EP1044191A2 - Pyrazolones de benzylidene, leur preparation et leur utilisation - Google Patents

Pyrazolones de benzylidene, leur preparation et leur utilisation

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Publication number
EP1044191A2
EP1044191A2 EP98961147A EP98961147A EP1044191A2 EP 1044191 A2 EP1044191 A2 EP 1044191A2 EP 98961147 A EP98961147 A EP 98961147A EP 98961147 A EP98961147 A EP 98961147A EP 1044191 A2 EP1044191 A2 EP 1044191A2
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EP
European Patent Office
Prior art keywords
alkyl
halogen
alkoxy
hydrogen
haloalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP98961147A
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German (de)
English (en)
Inventor
Joachim Rheinheimer
Matthias Witschel
Stefan Engel
Ernst Baumann
Wolfgang Von Deyn
Regina Luise Hill
Guido Mayer
Ulf Misslitz
Oliver Wagner
Martina Otten
Karl-Otto Westphalen
Helmut Walter
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BASF SE
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BASF SE
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Publication date
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Publication of EP1044191A2 publication Critical patent/EP1044191A2/fr
Withdrawn legal-status Critical Current

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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
    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • 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
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—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
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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
    • C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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 with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
    • 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
    • C07D231/14—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 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
    • C07D231/16—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
    • C07D231/14—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 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
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/32—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole 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
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole 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
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings

Definitions

  • the present invention relates to benzylidene pyrazolones of the formula I
  • R 2 if necessary subst. Ci-Cg-alkyl, optionally subst. -CC 6 alkoxy, halogen, nitro, cyano;
  • R 3 is hydrogen, halogen, nitro, cyano, a group NR 5 R 6 , OCOR 5 , NR 5 COR 6 , C0 2 R 5 , -COSR 5 , -CONR 5 R 6 , C ⁇ -C -alkoxyiminoalkyl, C ⁇ -C 6 -Alkylcarbonyl, optionally subst. -C 6 alkyl, optionally subst. Ci-C ⁇ alkoxy, optionally subst. Ci-C ⁇ -alkylthio, optionally subst. C -Cg alkenyl, optionally subst. C 2 -C 6 alkynyl, optionally subst. Phenyl, optionally subst. Phenoxy, a possibly subst. 5- or 6-membered saturated or unsaturated heterocycle which contains up to 4 Stick ⁇ atoms may contain up to 2 oxygen or sulfur atoms as ring members and / or;
  • R 3 ' R 4 is an optionally substituted saturated or unsaturated 2- or 3-membered bridge which may contain a sulfur atom which may have been oxidized to the sulfoxide or sulfone;
  • R 5 is hydrogen or, if necessary, subst. -C 6 "alkyl; R 6 if necessary subst. -C 6 alkyl;
  • R 7 water tof f, -C -C 6 alkyl or C ⁇ -C 4 haloalkyl
  • n 0, 1 or 2;
  • X is hydrogen, chlorine or bromine
  • the invention also relates to compositions which contain the compounds of the formula I, to the use of the compounds I and compositions containing them for combating harmful plants, to new benzoylpyrazoles of the formula II and to a process for the preparation of the compounds I and II.
  • Herbicidally active 4-benzoyl-pyrazoles are known from the literature, for example from EP-A 282 944 or WO 96/26206.
  • EP-A 282 944 only mentions generally that the reaction of 4-benzoyl -5-hydroxypyrazoles with acid halides should lead to 4-benzoyl -5-chloropyrazoles.
  • Benzylidenpyrazolone with z. T. herbicidal activity are known from US 4,382,948 and JP 61268670. All previous structures have a very specific substitution pattern in the phenyl part of benzylidene pyrazolone: for example, there is always a hydrogen or halogen atom or a trifluoromethyl or nitro group in the para position to the methine bridge.
  • the present invention also relates to stereoisomers of the compounds of the formula I. Both pure stereoisomers and mixtures thereof are covered.
  • the compounds of the formula I can exist as eis or trans isomers and, depending on the substitution pattern, can contain one or more chirality centers and can then also exist as enantiomers or mixtures of diastereomers.
  • the invention relates both to the pure isomers, enantiomers or diastereomers and to mixtures thereof.
  • benzylidene pyrazolones of the formula I and benzoylpyrazoles of the formula II can be prepared as described below.
  • Benzylidene pyrazolones of the formula Ia hydrogen
  • X hydrogen
  • Benzylidene pyrazolones of the formula Ia can be obtained by Knoevenagel condensation of pyrazolones of the formula III, in which the radicals R 1 and R 7 have the abovementioned meaning, and a substituted benzaldehyde of the formula IV, in which the radicals R 2 to R 4 have the abovementioned meaning, can be synthesized analogously to the method described in US 4,382,948.
  • the benzylidene pyrazolones Ib can preferably be obtained from ketones of the formula V, which are either known or can be prepared analogously to known compounds (see DE-A 19709118.0 and WO 96/26200), by reaction with acid halides.
  • Suitable acid halides are the halides of sulfuric acid, carbonic acid and phosphoric acid.
  • phosphorus oxybromide is preferably used.
  • the reaction can be carried out in the customary manner, either without or with a solvent which is inert under the reaction conditions.
  • the selectivity of the reaction can generally be controlled by adding a base which is not very nucloephilic, for example pyridine, dirnethylaminopyridine or dimethylformamide.
  • the reaction temperature is usually 0 ° C to 200 ° C, preferably 50 ° C to 140 ° C.
  • both isomers can be obtained on the newly formed double bond in the mixture.
  • the isomers can be separated if necessary (e.g. by crystallization, extraction or chromatography).
  • a by-product of this reaction are the compounds II, which, depending on the substitution pattern and reaction procedure, can be obtained in smaller, comparable or predominant proportions. In many cases, these compounds are new and of considerable interest as precursors for herbicidal active compounds (see, for example, EP-A 282 944).
  • -C-C 4 alkyl and the alkyl parts of other radicals such as.
  • -C 6 alkyl and the alkyl parts of other radicals such as. B. -C 6 alkoxy, -C 6 alkylcarbonyl, -C 6 alkylthi ⁇ : -C alkyl as mentioned above, and pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2nd -Dimethylpropyl, 1-Ethylpro- yl, Hexyl, 1, 1-Dirnethylpropyl, 1, 2 -Dimethylpropyl, 1-Methyl-pentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1, 1-Dirnethylbutyl, 1, 2 -Dirnethylbutyl, 1, 3 -Dimethylbutyl, 2,2-Dimethylbutyl, 2, 3 -Dimethylbutyl, 3, 3 -Dimethylbutyl, 1-Ethylbut
  • haloalkyl a C 1 -C 4 -alkyl radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, that is, for. B. chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl,
  • -C-C haloalkoxy a C ⁇ -C alkoxy radical as mentioned above, which is partially or completely by fluorine, chlorine,
  • Bromine and / or iodine is substituted, ie z.
  • C 2 -C 6 alkenyl ethenyl, prop-1-en-1-yl, prop-2 -en-l-yl, 1-methylethenyl, buten-1-yl, buten-2 -yl, butene-3 - yl, 1-methyl-prop-1-en-1-yl, 2-methyl-prop-1-en-1-yl, 1-methyl-prop-2-en-1-yl, 2-methyl-prop- 2 -en- 1-yl, penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methyl-but-1-en-1-yl, 2-methyl- but-1-en-1-yl, 3-methyl-but-1-en-l-yl, 1-methyl-but-2 -en-1-yl, 2-methyl-but-2-en-l- yl, 3-methyl-but-2-en-1-yl, 1-methyl-but-2 -en-1-yl, 2-methyl-but-2-en-l- yl, 3-methyl-
  • C 2 -C 6 alkynyl ethynyl, prop-1-in-1-yl, prop-2-in-1-yl, but-1-in-1-yl, but-1-in-3 -yl, But-1-in-4-yl, but-2-in-1-yl, pent-1-in-1-yl, pent-1-in-3-yl, pent-1-in-4-yl, Pent-l-in-5-yl, pent-2-in-l-yl, pent-2-in-4-yl,
  • Pent-2-in-5-yl 3-methyl-but-l-in-3-yl, 3-methyl-but-l-in-4-yl, hex-1-in-l-yl, hex l-in-3-yl, hex-l-in-4-yl, Hex-1-in-5-yl, hex-1-in-6-yl, hex-2-in-1-yl, hex-2-in-4-yl, hex-2-in-5-yl, Hex-2-in-6-yl, hex-3-in-l-yl, hex-3-in-2-yl, 3-methyl-pent-l-in-l-yl, 3-methyl-pent- l-in-3-yl, 3-methyl-pent-l-in-4-yl, 3-methyl-pent-l-in-5-yl, 4-methyl-pent-1-in-l-yl, 4-methyl-pent-2-yn-4-yl and 4-methyl-pent-2-yn-5
  • C 3 -C 6 cycloalkyl cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
  • an optionally substituted 5- or 6-membered sown ⁇ -saturated or unsaturated heterocycle which contains up to 4 Stick - atoms and / or up can contain 2 oxygen or sulfur atoms as ring members, such as 2 tetrahydrofuranyl, 3 tetrahydrofuranyl, 2 -Tetrahydrothienyl , 3-tetrahydrotienyl, 2 -pyrrolidinyl, 3 -pyrrolidinyl, 3 -isoxazolidinyl, 4 -isoxazolidinyl, 5 -isoxazolidinyl, 3 -isothiazolidinyl, 4 -isothiazolidinyl, 5 -isothiazolidinyl, 3 - pyrazolidinyl, 4 -pyrazolidinyl, 5 -pyrazolidinyl , 2-oxazolidinyl, 4-0xazolidinyl, 5 -oxazolidin
  • R 1 C ! -C 4 alkyl or C ⁇ -C haloalkyl
  • R 2 C ! -C -alkyl, -C-C 4 -haloalkyl, C ⁇ -C -alkoxy, -C-C -haloalkoxy, halogen, nitro, cyano;
  • R 3 is hydrogen, halogen, nitro, cyano, a group NR 5 R 6 , OCOR 5 , NR 5 COR 6 , C0 2 R 5 , -COSR 5 , -CONR 5 R 6 , C ⁇ -C -alkoxyiminoalkyl, C ⁇ -C - Alkylcarbonyl, optionally substituted by halogen, -CC alkoxy or phenyl -CC alkyl, where the phenyl ring can in turn be substituted by halogen, -C ⁇ alkyl or -C -alkoxy, optionally by halogen, C ⁇ -C alkoxy or phenyl substituted C ⁇ -C alkoxy, where the phenyl ring in turn can be substituted by halogen, C ⁇ -C alkyl or C ⁇ -C alkoxy, optionally substituted by halogen, C ⁇ -C alkoxy or phenyl substituted C ⁇ - C alkyl thio,
  • C 1 -C 4 -alkyl or C 1 -C 2 -alkoxy may be substituted, if appropriate ⁇ optionally substituted by C oder-C-alkyl or halogen-substituted C -Cg-alkenyl or C 2 -C 6 -alkynyl, optionally by C ⁇ -C 4 - Alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 4 -haloalkoxy, halogen, phenyl, cyano, alkoxycarbonyl or nitro substituted phenyl or phenoxy, an optionally substituted by C 1 -C 4 -alkyl, C ⁇ -C - Alkoxy, -C-C -haloalkyl, -C-C -haloalkoxy, halogen, phenyl, cyano or nitro substituted 5- or 6-membered saturated or unsaturated heterocycle, which
  • 1,3,4-triazolyl pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1, 3, 5 -triazinyl, 1, 2, 4 -triazinyl, 1, 2, 4, 5-tetrazinyl;
  • R 3 'R 4 is an optionally substituted saturated or ungesquestioned ⁇ preferential 2- or 3-membered bridge which can ent ⁇ hold a sulfur atom which may be oxidized to the sulfoxide or sulfone;
  • R 5 is hydrogen, -CC alkyl, which is unsubstituted or by halogen, -CC 4 alkoxy or phenyl, the phenyl ring being one to five substituents selected from the group: halogen, -C-alkyl or -C-alkoxy can wear, is substituted;
  • R 6 C ⁇ -C 4 alkyl, which is unsubstituted or substituted by halogen, C ⁇ -C 4 - alkoxy, or phenyl, where the phenyl ring tuenten to five Substi ⁇ selected from the group: halogen, C ⁇ ⁇ C alkyl, or C ⁇ -C - Can carry alkoxy, is substituted;
  • R 7 is hydrogen, -CC alkyl or C ⁇ -C haloalkyl
  • n 0.1 or 2;
  • X is hydrogen, chlorine or bromine
  • R 1 is methyl, ethyl
  • R 2 chlorine, methyl, methoxy
  • R 3 is hydrogen, methyl, benzyl, allyl, propin-3-yl, methoxy, ethoxy, 2-methoxyethoxy, methylthio, methylcarbonyl, methoxycarbonyl, dimethylaminocarbonyl, cyano, optionally substituted in the phenyl part by fluorine, chlorine, methyl or methoxy ; preferably optionally by fluorine, chlorine, methyl or methoxy subst.
  • R 4 is methyl
  • R 7 is hydrogen
  • R 2 C ⁇ -C 4 alkyl, -C-C -haloalkyl, C ⁇ -C -alkoxy, C ⁇ ⁇ C 4 -halogenal - koxy, halogen;
  • R 3 is a 5- or 6-membered saturated or unsaturated heterocycle which is unsubstituted or substituted by C 1 -C 6 alkyl, C 1 -C alkoxy, C 1 -C 4 haloalkyl, C 1 -C 6 haloalkoxy or halogen and is selected from the group: Tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl, isothiazolidinyl, pyrazolidinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, 1,2, 4-oxadiazolidinyl, 1,2,4-thiadiazolidinyl, 1, 2, 4-triazolidinyl, 1, 3, 4 -oxadiazolid 1,3, 4-thiadiazolidinyl, 1, 3, 4 -triazolidinyl, 2, 3 -dihydrofuranyl, 2, 5 -dihydrofuranyl
  • R 7 is hydrogen, C ⁇ -C alkyl or -CC haloalkyl
  • n 0, 1, 2;
  • d 1.28 (t); 3.27 (s) 3.46 (t); 3.72 (g), 4.62 (t); 7.64 (d); 7.73 (s); 8.16 (d).
  • the isomeric benzoylpyrazole was isolated in the chromatographic purification of the reaction mixture:
  • the compounds 1 and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides.
  • the herbicidal compositions containing 1 control plant growth on non-cultivated areas very well, especially when high amounts are applied. In crops such as wheat, rice, maize, soya and cotton, they act against weeds and weed grasses ⁇ , significantly without damaging the crops. This effect occurs especially at low application rates.
  • the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants.
  • the following crops are considered, for example:
  • the compounds 1 can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • the herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are, if possible not be hit while the active ingredients get on the leaves of growing unwanted plants or the uncovered floor area (post-directed, Iay-by).
  • the compounds 1 or the herbicidal compositions comprising them can be sprayed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprinkles or granules , Misting, dusting, scattering or
  • pouring can be applied.
  • the application forms depend on the purposes; in any case, they should guarantee the finest possible distribution of the active compounds according to the invention.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Example, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, Pr 'Opanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, eg. B. amines such as N-methylpyrrolidone or water.
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • emulsions, pastes or oil dispersions the benzylidene pyrazolones as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • the surface-active substances are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa- , Hepta- and octadecanols as well as fatty alcohol glycol ether, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene-octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenylphenol, glycol, , Alkyla
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules for example coated, impregnated and homogeneous granules, can be prepared by binding the active ingredients to solid carriers Herge ⁇ represents be.
  • Solid carriers are mineral soils such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium ⁇ nitrate, ureas and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range.
  • the formulations generally contain 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • the compounds I according to the invention can be formulated, for example, as follows:
  • Dissolved mixture which consists of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction from the boiling point 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.
  • the benzylidene pyrazolones can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups and applied together.
  • benzoic acid and its derivatives benzothiadiazinones, 2-aroyl-l, 3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinecarboxylic acid and their derivatives, chloroacetanilides, cyclohexan-1, 3- dione derivatives, diazines, dichloropropionic acid and their derivatives,
  • the application rates of active ingredient are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a.S.) depending on the control target, season, target plants and growth stage.
  • the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles.
  • the tubes were lightly sprinkled to promote germination and growth, and then covered with clear plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.
  • test plants were first grown to a height of 3 to 15 cm, depending on the growth habit, and then treated with the active ingredients suspended or emulsified in water.
  • the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
  • the application rate for post-emergence treatment was 0.125 and 0.0625 kg / ha a.S.
  • the plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species.
  • the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated.
  • Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
  • the comparative test listed in Table A shows the improved herbicidal activity of the compound 1,119 according to the invention compared to the compound A known from JP-A 61268670 (CA, 106: 209479).

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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)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
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Abstract

L'invention concerne des pyrazolones de benzylidène de la formule (I) dans laquelle les substituants et l'indice n ont la signification suivante: R1 désigne alkyle C¿1?-C6 éventuellement substitué; R?2¿ désigne alkyle C¿1?-C6 éventuellement substitué, alcoxy C1-C6 éventuellement substitué, halogène, nitro, cyano; R?3¿ désigne hydrogène, halogène, nitro, cyano, un groupe NR?5R6, OCOR5, NR5COR6, CO¿2R?5, -COSR5, -CONR5R6¿, alcoxyiminoalkyle C¿1?-C4, alkylecarbonyle C1-C6, alkyle C1-C6 éventuellement substitué, alcoxy C1-C6 éventuellement substitué, alkylthio C1-C6 éventuellement substitué, alkényle C2-C6 éventuellement substitué, alkinyle C2-C6 éventuellement substitué, phényle éventuellement substitué, phénoxy éventuellement substitué, un hétérocycle saturé ou insaturé à 5 ou 6 chaînons éventuellement substitué, pouvant contenir jusqu'à 4 atomes d'azote et/ou jusqu'à 2 atomes d'oxygène ou de soufre comme chaînons cycliques; R?4¿ désigne alkyle C¿1?-C6, halogénure d'alkyle C1-C4; ou R?3, R4¿ désignent un pont à 2 ou 3 éléments, saturé ou insaturé, éventuellement substitué, qui peut contenir un atome de soufre pouvant lui-même être oxydé pour former du sulfoxyde ou du sulfone; R5 désigne hydrogène ou alkyle C¿1?-C6 éventuellement substitué; R?6¿ désigne alkyle C¿1?-C6 éventuellement substitué; R?7¿ désigne hydrogène, alkyle C¿1?-C6 ou halogénure d'alkyle C1-C4; n vaut 0, 1 ou 2; X désigne hydrogène, chlore ou brome. Les composés obtenus selon l'invention sont présents aussi bien sous la forme trans que sous la forme cis ou bien peuvent être un mélange de ces isomères.
EP98961147A 1997-11-21 1998-11-06 Pyrazolones de benzylidene, leur preparation et leur utilisation Withdrawn EP1044191A2 (fr)

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DE19751722 1997-11-21
DE19751722 1997-11-21
PCT/EP1998/007099 WO1999026930A2 (fr) 1997-11-21 1998-11-06 Pyrazolones de benzylidene, leur preparation et leur utilisation

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CN (1) CN1283191A (fr)
AR (1) AR013776A1 (fr)
AU (1) AU757752C (fr)
BG (1) BG104471A (fr)
BR (1) BR9814232A (fr)
CA (1) CA2310087A1 (fr)
EA (1) EA200000560A1 (fr)
HU (1) HUP0100011A3 (fr)
IL (1) IL136111A0 (fr)
NZ (1) NZ505142A (fr)
PL (1) PL341679A1 (fr)
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DK1158857T3 (da) * 1999-03-05 2003-06-23 Basf Ag Herbicid blanding, indeholdende et 3-heterocyclyl-substitueret benzoylderivat og et tilsætningsstof
EP1286991B1 (fr) * 1999-12-02 2007-06-06 Basf Aktiengesellschaft Benzoylpyrazoles substitues en 3-(4,5-dihydroisoxazol-3-yle) et a anellation cyclopropyle
AU2359701A (en) * 1999-12-02 2001-06-12 Basf Aktiengesellschaft 3-(4,5-dihydroisoxazol-3-yl)-substituted benzoylpyrazoles
US6465395B2 (en) 2000-03-01 2002-10-15 Basf Aktiengesellschaft Substituted methylene pyrazolinones and the herbicidal use thereof
WO2006106954A1 (fr) * 2005-03-31 2006-10-12 Ishihara Sangyo Kaisha, Ltd. Composés de benzoylpyrazole, procédés servant à produire ceux-ci et herbicide contenant ceux-ci
US20100331315A1 (en) * 2009-06-18 2010-12-30 Mustapha Haddach Rhodanines and related heterocycles as kinase inhibitors
CN102408428B (zh) * 2011-07-26 2014-01-15 中国农业大学 1，2-氮杂环辛烷并吡唑烷酮类化合物及其制备方法与应用
JP2017075161A (ja) * 2015-11-26 2017-04-20 住友化学株式会社 有害生物防除組成物およびその用途
WO2017150209A1 (fr) * 2016-02-29 2017-09-08 住友化学株式会社 Composé hétérocyclique

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JPS5955872A (ja) * 1982-09-22 1984-03-31 Otsuka Chem Co Ltd ４，４−（α−メチルベンジリデン）−２−ピラゾ−ル−５−オン誘導体
JPS61268670A (ja) * 1985-05-22 1986-11-28 Hodogaya Chem Co Ltd ピラゾ−ル系化合物およびこれを含有する除草剤
IL85659A (en) 1987-03-17 1992-03-29 Nissan Chemical Ind Ltd 4-benzoylpyrazole derivatives,method for their preparation and herbicidal compositions containing them
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GB2224208A (en) * 1988-10-20 1990-05-02 Shell Int Research Fungicidal pyrazolyl aryl ketones
JPH0429129A (ja) * 1990-05-24 1992-01-31 Konica Corp ハロゲン化銀写真感光材料
JPH04253039A (ja) * 1991-01-30 1992-09-08 Toshiba Corp 有機非線形光学材料
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HUP0100011A3 (en) 2003-03-28
SK6952000A3 (en) 2001-02-12
HUP0100011A2 (hu) 2001-05-28
WO1999026930A3 (fr) 1999-08-19
US6271179B1 (en) 2001-08-07
JP2001524471A (ja) 2001-12-04
AU757752C (en) 2003-09-11
CA2310087A1 (fr) 1999-06-03
AU1667099A (en) 1999-06-15
EA200000560A1 (ru) 2000-12-25
AU757752B2 (en) 2003-03-06
US6500950B1 (en) 2002-12-31
BG104471A (en) 2001-08-31
BR9814232A (pt) 2000-10-03
CN1283191A (zh) 2001-02-07
NZ505142A (en) 2003-03-28
PL341679A1 (en) 2001-04-23
IL136111A0 (en) 2001-05-20
ZA9810625B (en) 2000-05-22
KR20010032321A (ko) 2001-04-16
AR013776A1 (es) 2001-01-10
WO1999026930A2 (fr) 1999-06-03

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