Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
• • 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
  • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
  • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
  • A01N41/10—Sulfones; Sulfoxides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/24—Sulfones; Sulfoxides having sulfone or sulfoxide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
  • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
  • C07C323/32—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to an acyclic carbon atom of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
  • C07C323/65—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfone or sulfoxide groups bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

• the present invention relates to benzoylcyclohexenone derivatives and their agriculturally acceptable salts, processes for their preparation, agents which contain such compounds and the use of the benzoylcyclohexenone derivatives, their salts and / or agents which contain them for combating harmful plants.
• Trisubstituted benzoylcyclohexenones are described in the prior art as herbicidally active compounds.
• EP 186 120 describes herbicidally active compounds of the general formula A
• R is C 1 -C 4 alkyl or C ⁇ -C 4 haloalkyl
• R 1 , R 2 , R 3 , R 4 , R 5 R 6 can be hydrogen or -CC-alkyl
• R 7 , R 8 independently of one another, inter alia, for halogen, -CC alkyl
• R 7 stands in particular for hydrogen.
• EP 0 319 075 discloses benzoylcyclohexenone derivatives of the general formula B
• X can be the same or different and means, inter alia, halogen, nitro, cyano, alkyl, haloalkyl, alkylthio, haloalkylthio, alkylsulfonyl, haloalkylsulfonyl, alkylsulfinyl, haloalkylsulfinyl, R is hydrogen or alkyl,
• R 1 represents hydroxy, cyano, nitro, alkylcarbonyl
• R 2 represents alkyl
• Y is alkylene, n and 1 is 0, 1, 2, 3, 4 or 5 and m is 0 or 1.
• EP 249 150 discloses 2-benzoylcyclohex-2-enones, the cyclohex-2-enone radical in the 3-position being linked to a thio substituent.
• the benzoylcyclohexenones known from the prior art are often unsatisfactory in their effectiveness against harmful plants. In addition, they are often not compatible with crop plants, but act unselectively against useful and harmful plants.
• the present invention is therefore based on the object of providing new herbicides with which harmful plants can be controlled better than hitherto.
• the new herbicides should advantageously have a high activity against harmful plants.
• crop tolerance is desirable.
• the present invention accordingly relates to benzoylcyclohexenone derivatives of the general formula I
• R 2 is Cx-Cg-alkyl or Cx-Ce-haloalkyl; R 3 halogen, cyano, nitro, Cx-Cg-alkyl, C; ⁇ _-C 5 -haloalkyl, Ci-Cg-alkoxy, Ci-C ß -haloalkoxy, C ⁇ -C 6 -alkylthio, C ⁇ -C 6 -haloalkylthio, Ci-C ß -alkylsulfinyl, Ci-C ⁇ -haloalkylsulfinyl C ⁇ -C 6 -alkylsulfonyl, C ⁇ -C 6 -haloalkylsulfonyl,
• R 4 hydroxy, SR 11 or NR 12 R 13 ;
• R 5 , R 6 , R 9 , R 10 independently of one another are hydrogen or C 1 -C 4 -alkyl
• R 7 , R 8 independently of one another hydrogen or -CC 4 alkyl or together with the carbon atom to which they are attached form a carbonyl group;
• n 0, 1 or 2;
• R 11 C ⁇ -C4 alkyl oer phenyl which may be partially or fully halogenated defined and / or may carry one to three of the strigdne groups: nitro, cyano, C 4 -alkyl, C 4 haloalkyl, C -C alkoxy or -C -C haloalkoxy;
• R 12 represents hydrogen, Ci-C-alkyl or -CC 4 alkoxy
• R 13 represents hydrogen or -CC-alkyl
• R 12 and R 13 with the nitrogen to which they are attached represent a 5- or 6-membered saturated, partially saturated or unsaturated nitrogen heterocycle, the given ⁇ optionally having one or two further hetero atoms selected from 0, S and N, and which may be partially or fully halogenated and / or may carry one, two or three of the following radicals: cyano, C 4 alkyl, C ⁇ -C4-haloalkyl, C ⁇ ⁇ C -alkoxy or C ⁇ -C 4 haloalkoxy;
• the invention further relates to processes for the preparation of the benzoylcyclohexenone derivatives of the formula I, herbicidal compositions which contain benzoylcyclohexenone derivatives of the formula I, and processes for controlling unwanted vegetation using the benzoylcyclohexenone derivatives of the formula I.
• the compounds of the formula I can contain one or more centers of chirality and are then present as enantiomers or mixtures of diastereomers.
• the invention relates both to the pure enantiomers or diastereomers and to their mixtures.
• the compounds of the formula I can also be used in the form of their agriculturally useful salts, the type of salt generally not being important, provided that it is compatible with agriculture.
• 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 are used.
• the cations used are, 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 if desired one to four hydrogen atoms by C ⁇ - C 4 alkyl, hydroxy -CC-alkyl, C !
• -C -alkoxy -CC 4 -alkyl hydroxy -CC -alkoxy -CC -alkyl, phenyl or benzyl can be replaced, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2- (2-hydroxyeth -l-oxy) eth-1-ylammonium,
• 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 butyrate.
• Alkylsulfonyl, haloalkylsulfonyl, trialkylsulfonium, trialkylsulfoxonium parts can be straight-chain or branched.
• Halogen is fluorine, chlorine, bromine or iodine.
• -C-C 6 alkyl -C-C 4 alkyl, as mentioned above, and z.
• Ci-Cg-haloalkyl C ⁇ -C -haloalkyl, as mentioned above, and for example for 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorhexyl, 6-chlorohexyl, 6-bromohexyl, 6th Iodohexyl and dodecafluorohexyl;
• z. B methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1, 1-dimethylethyloxy;
• Ci-Cg-alkoxy -CC alkoxy, as mentioned above, and z.
• -C -alkyl for example for methoxymethyl, ethoxymethyl, propoxymethyl, (l-methylethoxy) methyl, butoxymethyl, (l-methylpropoxy) methyl, (2-methylpropoxy) methyl, (1, 1-dirnethylethoxy) methyl, 2- (methoxy) ethyl, 2- (ethoxy) ethyl, 2- (propoxy) ethyl, 2- (1-methylethoxy) ethyl, 2- (butoxy) ethyl, 2- (1-methylpropoxy) ethyl, 2- (2nd -Methyl-propoxy) ethyl, 2- (1, 1-dimethylethyloxy) ethyl, 2- (methoxy) - propyl, 2- (ethoxy) propyl, 2- (propoxy) propyl, 2- (l-methylethoxy) ropyl, 2- (butoxy) propyl, 2- (1-methylpropoxy) ropyl, 2- (2-
• C ⁇ -C 4 -haloalkoxy a C ⁇ -C4-alkoxy as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, ie, for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2- Fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 2, 2-difluoroethoxy, 2,2, 2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2, 2-difluoroethoxy, 2, 2- dichloro-2-fluoroethoxy,
• Ci-C ⁇ -haloalkoxy -C-C 4 -haloalkoxy, as mentioned above, and for example 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorhexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy;
• Ci-Ce-alkylthio (Cx-Ce-alkylsulfanyl: -CC 6 -alkyl-S-): e.g. methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio or 1, 1-dimethylethylthio, Pentylthio, 1-methylbutylthio,
• Ci-C ⁇ -haloalkylthio a Ci-C ß- alkylthio radical, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethyl hylthio -Fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2, 2-difluoroethylthio, 2,2, 2-trifluoroethylthio, 2,2, 2-trichloroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2 , 2-difluoroethylthio, 2, 2-dichloro-2-fluoroethylthio, pent
• -C -C 6 -Halogenalkylsulfinyl -C -C 6 alkylsulfinyl, as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example fluoromethylsulfinyl, difluoromethylsulfinyl, trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethyl Fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2, 2-difluoroethylsulfinyl, 2,2, 2-trifluoroethylsulfinyl, 2, 2, 2-trichloroethylsulfinyl, 2-chloro-2-fluoroethyl
• 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, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2, 2-sulfonyl-2-fluoronyl, 2-2-difluoronyl 2-chloro-2, 2-difluoroethylsulfonyl, 2, 2-dichloro-2-fluoroethylsulfonyl,
• Examples of a 5- or 6-membered nitrogen heterocycle which can be saturated, partially saturated or unsaturated and which can contain one or two further heteroatoms selected from nitrogen, oxygen or sulfur are:
• 5-link rings such as:
• Tetrahydropyrrol-1-yl 2,3-dihydro-lH-pyrrol-l-yl, 2,5-dihydro-lH-pyrrol-l-yl, pyrrol-1-yl, tetrahydropyrazol-1-yl, tetrahydroisoxazol-2- yl, tetrahydroisothiazol-2-yl, tetrahydroimidazol-1-yl, tetrahydrooxazol-3-yl, tetrahydrothiazol-3-yl, 4,5-dihydro-lH-pyrazol-l-yl, 2,5-dihydro-lH-pyrazole l-yl, 2, 3-dihydro-1H-pyrazol-l-yl, 2, 5-dihydroisoxazol-2-yl, 2, 3-dihydroisoxazol-2-yl, 2, 5-dihydroisothiazol-2-yl, 2,
• 6-link rings such as:
• the variables R 1 to R 13 preferably have the following meanings, in each case individually or in combination: R 1 C 1 -C 4 alkyl, in particular methyl, ethyl or n-propyl, C 1 -C 4 haloalkyl, in particular trifluoromethyl or difluoromethyl, or C 1 -C 4 alkoxy-C 1 -C 2 alkyl, in particular methoxymethyl or ethoxymethyl;
• R 2 -C 4 alkyl such as methyl, ethyl or n-propyl or C ⁇ -C 4 haloalkyl such as trifluoromethyl or difluoromethyl;
• R 3 halogen, in particular fluorine, chlorine or bromine, cyano, nitro, -CC alkoxy, such as methoxy, ethoxy or n-propoxy,
• C ⁇ -C4-haloalkoxy in particular difluoromethoxy or trifluoromethoxy, C ⁇ -C4-alkylthio, in particular methylthio, ethylthio or n-propylthio, C ⁇ -C 4 -halogenoalkylthio, in particular trifluoromethylthio, difluoromethylthio or, C ⁇ ⁇ C alkyl sulfinyl especially methylsulfinyl, ethylsulfinyl or propylsulfinyl n-, C ⁇ -C 4 haloalkylsulfinyl, especially di- fluoromethylsulfinyl or trifluoromethylsulphinyl, C ⁇ -C 4 alkyl sulfonyl, in particular methylsulfonyl, ethylsulfonyl, propylsulfonyl or n-, C 1 -C 4 haloal
• R 4 is hydroxy, NR 12 R 13 or phenylthio, where the phenyl radical can be partially or completely halogenated and / or can carry one to three of the following groups: nitro, cyano, C 1 -C 4 alkyl, C ! -C 4 -haloalkyl, -C-C 4 alkoxy or -C-C 4 ⁇ haloalkoxy; especially hydroxy, phenylthio or NR 12 R 13 ;
• R 5 , R 6 , R 9 , R i -O independently of one another for hydrogen or C 1 -C 4 alkyl such as methyl or ethyl;
• R 7 , R 8 are hydrogen or -CC 4 alkyl, such as methyl or ethyl, or R 7 and R 8 together with the carbon atom to which they are attached form a carbonyl group; R 12 -C 4 alkoxy, especially methoxy or ethoxy;
• R 13 -C 4 alkyl in particular methyl or ethyl
• R 12 and R 13 form together with the nitrogen to which they TIALLY ⁇ are a 5- or 6-membered unsaturated hetero cyclus from having optionally one or two further hetero atoms selected from 0, N or S, and which may be partially or fully halogenated and / or may carry two or three of the following radicals: cyano, C 4 -alkyl, C 4 haloalkyl, C ⁇ -C 4 alkoxy or C ⁇ -C -haloalkoxy; in particular pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl, 1,2,3-triazol-l-yl, 1,2,4-triazol-l-yl or 1,3,4-tri azol-1-yl; in particular pyrrol-1-yl or pyrazol-1-yl.
• variable n is preferably 2.
• R 1 for -CC 4 alkyl or C] .- C 4 haloalkyl in particular for C 1 -C 4 -alkyl such as methyl, ethyl or n-propyl and especially for methyl.
• n is 2 and R 2 is C 1 -C 4 -alkyl, especially methyl, ethyl or propyl, in particular methyl or ethyl.
• R 3 for halogen such as fluorine, chlorine or bromine, cyano, nitro
• C ⁇ -C4-haloalkoxy or C ⁇ -C 4 alkylsulfonyl particularly preferably C ⁇ -C 4 alkoxy, C 1 -C 4 haloalkoxy, -CC alkyl sulfonyl and very particularly preferably for methoxy, difluoromethoxy, methyl sulfonyl or ethyl sulfonyl;
• halogen such as fluorine, chlorine or bromine, cyano
• Nitro or -CC 4 alkylsulfonyl especially for chlorine, cyano, nitro or Ci-C 4 alkylsulfonyl; particularly preferred for C 1 -C 4 -alkylsulfonyl and very particularly preferably for methylsulfonyl or ethylsulfonyl;
• C ⁇ -C 4 alkoxy such as methoxy or ethoxy, or C ⁇ -C 4 haloalkoxy
• C 1 -C 4 -haloalkoxy such as difluoromethoxy or trifluoromethoxy; and especially for difluoromethoxy.
• R 4 for phenylthio where the phenyl ring can be partially or completely halogenated and / or can carry one to three of the following radicals: nitro, cyano, C ⁇ -C 4 alkyl, C ! -C 4 haloalkyl, -CC alkoxy or Ci-Cj-haloalkoxy.
• R 5 , R 6 , R 9 , R 10 are hydrogen or methyl; R 7 , R 8 are hydrogen or methyl; or R 7 and R 8 together with the carbon atom to which they are attached form a carbonyl group; particularly preferably hydrogen or methyl.
• R 1 has the meanings given above and is in particular C 1 -C 4 -alkyl, especially methyl;
• R2 is C ⁇ -C 4 alkyl or C ⁇ -C 4 -haloalkyl, in particular
• R 3 represents -C 4 alkylsulfonyl or C 1 -C 4 haloalkylsulfonyl, in particular C 1 -C 4 alkylsulfonyl, especially methylsulfonyl;
• R 4 represents hydroxy;
• R 5 to R 10 represent hydrogen or methyl; n 2.
• R 1 for C ! -C 4 alkyl
• R 2 represents C 1 -C 4 alkyl, especially methyl, ethyl or propyl, especially methyl;
• R 3 for halogen such as chlorine, -CC 4 alkoxy such as methoxy
• C ⁇ -C 4 haloalkoxy such as difluoromethoxy or C ⁇ -C 4 alkyl sulfonyl is methylsulfonyl such as, in particular C ⁇ -C 4 alkoxy such as methoxy, C ⁇ -C -haloalkoxy such as difluoromethoxy or C ⁇ -C 4 alkylsulfonyl, such as methylsulfonyl, specifically for
• C ⁇ -C 4 haloalkoxy such as difluoromethoxy or C ⁇ -C 4 alkyl sulfonyl such as methylsulfonyl
• R 4 for hydroxy, phenylthio, where the phenyl radical can be partially or completely halogenated and / or can carry one to three of the following groups: nitro, cyano, C 1 -C 4 -alkyl,
• C 1 -C 4 haloalkyl C 1 -C 4 alkoxy or C 1 -C haloalkyl; N-methoxy-N-methylamino or 1-pyrazolyl; especially hydroxy;
• R 5 to R 10 are hydrogen or methyl; n 2.
• the compounds of the formula Ib in particular the compounds Ib.l to Ib.48, which differ from the compounds la.l to Ia.48 in that R 7 is methyl.
• the compounds of the formula Ic are also particularly preferred, in particular the compounds Ic .1 to Ic.48, which differ from the compounds Ia.1 to Ia.48 in that R 7 and R 8 are methyl.
• Equally extraordinarily preferred compounds of the mel For ⁇ Id in particular the compounds Id.l to Id.48, which differ from the compounds la.l to Ia.48 in that R 9 and R 10 are methyl.
• the compounds of the formula le in particular the compounds le.l to Ie.48, which differ from the compounds la.l to Ia.48 in that R 5 , R 6 , R 9 and R 10 for methyl and R 7 and R 8 together with the carbon atom to which they are attached form a carbonyl group.
• the compounds of the formula Ih in particular the compounds Ih.l to Ih.48, which differ from the compounds la.l to Ia.48 in that R 4 is phenylthio and R 7 and R 8 are methyl ,
• the compounds of the formula Ii are particularly preferred, in particular the compounds Ii .1 to Ii.48, which differ from the compounds Ia.1 to Ia.48 in that R 4 is phenylthio and R 9 and R 10 are methyl ,
• the compounds of the formula Ik in particular the compounds Ik.l to Ik.48, which differ from the compounds la.l to Ia.48 in that R 4 is phenylthio and R 5 , R 6 , R 9 and R! ° for methyl and R 7 and R 8 together with the carbon to which they are attached form a carbonyl group.
• the compounds of the formula I are prepared in a variety of ways.
• L 1 stands for a nucleophilically displaceable leaving group, such as halogen z. B. bromine or chlorine, hetaryl, e.g. B. imidazolyl or pyridyl, carboxylate, e.g. B. acetate or trifluoroacetate or the like.
• the activated carboxylic acid IVb can be used directly, as in the case of the carboxylic acid halides or generated in situ, e.g. B. with carbodiimides such as ethyl (3 '-dimethylamino-propyl) carbodiimide, dicyclohexylcarbodiimide, triphenylphosphine / azodicarboxylic acid ester, 2-pyridinedisulfide / triphenylphosphine, carbonyldiimidazole or the like.
• carbodiimides such as ethyl (3 '-dimethylamino-propyl) carbodiimide, dicyclohexylcarbodiimide, triphenylphosphine / azodicarboxylic acid ester, 2-pyridinedisulfide / triphenylphosphine, carbonyldiimidazole or the like.
• 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.
• Tertiary alkyl amines, pyridine or alkali metal carbonates are suitable as auxiliary bases.
• 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, organic nitriles such as acetonitrile, amides such as dimethylformamide or Dimethyl sulfoxide or esters such as ethyl acetate or mixtures thereof can be used.
• 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
• 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, the product of value 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.
• solvent e.g. Acetonitrile, methylene chloride, 1, 2-dichloroethane, dioxane, ethyl acetate, toluene or mixtures thereof can be used.
• Preferred solvents are acetonitrile and dioxane.
• Suitable bases are tertiary amines such as triethylamine, aromatic amines such as pyridine or alkali 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. 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 one
• 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. methylene chloride or Extracted ethyl acetate.
• the organic extract can with 5-10% alkali carbonate solution, e.g. B. sodium carbonate or potassium carbonate solution.
• 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.
• the ester is prepared as described above, and the reaction solution containing the ester is then mixed with a catalyst and the base, and the rearrangement reaction is carried out as described above.
• halogenating agents are 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 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 bicarbonates such as sodium bicarbonate and potassium bicarbonate, alkali metal alcoholates such as sodium methoxide, sodium ethanolate, potassium tert. butanolate or alkali metal hydrides, e.g. Sodium hydride. Triethylamine or pyridine are preferably used.
• solvents such.
• 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.
• the cyclohexanediones of the formula III used as starting materials are known or can be prepared by processes known per se (for example EP-A 71 707, EP-A 142 741, EP-A 243 313, US 4,249,937, WO 92/13821).
• the compounds HSR 11 and HNR 12 R 13 are also known or can be prepared by known processes.
• the amino group in compound VI is first converted into a thioalkyl group in step a).
• the compound VI with a nitrite (such as an organic nitrite (R-ONO), for example n-butyl nitrite, iso-amyl nitrite or tert-butyl nitrite, or an inorganic nitrite (for example sodium nitrite or potassium nitrite) in the presence of a mineral acid such as hydrochloric acid, sulfur ⁇ acid or phosphoric acid) in the presence of a dialkyl disulfide R 2 SSR 2, such as dimethyl disulfide, diethyl disulfide, etc., wherein R 2 has the abovementioned meaning, and reacted in the presence of a catalyst.
• a nitrite such as an organic nitrite (R-ONO), for example n-butyl nitrite, iso-amyl nitrite or tert-butyl
• the compounds of the formula VI are generally reacted with 1 to 3 equivalents of nitrite, 1 to 1.5 equivalents of nitrite are preferably used.
• An alkyl nitrite is preferably used as the nitrite.
• the reaction can be carried out in the presence of solvents.
• solvents for example, haloalkanes such as 1, 2-dichloroethane or methylene chloride, or aromatics such as benzene, toluene, chlorobenzene, nitrobenzene can be used.
• solvents for example, haloalkanes such as 1, 2-dichloroethane or methylene chloride, or aromatics such as benzene, toluene, chlorobenzene, nitrobenzene can be used.
• 1-3 equivalents of dialkyl disulfide, preferably 1-2 equivalents of dialkyl disulfide are used.
• Transition metals or transition metal salts can be used as catalysts, e.g. Copper powder, elemental copper in another form, e.g. Chips, wire, granules, shot, rods; Copper (I) salts, e.g. Copper-I-chloride, copper-I-bromide or copper-I-iodide; Copper (II) salts or elemental iodine; particularly preferably copper powder.
• Copper powder elemental copper in another form, e.g. Chips, wire, granules, shot, rods
• Copper (I) salts e.g. Copper-I-chloride, copper-I-bromide or copper-I-iodide
• Copper (II) salts or elemental iodine particularly preferably copper powder.
• the temperature for the reaction is generally 40 to 150 ° C, preferably 50 to 100 ° C, particularly preferably 60 to 90 ° C.
• the product can be used without further cleaning. If necessary, product cleaning can also take place, e.g. by distillation, crystallization etc.
• alkylthio or haloalkylthio compound consists in converting the compound of the formula VI in a manner known per se via diazotization into the corresponding diazonium salt and converting it into the corresponding mercapto compound using hydrogen sulfide, an alkali metal sulfide or a xantogenate.
• the mercapto compound obtained is then converted in terms of a Thioethersynthese by reaction with alkyl halides R 2 -Hal in the alkylthio or haloalkylthio group, thylthiooeuvre for example by reaction with methyl halide in the Me ⁇ or by reaction with chlorine or fluorine Bromdi- methane in the difluoromethylthio.
• Suitable solvents are inert organic solvents, for example hydrocarbons such as toluene or hexane, ethers such as diethyl ether, dimethoxyethane, methyl tert. -butyl ether, dioxane or tetrahydrofuran or alcohols such as methanol or ethanol.
• the thioether VII can be converted into the corresponding sulfinyl (halogen) alkyl compound by treatment with one equivalent of oxidizing agent (step b)). If a further equivalent of oxidizing agent is added, the corresponding sulfonyl (halogen) alkyl compound VIII is obtained from the sulfinyl (halogen) alkyl compound.
• oxidizing agent for example, tert. -Butyl hydroperoxide, organic peracids such as m-chloroperbenzoic acid, peracetic acid or trifluoroperacetic acid, hydrogen peroxide, if appropriate in the presence of a catalyst such as Wolfra at.
• the thio (halogen) alkyl compounds are preferably converted directly into the sulfonyl (halogen) alkyl compounds VIII by using two equivalents of oxidizing agents, if appropriate in the presence of a catalyst, such as tungstate.
• Suitable solvents are organic solvents which are inert to oxidation, such as, for example, chlorinated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride or 1,2-dichloroethane, aromatic hydrocarbons, e.g. B.
• chlorinated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride or 1,2-dichloroethane
• aromatic hydrocarbons e.g. B.
• the solvent used is preferably the underlying organic acid, for example formic, acetic or trifluoroacetic acid, optionally in a mixture with one or more of the abovementioned solvents.
• the reaction temperature is normally in the range between the melting point and the boiling point of the reaction mixture, preferably in the range from 0 ° C. to 150 ° C.
• reducing agents are hydrazines, metal hydrides such as aluminum hydride and complex hydrides derived therefrom such as lithium aluminum hydride, diisobutyl aluminum hydride or boranes, and nascent hydrogen, eg. 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.
• transition metals can be used as such or in a supported form, for example on activated charcoal, activated in the form of Me ⁇ metals, eg. 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 1 -C 4 -alcohols, such as methanol, ethanol, n-propanol, isopropanol or n-butanol, halogenated C 1 -C 6 -carbons substances such as dichloromethane, trichloromethane, trichloroethane, trichlorethylene, aromatic hydrocarbons such as benzene, toluene, xylenes, chlorobenzene, carboxylic acid esters such as acetic acid reethylester, aqueous solutions of inorganic acids, such as aqueous hydrochloric acid or organic acids and their mixtures with water.
• C 1 -C 4 -alcohols such as methanol, ethanol, n-propanol, isopropanol or n-butanol
• 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 60 ° 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.
• bromination of the sulfonylated aniline IX in step d) leads to 4-bromoaniline X.
• Suitable brominating agents for this purpose are conventional brominating agents such as bromine etc., preferably oligobromine compounds such as pyridinium tribromide, dioxane dibromide or quaternary ammonium polybromides such as tetrabutylammonium tribromide.
• the reaction is carried out in the presence of a base, such as alkali metal or alkaline earth metal carbonate, for example sodium, potassium, magnesium or calcium carbonate, alkali metal bicarbonate, for example sodium bicarbonate.
• a base such as alkali metal or alkaline earth metal carbonate, for example sodium, potassium, magnesium or calcium carbonate, alkali metal bicarbonate, for example sodium bicarbonate.
• Suitable solvents are inert organic solvents, such as, for example, aliphatic or cycloaliphatic hydrocarbons, for example n-hexane or cyclohexane, halogenated hydrocarbons, for example dichloromethane, trichloromethane, carbon tetrachloride, trichloroethane, trichlorethylene, heteroaromates such as pyridine, polar aprotic
• Solvents such as acetonitrile or anhydrous inorganic or organic acids such as acetic acid.
• the reaction temperature is normally between the melting point of the reaction mixture and 60 ° C., preferably in the range from 0 ° C. to 40 ° C.
• the reaction is preferably carried out in pyridine as a solvent or in a solvent mixture with a proportion of at least 80% by weight of pyridine.
• solvent mixtures come as further solvents, for example methanol, ethyl acetate, butyl acetate, water, etc., may be considered.
• the aniline IX is initially introduced in pyridine or a solvent mixture containing pyridine as a solution or suspension.
• the brominating agent is then added over a period of 1 minute and 5 hours, depending on the size of the reaction mixture.
• the addition is either direct, i.e. without solvent or together with a solvent.
• bromine is used as the brominating agent
• the addition is preferably carried out together with a suitable solvent, e.g. Pyridine to form pyridinium bromide.
• a suitable solvent e.g. Pyridine to form pyridinium bromide.
• a particularly high selectivity in the ratio of monobromo to dibromo compounds is achieved.
• the brominating agent and the aniline IX are used in a molar ratio of 1: 1 to 2: 1.
• the brominating agent is preferably used in equimolar amounts or in a slight excess.
• the reaction is usually carried out at temperatures from 20 ° C. to the boiling point of the solvent, preferably in the range from 60 to 85 ° C.
• the reaction time is 1 to 24 hours, preferably 2 to 12 hours, in particular 5 to 8 hours.
• Alkylthio or haloalkylthio group in step e) succeeds, for. B. in the manner previously described in step a). This gives the bromothioether XI.
• step f) The bromothioether XI is then subjected to an oxidation in step f) analogously to step b), the bromobenzene XII being obtained.
• the bromobenzene XII is then converted into the carboxylic acid IVa.
• XII can first be converted into the nitrile XIII (step g)) and then hydrolyzed to the carboxylic acid IVa (step h)).
• the nitrile XIII can be produced, for example, by reacting XII with copper (I) cyanide in the sense of a Rosenmund-von-Braun reaction (see, for example, Org. Synth. Vol III, 212 (1955)).
• the implementation is usually carried out at an elevated rate Temperature in the range above 100 ° C, preferably in the range from 120 to 180 ° C by.
• a suitable solvent is, for example, dimethylformamide.
• Step i) in Scheme 1 can also be accomplished by implementing the
• Bromine compound XII can be realized with carbon monoxide, a base and water under elevated pressure in the presence of a palladium, nickel, cobalt or rhodium catalyst.
• Nickel, cobalt, rhodium and especially palladium can be metallic or in the form of conventional salts such as in the form of halogen compounds, for example palladium (II) chloride, rhodium (III) chloride hydrate, acetates, e.g. As palladium (II) acetate, cyanides, etc. can be used in the known valence levels.
• R 7 R 18 where the radicals R 15 to R 18 for low molecular weight alkyl, for example C 1 -C 6 alkyl, cycloalkyl such as cyclohexyl, aryl, C 1 -C 4 alkylaryl, for. B. benzyl, phenethyl or aryloxy.
• Aryl is, for example, naphthyl, anthryl and preferably optionally substituted phenyl, the substituents only having 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 Ci-Cö-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 1 -C 6 -alkoxy radicals.
• A stands for a divalent organic radical, e.g. B. C ⁇ C 4 alkylene, 1, 2-cycloalkylene, ⁇ , ⁇ '-Ferrocendiyl, ⁇ , ⁇ -biphenyl or comparable bifunctional groups.
• the phosphine complexes can be prepared in a manner known per se. For example, one starts from customary commercially available metal salts such as palladium (II) chloride or palladium (II) acetate and adds the phosphine, for example P (C 6 H 5 ) 3 , P (nC 4 H 9 ) 3 , PCH 3 (C 6 H 5 ) 2 , 1, 2-bis (diphenylphosphino) ethane, tricyclohexylphosphine.
• metal salts such as palladium (II) chloride or palladium (II) acetate
• P (C 6 H 5 ) 3 , P (nC 4 H 9 ) 3 , PCH 3 (C 6 H 5 ) 2 1, 2-bis (diphenylphosphino) ethane, tricyclohexylphosphine.
• 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 bromine compound XII.
• the reaction partner water can also serve as a solvent at the same time, i. H. the maximum amount is not critical.
• Inert solvents which are customary for carboxylation reactions, 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 urine substances such as tetra-C 1 -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. Alkylamines, e.g. B. trialkylamines such as triethylamine, cyclic amines such as N-methylpiperidine or N, N '-dimethylpiperazine, pyridine, alkali metal or hydrogen carbonates, or tetraalkyl-substituted urea derivatives such as tetra-C 1 -C 4 alkyl urea, e.g. B. tetramethyl urea to name.
• the amount of base is not critical.
• 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.
• the conversion is achieved, for example, by converting the amino group into X with a nitrosating agent "NO + " into a diazonium group in analogy to processes known from the literature.
• the diazonium group thus produced is then reacted in a customary manner, it being possible to produce the R 3 radicals listed below:
• the hydroxy group is then converted into an alkoxy or haloalkoxy group in the sense of ether synthesis by reaction with alkyl halides, for example by reaction with methyl halide such as methyl iodide in the methoxy group or by reaction with
• Chlorine or bromodifluoromethane in the difluoromethoxy group is preferably carried out in the presence of a strong base.
• suitable bases are alkali metal hydroxides such as sodium or potassium hydroxide, alkali metal carbonates such as potassium or sodium carbonate or alkali metal hydrogen carbonate such as sodium hydrogen carbonate or organic bases, for example alcoholates such as sodium or potassium methylate or ethylate, in particular tertiary amines such as triethylamine or pyridine;
• R 3 Cx-Cö-alkylsulfinyl or haloalkylsulfinyl ⁇ cf. see scheme 1, step a) ⁇ .
• step b) in Scheme 1 Conversion of the diazonium group into the alkylthio or haloalkylthio group, then selective oxidation into a (halo) alkylsulfinyl group, cf.
• step b) in Scheme 1 using only one equivalent for the oxidation
• Suitable nitrosating reagents are: nitrosonium tetrafluoroborate, nitrosyl chloride, nitrosylsulfuric acid, the aforementioned alkyl nitrites or salts of nitrous acid, such as sodium nitrite.
• R 14 represents C 1 -C 6 -alkyl or Ci-Ce-haloalkyl, and R 1 and R 2 have the meanings mentioned above.
• Step n) gives compound XVI.
• suitable reducing agents for the sulfoxide XI '(n equal to 1) are metal hydrides such as lithium aluminum hydride, tributyltin hydride, CH 3 SiCl -NaI, PC1 / acetyl chloride, triphenylphosphine, tris (dimethylamino) phosphine-I 2 .
• Another suitable reducing agent is hydrogen in the presence of catalytic amounts of transition metals such as palladium. The Transition metals may be in a supported form, for example on activated carbon.
• Suitable reducing agents for the sulfone XI '(n equal to 2) are complex metal hydrides such as diisobutylaluminium hydride.
• the sulfones XI '(n equal to 2) can also be reduced to the sulfides XVI by heating with sulfur. XVI is then converted to acid IVa (n equals zero) using the procedures outlined in Scheme 1.
• R 1 and R 2 have the meanings mentioned above.
• the conversion of the amino group into X 'into a halogen, cyano, nitro, -C-C 6 alkyl, -C-C 6 haloalkyl, -C-C 6 alkoxy or Ci-Cö-haloalkoxy group under Compound XIV can be formed, for example, analogously to scheme 2.
• the reduction of the sulfoxide XIV (n 1) or the sulfone
• the acid IVa in which R 3 is N0 2 and n is 0, 1 or 2, can be prepared, for example, according to scheme 6.
• R 1 has the meanings mentioned above and n stands for 0, 1 or 2.
• reaction mixtures are generally worked up by known processes, for example by crystallization, aqueous-extractive workup, by chromatographic methods or by a combination of these methods.
• the carbon monoxide pressure was increased to 15 bar and the mixture was stirred at 140 ° C. for 24 h.
• the pressure was kept constant during the reaction by injecting carbon monoxide.
• the autoclave was then cooled and let down.
• the reaction discharge was sucked off through a depth filter and the phases were separated.
• the toluene phase was washed with triethylamine / water.
• the combined aqueous phases were adjusted to pH 1 with 18% hydrochloric acid and extracted with ethyl acetate.
• 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 herbicidal compositions comprising them can be sprayed or atomized, for example in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, old-dispersions, pastes, dusts, sprays or granules , Dusting, scattering, pouring or treating the seed or mixing with the seed. be applied.
• 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 from medium to high boiling point such as kerosene or diesel oil, also coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. B. paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, e.g. B. amines such as N-methylpyrrolidone or water.
• B. paraffin tetrahydronaphthalene
• alkylated naphthalenes or their derivatives alkylated benzenes or their derivatives
• alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol
• ketones such as cycl
• Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
• the benzoylcyclohexenones 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.
• 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, alkylphenyl, tribu
• 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.
• 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:
• I 20 parts by weight of an active ingredient of the general formula I are dissolved in a mixture consisting of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.
• aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
• V 3 parts by weight of an active ingredient of the general formula I are mixed with 97 parts by weight of finely divided kaolin.
• VI 20 parts by weight of an 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.
• Emulsifier based on ethoxylated castor oil A stable emulsion concentrate 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. that seed of a crop plant pretreated with the herbicidal compositions or active ingredients is applied. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit wherever possible, while the active ingredients are applied to the leaves of undesirable plants growing below them 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 their derivative
• 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, depending on the growth habit, and then treated with the active ingredients suspended or emulsified in water.
• the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
• the application rate for post-emergence treatment was 0.125 and 0.0625 kg a. S./ha.
• the plants were kept in a species-specific manner at temperatures of 10 to 25 ° C and 20 to 35 ° C.
• the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated.
• Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
• the plants used in the greenhouse experiments are composed of the following types:
• compound no. 2.1 shows a very good herbicidal action against ECHCG, ABUTH, CHEAL and POLPE in the post-emergence.
• compound no. 2.2 shows a very good herbicidal action against AVEFA, ECHCG, CHEAL and POLPE in the post-emergence.
• compound no. 2.5 shows a very good herbicidal action against ECHCG, SETFA, AMARE and CHEAL in the post-emergence.
• compound no. 2.4 shows a very good herbicidal action against ECHCG, SETFA, PHBPU and CHEAL in the post-emergence.
• compound no. 2.3 shows a very good herbicidal action against ECHCG, ABUTH, CHEAL and PHBPU in post-emergence.
• compound no. 2.6 shows a very good herbicidal action against ECHCG, SETFA, ABUTH and POLPE in the post-emergence.

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