Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
  • C07D261/20—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings condensed with carbocyclic rings or ring systems

Definitions

• the present invention relates to certain 3 - (, 5-d ⁇ hydro ⁇ soxazol-3-yl) - substituted benzoylcyclohexenone derivatives and processes for their preparation, agents which contain them, and the use of these derivatives or agents containing them for combating harmful plants.
• Herbicidal 2-benzoylcyclohexane-1,3-dione are known from WO 96/26200.
• R 3 is hydrogen, Ci-Cg-Alkvl or Hilogen;
• R 4, R 5 independently of one another What sers tof f, C ⁇ -C 4 alkyl or C ⁇ -C 4 haloalkyl;
• R 4 , R 5 together represent C 1 -C 4 -alkanedyl, which can carry one, two or three substituents selected from halogen or C 1 -C 4 -alkyl;
• R 6 stands for hydroxy, mercapto, halogen, OR 13 , SOR 14 , SR 13 or S0 2 R 14 s;
• R 7 , R 11 independently of one another represent hydrogen, -CC 4 -alkyl, -C-C 4 -alkylthio or -C-C 4 -alkoxycarbonyl;
• R 8 , R 10 , R 12 independently of one another are hydrogen or C 1 -C 4 alkyl
• R 9 for hydrogen, hydroxy, halogen, Ci-Cg-alkyl, -C-C 6 -haloalkyl, di (Ci-C ⁇ - alkoxy) ethyl, (Cx-Cs-alkoxy) (C ⁇ . -C 6 alkyl - Th ⁇ o) methyl, di (C ⁇ -C 6 -alkylth ⁇ o) methyl, Ci.-Cs-alkoxy, C ⁇ -C 5 -haloalkoxy, C ⁇ .
• R 7 and R 8 or R 11 and R 12 together are Ci-Cs-alkanediyl, a, the, two or three of halogen, cyano, C 4 -alkyl, C 4 haloalkyl or C ⁇ -C 4 - Alkoxycarbonyl can carry selected substituents;
• R 8 and R 9 or R 9 and R 12 together represent a chemical bond or Ci-Cs-alkanediyl, one, two or three under halogen, cyano, -CC 4 -alkyl, -C-C 4 haloalkyl or C.
• ⁇ _-C 4 alkoxy carbonyl can carry selected substituents;
• R 8 and R 12 together represent C ⁇ -C 4 -alkanedyl, which can carry one, two or three substituents selected from halogen, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxycarbonyl; or
• R 9 and R 10 together for -0- (CH 2 ) p -0-, -O- (CH 2 ) p -S-, -S- (CH 2 ) p -S- ⁇ -0- (CH 2 ) q - or -S- (CH) q - are capable of supporting 4 alkoxycarbonyl substituents selected from one, two or three of halogen, cyano, C 4 -alkyl, C 4 haloalkyl or C ⁇ -C;
• R 9 and R 10 together represent an oxygen atom
• alkyl, alkoxy and cycloalkyl radicals mentioned can be partially or completely halogenated and / or one, two or three under cyano, C 1 -C 4 alkoxy , -C ⁇ C 4 -Alkylth ⁇ o, D ⁇ (C ⁇ -C 4 -al- kyDammo, C ⁇ -C 4 -alkylcarbonyl, C ⁇ -C 4 -alkoxycarbonyl,
• C 1 -C 4 -alkoxy-C 4 -alkoxycarbonyl, C 1 -C 4 -alkylammocarbonyl, N, N-di- (-C-C 4 -alkyl) ammocarbonyl or C 3 -Cg-cycloalkyl can carry selected subscribers; Phenyl, phenyl-Ci-Cg-alkyl, phenylcarbonyl-Ci-Cg-alkyl, phenylcarbonyl, phenoxycarbonyl, phenoxy hiocarbonyl, heterocycyl, heterocyclyl-Ci-Cg-alkyl, heterocyclylcarbonyl-Ci-Cg-al - kyl, heterocyclylcarbonyl , heterocyclyloxycarbonyl, hetero- clyloxythiocarbonyl, wherein the said radicals the phenyl or heterocyclyl radical may be partially or fully halogenated and / or one, two or three
• R 14 represents Ci-Cg-alkyl, C 3 -Cg-alkenyl, C 3 -Cg-haloalkenyl, C 3 -Cg-alkynyl or C 3 -Cg-cycloalkyl, the alkyl and cycloalkyl radicals mentioned being partial or may be fully halogenated and / or one, two or three among cyano, C 4 -alkoxy, C 4 -Alkylth ⁇ o, di (C ⁇ .
• q 1, 2, 3, 4 or 5;
• herbicidal compositions which contain the compounds I and have a very good herbicidal action.
• processes for the preparation of these compositions and processes for controlling unwanted vegetation using the compounds I have been found.
• the compounds of the formula I can contain one or more centers of chirality and are then present as mixtures of enantiomers or diastereomers.
• 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
• Cations in particular ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and ammonium, where one to four hydrogen atoms pass through if desired C 1 -C 4 alkyl, hydroxy-C 1 -C 4 alkyl, CT . -C -alkoxy-Ci -C 4 -alkyl,
• Hydroxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, phenyl or benzyl can be replaced, preferably ammonium, dimethylammonium, dusopropylammonium, tetramethylammonium, tetrabutylammonium, 2 - (2 -hydroxy- eth- 1 -oxy) eth- 1 -ylammonium, di (2-hydroxyeth-1 -yl) ammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium lumions, preferably tri (Ci-C 4 alkyl) sulfonium and sulfoxium ions, preferably tri (C ⁇ . -C -alkyl) sulfoxonium, into consideration.
• Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C 1 -C 4 -alkanoic acids, preferably formate, acylate , Propionate and butyra.
• C 1 -C 4 -alkyl and the alkyl parts of C 1 -C 4 -alkylcarbonyl, phenyl-C 4 -C 4 -alkyl, phenylcarbonyl-C] .- C 4 -alkyl, heterocyclic-C 4 -C 4 -alkyl and heterocyclylcarbonyl -C] _- C 4 alkyl: e.g. B. methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1, 1 -dimethylethyl;
• Ci-Cg-alkyl as well as the alkyl parts of Ci -Cg-alkylcarbonyl-N- C 3 -Cg-alkenyl-N-C ⁇ -Cg-alkylaminocarbonyl, NC 3 -Cg-alkynyl-N-Ci-Cg-alkylaminocarbonyl, N- C ⁇ -Cg-Alkoxy-N-C ⁇ -Cg-alkylamino - carbonyl, C ⁇ -Cg-Alkoxyimino-C ⁇ -Cg-alkyl, phenyl-Ci-Cg-alkyl, phenylcarbonyl-Ci-Cg-alkyl, heterocyclyl-Ci-Cg- alkyl and heterocyclylcarbonyl-Ci-Cg-alkyl: C 1 -C 4 alkyl, as mentioned above, and z.
• -C-C 2 o-alkyl as the alkyl part of -C-C o-alkylcarbonyl: Ci-Cg-alkyl, as mentioned above, and z.
• C 1 -C 4 haloalkyl a C1.-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, bromomethyl, iodomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2, 2-difluoroethyl, 2, 2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,
• Ci -Cg haloalkyl C 1 -C 4 haloalkyl, as mentioned above, and z.
• B 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodo-pentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl or dodecafluorohexyl;
• Ci-C-alkoxy and the alkoxy parts of -C ⁇ Cg-alkoxycarbonyl, di- (C ⁇ -C -alkoxy) methyl, (C L -Cg-alkoxy) (Ci-Cg-alkylthio) methyl, N- (Cx -Cg-alkoxy) -N- (C ⁇ -Cg-alkyl) ammocarbonyl and C ⁇ -Cg-alkoxyimino-C ⁇ -Cg-alkyl .- C x -C alkoxy, as mentioned above, and z. B.
• C 1 -C 4 haloalkoxy a C 1 -C alkoxy radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, that is, for.
• Ci-Cg-haloalkoxy Ci-C -haloalkoxy, as mentioned above, and z.
• B 5 -Fluorpentoxy, 5 -Chlorpent ⁇ xy, 5 -Brompen oxy, 5 -Iodpentoxy, Undecafluorpentoxy, 6-Fluorhe- xoxy, 6-chlorine text> xy, 6-bromhexoxy, 6-iodohexoxy or dodeca- fluorohexoxy;
• -C-C 4 alkylthio z. B. methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1, 1-dimethylethylthio;
• Ci-Cg-alkylthio and the alkyl thiores e of (C ⁇ -Cg-alkoxy) (C ⁇ -Cg-alkylthio) methyl, di- (C ⁇ -Cg-alkylthio) methyl and Ci-Cg-alkylthiocarbonyl: C1 . -C 4 alkylthio, as mentioned above, and z. B.
• Ci -C -Halogenalkyl hio a Ci -C 4 alkyl hiorest, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, so z.
• Ci-C haloalkyl hio Ci -C 4 haloalkylthio, as mentioned above, and z.
• B. 5-fluoropentylthio, 5-chloro-ylt-hio, 5-bromopentylthio, 5-iodo-pentylthio, undecafluoropentyl-hio, 6-fluoro-hexylthio, 6-chlorohexylthio, 6-bromhexylthio, 6-iodohexylthio or dodecafluorhexylthio; Ci-Cg-alkylsulfmyl (Cx-C -alkyl -S ( 0) -): e.g.
• B methylsulfinyl, ethylsulfmyl, propylsulfmyl, 1-methylethylsulfmyl, butylsulfmyl, 1-methylpropylsulfmyl, 2 -methylpropylsulfonyl, 1, 1-dimethylethylsulfmyl, pentylsulfmyl, 1-methylbutylsulfylmylmulfylmylbutylsulfmyl, 2-methyl
• Ci-Cg -Halogenalkylsulfmyl Ci -Cg -Alkylsulf ylres, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, so z.
• fluoromethylsulfmyl difluoromethylsulfmyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfmyl, bromodifluoromethylsulfmyl, 2-fluoroethylsulfmyl, 2-chloroethylsulfmyl, 2-bromomethylsulfylnyl, 2-iodomethylsulfmyl, 2, 2, 2-fluorosulfmyl, 2, 2,2,2 -T ⁇ chlorethylsulfmyl, 2 -Chlor -2 -fluorethylsulfmyl, 2 -Chlor-2, 2 -difluorethylsulfl - nyl, 2, 2 -D ⁇ chlor-2 -fluorethylsulfmyl, PentafluorethylsulfI - nyl, 2 -Fluorpropylsulfmyl,
• Ci-Cg-Alkylsulfonyl a Ci -C 4 alkylsulfonyl, as mentioned above, and z.
• Ci-C-haloalkylsulfonyl a Ci-C-alkylsulfonyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, that is, for. B.
• fluoromethylsulfonyl difluoromethylsulfonyl, trifluoromethyl-sulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2, 2-sulfonyl, 2,2, 2-sulfonyl, 2,2-2-sulfonyl Chlorine -2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethyl-sulfonyl, 2,2,2-trichloroethylsulfonyl, pentafluoroethylsulfonyl
• 6-fluorohexylsulfonyl 6-bromhexylsulfonyl, 6 -lodhexylsulfonyl or dodecafluorohexylsulfonyl;
• (-C-C 4 alkylamino) carbonyl z.
• B methylaminocarbonyl, ethyl aminocarbonyl, propylammocarbonyl, 1-methylethylaminocarbonyl, butylaminocarbonyl, 1-methylpropylaminocarbonyl, 2-methylpropylaminocarbonyl or 1, 1-dimethylethylaminocarbonyl;
• C 2 -C o-alkenyl as the alkenyl part of C 2 -C 2 rj-alkenylcarbonyl: C 2 -Cg-alkenyl, as mentioned in the foregoing, and 8-pentadene-cen-l-yl, 8-heptadecen-l-yl and 8, 11-heptadecadien-l-yl;
• C 3 -Cg haloalkenyl a C 3 -Cg alkenyl radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, that is, for.
• C 3 -Cg-alkynyl and the alkynyl moieties of C 3 -Cg-alkynylcarbonyl, C 3 -Cg -alkynyloxycarbonyl, C 3 -Cg -mkinylaminocarbonyl,
• Ci-Cs-alkanediyl Cj . -C 4 -alkanedyl, as mentioned above, and pentane-1,5-dyl;
• N-bonded, 5-membered, partially saturated rings such as: 2, 3-dihydro-IH-py 'rrol- 1-yl, 2, 5 -Dihydro- lH-pyrrol - 1-yl, 4, 5 -Dihydro- 1H-pyrazole -1-yl, 2,5-dihydro-1H-yrazole -1-yl, 2,3-dihydro-1H-pyrazole - 1-yl, 2,5-dihydroisoxazole -2-yl, 2,3 - Dihydroisoxazole -2-yl, 2,5-dihydroisothiazole -2 -yl, 2,3-dihydroisoxazole -
• N-linked, 5-membered, unsaturated rings such as:
• N-linked, 6-membered, saturated rings such as: piperidin-1-yl, hexahydropyrimidin-1-yl, hexahydropyrazine-1-yl, hexahydropyridazin-1-yl, tetrahydro-1, 3-oxazin-3 -yl, tetrahydro - 1, 3 - thiazin-3 -yl, tetrahydro-1, 4 - thiazin-4 -yl, tetrahydro - 1, 4 - oxazin-4 -yl, tetrahydro-1, 2-oxazin -2 -yl;
• a bicyclic ring system can be formed with a fused-on phenyl ring or with a C 3 -Cg carboxy cycle or with a further 5- to 6-membered heterocycle.
• the phenyl radicals or heterocyclyl radicals are preferably unsubstituted or carry em, two or three halogen atoms and / or a nitro group, a cyano group, one or two methyl, trifluoromethyl, methoxy or trifluoromethoxy groups.
• R 1 for Ci-Cg-alkyl, Ci-Cg-haloalkyl, C ! -C 6 alkoxy or halogen
• C 1 -C 4 -alkyl preferably methyl, ethyl, n-propyl or l-propyl;
• Halogen preferably fluorine, chlorine or bromine;
• R 2 represents Ci-Cg-haloalkyl, Ci-C ß- alkylsulfonyl, halogen or nitro;
• C 1 -C 4 -haloalkyl preferably difluoromethyl or trifluoromethyl
• -CC alkyl sulfonyl preferably methyl sulfonyl or ethyl sulfonyl
• halogen preferably fluorine or chlorine
• C 1 -C 4 -alkylsulfonyl is particularly preferred, methylsulfonyl being the most preferred;
• R 3 represents hydrogen, -CC alkyl or halogen; in particular hydrogen, chlorine or methyl; particularly preferably hydrogen;
• R 4 for hydrogen, -CC 4 alkyl or -C ⁇ C 4 haloalkyl; in particular for hydrogen, methyl, ethyl, chloromethyl or bromomethyl; particularly preferably hydrogen or methyl;
• R 5 represents hydrogen or -CC 4 alkyl; especially for hydrogen or methyl; particularly preferably hydrogen; or R 4 , R 5 together represent a C 1 -C 4 -alkanediyl group; in particular represents a methanediyl group;
• R 6 for hydroxy, OR 13 , SR- 3 , SOR 14 or S0 2 R 14 ; especially for hydroxy, OR 13 or SR 13 ; particularly preferably hydroxy;
• R 7 'R 11 independently of one another for hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkylthio; in particular hydrogen, methyl or methylthio; particularly preferably hydrogen;
• R 8 'R 10 , R 12 independently of one another are hydrogen or methyl
• R 9 for hydrogen, hydroxy, Ci-Cg-alkyl or di (C ⁇ .-Cg-alk-oxy) methyl; in particular hydrogen or -CC 4 alkyl;
• R 9 and R 10 together represent an oxygen atom
• R 14 Ci-Cg-alkyl, which can be partially or completely halogenated and / or one, two or three under cyano, -C ⁇ C 4 alkoxy, C ⁇ -C 4 alkylthio, C ⁇ -C 4 alkylcarbonyl, C ⁇ -C 4 -alkoxycarbonyl or C 3 -Cg-cycloalkyl can carry selected substituents; Phenyl, phenyl -CC 4 -alkyl, phenylcarbonyl -CC 4 -alkyl, heterocyclyl, heterocyclyl -CC-C 4 -alkyl or heterocyclyl-carbonyl-C 1 -C 4 -alkyl, the phenyl or heterocyclyl radical of the radicals mentioned can be partially or completely halogenated and / or one, two or three of nitro, cyano, C 1 -C 4 -alkyl, the phenyl or heterocyclyl radical of the radicals mentioned can be partially or
• R 1 is C 1 -C 4 alkyl or halogen
• R 2 for -CC -haloalkyl, -CC . -C 4 alkylsulfonyl or halogen;
• R 3 is hydrogen
• R 4 represents hydrogen, -CC alkyl or -CC haloalkyl
• R 5 represents hydrogen or -CC 4 alkyl.
• R 7 and R 11 independently of one another for hydrogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkyl h ⁇ o;
• R 8 , R 10 , R 12 independently of one another represent hydrogen or methyl
• R 9 represents hydrogen, hydroxy, C ⁇ -Cg-alkyl or di (Ci-Cg-alkoxy) methyl
• R 7 and R 8 or R 8 and R 9 or R 9 and R 12 or R 8 and R 12 or R 11 and R 12 together stand for Ci-Cs-alkanediyl which is one, two or three under halogen, cyano, C ⁇ -C 4 -alkyl, C 4 -Halogenal - kyl or -CC 4 alkoxycarbonyl can carry selected substituents;
• R 9 and R 10 together represent an oxygen atom.
• R 6 is hydroxy, OR 13 or SR 13 ;
• Heterocyclyl is preferably a C-bonded 5-glide-unsaturated ring or a C-bonded 6-glueed-unsaturated ring, in particular pyridm-2-yl or pyridm-3-yl.
• the compounds of the formula Ia2 are also particularly preferred, in particular the compounds Ia.2. 1 to Ia2.77, which differ from the corresponding compounds lal.l to lal.77 in that R 9 is methyl.
• the compounds of the formula Ia3 in particular the compounds Ia3.1 to Ia3.77, which differ from the corresponding compounds Ial.l to Ial.77 in that R 9 and R 10 are methyl.
• the compounds of the formula Ia6 are particularly preferred, in particular the compounds Ia6.1 to Ia6.77, which differ from the corresponding compounds Ial.l to Ial.77 in that R 7 and R 8 together are pentane-1,5 -diyl stand.
• the compounds of the formula Ia7 in particular the compounds Ia7.1 to Ia7.77, which differ from the corresponding compounds Ial.l to Ial.77 in that R 8 and R 12 together for ethane-1 , 2-diyl.
• the compounds of the formula Ia8 in particular the compounds Ia8.1 to Ia8.77, which differ from the corresponding compounds Ial.l to Ial.77 in that R 7 , R 8 , R 11 and R 12 represents methyl and R 9 and R 10 together represent an oxygen atom.
• the compounds of the formula Ia9 are also particularly preferred, in particular the compounds Ia9.1 to Ia9.77, which differ from the compounds Ial.l to Ial.77 in that R 9 is hydroxyl.
• L 1 stands for hydroxy or a nucleophilically displaceable leaving group, such as halogen z. B. bromine, chlorine, hetaryl, e.g. B. imidazolyl, pyridyl, carboxylate, e.g. B. acetate, trifluoroacetate etc.
• Em activated benzoic acid derivative III (with L 1 OH) can be used directly, as in the case of the benzoyl halides or generated in situ, e.g. B. mt Dicyclohexylcaroodumid, T ⁇ phenyl - phosphane / Azodicarbonsaester, 2 - Py ⁇ dmdisulfld / Triphenylphosph- han, Carbonyldumidazol etc.
• auxiliary base is expediently used in equimolar amounts. Em slight excess of the auxiliary base z. B. 1.2 to 1.5 mol equivalents, based on II, may be advantageous.
• Suitable auxiliary bases are tertiary alkylammes, pyridine or alkali metal carbonates.
• a solvent for. B. chlorinated hydrocarbons such as methylene chloride, 1,2-dichloroethane, aromatic hydrocarbons such as toluene, xylene, chlorobenzene, ethers such as diethyl ether, methyl tert. -butyl ether, dimethoxyethane, tetrahydrofuran, dioxane, polar aprotic solvents such as acetomtril, dimethylformamide, dimethyl sulfoxide or esters such as ethyl acetate or mixtures thereof.
• benzoyl halides are used as the activated carboxylic acid component, it may be expedient to cool the reaction mixture to 0-10 ° C. when this reaction partner is added. The mixture is then stirred at 20-100 ° C., preferably at 25-50 ° C., until the reaction is complete. The workup is carried out in the usual manner, for. B. the reaction mixture is poured onto water, the product of value extracted. Particularly suitable solvents for this are methylene chloride, diethyl ether, dimethoxyethane and ethyl acetate. After drying the organic phase and removing the solvent, the crude ester I 'can be used for rearrangement without further purification.
• the rearrangement of the esters I * to the compounds of the formula I is advantageously carried out at from 20 to 40 ° C. in a solvent and in the presence of a base and, if appropriate, with the aid of a cyano compound as catalyst.
• a solvent for. B. acetonitrile, methylene chloride, 1, 2 -dichloroethane ,. Dioxane, ethyl acetate, dimethoxyethane, tetrahydrofuran, toluene or mixtures thereof can be used.
• Preferred solvents are acetonitrile and dioxane.
• Suitable bases are tertiary amines, such as triethylamine, pyridine or alkali carbonates, such as sodium carbonate, potassium carbonate, which are preferably used in an equimolar amount or up to a fourfold excess, based on the ester.
• Triethylamine or alkali carbonates are preferably used, preferably in a double equimolar ratio with respect to the ester.
• Inorganic cyanides such as sodium cyanide, potassium cyanide and organic cyano compounds such as acetone cyanohydrin and trimethylsilycyanide are suitable as cyano compounds. They are used in an amount of 1 to 50 mole percent, based on the ester. Acetone cyanohydrin or trimethylsilyl cyanide, e.g. B. in an amount of 5 to 15, preferably 10 mol percent, based on the ester.
• the reaction mixture is e.g. B. acidified with dilute mineral acid, such as 5% hydrochloric acid or sulfuric acid, with an organic solvent, e.g. B. extracted methylene chloride, ethyl acetate.
• the organic extract can with 5-10% alkali carbonate solution, e.g. B. sodium carbonate, potassium carbonate solution are extracted.
• the aqueous phase is acidified and the precipitate that forms is filtered off with suction and / or extracted with methylene chloride or ethyl acetate, dried and concentrated.
• cyclohexenones of the formula II are known or can be prepared by processes known per se (for example EP-A 71707, EP-A 142 741, EP-A 243 313, US 4,249,937, WO 92/13821).
• L 2 represents a leaving group such as halogen, e.g. B. chlorine, bromine or iodine, or sulfonate such as mesylate or triflate; bromine or triflate are preferred.
• halogen e.g. B. chlorine, bromine or iodine, or sulfonate such as mesylate or triflate; bromine or triflate are preferred.
• X represents halogen, preferably chlorine or bromine.
• oximes of the formula IV into the 4, 5-dihydroisoxazol-3-yl-benzene derivatives V can be carried out in a manner known per se via the intermediate stage of the hydroxamic acid chlorides. Nitrile oxides are generated from the latter in situ, which react with alkenes to give the desired products (cf., for example, Chem. Ber. 106, 3258-3274 (1973)). So the oxime IV z. B. oxidized with sodium hypochlorite and with an allyl halide, e.g. B.
• allyl chloride in an inert solvent such as methylene chloride, chloroform, tetrahydrofuran, diethyl ether, dioxane or acetonitrile to give 4,5-di-hydroisoxazol-3-yl-benzene derivative V.
• an inert solvent such as methylene chloride, chloroform, tetrahydrofuran, diethyl ether, dioxane or acetonitrile
• Suitable catalysts are, in particular, palladium ligand complexes in which the palladium is in oxidation state 0, metallic palladium, which may have been applied to a support, and preferably palladium (II) salts.
• the implementation Palladium (II) salts and metallic palladium are preferably carried out in the presence of complex ligands.
• tetrakis (tri-phenylphosphine) palladium can be used as the palladium (0) ligand complex.
• Metallic palladium is preferably coated on an inert support such as activated carbon, silicon dioxide, aluminum oxide, barium sulfate or calcium carbonate.
• the reaction is preferably carried out in the presence of complex ligands such as triphenylphosphine.
• Suitable palladium (II) salts are, for example, palladium acetate and palladium chloride. It is preferred to work in the presence of complex ligands such as triphenylphosphine.
• Suitable complex ligands for the palladium ligand complexes, or in the presence of which the reaction with metallic palladium or palladium (II) salts is preferably carried out, are tertiary phosphines, the structure of which is represented by the following formulas:
• z is the numbers 1 to 4 and the radicals R a to R ⁇ ? represent Ci-Cg-alkyl, C 3 -Cg-cycloalkyl, aryl -CC-C 2 alkyl or preferably aryl.
• Aryl stands for example for naphthyl and optionally substituted phenyl such as 2-tolyl and in particular for unsubstituted phenyl.
• the complex palladium salts can be prepared in a manner known per se, starting from commercially available palladium salts, such as palladium chloride or palladium acetate, and the corresponding phosphanes, such as, for. B. triphenylphosphane or 1, 2-bis (diphenylphosphano) ethane. Most of the complexed palladium salts are also commercially available.
• Preferred palladium salts are [(R) (+) 2,2'-bis (diphenylphosphine) -1,1'-binaphthyl] palladium (II) chloride, bis (triphenylphosphine) palladium (II) acetate and in particular bis ( riphenylphosphine) palladium (II) chloride.
• the palladium catalyst is used in the gel in a concentration of 0.05 to 5 mol%, preferably 1-3 mol%.
• Suitable bases are tertiary ames, such as, for example, N-methylpipe- ⁇ dm, ethyldus ⁇ propylamine, 1,8-B ⁇ sd ⁇ methylammonaphthalm or in particular triethylamine m.
• Alkali carbonate such as sodium carbonate or potassium carbonate, are also suitable. Mixtures of potassium carbonate and triethylamine are also suitable.
• nit ⁇ les such as benzonitrile and acetonitrile, aromatic hydrocarbons such as toluene, amides such as dimethylformamide, dimethylacetamide, tetra-C-Cd-alkylureas or N-methylpyrrolidone and preferably ethers such as tetrahydrofuran, methyl ter. serve butyl ether.
• ethers such as 1,4-dioxane and dimethoxyethane are preferred as solvents.
• L 3 stands for a Ci-Cg-alkoxy-Res and X for halogen, preferably - chlorine or bromine.
• Suitable bases and solvents are those mentioned above for the ring closure.
• L 4 stands for a nucleophilically displaceable leaving group, such as halogen, for. B. bromine or chlorine, acyloxy, e.g. B. acetyloxy, ethyl carbonyloxy, or alkylsulfonyloxy, e.g. B. methylsulfonyloxy or trifluoromethylsulfonyloxy;
• the compounds of formula XI can be used directly, such as. B. in the case of carboxylic acid halides, carboxylic acid anhydrides or m situ generated (z. B. by means of dicyclohexylcarbonyl-dumid, carbonyldumidazole, etc.).
• the starting compounds are generally used in an aquimolar ratio. However, it can also be advantageous to use one or the other component in excess.
• auxiliary base it may be advantageous to carry out the reaction in the presence of a base.
• the reactants and the auxiliary base are expediently used in equimolar amounts.
• Suitable auxiliary bases are tertiary alkylammes, such as triethylamine, aromatic ames, such as Py ⁇ dm, alkali metal carbonates, for.
• alkali metal bicarbonates such as sodium bicarbonate or potassium bicarbonate
• alkali metal alcoholates such as sodium methoxide, sodium methoxide, potassium tert-butoxide or alkali metal hydrates, e.g. B. sodium hydride.
• Triethylamine and Py ⁇ d are preferably used.
• chlorinated hydrocarbons such as methylene chloride, -1.2 dichloroethane, aromatic hydrocarbons, e.g. B.
• 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.
• Suitable halogenating agents are, for example, phosgene, diphosgene, triphosgene, thionyl chloride, oxalyl chloride, phosphorus oxychloride, phosphorus pentachloride, mesyl chloride, chloromethylene-N, N-dimethylammonium chloride, oxalyl bromide, phosphorus oxybromide etc.
• the starting compounds are generally used in an aquimolar ratio. It may also be advantageous to use one or the other component in excess.
• solvents such.
• reaction temperature is in the range from 0 ° C. to the boiling point of the reaction mixture.
• the processing can take place in a manner known per se to produce the product hm.
• the starting compounds are generally used in an aquimolar ratio. However, it can also be advantageous to use one or the other component in excess.
• Suitable bases are tertiary Alkylamme such as triethylamine, aro ⁇ matic nurse as Pyridm, alkali metal such suitable.
• alkali metal bicarbonates such as sodium bicarbonate or potassium bicarbonate
• alkali metal alcoholates such as sodium methoxide, sodium ethanolate, potassium tert-butoxide or alkali metal hydrates, such as.
• Sodium hydride or potassium tert-butoxide is preferably used.
• solvents such.
• reaction temperature is in the range from 0 ° C. to the boiling point of the reaction mixture.
• Suitable oxidizing agents are m-chloroperbenzoic acid, peroxyacetic acid, trifluoroperoxyacetic acid, hydrogen peroxide, optionally in the presence of a catalyst such as tungstate.
• the starting compounds are generally used in an aquimolar ratio. It can be advantageous to use one or the other component in excess.
• a solvent come e.g. B. chlorinated hydrocarbons, such as methylene chloride or 1, 2-D ⁇ chlorethan, aromatic hydrocarbons, for. B. toluene, xylene or chlorobenzene, ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane, polar aprotic solvents such as acetonitrile or dimethylfor mamide or esters, such as ethyl acetate, or mixtures thereof.
• chlorinated hydrocarbons such as methylene chloride or 1, 2-D ⁇ chlorethan
• aromatic hydrocarbons for. B. toluene, xylene or chlorobenzene
• ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane
• polar aprotic solvents such as acetonitrile or dimethyl
• 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.
• Table 2 lists compounds of the formula I which were prepared in an analogous manner or can be prepared.
• the 3- (4, 5-dihydroisoxazol-3-yl) -substituted benzoylcyclohexenone derivatives of the formula 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 the compounds of the formula I control vegetation very well on non-cultivated areas, especially when high amounts are applied. In crops such as wheat, rice, maize, soybeans and cotton, they act against weeds and grass weeds without causing any significant damage to crops. This effect occurs especially at low application rates.
• the compounds of the formula I or herbicidal compositions comprising 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 of the formula I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
• the compounds of the formula I or the herbicidal compositions comprising them can be, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or granules by spraying, atomizing, dusting, scattering or pouring.
• the application forms depend on the 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.
• mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. B. paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, e.g. B. amines such as N-methylpyrrolidone and water.
• mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin
• aliphatic, cyclic and aromatic hydrocarbons e.g. B. paraffins, tetrahydronaphthalene, alkylated naphthalen
• 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 can the 3- (4, 5-dihydroisoxazol-3-yl) -substituted benzoylcyclohexenone derivatives as such or dissolved in an oil or solvent, by means of wetting agents, adhesives, dispersants or emulsifiers in water be homogenized.
• wetting agents, adhesives, dispersants or emulsifiers it is also possible to prepare concentrates consisting of active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil, which are suitable for dilution with water.
• alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. B. 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 ethers, 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 nonylphenol, alkylphenol ether, ethoxylated isoo
• Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
• Granules e.g. B. coating, impregnation and homogeneous granules can be prepared 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 cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
• concentrations of the compounds of the formula I in the ready-to-use preparations can be varied within a wide range.
• the formulations contain from about 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 application rates of the compound of the formula I are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (as mentioned) depending on the control target, the season, the target plants and the growth stage.
• the 3 - (4, 5-d ⁇ hydro ⁇ soxazol-3-yl) - substituted benzoylcyclohexenone derivatives of the formula I can be mixed with numerous representatives of other herbicidal or wax-regulating active ingredient groups and applied together.
• Plastic flower pots with loamy sand with about 3.0% humus as a substrate served as culture vessels.
• the seeds of the test plants were sown separately according to species.
• the water-suspended or emulsified active ingredients were applied directly after sowing using finely distributing nozzles.
• the tubes were lightly sprinkled to encourage germination and growth, and then covered with clear plastic covers until the plants had grown. This cover causes the test plants to germinate evenly, provided that this has not been impaired by the active ingredients.
• test plants were first grown to a height of 3 to 15 cm according to the growth form and only 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 0.25 or 0.125 kg / ha a.S. (active substance).
• the plants were kept in a species-specific manner at temperatures of 10 b s 25 ° C or 20 to 35 ° C.
• the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to the individual treatments was evaluated.

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• Chemical & Material Sciences (AREA)
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• Dentistry (AREA)
• Pest Control & Pesticides (AREA)
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• 2000
  • 2000-11-29 US US10/130,021 patent/US6667333B2/en not_active Expired - Fee Related
  • 2000-11-29 EP EP00977591A patent/EP1242393A1/de not_active Withdrawn
  • 2000-11-29 CA CA002394005A patent/CA2394005A1/en not_active Abandoned
  • 2000-11-29 JP JP2001541885A patent/JP2003515595A/ja not_active Withdrawn
  • 2000-11-29 AU AU15248/01A patent/AU1524801A/en not_active Abandoned
  • 2000-11-29 WO PCT/EP2000/011907 patent/WO2001040200A1/de not_active Application Discontinuation
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