compositions according to the present invention may also comprise the compounds of formula I in association with, and preferably homogeneously dispersed in, one or more other pesticidally active compounds and, if desired, one or more compatible pesticidally acceptable diluents or carriers, surface-active agents and conventional adjuvants as hereinbefore described.
  • other pesticidally active compounds which may be included in, or used in conjunction with, the herbicidal compositions of the present invention include herbicides, for example to increase the range of weed species controlled for example alachlor
  • insecticides e.g. synthetic pyrethroids, e.g. permethrin and cypermethrin, and fungicides, e.g. carbamates, e.g. methyl N-(l-butyl-carbamoyl- benzimidazol-2-yl)carbamate, and triazoles e.g. l-(4-chloro-phenoxy)-3,3- dimethyl- l-(l,2,4-triazol-l-yl)-butan-2-one.
  • PesticidaUy active compounds and other biologically active materials which may be included in, or used in conjunction with, the herbicidal compositions of the present invention, for example those hereinbefore mentioned, and which are acids, may, if desired, be utilized in the form of conventional derivatives, for example alkali metal and amine salts and esters.
  • an article of manufacture comprising at least one of the
  • the containers will normally be of the types conventionally used for the storage of chemical substances which are solid at normal ambient temperatures and herbicidal compositions particularly in the form of concentrates, for example cans and drums of metal, which may be internally lacquered, and plastics materials, bottles or glass and plastics materials and, when the contents of the container is a solid, for example granular, herbicidal compositions, boxes, for example of cardboard, plastics materials and metal, or sacks.
  • the containers will normally be of sufficient capacity to contain amounts of the 2-cyano-l,3-dione derivative or herbicidal compositions sufficient to treat at least one acre of ground to control the growth of weeds therein but will not exceed a size which is convenient for conventional methods of handling.
  • the instructions will be physically associated with the container, for example by being printed directly thereon or on a label or tag affixed thereto.
  • the directions wiU normally indicate that the contents of the container, after dilution if necessary, are to be applied to control the growth of weeds at rates of application between 0.01 kg and 20 kg of active material per hectare in the manner and for the purposes hereinbefore described.
  • a soluble concentrate is formed from : Active ingredient (compound 1) 20% w/v
  • a wettable powder is formed from :
  • Active ingredient 50% w/w
  • An aqueous suspension concentrate is formed from: * active ingredient (compound 1): 50% w/v
  • SimUar aqueous concentrates may be prepared as described above by replacing the 2-cyano-l,3-dione (compound 1) by other compounds of formula (I).
  • the seeds were sown in 70 mm square, 75 mm deep plastic pots in non-sterile soU .
  • the quantities of seed per pot were as follows:- W Weeeedd s sppeecciieess A Apppprrooxx number of seeds/pot
  • the compounds used to treat the plants were appUed to the plants as described in (a).
  • a single pot of each crop and weed species was aUocated to each treatment, with unsprayed controls and controls sprayed with acetone alone.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

L'invention se rapporte à des dérivés de 2-cyano-1,3-dione de la formule (I) dans laquelle R1 et Ar sont tels que définis dans la description, ainsi qu'à l'utilisation de ces dérivés en tant qu'herbicides.
PCT/EP1995/000950 1994-03-17 1995-03-14 Derives de 2-cyano-1,3-dione utiles en tant qu'herbicides WO1995025099A1 (fr)

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GB9405229A GB9405229D0 (en) 1994-03-17 1994-03-17 Compositions of matter
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996026193A1 (fr) * 1995-02-24 1996-08-29 Basf Aktiengesellschaft Derives de phenyldicetone
WO1997013765A1 (fr) * 1995-10-09 1997-04-17 Idemitsu Kosan Co., Ltd. Derives de 2-cyano-1,3-dione et herbicides dont ils constituent le principe actif
WO1997019071A1 (fr) * 1995-11-23 1997-05-29 Basf Aktiengesellschaft Derives de 2-cyano-1,3-dione, leur preparation et leur utilisation comme herbicides
WO1997023491A1 (fr) * 1995-12-22 1997-07-03 Rhone-Poulenc Agriculture Ltd. Mouveaux herbicides
US5849928A (en) * 1996-03-22 1998-12-15 Rhone-Poulenc Agriculture Limited Herbicidal isoxazole and 2-cyano-1,3-dione compounds
EP0918056A1 (fr) * 1997-11-20 1999-05-26 Rhone-Poulenc Agriculture Ltd. Herbicides
WO2000014087A1 (fr) * 1998-09-04 2000-03-16 Aventis Cropscience Gmbh Derives de benzoyl, leur procede de production et leur utilisation comme herbicides et regulateurs de croissance des plantes
EP1160244A1 (fr) * 1993-07-30 2001-12-05 Rhone-Poulenc Agriculture Limited Dérivés d'isoxazole et leur utilisation comme herbicides
WO2003106448A3 (fr) * 2002-06-14 2004-03-04 Syngenta Participations Ag Nouveaux herbicides
WO2005123726A1 (fr) * 2004-06-17 2005-12-29 Bayer Cropscience Gmbh Pyridinylisoxazole et leur utilisation en tant qu'herbicides
WO2006045504A1 (fr) * 2004-10-21 2006-05-04 Syngenta Participations Ag Procede de preparation de pyrazoles
WO2011012620A2 (fr) 2009-07-31 2011-02-03 Syngenta Participations Ag Traitements pour l'alkylation de pyrazoles
CN118812500A (zh) * 2024-07-12 2024-10-22 东北农业大学 一种具有除草活性的取代芳基二酮腈类化合物、制备方法及应用

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EP0213892A2 (fr) * 1985-08-27 1987-03-11 Rohm And Haas Company Enols à activité herbicide
EP0326107A1 (fr) * 1988-01-26 1989-08-02 Bristol-Myers Squibb Company Bêta-cycloalkyl-bêta-oxopropionitriles antiarthritiques
EP0326108A1 (fr) * 1988-01-26 1989-08-02 Bristol-Myers Company Isoxazole-4-carboxamides comme antiarthrithiques
EP0496630A1 (fr) * 1991-01-25 1992-07-29 Rhone-Poulenc Agriculture Ltd. Herbicides à base de 2-cyano-1,3-dione
EP0496631A1 (fr) * 1991-01-25 1992-07-29 Rhone-Poulenc Agriculture Ltd. Herbicides à base de 2-cyano-1,3-dione

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0213892A2 (fr) * 1985-08-27 1987-03-11 Rohm And Haas Company Enols à activité herbicide
EP0326107A1 (fr) * 1988-01-26 1989-08-02 Bristol-Myers Squibb Company Bêta-cycloalkyl-bêta-oxopropionitriles antiarthritiques
EP0326108A1 (fr) * 1988-01-26 1989-08-02 Bristol-Myers Company Isoxazole-4-carboxamides comme antiarthrithiques
EP0496630A1 (fr) * 1991-01-25 1992-07-29 Rhone-Poulenc Agriculture Ltd. Herbicides à base de 2-cyano-1,3-dione
EP0496631A1 (fr) * 1991-01-25 1992-07-29 Rhone-Poulenc Agriculture Ltd. Herbicides à base de 2-cyano-1,3-dione

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1160244A1 (fr) * 1993-07-30 2001-12-05 Rhone-Poulenc Agriculture Limited Dérivés d'isoxazole et leur utilisation comme herbicides
US5846906A (en) * 1995-02-24 1998-12-08 Basf Aktiengesellschaft Herbicidally active phenyldiketone compounds
WO1996026193A1 (fr) * 1995-02-24 1996-08-29 Basf Aktiengesellschaft Derives de phenyldicetone
WO1997013765A1 (fr) * 1995-10-09 1997-04-17 Idemitsu Kosan Co., Ltd. Derives de 2-cyano-1,3-dione et herbicides dont ils constituent le principe actif
WO1997019071A1 (fr) * 1995-11-23 1997-05-29 Basf Aktiengesellschaft Derives de 2-cyano-1,3-dione, leur preparation et leur utilisation comme herbicides
WO1997023491A1 (fr) * 1995-12-22 1997-07-03 Rhone-Poulenc Agriculture Ltd. Mouveaux herbicides
US5849928A (en) * 1996-03-22 1998-12-15 Rhone-Poulenc Agriculture Limited Herbicidal isoxazole and 2-cyano-1,3-dione compounds
US6013805A (en) * 1996-03-22 2000-01-11 Rhone-Poulenc Agriculture Ltd Pentafluorothio-substituted isoxazoles
US6140528A (en) * 1996-03-22 2000-10-31 Rhone-Poulenc Agriculture Ltd Intermediates to herbicidal isoxazole and 2-cyano-1,3-dione compounds
EP0918056A1 (fr) * 1997-11-20 1999-05-26 Rhone-Poulenc Agriculture Ltd. Herbicides
AU752786B2 (en) * 1998-09-04 2002-10-03 Bayer Cropscience Ag Benzoyl derivatives, method for producing them and their use as herbicides and plant growth regulators
US6297196B1 (en) 1998-09-04 2001-10-02 Hoechst Schering Agrevo Gmbh Benzoyl derivatives, process for their preparation and their use as herbicides and plant growth regulators
WO2000014087A1 (fr) * 1998-09-04 2000-03-16 Aventis Cropscience Gmbh Derives de benzoyl, leur procede de production et leur utilisation comme herbicides et regulateurs de croissance des plantes
WO2003106448A3 (fr) * 2002-06-14 2004-03-04 Syngenta Participations Ag Nouveaux herbicides
WO2005123726A1 (fr) * 2004-06-17 2005-12-29 Bayer Cropscience Gmbh Pyridinylisoxazole et leur utilisation en tant qu'herbicides
US7678924B2 (en) 2004-10-21 2010-03-16 Syngenta Crop Protection, Inc. Process for the preparation of pyrazoles
EA010851B1 (ru) * 2004-10-21 2008-12-30 Зингента Партисипейшнс Аг Способ получения пиразолов
WO2006045504A1 (fr) * 2004-10-21 2006-05-04 Syngenta Participations Ag Procede de preparation de pyrazoles
WO2011012620A2 (fr) 2009-07-31 2011-02-03 Syngenta Participations Ag Traitements pour l'alkylation de pyrazoles
WO2011012620A3 (fr) * 2009-07-31 2011-06-09 Syngenta Participations Ag Traitements pour l'alkylation de pyrazoles
CN102471279A (zh) * 2009-07-31 2012-05-23 先正达参股股份有限公司 吡唑的烷基化方法
JP2013500945A (ja) * 2009-07-31 2013-01-10 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト ピラゾールのアルキル化のためのプロセス
US8563747B2 (en) 2009-07-31 2013-10-22 Syngenta Crop Protection, Llc Processes for the alkylation of pyrazoles
CN118812500A (zh) * 2024-07-12 2024-10-22 东北农业大学 一种具有除草活性的取代芳基二酮腈类化合物、制备方法及应用

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GB9405229D0 (en) 1994-04-27
AU1894295A (en) 1995-10-03

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