WO2002048140A1 - 5-'(pyrazol-4-yl)carbonyl!benzazolone als herbizide - Google Patents
5-'(pyrazol-4-yl)carbonyl!benzazolone als herbizide Download PDFInfo
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- WO2002048140A1 WO2002048140A1 PCT/EP2001/014476 EP0114476W WO0248140A1 WO 2002048140 A1 WO2002048140 A1 WO 2002048140A1 EP 0114476 W EP0114476 W EP 0114476W WO 0248140 A1 WO0248140 A1 WO 0248140A1
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- 0 CC(C1C(C)=*)NNC1=O Chemical compound CC(C1C(C)=*)NNC1=O 0.000 description 9
Classifications
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- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles 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
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- 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
- C07D417/14—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 three or more hetero rings
Definitions
- the present invention relates to 5- [(pyrazol-4-yl) carbonyl] benzazolones (hereinafter benzazolones), agents which contain such compounds and the use of the benzazolones or agents which contain them for combating harmful plants.
- benzazolones 5- [(pyrazol-4-yl) carbonyl] benzazolones
- WO 96/05197 discloses saccharin derivatives with herbicidal activity which are substituted on the benzene nucleus of the saccharin skeleton with a (5-hydroxypyrazol-4-yl) carbonyl radical.
- WO 97/30993 and WO 97/09327 describe dioxothiochroman derivatives and dihydrobenzothiophene derivatives with herbicidal activity which likewise have a (5-hydroxypyrazol-4-yl) carbonyl radical on the benzene nucleus of the sulfur heterocycles.
- benzene-condensed derivatives of ⁇ -butyrolactam with herbicidal activity are known, which likewise have a (5-hydroxypyrazol-4-yl) carbonyl radical.
- JP 10130627 describes u. a. Herbicides based on pyrazole derivatives of the general formula (a),
- R preferably represents hydrogen or methyl
- Q are hydrogen wherein R 1 is C ⁇ _ C 4 alkyl or C 2 -C 4 alkenyl 2 preferably, n-Pro- pylsulfonyl, tolylsulfonyl or cyclohexylsulfonyl.
- X represents C 1 -C 4 - (halogen) alkyl, C 2 -C 4 alkoxyalkyl, halogen, C 1 -C 4 - (halo) alkoxy.
- Y represents oxygen or a substituent on the alkylene chain.
- D stands for one Substituted or unsubstituted -CC 3 alkylene chain and p for an integer from 0 to 3.
- the variable m stands for an integer from zero to six and n for an integer from zero to two.
- PCT / EP 00/04040 discloses 4- (3 ', 4' heterocyclylbenzoyl) pyrazoles.
- benzoxazolyl, benzimidazolyl, benzothiazolyl and benzotriazinyl are mentioned as heterocyclic radicals.
- the compounds have herbicidal activity.
- the present invention is therefore based on the object of providing new compounds with herbicidal activity which preferably have a higher activity than the herbicidal substances of the prior art and / or better selectivity towards harmful plants.
- the present invention relates to pyrazolylcarbonylbenzazolones of the general formula I
- R 1 is halogen, C ⁇ -C 4 -alkyl, C 4 haloalkyl, C ⁇ -C 4 hydroxyalkyl, C ⁇ -C -alkoxy-C ⁇ -C 4 -alkyl, C 4 -haloalkoxy-C ⁇ -C 4 - alkyl, -CC 4 -haloalkylthio -CC-C alkyl,
- R 2 is hydrogen, hydroxy, nitro, amino, Ci-C ⁇ -alkylamino,
- R 3 is hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -haloalkoxy- 4 -C 4 -alkyl or halogen;
- R 4a , R 4b independently of one another can have the meanings given for R 4 and R b can stand for hydrogen;
- R 5 independently of one another for hydrogen, C ⁇ -C 6 -alkyl, C ⁇ -C 6 -haloalkyl, C ⁇ -C 6 -alkoxy-C ⁇ -C 6 -alkyl, (C ⁇ -C 6 -halogenalkoxy) -C ⁇ -C 5 -alkyl , C 2 -C 6 alkenyl,
- R 6 is hydrogen, C 1 -C 4 -alkyl, C 4 -C 4 -haloalkyl,
- Pz represents a radical of the formula Ha or Ilb
- R 8 are hydrogen, C 6 alkyl, C 3 -C 6 cycloalkyl, Ci-C ⁇ haloalkyl, hydroxy, Ci-C 6 alkoxy or C C ß haloalkoxy;
- R 9 is hydrogen, halogen, Ci-C 6 -alkyl, C 6 haloalkyl,
- Phenoxycarbonyl phenyloxythiocarbonyl, phenylaminocarbonyl
- Heterocyclyl-C 2 -Cg-alkenylcarbonyl where the phenyl and heterocyclyl radicals of the 18 latter substituents can be partially or completely halogenated and / or can carry one, two or three of the following radicals: nitro, cyano,
- C ⁇ -Cg-alkyl C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or C 3 -Cg cycloalkyl, where the four radicals mentioned can be partially or completely halogenated and / or one, two or three of the following groups can wear: Cyano, Cx-C 4 -alkoxy, C ⁇ -C 4 -haloalkoxy, C ⁇ -C 4 -alkylthio, C ⁇ -C 4 -haloalkylthio, C ⁇ ⁇ C 4 -alkylcarbonyl, Cx-C 4 -alkoxycarbonyl or C ⁇ -C haloalkoxycarbonyl;
- Heterocyclylcarbonyl where the phenyl or heterocyclyl radical of the six last-mentioned substituents can be partially or completely halogenated and / or can carry one, two or three of the following radicals: nitro, cyano, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkoxy or C ⁇ -C haloalkoxy; and
- R 15 is hydrogen, C ⁇ -C 6 alkyl or C 3 -C 6 alkenyl, C 3 -Cg alkynyl; means
- herbicidal compositions which contain pyrazolyl derivatives of the formula I and have a very good herbicidal action.
- methods for controlling unwanted vegetation using the pyrazolyl derivatives of the formula I have been found.
- the compounds of the formula I can contain one or more centers of chirality and are then present as enantiomers or diastereomer mixtures.
- the invention relates both to the pure enantiomers or diastereomers and to their mixtures.
- the compounds of the formula I can also be present in the form of their agriculturally useful salts, the type of salt generally not being important. In general, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the herbicidal activity of the compounds I
- ions of the alkali metals preferably lithium, sodium and potassium, the alkaline earth metals, preferably calcium and magnesium, and the transition metals, preferably manganese, copper, zinc and iron, and ammonium come as cations, where if desired one to four hydrogen atoms by C ⁇ ⁇ C 4 -alkyl, hydroxy-C ⁇ -C 4 -alkyl, C ⁇ -C-alkoxy-C ⁇ -C 4 -alkyl, hydroxy-C ⁇ -C 4 -alkoxy-C ⁇ -C 4 -alkyl, phenyl or benzyl can be replaced, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2- (2-hydroxyeth-l-oxy) eth-l-ylammonium,
- Tri (C ⁇ -C-alkyl) sulfonium and sulfoxonium ions preferably tri (C ⁇ -C 4 -alkyl) sulfoxonium, into consideration.
- Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate,
- Ha also represents the tautomeric forms Ha 'and Ha''
- Ilb also represent the tautomeric forms llb 'and Ilb' '.
- N — alkynyl — N — alkoxyaminocarbonyl, alkenyl, alkynyl, haloalkenyl, haloalkynyl, alkenyloxy, alkynyloxy, alkanediyl, alkenediyl, alkadienediyl or alkynediyl parts can be straight-chain or branched.
- halogenated substituents preferably carry one to five identical or different halogen atoms. Halogen is fluorine, chlorine, bromine or iodine.
- - C ⁇ -C-alkyl for: z. B. methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropy1, 2-methylpropyl or 1,1-dimethylethyl;
- haloalkyl for: a C ⁇ -C — alkyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, that is, for. B.
- C ⁇ -C 4 -haloalkoxy-C ⁇ -C 4 -alkyl C ⁇ -C 4 -haloalkoxy-C ⁇ -C 4 -alkoxy, C ⁇ -C -haloalkoxy-C ⁇ -Cg-alkyl, C ⁇ -C 4 -haloalkoxy-C ⁇ - C 6 -alkoxy, C ⁇ -C 4 -haloalkoxy-C 3 -Cg-alkenyl, C ⁇ -C-haloalkoxy-C 3 -Cg-alkynyl for: a C ⁇ -C alkoxy radical, as mentioned above, partially or completely through
- Fluorine, chlorine, bromine and / or iodine is substituted, e.g. Fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2 — fluoroethoxy, 2 — chloroethoxy, 2 — bromomethoxy, 2 — iodoethoxy, 2,2 — difluoroethoxy, 2,2,2 — trifluoroethoxy, 2 — chloro-2 — fluoroethoxy,
- C ⁇ ⁇ C 4 haloalkoxy for: C ⁇ ⁇ C 4 —haloalkoxy, as mentioned above, as well as, for example, 5 — fluoropentoxy, 5 — chloropentoxy, 5 — bromopentoxy, 5 — iodopentoxy, undecafluoropentoxy, 6 — fluorohexoxy, 6 — chlorohexoxy, 6 — bromohexoxy , 6 — iodohexoxy or dodecafluorohexoxy;
- C ⁇ -C 4 -alkylthio (C ⁇ -C 4 -alkylsulfanyl: C ⁇ -C-alkyl-S-) for: e.g. methylthio, ethylthio, propylthio, 1 — methylethylthio, butylthio, 1– ethylpropylthio, 2 — methylpropylthio or 1, 1— dimethylethylthio;
- C -C 6 haloalkylthio for: C ⁇ -C 4 haloalkylthio, as mentioned above, and 5 — fluoropentylthio
- C ⁇ -Cg-alkylsulfinyl C ⁇ -C 4 -alkylsulfinyl, as mentioned above, and pentylsulfinyl, 1 - ethylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2, 2-dimethyl-propylsulfinyl, 1-ethyl-propylsulfinyl, 1, 1-propylsulfinyl, 1, 1 1, 2-dimethyl propylsulfinyl, hexylsulfinyl, 1-methylpentylsulfinyl,
- haloalkylsulfinyl C ⁇ ⁇ C — alkylsulfinyl, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethylsulfinyl, difluoromethylsulfinyl, trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethylsulfonyl, 2-fluorinated methylsulfonyl , 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl1, 2, 2-difluoroethylsulfinyl, 2,2, 2-trifluoroethylsulfinyl, 2,2, 2-trichloroethylsulfinyl, 2-chloro-2
- C ⁇ -Cg-haloalkylsulfinyl C ⁇ -C 4 -haloalkylsulfinyl, as mentioned above, and 5 — fluoropentylsulfinyl, 5 — chloropentylsulfinyl, 5 — bromopentylsulfinyl,
- C ⁇ -Cg-alkylsulfonyl C ⁇ -C 4 -alkylsulfonyl, as mentioned above, and pentylsulfonyl, imethylbutylsulfonyl, 2-methylbutylsulfonyl, 3-ethylbutylsulfonyl, 1, 1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, 2, dimethylpropylsulfonyl, 2 Ethyl propylsulfone 1, hexylsulfonyl, 1-methylpentylsulfonyl, 2-ethylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1, 1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfon
- 6-fluorohexylsulfonyl 6-bromohexylsulfonyl, 6-iodohexylsulfonyl or dodecafluorohexylsulfonyl;
- - C ⁇ -C 6 alkylamino methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1,1-dimethylethylamino, pentylamino, 1-methylbutylamino, 2-methylbutylamino, 3-methylbutylamino 2-dimethylpropylamino, 1-ethylpropylamino, hexylamino, 1, 1-dimethylpropylamino, 1,2-dimethylpropylamino, 1-methylpentylamino, 2-methylpentylamino, 3-methylpentylamino, 4-methylpentylamino, 1, 1-dimethylbutylamino, 1,2-dimethylbut 1,3-dimethylbutylamino, 2, 2-dimethylbutylamino, 2, 3-dimethylbutylamino, 3, 3-dimethylbutylamino
- Di- (C ⁇ -Cg-alkyl) amino di- (C ⁇ -C-alkyl) amino as mentioned above, and N, N-dipentylamino, N, N-dihexylamino, N-methyl-N-pentylamino, N-ethyl- N-pentylamino, N-methyl-N-hexylamino or N-ethyl-N-hexylamino
- Cx-C-alkylcarbonyl e.g. Methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl or 1, 1-dimethylethylcarbonyl;
- C ⁇ - ⁇ C 6 -alkylcarbonyl and the alkylcarbonyl radicals of C ⁇ -C 6 -alkylcarbonylamino: C ⁇ -C 4 -alkylcarbonyl, as mentioned above, and for example pentylcarbonyl, 1-methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 2.2— Dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, hexylcarbonyl, 1, 1-dimethylpropylcarbonyl, 1, 2-dimethylpropylcarbonyl, 1-methylpentylcarbonyl, 2-ethylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentylcarbonyl, 1, 1-dimethylbutylcarbonyl, 1, 2 , 3-dimethylbutylcarbonyl, 2, 2, —dimethylbutylcarbonyl, 2, 3 — dimethylbutylcarbonyl, 3, 3
- - C ⁇ -C 4 -Halogenalkylcarbonyl a C ⁇ ⁇ C 4 alkylcarbonyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example chloroacetyl, dichloroacetyl, trichloroacetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl , Chlorofluoroacetyl, dichlorofluoroacetyl, chlorodifluoroacetyl,
- 2,2,2-trichloroethylcarbonyl pentafluoroethylcarbonyl, 2-fluoropropylcarbonyl, 3-fluoropropylcarbonyl, 2,2-difluoropropylcarbonyl, 2,3-di-fluoropropylcarbonyl, 2-chloropropylcarbonyl, 3-chloropropylcarbonyl,
- C ⁇ -C 4 -haloalkylcarbonyl radical as mentioned above, and 5-fluoropentylcarbonyl, 5-chloropentylcarbonyl, 5-bromopentylcarbonyl, per fluoropentylcarbonyl, 6 -fluorohexylcarbonyl, 6-chlorohexylcarbonyl,
- - C ⁇ ⁇ C 4 -haloalkoxycarbonyl a C ⁇ -C 4 alkoxycarbonyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethoxycarbonyl, difluoromethoxycarbonyl, trifluoromethoxycarbonyl, chlorodifluoromethoxycarbonyl, bromodifluoromethyl, bromodifluoromethyl —Fluoroethoxycarbony1, 2 — chloroethoxycarbonyl, 2 — bromoethoxycarbonyl,
- C ⁇ -C 6 -haloalkoxycarbonyl a C ⁇ -C 4 -haloalkoxycarbonyl radical as mentioned above, and 5-fluoropentoxycarbonyl, 5-chloropentoxycarbonyl, 5-bromopentoxycarbonyl, 6-fluorohexoxycarbonyl, 6-chlorohexoxycarbonyl or 6-bromohexoxycarbonyl; - (Cx-C4 alkyl) carbonyloxy: acetyloxy, ethylcarbonyloxy, propylcarbonyloxy, 1-Methylethylcarbonyloxy, butylcarbonyloxy, 1-Methylpropylcarbonyloxy,
- Di- (C ⁇ -C 4 alkyl) aminocarbonyl e.g. B.
- N, N-di- (1-methylethyl) aminocarbonyl N, N-dipropylaminocarbonyl, N, N-dibutylaminocarbonyl,
- N-butyl-N-pentylaminocarbonyl N, N-dipentylaminocarbonyl, N-propyl-N-hexylaminocarbonyl, N-butyl-N-hexylaminocarbonyl, N-pentyl-N-hexylaminocarbonyl or N, N-dihexylaminocarbonyl;
- Di- (C ⁇ -Cg-alkyl) aminothiocarbonyl e.g.
- N, N Dipropylaminothiocarbonyl, N, N-Dibutylaminothiocarbony1, N, N-Di- (1-methylpropyl) —aminothiocarbonyl, N, N-Di- (2-methylpropyl) —aminothiocarbonyl, N, N-Di- (1, 1 -dimethylethyl) —aminothiocarbonyl, N-ethyl-N-methylaminothiocarbonyl, N-methyl-N-propylaminothiocarbonyl, N-methyl-N- (1-methylethyl) —aminothiocarbonyl, N-butyl-N-methylaminothiocarbonyl, N-methyl-N- (1-meth-i-propyl) -aminothiocarbonyl, N -methyl-N- (2-methyl-propyl) -aminothiocarbonyl, N- (l, 1-di
- N-ethyl-N- (1-methylethyl) aminothiocarbonyl N-butyl-N-ethylaminothiocarbonyl, N-ethyl-N- (1-methylpropyl) aminothiocarbonyl,
- C ⁇ -Cg-hydroxyalkyl C ⁇ -Cg-alkyl substituted by one to three OH groups, e.g. B hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1,2-bishydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 2,2-dimethyl-3-hydroxypropyl;
- Phenyl-C ⁇ -C 6 alkyl C ⁇ -Cg-alkyl substituted by a phenyl radical, e.g. B. benzyl, 1-phenylethyl and 2-phenylethyl, where the phenyl radical may be partially or completely halogenated in the manner indicated or may have one to three of the substituents indicated above for phenyl;
- a phenyl radical e.g. B. benzyl, 1-phenylethyl and 2-phenylethyl, where the phenyl radical may be partially or completely halogenated in the manner indicated or may have one to three of the substituents indicated above for phenyl;
- Heterocyclyl-C ⁇ -C 6 alkyl is accordingly a C ⁇ -Cg-alkyl substituted by a heterocyclyl radical
- C ⁇ -Cg-alkoxy-C ⁇ -Cg-alkyl C ⁇ -Cg-alkoxy, as mentioned above, substituted C ⁇ -Cg-alkyl, e.g. methoxymethyl, ethoxymethyl, propoxymethyl, (l-methylethoxy) methyl, butoxymethyl, (1- methylpropoxy) methy1, (2 methylpropoxy) methyl, (1, 1-dimethylethoxy) methyl, 2-methoxy) ethyl, 2- (ethoxy) ethyl, 2- (propoxy) ethyl, 2- 1-methylethoxy) ethyl, 2- (butoxy) ethyl , 2- 1-methylpropoxy) ethyl, 2- (2-methylpropoxy) ethyl, 2- 1, 1-dirnethylethoxy) ethyl, 2- (methoxy) -propy1, 2-ethoxy) propy1, 2- (propoxy) propy1, 2 - 1-methylethox) —prop
- C ⁇ -Cg-alkoxy-C ⁇ -Cg-alkoxy C ⁇ -Cg-alkoxy, as well as the alkoxyalkoxy parts of C ⁇ -Cg-lkoxy-C ⁇ -Cg-alkoxycarbonyl: C ⁇ -Cg-alkoxy, as mentioned above, substituted C ⁇ -Cg-alkoxy, i.e. e.g.
- C 3 -Cg haloalkenyl a C 3 -C 6 alkenyl radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 2-chloroallyl, 3-chloroallyl, 2, 3-dichlorallyl, 3,3-dichlorallyl, 2,3, 3-trichlorallyl, 2,3-dichlorobut-2-enyl, 2-bromoallyl, 3-bromoallyl, 2, 3-dibromoallyl, 3, 3-dibromoallyl, 2, 3, 3-tribromoallyl or 2,3-dibromobut-2-enyl;
- C 3 -Cg haloalkynyl a C 3 -Cg alkynyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine; B.
- C ⁇ -Cg-alkanediyl methanediyl, ethane-1, 1-diyl, ethane-l, 2-diyl, propane-l, l-diyl, propane-l, 2-diyl, propane-l, 3-diyl, propane 2,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, 2-methyl-propane-1,3-diyl, 2-methyl-propane-l, 2-diyl, 2-methyl-propane-l, 1-diyl, 1-methyl-1-propane-1,2-diy1, 1-methyl-propane-2,2-diyl, 1- Methyl-propane-l, 1-diyl, pentane-1, 1-diyl, pentane-l, 2-diyl, pentane-1
- C 2 -C 6 -alkenediyl ethene-1, 1-diyl, ethene-1, 2-diyl, 1-propene-1, 1-diyl, 1-propene-1, 2-diyl, 1-propene-1, 3-diyl, 2-propene-1, 1-diyl, 2-propene-1, 2-diyl, 2-propene-1, 3-diyl, 1-butene-1, 1-diyl, 1-butene-1, 2-diyl, 1-butene-l, 3-diyl, 1-butene-l, 4-diyl, 2-butene-l, 1-diyl, 2-butene-l, 2-diyl, 2-butene-l, 3-diyl, 2-butene-l, 4-diyl, 3-butene-l, 1-diyl, 3-butene-l, 2-diyl, 3-butene-l, 2-butene-l,
- C 3 -Cg cycloalkyl and also the cycloalkyl parts of C 3 -Cg cycloalkylamino and C 3 -Cg cycloalkylcarbonyl: eg cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
- Aryl means carbocyclic aromatic compounds such as phenyl or naphthyl
- a 3- to 7-membered heterocyclyl is understood to mean a saturated, partially saturated or unsaturated 3, 4, 5, 6 or 7-membered heterocyclic ring which has one, two, three or four identical or different heteroatoms, selected from the following group: contains oxygen, sulfur or nitrogen;
- B. C-linked 5-membered rings such as:
- Tetrahydropyran-4-yl piperidine-2-yl, piperidine-3-l, piperidine-4-yl, tetrahydrothiopyran-2-yl, Tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 2H-3, 4-dihydropyran-6-y1, 2H-3, 4-dihydropyran-5-y1, 2H-3, 4-dihydropyran-4-yl, 2H- 3,4-dihydropyran-3-yl, 2H-3,4-dihydropyran-2-yl, 2H-3,4, -dihydropyran-6-yl, 2H-3,4, -dihydrothiopyran-5-yl, 2H-3, 4-dihydrothiopyran-4-yl, 2H-3,4-dihydropyran-3-yl, 2H-3,4, 4-dihydropyran-2-yl, 1,2,3,4-tetra
- N-linked 5-membered rings such as:
- N-linked 6-membered rings such as:
- N-linked cyclic imides such as:
- variables A, R 1 to R 15 preferably have the following meanings, in each case individually or in combination:
- R 6 is not hydrogen.
- R 6 stands for C ⁇ -C 4 alkyl and very particularly preferably for methyl.
- A is O or NR 6 , in which R 6 has the meanings mentioned above.
- Particularly preferred in another group is O or NR 6 , in which R 6 has the meanings mentioned above.
- Connections A stands for S or S0 2 stands.
- R 1 halogen, C ⁇ -C 4 alkyl, C ⁇ -C 4 alkoxy, especially methyl, methoxy or chlorine.
- R 2 has the meanings mentioned, different from hydrogen, in particular
- R 2 particularly preferably represents C ⁇ -C 4 -alkyl or C 3 -Cg-alkenyl. Also particularly preferred are those compounds I in which R 2 is C 3 -C 6 -alkynyl, (1,3-dioxolan-2-yl) methyl, 2- (1,3-dioxolan-2-yl) ethyl or Benzyl is in which the phenyl ring can be unsubstituted or can have 1 or 2 substituents selected from halogen, methyl or methoxy.
- R 3 C ⁇ -C 4 alkyl, halogen and especially hydrogen.
- A stands for O or S, R 1 for methyl, R 3 for hydrogen and R 2 for a substituent other than hydrogen, in particular for one of the substituents indicated above as preferred and especially for C- L -C - Alkyl, C 3 -C 6 -alkynyl, C 3 -C 6 -alkenyl, (1,3-dioxolan-2-yl) methyl, 2- (1,3-dioxolan-2-yl) ethyl or for benzyl, wherein the phenyl ring may be unsubstituted or may have 1 or 2 substituents selected from halogen, methyl or methoxy.
- ONR 14 R 15 or N-linked heterocyclyl which can be partially or completely halogenated and / or can carry one, two or three of the following radicals: nitro, cyano, CC 4 alkyl, C ⁇ -C 4 haloalkyl,
- C ⁇ -C 4 alkoxy or C ⁇ -C 4 haloalkoxy in particular hydroxy, OR 10 and 0S0 2 R X1 , especially hydroxy, C ⁇ -C-alkyloxy, 0-CH 2 -phenyl, phenylcarbonyloxy, 2-, 3- or 4-fluorophenylcarbonyloxy, cyclopropylcarbonyloxy, C ⁇ -C 4 sulfonyloxy, Phenylsulfonyloxy and
- R 8 C ⁇ -C 6 alkyl, C 3 -C 6 cycloalkyl, in particular C ⁇ -C alkyl and cyclopropyl;
- R 9 is hydrogen or C ⁇ -C alkyl, especially hydrogen or C ⁇ -C 4 alkyl.
- R 8 represents a C 3 -C 6 -cycloalkyl group, especially when A is S, SO or S0 2 .
- R 7 hydroxy, halogen, OR 10 , SR 10 , S0 2 R 1: L , OS0 2 R 1: L , NR 1 R 15 , 0NR 14 R 15 or N-linked heterocyclyl, which can be partially or completely halogenated and / or can carry one, two or three of the following radicals: nitro, cyano, C ⁇ -C 4 alkyl, C ⁇ -C haloalkyl, C ⁇ -C alkoxy or C ⁇ -C 4 haloalkoxy, especially hydroxy, OR 10 and OS0 2 R 1: l ?
- R 8 is C ⁇ -C 4 alkyl, C 3 -Cg cycloalkyl; especially cyclopropyl;
- R 9 is hydrogen or C ⁇ -C 4 alkyl.
- R 7 for hydroxy, C ⁇ -C 4 alkyloxy, acetoxy, 0-CH 2 phenyl,
- R 8 for C ⁇ -C 4 alkyl or cyclopropyl
- R 9 represents hydrogen or C ⁇ -C 4 alkyl.
- Examples of particularly preferred radicals of the general formula Ila are the radicals Ilal to IIa90 given in Table 1.
- Examples of particularly preferred compounds of the general formula I according to the invention are the benzazolonylcarbonylpyrazoles I given in Tables 2 to 25 below, in which R 1 , R 2 , R 3 and A each have the meanings given in one row of Table A.
- Table 5 Compounds I-ld.l to I-ld.3960
- Table 6 Compounds I-le.l to I-le.3960
- Table 9 Compounds I-lh.l to I-lh.3960
- Table 10 Connections I-li.l to I-li. 3960
- the compounds of the formula I in which R 7 is hydroxy are prepared by reacting an activated carboxylic acid IVb or a carboxylic acid IVa, which is preferably activated in situ, with 5-hydroxypyrazole of the formula III to give the acylation product and subsequent rearrangement.
- L 1 stands for a nucleophilically displaceable leaving group, such as halogen z.
- B bromine or chlorine, hetaryl, for example imidazolyl or pyridyl, carboxylate, for example acetate or trifluoroacetate etc.
- the activated carboxylic acid IVb can be used directly, as in the case of the benzoyl halides, or generated in situ, e.g. with a carbodiimide such as ethyl (3'-dimethylaminopropyl) carbodiimide, dicyclohexylcarbodiimide, triphenylphosphine / azodicarboxylic acid ester, 2-pyridine disulfide / triphenylphosphine, carbonyldiimidazole etc.
- a carbodiimide such as ethyl (3'-dimethylaminopropyl) carbodiimide, dicyclohexylcarbodiimide, triphenylphosphine / azodicarboxylic acid ester, 2-pyridine disulfide / triphenylphosphine, carbonyldiimidazole etc.
- auxiliary base it may be advantageous to carry out the acylation reaction in the presence of a base.
- the reactants and the auxiliary base are expediently used in equimolar amounts.
- a small excess of the auxiliary base z. B. 1.2 to 1.5 molar equivalents, based on IVa or IVb, may be advantageous under certain circumstances.
- Suitable auxiliary bases are tertiary alkylamines, pyridine, 4-dimethylaminopyridine or alkali metal carbonates.
- a solvent for. B. chlorinated hydrocarbons such as methylene chloride or 1,2-dichloroethane, aromatic hydrocarbons such as toluene, xylene or chlorobenzene, ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane, polar aprotic solvents such as acetonitrile, dimethylformamide or dimethyl - Sulfoxide or esters such as ethyl acetate or mixtures thereof are used.
- halides are used as the activated carboxylic acid component, it may be expedient to cool the reaction mixture to 0 ° C. to 10 ° C. when this reaction partner is added. The mixture is then stirred at 20 ° C. to 100 ° C., preferably at 25 ° C. to 50 ° C., until the reaction is complete. The workup is carried out in the usual manner, for. B. the reaction mixture is poured onto water and the product of value is extracted. Methylene chloride, diethyl ether and ethyl acetate are particularly suitable as solvents for this. After drying the organic phase and removing the solvent, the crude ester can be used for rearrangement without further purification.
- the rearrangement of the esters to the compounds of the formula I is advantageously carried out at from 20 ° C. to 100 ° C. in a solvent and in the presence of a base and, if appropriate, using a cyano compound as a catalyst.
- a solvent for example, acetonitrile, methylene chloride, 1,2-dichloroethane, dioxane, ethyl acetate, toluene or mixtures thereof can be used as solvents.
- Preferred solvents are acetonitrile and dioxane.
- Suitable bases are tertiary amines such as triethylamine, aromatic amines such as pyridine or alkali metal carbonates such as sodium carbonate or potassium carbonate, which are preferably used in an equimolar amount or up to a fourfold excess, based on the ester.
- Triethylamine or alkali carbonate are preferably used, preferably in a double equimolar ratio with respect to the ester.
- Inorganic cyanides such as sodium cyanide or potassium cyanide and organic cyano compounds such as acetone cyanohydrin or trimethylsilyl cyanide are suitable as cyano compounds. They are used in an amount of 1 to 50 mole percent, based on the ester. Preferably acetone cyanohydrin or trimethylsilyl cyanide, e.g. in an amount of 5 to 15, preferably about 10 mole percent, based on the ester.
- the reaction mixture is e.g. B. with dilute mineral acid, such as
- 5% hydrochloric acid or sulfuric acid acidified, with an organic solvent, e.g. B. extracted methylene chloride or ethyl acetate.
- the organic extract can be mixed with 5-10% alkali carbonate solution, e.g. B. sodium carbonate or potassium carbonate solution can be extracted.
- the aqueous phase is acidified and the precipitate which forms is filtered off with suction and / or extracted with methylene chloride or ethyl acetate, dried and concentrated.
- compound la stands for a compound of the general formula I, in which Pz stands for a pyrazolyl radical of the general formula Ha and compound Ib speaking for a compound of general formula I, wherein Pz stands for a radical Ilb.
- Suitable halogenating agents are, for example, phosgene, diphosgene, triphosgene, thionyl chloride, oxalyl chloride,
- Phosphorus oxychloride Phosphorus oxychloride, phosphorus pentachloride, mesyl chloride, chloromethylene-N, N-dimethylammonium chloride, oxalyl bromide, phosphorus oxybromide etc.
- L 2 stands for a nucleophilically displaceable leaving group, such as halogen, for example chlorine or bromine, hetaryl, for. B. imidazolyl, carboxylate, e.g. B. acetate, or sulfonate, e.g. B. mesylate or triflate etc.
- halogen for example chlorine or bromine
- hetaryl for.
- the reactants and the base are expediently used in equimolar amounts.
- a slight excess of the base, e.g. B. 1.1 - 1.5 molar equivalents, based on I can be advantageous under certain circumstances.
- Suitable .bases are tertiary amines, pyridines, alkali metal carbonates or alkali metal hydrides.
- Suitable solvents are, for. B. chlorinated hydrocarbons such as methylene chloride or 1,2-dichloroethane, aromatic hydrocarbons such as toluene, xylene or chlorobenzene, ethers such as diethyl ether, meth 1-tert-butyl ether, tetrahydrofuran, dioxane or di ethoxyethane, polar aprotic solvents such as acetoni- tril, dimethylformamide or dimethyl sulfoxide or esters such as ethyl acetate and mixtures thereof.
- chlorinated hydrocarbons such as methylene chloride or 1,2-dichloroethane
- aromatic hydrocarbons such as toluene, xylene or chlorobenzene
- ethers such as diethyl ether
- R 7 OS0 2 CH 3 or OS0 2 -tolyl
- the mixture is then stirred at 20 ° C. to 100 ° C., preferably at 20 ° C. to 75 ° C., until the reaction is complete.
- the workup is carried out in the usual manner, for. B. the reaction mixture is poured onto water, the product of value extracted.
- Solvents such as methylene chloride, ethyl acetate, methyl tert-butyl ether or diethyl ether are particularly suitable as solvents for this. After the organic phase has dried and the solvent has been removed, the crude product can, if appropriate, also be purified by column chromatography on silica gel. Solvents such as methylene chloride, ethyl acetate, cyclohexane, petroleum ether, methanol, acetone or chloroform and mixtures thereof are suitable as eluents.
- the compounds of formula V ⁇ , Vß, V ⁇ or v ⁇ can be used directly, such as. B. in the case of carboxylic acid halides or generated in situ, e.g. activated carboxylic acids (with carboxylic acid and dicyclohexylcarbodiimide etc.).
- Suitable oxidizing agents are m-chloroperbenzoic acid, peroxyacetic acid, trifluoroperoxyacetic acid, hydrogen peroxide, if appropriate in the presence of a catalyst such as tungstate.
- the starting compounds are generally used in an equimolar ratio. However, it can also be advantageous to use one or the other component in excess.
- reactants and the base are expediently used in equimolar amounts.
- Suitable bases are tertiary alkyl amines such as triethylamine, aromatic amines such as pyridine, alkali metal carbonates, e.g. As sodium carbonate or potassium carbonate, alkali metal hydrogen carbo- nates, such as sodium hydrogen carbonate and potassium hydrogen carbonate, alkali metal alcoholates such as sodium methoxide, sodium ethanolate, potassium tert. -butanolate or alkali metal hydrides, e.g. B. sodium hydride. Triethylamine or pyridine are preferably used.
- Chlorinated hydrocarbons such as methylene chloride or 1,2-dichloroethane
- aromatic hydrocarbons e.g. Toluene, xylene or chlorobenzene
- ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane
- polar aprotic solvents such as acetonitrile, dimethylformamide or dimethyl sulfoxide or esters such as ethyl acetate, or mixtures thereof.
- reaction temperature is in the range from 0 ° C. to the boiling point of the reaction mixture.
- the product can be worked up in a manner known per se.
- compounds Ia, Ib or mixtures thereof can be formed in processes B to D.
- the latter can be separated using classic separation methods such as e.g. B. crystallization, chromatography, etc., are separated.
- M stands for a metal, in particular for an alkali metal such as lithium or sodium, an alkaline earth metal such as.
- R 7 preferably has no acidic hydrogen atoms.
- the reaction is usually carried out at temperatures from -100 ° C. to the reflux temperature of the reaction mixture.
- Inert aprotic solvents such as ethers, for example diethyl ether, tetrahydrofuran, are suitable as solvents.
- the compounds of formula 5b are generally used in excess, but it may also be advantageous to use them in equimolar amounts or in deficit. The processing takes place towards the product.
- the metalated pyrazole derivatives of the formula VII can be prepared in a manner known per se by reacting pyrazoles halogenated in the 4-position with metals such as lithium, sodium, magnesium etc. or with organometallic compounds such as. B. Butyllithium are formed. However, it is also possible to directly metalate pyrazoles which are linked to hydrogen in the 4-position, for. B. with the above metals or organometallic compounds.
- the reactions are generally carried out in an inert aprotic solvent, preferably in ethers such as diethyl ether, tetrahydrofuran etc.
- the reaction temperature is in the range from -100 ° C. to the level of the 20 boiling point of the reaction mixture.
- the compounds of formula VII are preferably generated in situ and implemented directly.
- the 5-hydroxypyrazoles of the formula III used as starting materials are known or can be prepared per se by known methods.
- 25 driving can be produced, such as in EP-A
- 1,3-dimethyl-5-hydroxypyrazole is also a commercially available compound.
- alkylating agents V ⁇ , sulfonylating agents Vß, phosphonation agents V ⁇ and v ⁇ , and the compounds Vl ⁇ , 35 Vlß, Vl ⁇ , Vl ⁇ and Vl ⁇ are also known or can be prepared by known processes.
- the carboxylic acids of the general formula IVa or their activated derivatives IVb are new and likewise the subject of the present invention.
- Scheme 1 illustrates a general approach to the preparation of compounds of Formula IVa, wherein A is oxygen or NR 6 . 45 Scheme 1:
- step a) the bromination of the nitro compounds VIII takes place in the meta position to the nitro group.
- Common brominating agents for this purpose are bromine, N-bromosuccinimide,
- N-bromohydantoin or pyridinium perbromide which are optionally used together with a Lewis acid such as FeBr 3
- the bromination is usually carried out in an inert solvent.
- Suitable solvents are aliphatic or cycloaliphatic hydrocarbons, for example n-hexane or cyclohexane, halogenated hydrocarbons, for example dichloromethane, trichloromethane, tetrachloromethane, trichloroethane, trichlorethylene, heteroaromates such as pyridine or anhydrous inorganic or organic acids, such as acetic acid.
- Typical reaction temperatures are in the range from -15 ° C to 150 ° C, preferably in the range from -15 ° C to 100 ° C.
- Processes for the bromination of nitro compounds are known, for. B. from Organikum, 16th ed., 1986, p. 315.
- reducing agents are hydrazines, metal hydrides such as aluminum hydride and guided complex hydrides such as lithium aluminum hydride, diisobutyl aluminum hydride, or boranes, and nascent hydrogen, e.g. B. iron, zinc or tin in the presence of acids such as hydrochloric acid or carboxylic acids such as acetic acid.
- Another suitable reducing agent is hydrogen in the presence of catalytic amounts of transition metals such as nickel, palladium, platinum, ruthenium or rhodium.
- the transition metals can be used as such or in supported form, for example on activated carbon, in the form of activated metals, e.g. B. Raney nickel, or in the form of soluble complex compounds.
- the reaction is preferably carried out in a solvent. Suitable solvents for the reduction are dependent on the solubility of the substrate to be hydrogenated and the chosen reducing agent, for example C ⁇ -C 4 alcohols, such as methanol, ethanol, n-propanol, isopropanol or n-butanol, halogenated C ⁇ -C 6 hydrocarbons, such as Dichloromethane, trichloromethane, trichloroethane, trichlorethylene, aromatic hydrocarbons, such as benzene, toluene, xylenes, chlorobenzene, aqueous solutions of inorganic acids, such as aqueous hydrochloric acid or organic acids and their mixtures with water.
- C ⁇ -C 4 alcohols such as m
- the reduction is usually carried out at temperatures in the range from -15 ° C. to +100 ° C., preferably in the range from 0 ° C. to 40 ° C.
- the reduction with hydrogen usually takes place at a hydrogen pressure in the range from 1 to 50 bar.
- the catalytic hydrogenations are preferably carried out using hydrogen in the range from 1 to 10 bar.
- the condensation of the 3-bromoaniline X to form the heterocycle in step c) is achieved by reacting the compound X with a carbonic acid equivalent, such as methyl chloroformate, phosgene or its synthesis equivalents such as diphosgene or triphosgene, under the conditions customary for phosgenation.
- a carbonic acid equivalent such as methyl chloroformate, phosgene or its synthesis equivalents such as diphosgene or triphosgene
- the cyclization is generally carried out under neutral to acidic reaction conditions at temperatures in the range from 0 ° C. to 150 ° C. and preferably in the range from 20 ° C. to 120 ° C.
- the phosgenation is usually carried out in a solvent.
- Aliphatic or cycloaliphatic hydrocarbons such as n-hexane or cyclohexane, halogenated hydrocarbons such as dichloromethane, trichloromethane, trichloroethane, trichlorethylene, aromatic hydrocarbons such as benzene, aliphatic ethers such as diethyl ether, methyl tert-butyl ether or cyclic ethers are particularly suitable as solvents , such as tetrahydrofuran or dioxane.
- Methods for phosgenation are known, see for example Justus Liebigs Ann. Chem., 1978, No. 2, 193-213; j. Med. Chem., 1987, 30, N 7, 1166-1176, J. Heterocycl. Chem. 1991, 28 (8), 1937-1939; J. Nat. Prod. 1995, 58 (3), 456-458.
- step d) succeeds, for example, by reacting the 5-bromobenzazol-2-one XI obtained in step c) with R 2 -L or its precursor, where L stands for a nucleophilically displaceable leaving group.
- Suitable leaving groups are, for example, halogen such as chlorine, bromine or iodine, carboxylate such as acetate or trifluoroacetate or sulfonates such as tosylate, mesylate or triflate.
- the reaction is preferably carried out in the presence of an auxiliary base, e.g. B.
- alkali or alkaline earth carbonates such as sodium, potassium, magnesium or calcium carbonate
- alkali or alkaline earth hydrides for example sodium hydride
- tertiary alkylamines for example triethylamine
- aromatic amines for example pyridine, DMPU.
- the reaction is usually carried out at temperatures in the range from -15 ° C to 150 ° C and preferably at 0 ° C to 100 ° C.
- the reaction is usually carried out in a solvent.
- Suitable solvents are, for example, the abovementioned inert hydrocarbons, the abovementioned halogenated hydrocarbons, aromatic hydrocarbons, such as benzene, toluene, xylene or chlorobenzene, the abovementioned acyclic or cyclic ethers, and also polar aprotic solvents such as dimethylformamide, acetonitrile or dimethyl sulfoxide.
- the successive reaction of XII with magnesium or alkylmagnesium halides to give the corresponding Grignard compound and the subsequent reaction of the Grignard compound with carbon dioxide then gives the carboxylic acid IVa (step e)).
- Usual reaction temperatures are in the range from -15 ° C to 150 ° C, preferably in the range from -15 ° C to 100 ° C.
- Suitable solvents are anhydrous solvents, in particular the aforementioned inert cyclic or acyclic hydrocarbons, the aforementioned aromatic hydrocarbons or the aforementioned acyclic or cyclic ethers.
- the benzazolone-5-carboxylic acid IVa is obtained by introducing dry carbon dioxide into the solution of the Grignard compound corresponding to XII and subsequent aqueous workup. The carbon dioxide pressure is usually 1 to 6 bar.
- XII can be converted into the carboxylic acid IVa by halogen-metal exchange with an alkali metal alkyl, for example a lithium alkyl such as methyl lithium, n-butyllithium or tert-butyllithium and subsequent reaction of the lithiation product with CO 2 become.
- alkali metal alkyl for example a lithium alkyl such as methyl lithium, n-butyllithium or tert-butyllithium and subsequent reaction of the lithiation product with CO 2 become.
- Usual reaction temperatures are in the range from -100 ° C to 0 ° C, preferably in the range from -78 ° C to -50 ° C.
- Suitable solvents are anhydrous solvents, in particular the aforementioned inert hydrocarbons, the aforementioned aromatic hydrocarbons or the aforementioned acyclic or cyclic ethers.
- Introducing dry carbon dioxide into the solution of the lithiation product of XII gives the
- Reaction step e) in scheme 1 can also be carried out by reacting XII with carbon monoxide, a base and water under elevated pressure in the presence of a palladium, nickel, cobalt or rhodium catalyst.
- the catalysts nickel, cobalt, rhodium and in particular palladium can be metallic or in the form of conventional salts such as in the form of halogen compounds, for example palladium (H) chloride, rhodium (III) chloride hydrate, acetates, for.
- palladium (II) acetate, cyanides, etc. can be used in the known valence levels.
- metal complexes with tertiary phosphines, metal alkylcarbonyls, metal carbonyls, eg. B. C0 2 (CO) 8 , Ni (CO) 4 metal carbonyl complexes with tertiary phosphines, for. B.
- radicals R 24 to R 26 for low molecular weight alkyl for example C ⁇ -Cg-alkyl, aryl, C ⁇ -C-alkylaryl, for.
- Aryl is, for example, naphthyl, anthryl and preferably optionally substituted phenyl, although the substituents only need to be considered for their inertness to the carboxylation reaction, otherwise they can be varied widely and include all inert C-organic radicals such as
- C ⁇ -Cg-alkyl radicals for example methyl, carboxyl radicals such as COOH, COOM (M is for example an alkali metal, alkaline earth metal or ammonium salt), or C-organic radicals bound via oxygen such as C ⁇ -C 6 alkoxy radicals.
- A stands for a divalent organic radical, e.g. B. C ⁇ -C 4 alkyls, 1,2-cycloalkylene, ⁇ , ⁇ '-ferrocendiyl, ⁇ , ⁇ -biphenyl or comparable bifunctional groups.
- the preparation of the phosphine complexes can be carried out in a manner known per se, e.g. B. as described in the documents mentioned.
- customary commercially available metal salts such as palladium (H) chloride or palladium (II) acetate are used and the phosphine is added, for example P (CgH 5 ) 3 , P (nC 4 Hg) 3 , PCH 3 (CgH 5 ) 2 , 1,2-bis (diphenylphosphino) ethane.
- the amount of phosphine, based on the transition metal is usually 0 to 20, in particular 0.1 to 10 molar equivalents, particularly preferably 1 to 5 molar equivalents.
- the amount of transition metal is not critical. Of course, for reasons of cost, you will rather get a small amount, e.g. from 0.1 to 10 mol%, in particular 1 to 5 mol%, based on the starting material IVa.
- the reaction is carried out with carbon monoxide and at least equimolar amounts of water, based on the bromide obtained in step d).
- the reactant water can also serve as a solvent, i.e. H. the maximum amount is not critical.
- Suitable inert solvents for carboxylation reactions are customary solvents such as hydrocarbons, for example toluene, xylene, hexane, pentane, cyclohexane, ether, for example methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted amides such as dimethylformamide, per-substituted ureas such as tetra-C ⁇ - C 4 alkylureas or nitriles such as benzonitrile or acetonitrile.
- hydrocarbons for example toluene, xylene, hexane, pentane, cyclohexane, ether, for example methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted amides such as dimethylformamide, per-substituted
- one of the reactants, in particular the base is used in excess, so that no additional solvent is required.
- Bases suitable for the process are all inert bases which are able to bind the hydrogen iodide or hydrogen bromide released during the reaction.
- tertiary amines such as tert-alkyl amines, e.g. B. trialkylamines such as triethylamine, cyclic amines such as N-methylpiperidine or N, -Dimethy1- piperazine, pyridine, alkali metal or hydrogen carbonates, or tetra alkyl-substituted urea derivatives such as tetra-C ⁇ -C 4 alkyl urea, for. B. tetramethyl urea to name.
- the amount of base is not critical. Usually 1 to 10, in particular 1 to 5 moles are used. If the base is simultaneously used as a solvent, the amount is generally such that the reactants are dissolved, unnecessarily high excesses being avoided for reasons of practicality in order to save costs, to be able to use small reaction vessels and to ensure maximum contact for the reactants.
- the carbon monoxide pressure is adjusted so that there is always an excess of CO, based on the bromide.
- the carbon monoxide pressure at room temperature is preferably 1 to 250 bar, in particular 5 to 150 bar CO.
- the carbonylation is generally carried out continuously or batchwise at temperatures from 20 ° C. to 250 ° C., in particular at 30 ° C. to 150 ° C.
- carbon monoxide is expediently pressed continuously onto the reaction mixture in order to maintain a constant pressure.
- reaction step e) and then reaction step d) can also be carried out first.
- the substituted acetophenone XIII can be prepared by Friedel-Crafts acylation in step f).
- the acetyl group can be introduced in a known manner by reacting compound VIII with acetic acid or activated acetic acid, such as acetic anhydride or acetyl chloride, in the presence of a Lewis acid such as aluminum trichloride, boron trifluoride or trifluoroacetic acid under anhydrous conditions.
- a Lewis acid such as aluminum trichloride, boron trifluoride or trifluoroacetic acid under anhydrous conditions.
- Lewis acid such as aluminum trichloride, boron trifluoride or trifluoroacetic acid
- this complex is hydrolytically cleaved.
- Friedel-Crafts acylations are usually carried out in a solvent.
- Suitable solvents are the aforementioned cyclic and acyclic hydrocarbons, the aforementioned halogenated hydrocarbons, aromatic hydrocarbons such as nitrobenzene or the aforementioned ethers.
- the reaction temperatures are generally in the range from 0 ° C. to 150 ° C. and preferably in the range from 20 ° C. to 120 ° C. Methods for introducing acyl groups are known, see, for example, Organikum, 16th ed. 1986, p. 325.
- the substituted acetophenone XIII is then reduced to the amino compound XIV in step g).
- the reduction is carried out in the manner described in step b) in scheme 1.
- the aniline derivative XIV is then phosgenated in step h) in the manner described in step c) in Scheme 1.
- the substituent R 2 can be introduced analogously to step d) in scheme 1 (step i) in scheme 2).
- the conversion of the compound XVI obtained in step i) in Scheme 2 into the benzazolonecarboxylic acid IVa is achieved using the haloform reaction.
- a halogenating agent such as hypohalite, for example hypochlorite, or chlorine in alkaline solution is allowed to act on the compound XVI.
- a trihalomethylcarbonyl derivative is initially formed which is hydrolytically cleaved under the alkaline reaction conditions to form the desired benzazolonecarboxylic acid IVa.
- suitable Bases are especially alkali hydroxides, such as sodium or potassium hydroxide. The reaction is usually carried out in solution.
- Particularly suitable solvents are water, mixtures of water and organic solvents, such as C 4 -C 4 alcohols, for example methanol, ethanol, propanol, butanol, or the aforementioned ethers.
- Usual reaction temperatures are in the range from 0 ° C to 150 ° C, preferably in the range from 20 ° C to 120 ° C.
- For the Haloform reaction see, for example, Organikum, 16th ed. 1986, p. 375.
- a in formula IVa is sulfur
- the benzazolonecarboxylic acids of the general formula IVa can also be prepared in the manner shown in scheme 3.
- the conversion of the 2-aminobenzothiazole XVII into the 2-halobenzothiazole compound XVIII succeeds in known manner under Sandmeyer conditions (step k)). In this way, further functionalities can be introduced in the 2-position of the benzothiazole ring.
- the 2-aminobenzothiazole XVII is first reacted with inorganic or organic nitrite, such as sodium nitrite in the presence of acid, such as hydrochloric acid or with tert-butyl nitrite.
- the diazonium salt obtained is then reacted with an inorganic halide, such as sodium chloride with the addition of copper, or with a Cu (I) halide, such as Cu (I) chloride.
- the reaction is usually carried out at temperatures in the range from 0 ° C. to 150 ° C. and preferably in the range from 20 ° C. to 100 ° C.
- Suitable solvents are in particular water or mixtures of water with organic solvents such as the abovementioned alcohols or ethers.
- the 2-halobenzothiazole compound XVIII can then in step 1) under acidic or alkaline conditions to
- compound XVIII is mixed with a base, such as alkali or alkaline earth hydroxide, for example sodium, potassium or magnesium hydroxide, or alkali alcoholate, such as sodium or potassium methylate, or with an acid, such as hydrochloric acid.
- a base such as alkali or alkaline earth hydroxide, for example sodium, potassium or magnesium hydroxide, or alkali alcoholate, such as sodium or potassium methylate, or with an acid, such as hydrochloric acid.
- suitable solvents are polar aprotic solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or acetonitrile, ethers such as tetrahydrofuran or dioxane, water and mixtures of water with the abovementioned alcohols, ethers or polar aprotic solvents.
- the hydrolysis is usually carried out at 0 ° C to 150 ° C and preferably at 20 ° C to 120 ° C.
- hydrolysis of halogen heteroaromatics to keto compounds see also J. Med. Chem. 1977, 20, no. 6, 791-796.
- step d) The introduction of the substituent R 2 into the compound XIX in step m) is carried out as described in step d) in scheme 1.
- the benzazolone methyl ester XX obtained in step m) is set with alkali metal hydroxide, for. B. lithium, sodium or potassium hydroxide, with alkaline earth metal hydroxide such as magnesium hydroxide or with alkali iodides such as sodium iodide in a suitable solvent, preferably in the absence of oxygen.
- Typical reaction temperatures are in the range from 0 ° C to 200 ° C and in particular in the range from 20 ° C to 180 ° C.
- Suitable solvents are the aforementioned aliphatic or cycloaliphatic hydrocarbons, the halogenated hydrocarbons, the aromatic table hydrocarbons, the aforementioned ethers and alcohols, aqueous, single-phase systems and pyridine.
- saponification see, for example, Organikum, 16, Ed. 1986, p. 415, Mc Murry, Org. React. 1976, 24, 187; Taschner et al., Rocz. Chem. 1956, 30, 323; Houben-Weyl: "Methods of Organic Chemistry", Volume E 8 b 1994; P. 1010 f .; J. Chem. Soc.
- the 2-chlorobenzothiazole compounds XXII can be prepared in a Sandmeyer reaction in step o).
- the reaction conditions required for this correspond to those of step k) in scheme 3.
- the 2-chlorobenzothiazole XXII can be brominated in an analogous manner to step a) in scheme 1, the bromine substituent selectively entering in the ortho position to R i (step p)) ,
- the compound XXIII is then basic hydrolyzed under the conditions given for step 1) in scheme 3 (step q)).
- the substituent R 2 can be introduced into XXIV under the conditions described for step d) in scheme 1.
- the carboxy group (step s)) is introduced in accordance with the reaction conditions described in step e) in Scheme 1.
- the 2-chlorobenzothiazoles xxil are then subjected to a freeze in step u) under the conditions specified in step f) in scheme 2 Subject to del-Crafts acylation to give compound XXVII.
- the hydrolysis of XXVII is carried out in an anologic manner as described for reaction step q) in Scheme 4.
- the introduction of the substituent R 2 in XXVIII in step w) takes place in a known manner, as described for example in step d) in scheme 1.
- the final haloform reaction in step x) under the conditions given in step j) in scheme 2 converts the substituted acetophenone XXIX into the desired benzazolonecarboxylic acid IVa, with loss of one carbon atom.
- the known o-chloronitrobefrg ⁇ .e of the general formula XXX are first converted into the corresponding thioethers XXXI with alkali salts of benzyl mercaptan (step 1)).
- the substitution is usually carried out in one of the abovementioned aliphatic or cycloaliphatic hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, ethers, denatures. thylformamide, NMP, sulfolane or dimethyl sulfoxide.
- Usual reaction temperatures are in the range from 0 ° C to 250 ° C and preferably in the range from 50 ° C to 175 ° C.
- Methods for nucleophilic substitution are known, see also A. Bagno et al., J. Chem. Soc. Perkin Trans II, 1991 (5), 651-655; JR Beck et al., J. Org. Chem., 1978, 43, no. 10, 2048-20
- step 2 The compound XXXI is then reduced in step 2) to the amino compound XXXII.
- the reaction conditions required for this correspond to those for step b) in Scheme 1.
- the amino compound XXXII is then cyclized under the reaction conditions described in step c) in Scheme 1 using carbonic acid equivalents to give the benzothiazolone XXXIII (step 3)).
- the subsequent introduction of the substituent R 2 succeeds under the reaction conditions described in step d) in scheme 1 (step 4)).
- Friedel-Crafts acylation of compound XXXIV enables the acetyl group to be introduced in the ortho position to the substituent R (step 5)).
- the reaction conditions required for this correspond to those of step f) in scheme 2.
- the desired benzazolonecarboxylic acid IVa can be obtained from the compound XXXV by a haloform reaction (step 6)).
- the reaction conditions required for this correspond to those in step j) in Scheme 2.
- ether cleavage takes place at temperatures in the range from -15 ° C to 150 ° C. preferably in the range from 0 ° C to 100 ° C.
- a Lewis acid such as aluminum trichloride, aluminum tribromide or hydrohalic acids, such as hydroiodic acid or hydrobromic acid.
- the compounds I of Examples 4 to 47 were prepared in an analogous manner by reacting the respective carboxylic acid IVa with the 5-hydroxypyrazole III and, if appropriate, subsequently derivatizing the compound I obtained in this way.
- the compounds I 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 I control vegetation very well on non-cultivated areas, particularly when high amounts are applied. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. 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 I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
- the compounds I or the 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, sprays or granules. Misting, dusting, scattering, watering or treating the seed or mixing with the seed can be used.
- the application forms depend on the use purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
- the herbicidal compositions comprise a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of I and auxiliaries customary for the formulation of crop protection agents.
- Kerosene or diesel oil also coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol,
- 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 compounds of the formula I, 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, 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 and of fatty alcohol glycol ether, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenyl, alylphenol, , Tributy
- Granules e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers.
- 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 corn 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:
- V 3 parts by weight of the active ingredient of the general formula I are mixed with 97 parts by weight of finely divided kaolin. In this way, a dust is obtained which contains 3% by weight of the active ingredient.
- VI 20 parts by weight of the active ingredient of the general formula I are intimately mixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
- the herbicidal compositions or the active compounds can be applied pre- or post-emergence or together with the seeds of a crop. There is also the possibility of applying the herbicidal compositions or active ingredients. ren that seed of a crop plant pretreated with the herbicidal compositions or active ingredients is applied. If the active ingredients are less compatible for certain crop plants, application techniques can be used in which the herbicides are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not struck wherever possible, while the active ingredients grow on the leaves below them unwanted plants or the uncovered floor area (post-directed, lay-by).
- the application rates of active ingredient I are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a.s.), depending on the control target, the season, the target plants and the growth stage.
- the compounds I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
- active compound groups for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and their derivatives, aminotriazoles, anilides, (het) -aryloxyalkanoic acid and their derivatives, benzoic acid and their derivatives, benzothiadiazinones, 2 -Aroyl-l, 3-cyclohexanediones, 2-hetaroyl-l, 3-cyclohexanediones, hetaryl-aryl ketones, benzylisoxazolidinones, meta-CF 3 -phenyl derivatives, carbamates, quinoline carboxylic acid and their derivatives, chloroacetanilides, cyclohexenono - ximether derivatives, diazines, dichloropropionic acid and
- Plastic pots with loamy sand with about 3.0% humus as substrate served as culture vessels.
- the seeds of the test plants were sown separately according to species.
- 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 transparent 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 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 the post-emergence treatment was 31.3, 62.5, 125 and / or 250 g / ha of active substance (on page).
- 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. At least 95% damage corresponds to a very good herbicidal action.
- the plants used in the greenhouse experiments are composed of the following types:
- the compound I-la.H29 from Example 1 showed a very good herbicidal action against CHEAL, SETFA, STEME and THLAR in the post-emergence.
- the compound I-lb.1129 from Example 2 showed a very good herbicidal action against CHEAL, ECHCG, PARPH, STEME and THLAR in post-emergence.
- the compound l-lc.1131 from Example 12 showed a very good post-emergence bicidal activity against BRAPL. AMARE, CHEAL, ECHCG and SETFA.
- the compound I-ly.1131 from Example 46 showed a very good herbicidal action against BRAPL in the post-emergence. PHBPU, CHEAL, ECHCG and SETFA.
- the compound I-Ig.H31 from Example 14 showed a very good herbicidal activity against BRAPL in the post-emergence.
- the compound I-la.6 from Example 9 showed a very good herbicidal action against BIDPI, CHEAL, POLPE and SETFA in the post-emergence.
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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)
- Environmental Sciences (AREA)
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Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2002229640A AU2002229640A1 (en) | 2000-12-11 | 2001-12-10 | 5-((pyrazol-4-yl)carbonyl)benzazolone as herbicide |
EP01990536A EP1347969B1 (de) | 2000-12-11 | 2001-12-10 | 5-'(pyrazol-4-yl)carbonyl!benzazolone als herbizide |
DE50105736T DE50105736D1 (de) | 2000-12-11 | 2001-12-10 | 5-'(pyrazol-4-yl)carbonyl!benzazolone als herbizide |
US10/433,033 US20040033899A1 (en) | 2000-12-11 | 2001-12-10 | 5[(pyrazol-4-yl)carbonyl]benzazolone as herbicide |
AT01990536T ATE291579T1 (de) | 2000-12-11 | 2001-12-10 | 5-'(pyrazol-4-yl)carbonylöbenzazolone als herbizide |
CA002431268A CA2431268A1 (en) | 2000-12-11 | 2001-12-10 | 5-[(pyrazol-4-yl)carbonyl]benzazolone as herbicide |
JP2002549671A JP2004526682A (ja) | 2000-12-11 | 2001-12-10 | 除草剤としての5−[(ピラゾール−4−イル)カルボニル]ベンゾアゾロン |
Applications Claiming Priority (2)
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DE10061657 | 2000-12-11 | ||
DE10061657.7 | 2000-12-11 |
Publications (1)
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WO2002048140A1 true WO2002048140A1 (de) | 2002-06-20 |
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PCT/EP2001/014476 WO2002048140A1 (de) | 2000-12-11 | 2001-12-10 | 5-'(pyrazol-4-yl)carbonyl!benzazolone als herbizide |
Country Status (9)
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US (1) | US20040033899A1 (de) |
EP (1) | EP1347969B1 (de) |
JP (1) | JP2004526682A (de) |
AR (1) | AR031786A1 (de) |
AT (1) | ATE291579T1 (de) |
AU (1) | AU2002229640A1 (de) |
CA (1) | CA2431268A1 (de) |
DE (1) | DE50105736D1 (de) |
WO (1) | WO2002048140A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004024724A1 (fr) * | 2002-09-13 | 2004-03-25 | Hunan Research Institute Of Chemical Industry | Composes d'heterocycles condenses a substitution par heterocycles, avec pouvoir bioactif |
CN110950848A (zh) * | 2018-09-27 | 2020-04-03 | 徐诺药业 | 新型氨基吡唑类衍生物的合成与应用 |
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WO2023056982A1 (zh) * | 2021-10-09 | 2023-04-13 | 山东先达农化股份有限公司 | 一种化合物及其制备方法和应用、一种杀草剂 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2000068228A1 (de) * | 1999-05-07 | 2000-11-16 | Basf Aktiengesellschaft | 4-(3',4'-heterocyclylbenzoyl) pyrazole als herbizide |
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US5367289A (en) * | 1991-11-27 | 1994-11-22 | Sensormatic Electronics Corporation | Alarm tag for an electronic article surveillance system |
DE4427997A1 (de) * | 1994-08-08 | 1996-02-15 | Basf Ag | 5-Hydroxypyrazol-4-yl-carbonyl-substituierte Saccharinderivate |
US5650770A (en) * | 1994-10-27 | 1997-07-22 | Schlager; Dan | Self-locating remote monitoring systems |
DE19532312A1 (de) * | 1995-09-01 | 1997-03-06 | Basf Ag | Pyrazol-4-yl-benzoylderivate |
DE59707423D1 (de) * | 1996-02-24 | 2002-07-18 | Basf Ag | Pyrazol-4-yl-hetaroylderivate als herbizide |
IL119509A (en) * | 1996-10-28 | 2000-02-17 | Hi G Tek Ltd | Electronic tag |
US5955951A (en) * | 1998-04-24 | 1999-09-21 | Sensormatic Electronics Corporation | Combined article surveillance and product identification system |
-
2001
- 2001-12-06 AR ARP010105672A patent/AR031786A1/es not_active Application Discontinuation
- 2001-12-10 CA CA002431268A patent/CA2431268A1/en not_active Abandoned
- 2001-12-10 US US10/433,033 patent/US20040033899A1/en not_active Abandoned
- 2001-12-10 AT AT01990536T patent/ATE291579T1/de not_active IP Right Cessation
- 2001-12-10 EP EP01990536A patent/EP1347969B1/de not_active Expired - Lifetime
- 2001-12-10 WO PCT/EP2001/014476 patent/WO2002048140A1/de active IP Right Grant
- 2001-12-10 DE DE50105736T patent/DE50105736D1/de not_active Expired - Fee Related
- 2001-12-10 AU AU2002229640A patent/AU2002229640A1/en not_active Abandoned
- 2001-12-10 JP JP2002549671A patent/JP2004526682A/ja not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2000068228A1 (de) * | 1999-05-07 | 2000-11-16 | Basf Aktiengesellschaft | 4-(3',4'-heterocyclylbenzoyl) pyrazole als herbizide |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004024724A1 (fr) * | 2002-09-13 | 2004-03-25 | Hunan Research Institute Of Chemical Industry | Composes d'heterocycles condenses a substitution par heterocycles, avec pouvoir bioactif |
CN110950848A (zh) * | 2018-09-27 | 2020-04-03 | 徐诺药业 | 新型氨基吡唑类衍生物的合成与应用 |
CN110950848B (zh) * | 2018-09-27 | 2024-03-26 | 徐诺药业 | 新型氨基吡唑类衍生物的合成与应用 |
Also Published As
Publication number | Publication date |
---|---|
EP1347969B1 (de) | 2005-03-23 |
US20040033899A1 (en) | 2004-02-19 |
AU2002229640A1 (en) | 2002-06-24 |
ATE291579T1 (de) | 2005-04-15 |
JP2004526682A (ja) | 2004-09-02 |
DE50105736D1 (de) | 2005-04-28 |
AR031786A1 (es) | 2003-10-01 |
CA2431268A1 (en) | 2002-06-20 |
EP1347969A1 (de) | 2003-10-01 |
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