WO2021204884A1 - 3-(4-alkenyl-phenyl)-3-pyrrolin-2-ones and their use as herbicides - Google Patents

3-(4-alkenyl-phenyl)-3-pyrrolin-2-ones and their use as herbicides Download PDF

Info

Publication number
WO2021204884A1
WO2021204884A1 PCT/EP2021/059077 EP2021059077W WO2021204884A1 WO 2021204884 A1 WO2021204884 A1 WO 2021204884A1 EP 2021059077 W EP2021059077 W EP 2021059077W WO 2021204884 A1 WO2021204884 A1 WO 2021204884A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
alkoxy
halogen
methyl
plants
Prior art date
Application number
PCT/EP2021/059077
Other languages
German (de)
French (fr)
Inventor
Guido Bojack
Andreas REMBIAK
Alfred Angermann
Hartmut Ahrens
Estella BUSCATÓ ARSEQUELL
Lars ARVE
Elisabeth ASMUS
Christopher Hugh Rosinger
Elmar Gatzweiler
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Publication of WO2021204884A1 publication Critical patent/WO2021204884A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/54—Spiro-condensed
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/30—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety

Definitions

  • the present invention relates to new herbicidally active 3-phenylpyrrolin-2-ones according to the general formula (I) or agrochemically acceptable salts thereof, and their use for controlling weeds and grass weeds in crops of useful plants.
  • bicyclic 3-phenylpyrrolin-2-one derivatives EP 0355599 A1 and EP 0415211 A2
  • substituted monocyclic 3-phenylpyrrolin-2-one derivatives EP 0377893 A2 and EP 0442077 A2 with herbicidal, insecticidal or fungicidal effect described.
  • 4-Alkynyl-substituted-3-phenylpyrrolin-2-ones with herbicidal action are also from WO 98/05638 A2, WO 01/74770 A1, WO 2015/032702 A1, WO 2015/040114 A1, WO 2017/060203 A1 or WO 2019/219587 Al known.
  • the effectiveness of these herbicides against harmful plants depends on numerous parameters, for example on the application rate used, the form of preparation (formulation), the harmful plants to be controlled, the range of harmful plants, the climatic and soil conditions and the duration of the action or the rate of degradation of the herbicide.
  • the object of the present invention is therefore to provide new compounds which do not have the disadvantages mentioned.
  • the present invention therefore relates to new substituted 3-phenylpyrrolin-2-ones of the general formula (I), or an agrochemically acceptable salt thereof, wherein
  • R 1 (C 1 -C 6 ) -alkyl, halogen- (C 1 -C 6 ) -alkyl, (C 1 -C 6 ) -alkoxy, halogen- (C 1 -C 6 ) -alkoxy, (C 1 - C 4 ) -
  • R 2 hydrogen, (C 1 -C 6 ) -alkyl, (C 1 -C 4 ) -alkoxy- (C 1 -C 4 ) -alkyl, halogen- (C 1 -C 6 ) -alkyl, (C 3 - C 6 ) - Cycloalkyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 4 ) -alkyl, (C 2 -C 6 ) -alkenyl, (C 2 -C 6 ) -alkynyl, (C 1 - C 6 ) alkoxy or halogen (C 1 -C 6 ) alkoxy,
  • R 11 is fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) alkyl,
  • R 12 is hydrogen, fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) alkyl
  • G is hydrogen, a leaving group L or a cation E, where L is one of the following radicals wherein
  • R 3 is (Ci-C *) - alkyl or (C 1-C3) - alkoxy- (C 1 -C 4 ) -alkyl,
  • R 4 is (C 1 -C 4 ) - alkyl, R 5 (C 1 -C 4 ) - alkyl, an unsubstituted phenyl or a single or multiple with halogen, (Ci-
  • R 7 'R 8 is each independently methyl, ethyl, phenyl, or together with the nitrogen atom to which sre are bonded, form a saturated 5-, 6- or 7-membered ring, one ring carbon atom optionally being replaced by an oxygen or Sulfur atom can be replaced
  • E is an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent of aluminum, an ion equivalent of a transition metal, a magnesium-halogen cation or an ammonium ion, in which one, two, three or all four hydrogen atoms are optionally replaced by the same or various radicals from the groups (Ci-C 10) - alkyl or (C3-C?) - Cycloalkyl, which are each independently substituted one or more times with fluorine, chlorine, bromine, cyano, hydroxy or by one or more Oxygen or sulfur atoms can
  • Halogen fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine and particularly preferably fluorine or chlorine.
  • Alkyl saturated, straight-chain or branched hydrocarbon radical with 1 to 6, preferably 1 to 4 carbon atoms, for example (but not limited to) C 1 -C 6 -alkyl such as methyl, ethyl,
  • This group is in particular a C1-C4 alkyl group, e.g. B. a methyl, ethyl, propyl, 1-methylethyl (isopropyl), butyl, 1 -methylpropyl (sec.Butyl - ), 2-methylpropyl (isobutyl) or 1, 1 -dimethy lethy 1- (tert-butyl) group.
  • a C1-C4 alkyl group e.g. B. a methyl, ethyl, propyl, 1-methylethyl (isopropyl), butyl, 1 -methylpropyl (sec.Butyl - ), 2-methylpropyl (isobutyl) or 1, 1 -dimethy lethy 1- (tert-butyl) group.
  • alkylsulfanyl alkylsulfinyl, alkylsulfonyl, haloalkyl or haloalkylsulfanyl
  • this definition also applies to alkyl as part of a compound substituent, for example cycloalkylalkyl or hydroxyalkyl.
  • Alkenyl unsaturated straight-chain or branched hydrocarbon groups with 2 to 6 and preferably 2 to 4 carbon atoms and a double bond in any position, for example (but not limited to) Ca-Ce-alkenyl, such as vinyl, allyl, (E) -2- Methylvinyl, (Z) -2-methylvinyl, isopropenyl, homoallyl, (E) -But-2-enyl, (Z) -But-2-enyl, (E) -But-1-enyl, (Z) -But- l-enyl, 2-methylprop-2-enyl, l-methylprop-2-enyl, 2-methylprop-l-enyl, (E) -1 -methylprop-1-enyl, (Z) -1 -methylprop-1 -enyl, Pent-4-enyl, (E) -Pent-3-enyl, (Z) -Pent-3-enyl, (E) -Pent
  • the group is in particular vinyl or allyl. Unless otherwise defined, this definition also applies to alkenyl as part of a compound substituent, for example haloalkenyl.
  • Alldnyl straight-chain or branched hydrocarbon groups with 2 to 6 and preferably 2 to 4 carbon atoms and a triple bond in any position, for example (but not limited to) Ca-Ce-alkynyl, such as ethynyl, prop-1-ynyl, prop-2 -ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, 1-methylprop-2-ynyl, pent-1-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4 -ynyl, 2-methylbut-3-ynyl, 1-methylbut-3-ynyl, 1-methylbut-2-ynyl, 3-methylbut-1-ynyl, 1-ethylprop-2-ynyl,
  • alkynyl group is in particular ethynyl, prop-1-ynyl or prop-2-ynyl. Unless otherwise defined, this definition also applies to alkynyl as part of a compound substituent, for example haloalkynyl.
  • Alkoxy saturated, straight-chain or branched alkoxy radicals having 1 to 6 and preferably 1 to 4 carbon atoms, for example (but not limited to) C 1 -C 6 alkoxy such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy , 2-methylpropoxy, 1,1-
  • Carbon ring members such as (but not limited to) cyclopropyl, cyclopentyl and cyclohexyl. Unless otherwise defined, this definition also applies to cycloalkyl as part of a compound substituent, for example cycloalkylalkyl.
  • Haloalkyl / haloalkyl straight-chain or branched alkyl groups with 1 to 6, preferably 1 to 4 carbon atoms (as described above), some or all of the hydrogen atoms in these groups being replaced by halogen atoms as described above, for example (but not limited to) Ci -Cs-haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2.2 , 2- Trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluor
  • haloalkyl as part of a compound substituent, for example haloalkylaminoalkyl.
  • Haloalkenyl and haloalkynyl are defined analogously to haloalkyl, but instead of
  • Alkyl groups, alkenyl or alkynyl groups are present as part of the substituent.
  • Haloalkoxy straight-chain or branched alkoxy groups having 1 to 6, preferably 1 to 3 carbon atoms (as described above), some or all of the hydrogen atoms in these groups being replaced by halogen atoms as described above, for example (but not limited to) C 1 -C 3 -haloalkoxy such as chloromethoxy, bromomethoxy, dichloromethoxy,
  • Trichloromethoxy fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2- fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and 1,1,1-trifluoroprop-2-oxy.
  • this definition also applies to haloalkoxy as part of a compound substituent, for example haloalkoxy alkyl.
  • the compounds of the formula (I) can exist as geometric and / or optical isomers or isomer mixtures in various compositions. For example, depending on the linkage of the substituent R 1 , both enantiomers and cis / trans isomers can occur. The latter are defined as follows:
  • R 1 (C 1 -C 6 ) -alkyl, halogen- (C 1 -C 6 ) -alkyl, (C 1 -C 6 ) -alkoxy, halogen- (C 1 -C 6 ) -alkoxy, (C 1 - C 4 ) -
  • R 2 hydrogen, (C 1 -C 6 ) -alkyl, (C 1 -C4) alkoxy- (C 2 -C4) -alkyl, halogen- (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) - cycloalkyl, (C 2 -C 6) alkenyl or (C 2 -C 6) alkynyl,
  • X is (C 1 -C 6) - alkyl, halo (C 1 -C 6) alkyl, (C 3 -C 6 ) -cycloalkyl, (C 1 -C 6 ) -alkoxy, halogen- (C 1 -C 6 > alkoxy, bromine, chlorine or fluorine,
  • R 10 is hydrogen, fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) alkyl
  • R 11 is fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) is -alkyl
  • R 12 is hydrogen, fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) alkyl
  • G is hydrogen, a leaving group L or a cation E, where L is one of the following radicals wonn
  • R 3 is (C 1 -C 4 ) -alkyl or (C 1-C3) -alkoxy- (C 1 -C 4 ) -alkyl,
  • R 4 is (C 1 -C 4 ) - alkyl, R 5 (C 1 -C 4 ) - alkyl, an unsubstituted phenyl or a single or multiple with halogen, (Ci- C4) - alkyl, halogen (C 1 - Is C 4 ) alkyl or (C 1 -C 4 ) alkoxy substituted phenyl,
  • E is an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent of aluminum, an ion equivalent of a transition metal, a magnesium-halogen cation or an ammonium ion in which one, two, three or all four hydrogen atoms are optionally replaced by identical or different radicals the groups (Ci-C 10) - alkyl or (C3-C?) - Cy cloalkyl, which are each independently substituted one or more times with fluorine, chlorine, bromine, cyano, hydroxy or by one or more oxygen or sulfur atoms may be interrupted, a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, for example morpholinium, thiomorpholinium, piperidinium, pyrrolidinium or protonated 1,4-diazabicyclo [1.1.2] octane (DABCO) or 1,5-diazabicyclo [4.3.0 ] undec-7
  • R 1 (C 1 -C 6 ) -alkyl, (C 1 -C 6 ) -alkoxy, halogen- (C 1 -C 6 ) -alkoxy, (C 1 -C 4 ) -alkoxy- (C 1 -C 4 ) -alkyl or (C 1 -C 6 ) -alkoxy- (C2-C4) -alkoxy,
  • R 2 hydrogen (, C 1 -C 4 ) - alkyl, methoxyethyl, ethoxyethyl, halogen (Ci-C2) -alkyl, cyclopropyl, (C2-C4) -alkenyl, (C2-C4) -alkynyl, (C 1 - C 4 ) -alkoxy or halogen- (C 1 -C 4 ) -alkoxy,
  • Y is (C 1 -C 6 ) -alkyl, halogen- (C 1 -C 6 ) -alkyl or (C 1 -C 6 ) -alkoxy,
  • R 10 is hydrogen
  • R 11 is (C 1 -C 6 ) -alkyl or halo (C 1 -C 6 ) -alkyl
  • R 12 is hydrogen or (C 1 -C 6 ) alkyl G is hydrogen, a leaving group L or a cation E, where L is one of the following radicals
  • R 3 (C 1 -C 4 ) - alkyl or (Ci-C2> alkoxy- (Ci-C 2 > alkyl,
  • R 4 is (C 1 -C 4 ) alkyl
  • E is an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent of aluminum, an ion equivalent of a transition metal, a magnesium-halogen cation or an ammonium ion in which one, two, three or all four hydrogen atoms are optionally replaced by identical or different radicals from the Groups (Ci-C 10) - alkyl or (C3-C7) -Cy cloalkyl.
  • R 1 is methoxy or methoxy ethoxy
  • R 2 is hydrogen or methyl
  • X is methyl, bromine or chlorine
  • Y is methyl, ethyl or methoxy
  • R 10 is hydrogen
  • R 11 is methyl or trifluoromethyl
  • R 12 is hydrogen
  • G is hydrogen, a leaving group L or a cation E, where
  • L is one of the following residues wherein R 3 is methyl, ethyl, i-propyl or t-butyl,
  • R 4 is methyl or ethyl
  • E is a sodium ion or a potassium ion.
  • the preparation of the compounds of the general formula (I) according to the invention is known in principle or can be carried out on the basis of processes known from the literature, for example by a) a compound of the general formula (II), in which R 1 , R 2 , X, Y, R 10 , R 11 and R 12 have the meanings given above and R 9 is alkyl, preferably methyl or ethyl, optionally in the presence of a suitable solvent or diluent with a suitable Base cyclized with formal elimination of the group R 9 OH, or b) a compound of the general formula (Ia), in which R 1 , R 2 , X, Y, R 10 , R 11 and R 12 have the meanings given above, for example with a compound of the general formula (III), in which L has the meaning given above and Hal can stand for a halogen, preferably chlorine or bromine or a sulfonic acid group, optionally in the presence of a suitable solvent or diluent and a suitable base
  • Z-CR 10 CR 11 R 12 (V) in which Z represents a suitable leaving group and R 10 , R 11 and R 12 have the meaning given above, optionally in the presence of suitable catalysts and a suitable base.
  • leaving group U for example, halogen atoms such as chlorine, bromine or iodine, alkyl sulfonic ester groups such as triflate, mesylate or nonaflate are suitable.
  • leaving group Z for example, magnesium chloride, magnesium bromide, zinc chloride, a trialkyltin radical, carboxyl and boronic acid radicals such as -B (OH) 2 or -B (O-alkyl) 2 come into consideration.
  • Pd ° complexes in particular are very suitable as catalysts, and in many cases the addition of Cu® salts can also be very advantageous.
  • Ligands such as 1,4-bis (diphenylphosphino) butane can also be used.
  • the precursors of the general formula (II) can be carried out in analogy to known processes, for example by reacting an amino acid ester of the general formula (VI), in which R 1 , R 2 and R 9 have the meaning described above, with a phenylacetic acid of the general formula ( VH), in which X, Y, R 10 , R 11 and R 12 have the meaning described above, optionally through Addition of a dehydrating agent and, if appropriate, in the presence of a suitable solvent or diluent, are prepared.
  • Amino esters of the general formula (VI) are known from the literature, for example from WO 2006/000355.
  • the required precursors of the general formula (VII) can be obtained, for example, by adding a compound of the general formula (IX) in which X, Y and U have the meaning given above and R 13 is hydrogen, alkyl, preferably methyl or ethyl, according to the cross-coupling method already described, reacts with a compound of the general formula (V) in which Z, R 10 , R 11 and R 12 have the meaning given above: If R 13 is alkyl, preferably methyl or ethyl, the required precursors of the general formula (VH) can be obtained by cleavage of the ester of the general formula ( ⁇ ) in which X, Y, R 10 , R 11 and R 12 die has the meaning given above, can be obtained by standard methods:
  • the required precursors of the general formula (IX) can be obtained, for example, by introducing an acetate unit into compounds of the general formula (XI) in which X, Y and U have the meanings given above, according to processes known in the literature.
  • Precursors of the general formula (XI) can in turn be obtained from commercially available amino nitrophenols by common standard methods such as bromination and / or alkylation.
  • the present invention also relates to compounds of the formula ( ⁇ ) in which the radicals have the following meanings:
  • X is methyl, bromine, or chlorine
  • Y is methyl, ethyl or methoxy
  • R 10 is hydrogen
  • R 11 is methyl or trifluoromethyl
  • R 12 is hydrogen
  • R 13 is hydrogen, methyl or ethyl.
  • the compounds of the formula (I) according to the invention (and / or their salts), hereinafter referred to collectively as “compounds according to the invention”, have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous annual harmful plants.
  • the present invention therefore also relates to a method for controlling unwanted plants or for regulating the growth of plants, preferably in plant crops, in which one or more compounds according to the invention are applied to the plants (for example harmful plants such as monocotyledonous or dicotyledonous weeds or unwanted crop plants), the seed
  • the compounds according to the invention can be applied, for example, by pre-sowing (if necessary also by incorporation into the soil), pre-emergence or post-emergence methods.
  • the compounds according to the invention are applied to the surface of the earth before germination, either the emergence of the weed seedlings is completely prevented or the weeds grow to the cotyledon stage, but then stop growing.
  • the compounds according to the invention can have selectivities in useful crops and can also be used as nonselective herbicides.
  • the active compounds can also be used for controlling harmful plants in crops of known or still to be developed genetically modified plants.
  • the transgenic plants are usually characterized by particularly advantageous properties, for example by resistance to certain active ingredients used in the agricultural industry, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
  • Other special properties relate, for example, to the crop in terms of quantity, quality, shelf life, composition and special ingredients.
  • transgenic plants with an increased starch content or a changed quality of the starch or those with a different fatty acid composition of the harvested material are known.
  • Other special properties are tolerance or resistance to abiotic stressors e.g. heat, cold, drought, salt and ultraviolet radiation.
  • the use of the compounds of the formula (I) according to the invention or their salts in economically important transgenic crops of useful and ornamental plants is preferred,
  • the compounds of the formula (I) can be used as herbicides in crops of useful plants which are resistant to the phytotoxic effects of the herbicides or which have been made resistant by genetic engineering.
  • new plants with modified properties can be produced with the aid of genetic engineering (see e.g. EP 0221044, EP 0131624).
  • genetic modifications of crop plants for the purpose of modifying the starch synthesized in the plants e.g.
  • transgenic crop plants which are resistant to certain herbicides of the glufosinate type ( See, for example, EP 0242236 A, EP 0242246 A) or glyphosate (WO 92/000377 A) or the sulfonylureas (EP 0257993 A, US 5,013,659) or are resistant to combinations or mixtures of these herbicides by “gene stacking”, such as transgenic crops e.g. . B. corn or soy with the trade name or the designation Optimum TM GAT TM (Glyphosate ALS Tolerant).
  • transgenic crop plants for example cotton, with the ability to produce Bacillus thuringiensis toxins (Bt toxins), which make the plants resistant to certain pests (EP 0142924 A, EP 0193259 A).
  • Bacillus thuringiensis toxins Bacillus thuringiensis toxins
  • transgenic crop plants with modified fatty acid composition WO 91/013972 A
  • genetically modified crop plants with new ingredients or secondary substances, e.g. new phytoalexins, which cause increased disease resistance EP 0309862 A, EP 0464461
  • nucleic acid molecules can be introduced into plasmids which allow mutagenesis or a sequence change by recombination of DNA sequences.
  • base exchanges can be carried out, partial sequences can be removed or natural or synthetic sequences can be added.
  • adapters or linkers can be attached to the fragments, see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd edition. Cold Spring Haibor Laboratory Press, Cold Spring Haibor, NY; or Winnacker "Genes and Clones", VCH Weinheim 2nd edition 1996
  • the production of plant cells with a reduced activity of a gene product can be achieved, for example, by expressing at least one corresponding antisense RNA, one sense RNA to achieve a cosuppression effect or by expressing at least one appropriately constructed ribozyme that specifically cleaves transcripts of the above-mentioned gene product.
  • DNA molecules can be used that include the entire coding sequence of a gene product including any flanking sequences that may be present, as well as DNA molecules that only include parts of the coding sequence, these parts having to be long enough to be in the cells to bring about an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but which are not completely identical.
  • the synthesized protein can be localized in any desired compartment of the plant cell.
  • the coding region can be linked with DNA sequences that guarantee the localization in a certain compartment.
  • sequences are known to the person skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Nall. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1: 95-106 (1991)).
  • the expression of the nucleic acid molecules can also take place in the organelles of the plant cells.
  • the transgenic plant cells can be regenerated into whole plants using known techniques.
  • the compounds (I) according to the invention can preferably be used in transgenic crops which are effective against growth substances, such as 2,4-D, dicamba or against herbicides, the essential plant enzymes, e.g.
  • acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydoxyphenylpyruvate Dioxygenases (HPPD) inhibit or are resistant to herbicides from the group of sulfonylureas, glyphosates, glufosinals or benzoylisoxazoles and analogous active ingredients, or to any combination of these active ingredients.
  • ALS acetolactate synthases
  • EPSP synthases glutamine synthases
  • HPPD hydoxyphenylpyruvate Dioxygenases
  • the compounds according to the invention can particularly preferably be used in transgenic crop plants which are resistant to a combination of CHyphosates and ghifosinates, glyphosals and sulfonylureas or imidazolinones.
  • the compounds according to the invention can very particularly preferably be used in transgenic crop plants such as, for. B. corn or soy with the trade name or the designation OptimumTM GATTM (Glyphosate ALS Tolerant) can be used.
  • the active ingredients according to the invention are used in transgenic crops, in addition to the effects on harmful plants observed in other crops, effects that are specific for the application in the respective transgenic crop, for example a modified or specially expanded weed spectrum that can be controlled, often occur Application rates that can be used for the application, preferably good compatibility with the herbicides to which the transgenic culture is resistant, and influencing the growth and yield of the transgenic crop plants.
  • the invention therefore also relates to the use of the compounds of the formula (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
  • the compounds according to the invention can be used in the customary preparations in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules.
  • the invention therefore also relates to herbicidal and plant growth-regulating agents which contain the compounds according to the invention.
  • the compounds according to the invention can be formulated in various ways, depending on the prevailing biological and / or chemico-physical parameters.
  • Possible formulation options include, for example: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions , Suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), dressings, granules for litter and soil application, granules (GR) in the form of micro, spray, lift - and adsorption granules, water-dispersible granules (WG), water-soluble granulates (SG), UL V formulations, microcapsules and waxes.
  • WP wettable powders
  • SP water-soluble powders
  • EC emul
  • combination partners for the compounds according to the invention in mixture formulations or in the tank mix for example, known active ingredients which act on an inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpymvylshikimate-3-phosphate synthase, glutamine synthetase, p-Hydroxyphenylpymvat-Dioxygenase, Phytoendesaturase, Photosystem I, Photosystem ⁇ or Protoporphyrinogen-Oxidase based, can be used, as for example from Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 16th edition, The British Crop Protection Council and the Royal Soc.
  • herbicidal mixing partners are:
  • Fenoxaprop-P Fenoxaprop-Ethyl
  • Fenoxaprop-P-Ethyl Fenoxasulfone
  • Fenpyrazone Fenquinotrione
  • Fentrazamid Flamprop, Flamprop-Isoproyl, Flamprop-Methyl, Flamprop-M-
  • halauxifen halauxifen-methyl, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, Haloxyfop-methyl, haloxyfop-P-methyl, haloxifop sodium,
  • COs differ from LCOs in that they lack the pendant fatty acid chain that is characteristic of LCOs.
  • COs sometimes also as N-acetylchitooligosaccharides, also made up of GlcNAc residues, but have side chain decorations that are derived from chitin molecules [(CeHnNOsJn, CAS No. 1398-61-4] and chitosan molecules [(CsHiiN04) n, CAS No.
  • chitin compounds chlormequat chloride, cloprop, cyclanilide, 3 - (cycloprop- 1 -eny l) propionic acid, daminocide, dazomet, dazomet sodium, n-decanol, dikegulac, dikegulac sodium, endothal, endothal dipotassium, disodium and mono (N, N-dimethylalkylammonium), ethephon, flumetralin, flurenol, flurenol-butyl, flurenol-methyl, flurprimidol, forchlorfenuron, gibberellic acid, inabenfid, indol-3-acetic acid (IAA), 4-indol-3-ylbutyric acid, isoprothiol-3-ylbutyric acid , Probenazole, jasmonic acid, jasmone acid or derivatives thereof (e.g.
  • lipo-chitooligosaccharides LCO, sometimes also referred to as symbiotic nodulation (Nod) signals (or Nod factors) or as Myc factors)
  • Nod symbiotic nodulation
  • Myc myc factors
  • LCOs differ in the number of CHcNAc residues in the backbone, in the length and the degree of saturation of the fatty acyl chain and in the substitutions of reducing and non-reducing sugar residues), linoleic acid or derivatives thereof, linolenic acid or derivatives thereof, maleic hydrazide , Mepiquat chloride, mepiquat pentaborate, 1-methyl cyclopropene, 3'-methylabscisic acid, 2- (1-naphthyl) acetamide, 1-naphthylacetic acid, 2-naphthyloxyacetic acid, nitrophenolate mixture, 4-oxo-4 [(2-phenylethyl) amino] butyric acid , Paclobutrazole, 4-phenylbutyric acid, N-phenylphthalamic acid, Prohexadione, Prohexadione-Calcium, Prohydrojasmone, Salicylic acid,
  • Safeners which can be used in combination with the compounds of the formula (I) according to the invention and optionally in combinations with other active ingredients such as insecticides, acaricides, herbicides, fungicides as listed above, are preferably selected from the group consisting of:
  • ⁇ is a natural number from 0 to 5, preferably 0 to 3;
  • RA is halogen, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) alkoxy, nitro or halo (C 1 -C 4 ) -alkyl;
  • WA is an unsubstituted or substituted divalent heterocyclic radical from the group of partially unsaturated or aromatic five-membered ring heterocycles with 1 to 3 hetero ring atoms from the group N and O, with at least one N atom and at most one O atom in the ring, preferably one Remainder from group (WA 1 ) to (WA 4 ), nu is 0 or 1;
  • RA 2 is ORA 3 , SRA 3 or NRA 3 RA 4 or a saturated or unsaturated 3 to 7-membered heterocycle with at least one N atom and up to 3 heteroatoms, preferably from the group O and S, which has the N- Atom is connected to the carbonyl group in (S1) and is unsubstituted or substituted by radicals from the group (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) alkoxy or optionally substituted phenyl, preferably a radical of the formula ORA 3 , NHRA 4 or N (CH3) 2, in particular of the formula ORA 3 ;
  • RA 3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably with a total of 1 to 18 carbon atoms;
  • RA 4 is hydrogen, (C 1 -C 6) - alkyl, (C 1 -C 6) -alkoxy or substituted or unsubstituted phenyl;
  • RA 5 is H, (C 1 -C 6 ) -alkyl, halogen- (C 1 -C 6 ) -alkyl, (C 1-C4) -alkoxy- (C i-Cs) -alkyl, cyano or COORA 9 , wherein RA 9 is hydrogen, (Ci-Cs) - alkyl, halogen (C 1 -C 6 ) alkyl, (C 1 -C 4 A) alkoxy (C 1 -C 4 ) - alkyl, (C 1 - C 6 ) -hydroxyalkyl, (C3-Ci2) -cycloalkyl or tri- (C 1 -C 4 ) -alkyl-silyl; RA 6, RA 7, RA 8 are identical or different hydrogen, (C 1 -C 6) - alkyl, halo (C 1 -C 6) alkyl, (Cs-Ci2) -Cy cloalkyl or substituted
  • dichlorophenylpyrazole carboxylic acid Sl b
  • compounds such as 1- (2,4-dichlorophenyl) -5-methyl-pyrazole-3-carboxylic acid ethyl ester (Sl-2), 1- (2,4-dichlorophenyl) -5 -isopropyl-pyrazole-3-carboxylic acid ethyl ester (Sl-3),
  • Diphenyl-2-isoxazoline-3-carboxylic acid (Sl e ), preferably compounds such as
  • RB 1 is halogen, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) alkoxy, nitro or halo (C 1 -C 4 ) -alkyl; ns is a natural number from 0 to 5, preferably 0 to 3;
  • RB 2 is ORB 3 , SRB 3 or NRB 3 RB 4 or a saturated or unsaturated 3- to 7-membered heterocycle with at least one N atom and up to 3 heteroatoms, preferably from the group O and S, which has the N- Atom is connected to the carbonyl group in (S2) and is unsubstituted or substituted by radicals from the group (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -alkoxy or optionally substituted phenyl, preferably a radical of the formula ORB 3 , NHRB 4 or N (CH3) 2, in particular of the formula ORB 3 ; RB 3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably with a total of 1 to 18 carbon atoms;
  • RB 4 is hydrogen, (C 1 -C 6 ) -alkyl, (C 1 -C 6 ) -alkoxy or substituted or unsubstituted phenyl;
  • TB is a (Ci or C2) -alkanediyl chain which is unsubstituted or substituted with one or two (Ci- C4) alkyl radicals or with [(C 1-C3) -alkoxy] -carbony 1; preferably: a) compounds of the 8-quinolinoxyacetic acid type (S2 a ), preferably (5-chloro-8-quinolinoxy) acetic acid (l-methylhexyl) ester ("Cloquintocet-mexyl”) (S2-1), (5- Chloro-8-quinolinoxy) acetic acid (1,3-dimethyl-but-1 -yl) ester (S2-2), (5-chloro-8-quinolinoxy) acetic acid 4-allyloxy-butyl ester (S2-3),
  • Rc 1 is (C 1 -C 4 ) -alkyl, halo- (C 1 -C 4 ) -alkyl, (C2-C4) -alkenyl, halo- (C2-C4) -alkenyl, (C3-C7) -cycloalkyl , preferably dichloromethyl;
  • Rc 2 , Rc 3 are identically or differently hydrogen, (C 1 -C 4 ) A-alkyl, (C2-C4) -alkenyl, (C2-C4) -alkynyl,
  • Thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or Rc 2 and Rc 3 together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine, piperidine, morpholine, hexahydropyrimidine or benzoxazine ring; preferably:
  • Safener are used, such as. B. "Dichlormid” (N, N-diallyl-2,2-dichloroacetamide) (S3-1),
  • R-29148 (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer (S3-2)
  • R-28725" (3-dichloroacetyl-2,2, -dimethyl- 1,3-oxazolidine) from Stauffer (S3-3)
  • PPG-1292 N-Allyl-N - [(1,3-dioxolan-2-yl) methyl] dichloroacetamide
  • AD-67 or "MON 4660” (3-dichloroacetyl-1-oxa-3-aza-spiro [4,5] decane) from Nitrokemia or Monsanto (S3-7),
  • AD is SO2-NRD 3 -C0 or CO-NRD 3 -SC> 2
  • XD is CH or N;
  • RD 1 is CO-NRD 5 RD 6 or NHCO-RD 7 ;
  • RD 2 is halogen, halogen- (C 1 -C 4 ) -alkyl, halogen- (C 1 -C 4 ) -alkoxy, nitro, (C 1 -CA 4 ) l-alkyl, (C 1 -C 4 ) - Alkoxy, (C 1 -C 4 ) -alkylsulfonyl, (C 1 -C 4 ) -alkoxy carbony 1 or (C 1 -C4) -alkyl carbonyl;
  • RD 3 is hydrogen, (Ci-C *) -alkyl, (C2-C4) -alkenyl or (C2-C4) -alkynyl;
  • RD 4 is halogen, nitro, (C 1 -C 4) - alkyl, halo (C 1 -C 4) alkyl, halo (C 1 -C 4) alkoxy, (C 3 -C 6) - cycloalkyl , Phenyl, (C 1 -C 4 ) alkoxy, cyano, (C 1 -C 4 ) alkylthio, (C 1 -C 4 ) alkylsulfinyl, (C 1 -C 4 ) alkylsulfonyl, (C 1 -C 4 ) -alkoxy carbonyl or (C 1 -CA 4 ) l-kylcaibonyl;
  • RD 5 is hydrogen, (C 1 -C 6 ) alkyl, (C 3 -C 6 ) cycloalkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (Cs- CeJ- Cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl containing VD heteroatoms from the group nitrogen, oxygen and sulfur, the last seven radicals being replaced by VD substituents from the group halogen, (C 1 -C 6 ) -alkoxy, halogen- (C 1 -C 6 ) -alkoxy, (C1-C2) -alkylsulfinyl, (C 1 -C 2 ) -alkylsulfonyl, (C 3 -C 6 ) -cycloalkyl, (C 1 -C 4 ) -alkoxy carbonyl, (C 1 -C 4 ) - Alkylcaibon
  • RD 6 is hydrogen, (C 1 -C 6 ) -alkyl, (C 2 -C 6 ) -alkenyl or (C 2 -C 6 ) -alkynyl, the last three radicals being replaced by VD radicals from the group halogen, hydroxy, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -alkoxy and (C 1 -C 4 ) -alkylthio are substituted, or
  • RD 7 is hydrogen, (C 1 -C 4 ) -alkylamino, di- (C 1 -C 4 ) -alkylamino, (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, where the 2 last-mentioned radicals by VD substituents from the group halogen, (Ci- C4) -alkoxy, halogen- (C 1 -C 6 ) -alkoxy and (C 1 -C 4 ) alkylthio and in the case of cyclic radicals also (Ci- C 4 ) alkyl and halo (C 1 -C 4 ) alkyl are substituted; nD is 0, 1 or 2; mD is 1 or 2;
  • VD is 0, 1, 2 or 3; Preferred of these are compounds of the N-acylsulfonamide type, for example of the following formula (S4 a ), which z. B. are known from WO-A-97/45016 wherein
  • RD 4 halogen (Ci-C4> alkyl, (C 1 -C 4 ) -alkoxy, CF 3; mo 1 or 2;
  • VD is 0, 1, 2 or 3; as Acylsulfamoylbenzoic acid amides, for example of the following formula (S4 b ), which are known, for example, from WO-A-99/16744,
  • RD RD 8 and 9 are independently hydrogen, (C 1 -C 8) - alkyl, (C 3 -C 6) -cycloalkyl, (C 3 -C 6) - alkenyl, (C 3 -C 6) -alkynyl,
  • RD 4 is halogen, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -alkoxy, CF 3 mD 1 or 2; for example 1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3-methylurea, 1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3,3-dimethylurea, 1- [4- (N-4 , 5-dimethylbenzoylsulfamoyl) phenyl] -3-methylurea, as
  • RD 4 is halogen, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) alkoxy, CF 3; mn 1 or 2;
  • RD 5 hydrogen, (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (Ca-GO-alkenyl, (C 2 -C 6 ) -alkynyl, (C 3 -C 6 ) -cycloalkenyl means.
  • RE 1 , RE 2 are independently halogen, (C 1 -C 4 ) - alkyl, (C 1 -C 4 ) - alkoxy, halogen (C 1 -C 4 ) - alkyl, (C 1 -C 4 ) - Alkylamino, di (C 1 -C 4 ) alkylamino, nitro; AE is COORE 3 or COSRE 4
  • RE 3 , RE 4 are independently hydrogen, (C 1 -C 4 ) -alkyl, (C 2 -C 6 ) -alkenyl, (C2-C4) -alkynyl, cyanoalkyl, halogen- (C 1 -C 4 ) - alkyl, phenyl, nitrophenyl, benzyl, halobenzyl, pyridinylalkyl and alkylammonium, ns 1 is 0 or 1
  • ⁇ , ⁇ are independently 0, 1 or 2, preferably:
  • RF 3 is hydrogen, (C 1 -C 6 ) -alkyl, (C2-C4) -alkenyl, (C2-C4) -alkynyl, or aryl, where each of the aforementioned C-containing radicals is unsubstituted or by one or more, preferably up to is substituted to three identical or different radicals from the group consisting of halogen and alkoxy; mean, or their salts, preferably compounds in which XF CH, nF is an integer from 0 to 2,
  • RF 2 is hydrogen or (C 1 -C 4 ) -alkyl
  • RF 3 is hydrogen, (C 1 -C 6 ) -alkyl, (C2-C4) -alkenyl, (C2-C4) -alkynyl, or aryl, where any of the
  • the aforementioned C-containing radicals are unsubstituted or substituted by one or more, preferably up to three, identical or different radicals from the group consisting of halogen and alkoxy, or their salts.
  • Active ingredients from the class of the 3- (5-tetrazolylcaibonyl) -2-quinolones (S9) for example 1,2-dihydro-4-hydroxy-1-ethyl-3 - (5-tetrazolylcarbonyl) -2-quinolone (C. AS-Reg.Nr. 219479-18-2), 1, 2-Dihydro-4-Hydroxy- 1 -methy 1-3 - (5 -tetrazoly 1-carbony l) -2-quinolone (CAS-Reg. No. 95855-00-8), as described in WO-A-1999/000020.
  • YG, ZG independently of one another O or S, no an integer from 0 to 4,
  • RG 2 (Ci-Cie) -alkyl, (C 2 -C 6 ) -alkenyl, (C 3 -C 6 ) -cycloalkyl, aryl; Benzyl, halobenzyl,
  • RG 3 is hydrogen or (C 1 -C 6 ) - alkyl.
  • Sil Active ingredients of the type of oxyimino compounds (Sil), which are known as seed dressings, such as. B.
  • Oxabetrinil ((Z) -l, 3-Dioxolan-2-ylmethoxyimino (phenyl) acetonitril) (Sll-1), which is known as a seed dressing safener for millet against damage from metolachlor
  • Fluofenim (l- (4 -Chlorophenyl) -2,2,2-trifluoro-l-ethanon-0- (l, 3-dioxolan-2-ylmethyl) oxime) (Sll-2), which is known as a seed dressing safener for millet against damage from metolachlor is and
  • Cyometrinil or “CGA-43089” ((Z) -Cyanomethoxyimino (phenyl) acetonitrile) (Sll-3), which is known as a seed dressing safener for millet against damage from metolachlor.
  • S12 Active ingredients from the class of isothiochromanones (S12), such as methyl [(3 -oxo-lH-2-benzothiopyran-4 (3H) -ylidene) methoxy] acetate (CAS reg. No. 205121-04-6 ) (S12-1) and related compounds from WO-A-1998/13361.
  • S12 isothiochromanones
  • Naphthalic anhydride (1,8-naphthalenedicarboxylic acid anhydride) (S13-1), which is known as a seed dressing safener for maize against damage from thiocarbamate herbicides
  • Fenclorim (4,6-dichloro-2-phenylpyrimidine) (S13-2) known as a safener for pretilachlor in sown rice
  • MG 191 (CAS-Reg.Nr. 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia, which is known as a safener for maize,
  • Mephenate (4-chlorophenyl methyl carbamate) (S13-9).
  • Active ingredients which, in addition to a herbicidal effect against harmful plants, also have a safener effect on crop plants such as rice, such as. B.
  • CSB (1-bromo-4- (chloromethylsulfonyl) benzene) from Kumiai, (CAS Reg. No. 54091-06-4), which is known as a safener against damage from some herbicides in rice.
  • RH 1 denotes a halogen (C 1 -C 6 ) alkyl radical
  • RH 2 is hydrogen or halogen
  • RH 3 , RH 4 independently of one another are hydrogen, (Ci-Ci6) -alkyl, (C2-Cie) -alkenyl or (Ca-Cie) -alkynyl, each of the last-mentioned 3 radicals being unsubstituted or by one or more radicals from the group consisting of halogen , Hydroxy, cyano, (C 1 -C 4 ) -alkoxy, halogen- (C 1 -C 4 ) -alkoxy, (C 1 -C 4 ) -alkylthio, (C 1 -C 4 ) -alkylamino, di [( C 1 -C 4 alkyl] amino, [(C 1 -C 4) alkoxy] carbonyl, [halo (C 1 -C 4 ) alkoxy] carbonyl, (C 3 -C 6 ) cycloalkyl that is unsubstituted or substituted, phenyl that
  • RH 3 is (C 1 -C 4 ) -alkoxy, (C2-C4) -alkenyloxy, (C 2 -C 6 ) -alkinyloxy or halogen- (C2-C4) -alkoxy and
  • RH 4 denotes hydrogen or (C 1 -C 4 ) -alkyl or
  • RH 3 and RH 4 together with the directly bonded N atom form a four- to eight-membered heterocyclic ring which, in addition to the N atom, can also contain further hetero-ring atoms, preferably up to two further hetero-ring atoms from the group N, O and S and which is unsubstituted or by one or more radicals from the group consisting of halogen, cyano, nitro, (C 1 -C 4 ) alkyl, halogen (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, halogen ( C 1 -C 4 ) -alkoxy and (C 1 -C 4 ) -alkylthio is substituted.
  • Wettable powders are preparations that are uniformly dispersible in water, which in addition to the active ingredient, in addition to a diluent or inert substance, also ionic and / or nonionic surfactants (wetting agents, dispersants), e.g.
  • polyoxyethylated alkylphenols polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkane sulfonates,
  • Alkylbenzenesulfonates sodium lignosulfonic acid, sodium 2,2'-dinaphthylmethane-6,6'-disulfonic acid, sodium dibutylnaphthalene-sulfonic acid or sodium oleoylmethyltaurinate.
  • the herbicidally active ingredients are finely ground, for example, in customary apparatus such as hammer mills, blower mills and air jet mills and simultaneously or subsequently mixed with the formulation auxiliaries.
  • Emulsifiable concentrates are produced by dissolving the active ingredient in an organic solvent, e.g. butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of an ionic and / or nonionic type (emulsifiers).
  • organic solvent e.g. butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents.
  • alkylarylsulphonic acid calcium salts such as calcium dodecylbenzenesulphonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products
  • alkyl polyethers such as sorbitan oxyethane fatty esters, eg sorbitan oxyethyl fatty esters, sorbitan oxyethyl esters such as sorbitan oxyethyl fatty esters, eg sorbitan oxyethyl fatty esters, sorbitan oxyethylene fatty esters, sorbitan oxyethylene fatty esters, sorbitan oxyethylene fatty esters, sorbitan oxyethyl esters such as sorbitan oxyethyl fatty esters, sorbitan oxyethyl esters, sorbitan oxye
  • Dusting agents are obtained by grinding the active ingredient with finely divided solid substances, e.g. talc, natural clays such as kaolin, bentonite and ityrophyllite, or diatomaceous earth.
  • Suspension concentrates can be water or oil based. They can be produced, for example, by wet grinding using commercially available bead mills and, if necessary, the addition of surfactants, such as those already listed above for the other types of formulation.
  • Emulsions for example oil-in-water emulsions (EW) can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as those already listed above for the other types of formulation.
  • Granules can be produced either by spraying the active ingredient onto adsorptive, granulated inert material or by applying active ingredient concentrates using adhesives, e.g. polyvinyl alcohol, sodium polyacylate or mineral oils, to the surface of carrier materials such as sand, kaolinite or granulated inert material.
  • Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules - if desired as a mixture with fertilizers.
  • Water-dispersible granules are usually by the usual methods such as
  • the agrochemical preparations generally contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of compounds according to the invention.
  • the active ingredient concentration in wettable powder is
  • the active ingredient concentration can be about 1 to 90, preferably 5 to 80% by weight.
  • Dust-like formulations contain 1 to 30% by weight of active ingredient, preferably mostly 5 to 20% by weight of active ingredient
  • sprayable solutions contain about 0.05 to 80, preferably 2 to 50% by weight of active ingredient.
  • the active ingredient content depends in part on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used.
  • the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the active ingredient formulations mentioned contain, where appropriate, the usual adhesive,
  • wetting agents wetting agents, dispersing agents, emulsifying agents, penetration agents, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and agents that influence pH and viscosity.
  • combinations with other pesticidally active substances such as insecticides, acaricides, herbicides, fungicides, and with safeners, fertilizers and / or growth regulators, for example in the form of a finished formulation or as a tank mix, can also be produced.
  • the formulations present in commercially available form are, if appropriate, diluted in the customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules using water.
  • Preparations in the form of dust, soil granules or granules as well as sprayable solutions are usually no longer diluted with other inert substances before use.
  • the required application rate of the compounds of the formula (I) and their salts varies with the external conditions such as temperature, humidity and the type of herbicide used.
  • It can fluctuate within wide limits, for example between 0.001 and 10.0 kg / ha or more of active substance, but is preferably between 0.005 and 5 kg / ha, more preferably in the range from 0.01 to 1.5 kg / ha, in particular preferably in the range from 0.05 to 1 kg / ha g / ha. This applies to both pre-emergence and post-emergence use.
  • Carrier material means a natural or synthetic, organic or inorganic substance with which the active ingredients are mixed or combined for better applicability, especially for application to plants or parts of plants or seeds.
  • the carrier which can be solid or liquid, is generally inert and should be agriculturally useful.
  • Suitable solid or liquid carriers are: for example ammonium salts and natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals such as highly disperse silica, aluminum oxide and natural or synthetic silicates, resins, waxes, solid Fertilizers, water, alcohols, especially butanol, organic solvents, mineral and vegetable oils and derivatives thereof. Mixtures of such carriers can also be used.
  • Solid carriers for granules are: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours and granules made from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks.
  • Liquefied gaseous extenders or carriers are liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide.
  • Adhesives such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and also natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Further additives can be mineral and vegetable oils. If water is used as an extender, it is also possible, for example, to use organic solvents as auxiliary solvents.
  • liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylene or dichloromethane, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, mineral and vegetable oils, alcohols such as Butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • aromatics such as xylene, toluene or alkylnaphthalenes
  • chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylene or dichloromethane
  • aliphatic hydrocarbons such as
  • the agents according to the invention can additionally contain further components, such as, for example, surface-active substances.
  • Suitable surface-active substances are emulsifiers and / or foam-generating agents, dispersants or wetting agents with ionic or non-ionic properties or mixtures of these surface-active substances.
  • salts of polyacrylic acid salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulfosulfinic acid esters (preferably alkylphenols, tauric acid esters) polyethoxylated alcohols or phenols, fatty acid esters of polyols, and derivatives of the compounds containing sulphates, sulphonates and phosphates, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, protein hydrolysates, lignin sulphite waste liquors and methyl cellulose.
  • a surface-active substance is necessary if one of the active substances and / or one of the inert carriers is not soluble in water and if the application takes place in water.
  • the proportion of surface-active substances is between 5 and 40 percent by weight of the agent according to the invention.
  • Dyes such as inorganic pigments, e.g. iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes will.
  • the agents and formulations according to the invention contain between 0.05 and 99% by weight, 0.01 and 98% by weight, preferably between 0.1 and 95% by weight, particularly preferably between 0.5 and 90% Active ingredient, very particularly preferably between 10 and 70 percent by weight.
  • the active ingredients or agents according to the invention can be used as such or depending on their respective physical and / or chemical properties in the form of their formulations or the use forms prepared therefrom, such as aerosols, Kipseisuspensions, cold mist concentrates, hot mist concentrates, encapsulated granules, fine granules, flowable concentrates for the Treatment of seeds, ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, macrogranulates, microgranulates, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, foams, Pastes, pesticide-coated seeds, suspension concentrates, suspension-emulsion concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, dusts and granulates, water-soluble granulates or tablets, water-soluble powders for seed treatment, wettable powders
  • the formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one customary extender, solvent or diluent, emulsifier, dispersant and / or binding or fixing agent, wetting agent, water repellant, optionally siccatives and UV stabilizers and optionally dyes and pigments, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and other processing aids.
  • the agents according to the invention not only include formulations which are already ready to use and can be applied to the plant or seed with a suitable apparatus, but also commercial concentrates which have to be diluted with water before use.
  • the active compounds according to the invention can be used as such or in their (commercially available) formulations and in the use forms prepared from these formulations as a mixture with other (known) active compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers , Safeners or semiochemicals are present.
  • active compounds such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers , Safeners or semiochemicals are present.
  • the treatment according to the invention of the plants and plant parts with the active ingredients or agents is carried out directly or by acting on their surroundings, living space or storage room using the customary treatment methods, for example by dipping, spraying, spraying, sprinkling, Evaporation, atomization, misting, (scattering) scattering, foaming, brushing, spreading, watering (drenching), drip irrigation and, in the case of propagation material, especially seeds, by dry dressing, wet dressing, slurry dressing, encrusting, single or multi-layer coating, etc. It it is also possible to apply the active ingredients according to the ultra-low volume method or to inject the active ingredient preparation or the active ingredient itself into the soil.
  • transgenic seeds with the active ingredients or agents according to the invention are of particular importance.
  • the heterologous gene in transgenic seed can originate, for example, from microorganisms of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, CHomus or CHiocladium.
  • This heterologous gene preferably originates from Bacillus sp., The gene product having an effect against the European corn borer and / or Western Com Rootworm.
  • the heterologous gene is particularly preferably derived from Bacillus thuringiensis.
  • the agent according to the invention is applied to the seed alone or in a suitable formulation.
  • the seed is preferably treated in a state in which it is so stable that no damage occurs during the treatment.
  • the seed can be treated at any point between harvest and sowing.
  • seeds are used that have been separated from the plant and freed from cobs, peels, stems, husks, wool or pulp.
  • seeds can be used that have been harvested, cleaned and dried to a moisture content of less than 15% by weight.
  • seeds can also be used which, after drying, have been treated with water, for example, and then dried again.
  • care when treating the seed, care must be taken to ensure that the amount of the agent according to the invention and / or further additives applied to the seed is selected so that the germination of the seed is not impaired or the plant resulting therefrom is not damaged. This is especially important for active ingredients that can show phytotoxic effects when applied in certain amounts.
  • the agents according to the invention can be applied immediately, that is to say without containing further components and without having been diluted.
  • suitable formulations and methods for seed treatment are and will be known to the person skilled in the art ⁇ , ⁇ . described in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430, US 5,876,739, US 2003/0176428 A1, WO 2002/080675 A1, WO 2002/028186 A2.
  • the active compounds according to the invention can be converted into the customary seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other coating compositions for seeds, and also ULV formulations.
  • customary seed dressing formulations such as solutions, emulsions, suspensions, powders, foams, slurries or other coating compositions for seeds, and also ULV formulations.
  • These formulations are prepared in a known manner by mixing the active ingredients with customary additives, such as customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also water.
  • customary additives such as customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also water.
  • Suitable dyes which can be contained in the seed dressing formulations which can be used according to the invention are all dyes customary for such purposes. Both pigments which are sparingly soluble in water and dyes which are soluble in water can be used here. Examples are those under the names Rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1 known dyes.
  • Suitable wetting agents which can be contained in the seed dressing formulations which can be used according to the invention are all substances which are customary for the formulation of agrochemical active ingredients and which promote wetting.
  • Alkylnaphthalene sulfonates such as diisopropyl or diisobutyl naphthalene sulfonates, can preferably be used.
  • Suitable dispersants and / or emulsifiers which can be contained in the seed dressing formulations which can be used according to the invention are all nonionic, anionic and cationic dispersants customary for the formulation of agrochemical active ingredients.
  • Nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants can preferably be used.
  • Suitable nonionic dispersants are, in particular, ethylene oxide-propylene oxide block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ethers and their phosphated or sulfated derivatives.
  • Suitable anionic dispersants are, in particular, lignosulfonates, polyacrylic acid salts and arylsulfonate-formaldehyde condensates.
  • All foam-inhibiting substances customary for the formulation of agrochemical active ingredients can be contained as defoamers in the seed dressing formulations which can be used according to the invention. Silicone defoamers and magnesium stearate can preferably be used. All substances which can be used in agrochemical agents for such purposes can be present as preservatives in the seed dressing formulations which can be used according to the invention. Examples are dichlorophene and benzyl alcohol hemiformal.
  • Secondary thickeners which can be contained in the seed dressing formulations which can be used according to the invention are all substances which can be used in agrochemical compositions for such purposes. Cellulose derivatives, acrylic acid derivatives, xanthan gum, modified clays and highly disperse silicic acid are preferred.
  • adhesives which can be contained in the seed dressing formulations which can be used according to the invention all conventional binders which can be used in seed dressings are suitable.
  • Polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose may be mentioned as preferred.
  • the seed dressing formulations which can be used according to the invention can be used either directly or after prior dilution with water for the treatment of seeds of the most varied of types, including seeds of transgenic plants. In this context, additional synergistic effects can also occur in cooperation with the substances formed by expression.
  • all mixing devices which can customarily be used for dressing are suitable. In detail, the procedure for dressing is to put the seed in a mixer, add the desired amount of dressing formulations either as such or after prior dilution with water and mix until the formulation is evenly distributed on the seed . If necessary, this is followed by a drying process.
  • the active compounds according to the invention are suitable for protecting plants and plant organs, for increasing crop yields and improving the quality of the crop, given good plant tolerance, favorable warm-blooded toxicity and good environmental compatibility. They can preferably be used as crop protection agents. They are effective against normally sensitive and resistant species and against all or individual stages of development.
  • plants which can be treated according to the invention maize, soybeans, cotton, Brassica oil seeds such as Brassica napus (e.g. canola), Brassica rapa, B. juncea (e.g. (field) mustard) and Brassica carinata, rice, Wheat, sugar beet, sugar cane, oats, rye, barley, millet, triticale, flax, wine and various fruits and vegetables from various botanical taxa such as Rosaceae sp.
  • Brassica oil seeds such as Brassica napus (e.g. canola), Brassica rapa, B. juncea (e.g. (field) mustard) and Brassica carinata, rice, Wheat, sugar beet, sugar cane, oats, rye, barley, millet, triticale, flax, wine and various fruits and vegetables from various botanical taxa such as Rosaceae sp.
  • Brassica oil seeds such as Brassica napus (e.g. canola), Brassica rapa
  • Theaceae sp. Sterculiceae sp., Rutaceae sp. (e.g. lemons, organs and grapefruit); Solanaceae sp. (for example tomatoes, potatoes, pepper, eggplant), Liliaceae sp., Compositae sp. (e.g. lettuce, artichoke and chicory - including root chicory, endive or common chicory), Umbelliferae sp. (e.g., carrot, parsley, celery and celeriac), Cucurbitaceae sp. (e.g., cucumber - including pickles, squash, watermelon, bottle gourd, and melons), Alliaceae sp.
  • Solanaceae sp. for example tomatoes, potatoes, pepper, eggplant
  • Liliaceae sp. Compositae sp.
  • Umbelliferae sp. e.g., carrot, parsley, celery and celeriac
  • Cruciferae sp. for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes, horseradish, cress and Chinese cabbage
  • Leguminosae sp. for example peanuts, peas, and beans - such as runner bean and field bean
  • Chenopodiaceae sp. for example Swiss chard, fodder beet, spinach, beetroot), Malvaceae (for example okra), Asparagaceae (for example asparagus); Useful plants and ornamental plants in gardens and forests; as well as genetically modified species of these plants.
  • plants and their parts can be treated according to the invention.
  • plant species and plant cultivars occurring in the wild or obtained by conventional biological breeding methods such as crossing or protoplast fusion, as well as their parts are treated.
  • transgenic plants and plant cultivars which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetically modified organisms), and their parts are treated.
  • the term “parts” or “parts of plants” or “plant parts” has been explained above. According to the invention, it is particularly preferred to treat plants of the plant varieties which are commercially available or in use. Plant cultivars are understood to be plants with new properties (“traits”) that have been bred by conventional breeding, by mutagenesis or by recombinant DNA technology. These can be varieties, races, bio and genotypes.
  • the treatment method according to the invention can be used for the treatment of genetically modified organisms (GMOs), e.g. B. plants or seeds can be used.
  • GMOs genetically modified organisms
  • Genetically modified plants are plants in which a heterologous gene has been stably integrated into the genome.
  • heterologous gene means essentially a gene which is provided or assembled outside the plant and which when introduced into the cell nucleus genome, the chloroplast genome or the mitochondrial genome of the transformed plant gives new or improved agronomic or other properties that it gives an interesting Protein or polypeptide expressed or that it is another gene that is present in the plant or others Genes that are present in the plant are downregulated or switched off (for example by means of antisense technology, cosuppression technology or RNAi technology [RNA interference]).
  • a heterologous gene that is present in the genome is also called a transgene.
  • a transgene that is defined by its specific presence in the plant genome is called a transformation or transgenic event.
  • the treatment according to the invention can also lead to superadditive (“synergistic”) effects.
  • the following effects are possible that go beyond the effects that are actually to be expected: reduced application rates and / or expanded spectrum of activity and / or increased effectiveness of the active ingredients and compositions that can be used according to the invention, better plant growth, increased tolerance to high or low levels Temperatures, increased tolerance to drought or water or soil salt content, increased flowering capacity, easier harvesting, accelerated ripening, higher yields, larger fruits, higher plant height, more intense green color of the leaves, earlier flowering, higher quality and / or higher nutritional value of the harvested products, higher sugar concentration in the fruits, better storability and / or processability of the harvest products.
  • Plants and plant cultivars which are preferably treated according to the invention include all plants which have genetic material which gives these plants particularly advantageous, useful characteristics (regardless of whether this was achieved by breeding and / or biotechnology).
  • nematode-resistant plants are described, for example, in the following US patent applications: 11 / 765,491, 11 / 765,494, 10 / 926,819, 10 / 782,020, 12 / 032,479, 10 / 783,417, 10 / 782,096, 11 / 657,964, 12 / 192,904, 11 / 396,808, 12 / 166,253, 12 / 166,239, 12 / 166,124, 12 / 166,209, 11 / 762,886, 12 / 364,335, 11 / 763,947, 12 / 252,453, 12 / 209,354, 12 / 491,396 and 12 / 497,221.
  • Plants which can be treated according to the invention are hybrid plants which already express the properties of heterosis or the hybrid effect, which generally leads to higher yields, higher vigor, better health and better resistance to biotic and abiotic stress factors.
  • Such plants are typically created by crossing an inbred male sterile parent line (the female cross partner) with another inbred male fertile parent line (the male cross partner).
  • the hybrid seeds are typically harvested from the male-sterile plants and sold to propagators.
  • Male-sterile plants can sometimes (e.g. in the case of maize) by detaching (ie mechanical removal of the male genital organs or the male flowers); however, it is more common that male sterility is due to genetic determinants in the plant genome.
  • Tapetum cells is expressed in the stamens. Fertility can then be restored by expressing a ribonuclease inhibitor such as barstar in the tapetum cells.
  • Plants or plant cultivars which are obtained using methods of plant biotechnology, such as genetic engineering which can be treated according to the invention are herbicide-tolerant plants; H. Plants that have been made tolerant to one or more specified herbicides. Such plants can be obtained either by genetic transformation or by selection of plants which contain a mutation which confers such herbicide tolerance.
  • Herbicide-tolerant plants are, for example, glyphosate-tolerant plants, ie plants which have been made tolerant to the herbicide CHyphosate or its salts. Plants can be made tolerant to CHyphosate using various methods. For example, glyphosate-tolerant plants can be obtained by transforming the plant with a gene that codes for the enzyme S-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonella typhimurium (Comai et al., 1983, Science 221, 370-371), the CP4 gene of the bacterium Agrobacterium sp.
  • EPSPS S-enolpyruvylshikimate-3-phosphate synthase
  • Hyphosate-tolerant plants can also be obtained by expressing a gene which codes for a glyphosate acetyltransferase enzyme. Glyphosate-tolerant plants can also be obtained by selecting plants which contain naturally occurring mutations of the genes mentioned above. Plants expressing EPSPS genes that confer glyphosate tolerance are described. Plants which confer other genes that confer glyphosate tolerance, e.g., decarboxylase genes, are described.
  • Other heat-resistant plants are, for example, plants that have been made tolerant to herbicides which inhibit the enzyme CHutamine synthase, such as bialaphos, phosphinotricin or ghifosinale.
  • Such plants can be obtained by expressing an enzyme that detoxifies the herbicide or a mutant of the enzyme glutamine synthase that is resistant to inhibition.
  • Such an effective detoxifying enzyme is, for example, an enzyme which codes for a phosphinotricin acetyltransferase (such as the bar or pat protein from Streptomyces species). Plants expressing an exogenous phosphinotricin acetyltransferase have been described.
  • hydroxyphenylpyruvate dioxygenase HPPD
  • HPPD hydroxyphenylpyruvate dioxygenase
  • the hydroxyphenylpyruvate dioxygenases are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is converted to homogenate.
  • Plants tolerant to HPPD inhibitors can be transformed with a gene encoding a naturally occurring resistant HPPD enzyme or a gene encoding a mutated or chimeric HPPD enzyme, as in WO 96/38567 , WO 99/24585, WO 99/24586, WO 2009/144079, WO 2002/046387 or US 6,768,044.
  • Tolerance to HPPD inhibitors can also be achieved by transforming plants with genes which code for certain enzymes which enable the formation of homogenate despite the inhibition of the native HPPD enzyme by the HPPD inhibitor. Such plants are described in WO 99/34008 and WO 02/36787.
  • the tolerance of plants to HPPD inhibitors can also be improved by transforming plants, in addition to a gene that codes for an HPPD-tolerant enzyme, with a gene that codes for a prephenate dehydrogenase enzyme, as in WO 2004/024928 is described.
  • plants can be made even more tolerant of HPPD inhibitors by inserting a gene into their genome which codes for an enzyme that metabolizes or degrades HPPD inhibitors, such as CYP450 enzymes (see WO 2007/103567 and WO 2008/150473 ).
  • ALS inhibitors include, for example, sulfonylurea, imidazolinone, triazolopyrimidines, pyrimidinyloxy (thio) benzoates and / or Sulfonylaminocarbonyltriazolinone herbicides.
  • ALS also known as acetohydroxy acid synthase, AHAS
  • AHAS acetohydroxy acid synthase
  • Further plants that are tolerant of imidazolinones and / or sulfonylureas can be obtained by induced mutagenesis, selection in cell cultures in the presence of the herbicide or by mutation breeding (cf., for example, US Pat. No. 5,084,082 for soybeans, WO 97/41218 for rice, US Pat. No. 5,773,702 for sugar beet and WO 99/057965, for lettuce US 5,198,599 or for sunflower WO 01/065922).
  • Plants or plant cultivars which were obtained by methods of plant biotechnology, such as genetic engineering), which can also be treated according to the invention, are tolerant of abiotic stress factors. Such plants can be obtained by genetic transformation or by selection of plants which contain a mutation which confers such stress resistance. Particularly useful plants with stress tolerance include the following: a. Plants which contain a transgene which is able to reduce the expression and / or activity of the gene for the poly (ADP-ribose) polymerase (PARP) in the plant cells or plants. b. Plants which contain a stress tolerance-promoting transgene which is able to reduce the expression and / or activity of the genes of the plants or plant cells coding for PARC; c.
  • PARP poly (ADP-ribose) polymerase
  • Plants which contain a stress tolerance-promoting transgene which codes for an enzyme of the nicotinamide adenine dinucleotide salvage biosynthetic pathway that is functional in plants including nicotinamidase, nicotinate phosphoribosyl transferase, nicotinic acid mononucleotide adenyl transferase or nicotinic antide adenine dinucleotide transferase.
  • Plants or plant varieties (which were obtained by methods of plant biotechnology, such as genetic engineering), which can also be treated according to the invention, have a changed amount, quality and / or shelf life of the harvested product and / or changed properties of certain components of the harvested product, such as: 1) Transgenic plants that synthesize a modified starch which, in terms of their chemical-physical properties, in particular the amylose content or the amylose / amylopectin The ratio, the degree of branching, the average chain length, the distribution of the side chains, the viscosity behavior, the gel strength, the starch size and / or starch commorphology is changed in comparison with the synthesized starch in wild-type plant cells or plants, so that this modified starch is better for certain applications suitable 2) transgenic plants that synthesize non-starch carbohydrate polymers, or
  • Non-starch carbohydrate polymers whose properties are changed compared to wild-type plants without genetic modification. Examples are plants that produce polyfructose, in particular of the inulin and levan type, plants that produce alpha-1,4-glucans, plants that produce alpha-1,6-branched alpha-1,4-glucans and plants that produce Alteman produce. 3) Transgenic Plants That Produce Hyaluronan.
  • Transgenic plants or hybrid plants such as onions with certain properties such as "high soluble solids content”, low heat ("low pungency”, LP) and / or long storage life ("long storage", LS ).
  • Plants or plant cultivars which were obtained by methods of plant biotechnology, such as genetic engineering), which can likewise be treated according to the invention, are plants such as cotton plants with modified fiber properties.
  • Such plants can be obtained by genetic transformation or by selection of plants which contain a mutation which confers such altered fiber properties; these include: a) plants such as cotton plants which contain a modified form of cellulose synthase genes, b) plants such as cotton plants which contain a modified form of rsw2- or rsw3 -homologous nucleic acids, such as cotton plants with an increased expression of sucrose phosphate synthase; c) Plants such as cotton plants with an increased expression of sucrose synthase; d) Plants such as cotton plants in which the timing of the flow control of the plasmodesmata is changed at the base of the fiber cell, e.g.
  • Plants such as cotton plants with fibers with altered reactivity, e.g. B. by expression of the N-acetylglucosamine transferase gene, including nodC, and of chitin synthase genes.
  • Plants or plant cultivars (which were obtained by methods of plant biotechnology, such as genetic engineering), which can likewise be treated according to the invention, are plants such as rapeseed or related Brassica plants with modified properties of the oil composition.
  • Such plants can be obtained by genetic transformation or by selection of plants which contain a mutation which confers such altered oil properties; these include: a) Plants such as rape plants that produce oil with a high oleic acid content; b) Plants such as rape plants that produce oil with a low linolenic acid content. c) Plants such as rapeseed that produce oil with a low content of saturated fat. Plants or plant varieties (which can be obtained by methods of plant biotechnology, such as genetic engineering), which can also be treated according to the invention, are plants such as potatoes, which are virus-resistant, e.g.
  • Plants or plant cultivars which were obtained by methods of plant biotechnology, such as genetic engineering), which can also be treated according to the invention, are plants such as rapeseed or related Brassica plants with changed properties in the case of seed shattering. Such plants can, by genetic transformation or by selection of plants containing a mutation, confer such altered traits and include plants such as oilseed rape with delayed or reduced seed loss.
  • Particularly useful transgenic plants that can be treated according to the invention are plants with transformation events or combinations of transformation events which are the subject of petitions issued or pending in the USA at the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA) are for the non-regulated status.
  • APHIS Animal and Plant Health Inspection Service
  • USA United States Department of Agriculture
  • the information on this is available at any time from APHIS (4700 River Road Riverdale, MD 20737, USA), eg via the Internet site http://www.aphis.usda.gov/brs/not_reg.html.
  • APHIS American Type 1
  • - Petition identification number of the petition.
  • the technical description of the transformation event can be found in the individual petition document available from APHIS on the website via the petition number.
  • Transgenic phenotype the trait given to the plant by the transformation event.
  • - Transformation event or line the name of the event or events (sometimes referred to as line (s)) for which non-regulated status is requested.
  • transgenic plants which can be treated according to the invention are plants with one or more genes which code for one or more toxins, are the transgenic plants which are sold under the following trade names: YIELD GARD® (for example maize, cotton, Soybeans), KnockOut® (e.g. corn), BiteGard® (e.g. corn), BT-Xtra® (e.g. corn), StarLink® (e.g. corn), Bollgard® (cotton), Nucotn® (cotton), Nucotn 33B® (cotton), NatureGard® (e.g.
  • Herbicide-tolerant plants to be mentioned are, for example, maize varieties, cotton varieties and soybean varieties, which are sold under the following trade names: Roundup Ready® (glyphosate tolerance, e.g. corn, cotton, soybean), Liberty Link® (phosphinotricintolerance, e.g. rips) , IMI® (imidazolinone tolerance) and SCS® (sylphonyl urea tolerance), for example corn.
  • the herbicide-resistant plants (plants traditionally bred for herbicide tolerance) that should be mentioned include the varieties sold under the name Clearfield® (e.g. maize).
  • the 1H-NMR data of selected examples are noted in the form of 1H-NMR peak lists. For each signal peak, first the ⁇ value in ppm and then the signal intensity is listed in round brackets. The ⁇ -value - signal intensity number pairs of different signal peaks are listed separated from each other by semicolons.
  • the peak list of an example therefore has the form: ⁇ (intensity 1 *; ⁇ 2 (intensity i );; ⁇ i (intensity ⁇ ;.; ⁇ n (intensity ,,)
  • the intensity of sharp signals correlates with the height of the signals in a printed example of an NMR spectrum in cm and shows the real relationships between the signal intensities. Broad signals may show multiple peaks or the center of the signal and their relative intensity compared to the most intense signal in the spectrum.
  • 1 H-NMR printouts can show solvent signals, signals of stereoisomers of the target compounds, which are also the subject of the invention, and / or peaks of impurities.
  • connection signals in the delta range of solvents and / or water our lists of 1H-NMR peaks show the usual solvent peaks, for example peaks from DMSO in DMSO-De and the peak from water, which are usually on average have a high intensity.
  • the peaks of stereoisomers of the target compounds and / or peaks of impurities usually have, on average, a lower intensity than the peaks of the target compounds (for example with a purity of> 90%).
  • Such stereoisomers and / or impurities can be typical of the particular manufacturing process. Your peaks can thus help to identify the reproduction of our manufacturing process based on “by-product fingerprints”.
  • An expert who calculates the peaks of the target compounds with known methods can isolate the peaks of the target compounds as required, with additional intensity filters being used if necessary. This isolation would be similar to the relevant peak picking in the classical 1H-NMR interpretation.
  • the reaction mixture was concentrated to dryness in vacuo.
  • the mixture was allowed to come to room temperature, stirred for 1 h, admixed with 1.02 g (0.88 mmol) of tetrakis (triphenylphosphine) palladium (0) and then a solution of 4.00 g (14.75 mmol) of methyl (4-bromo-2-ethyl- 6-methylphenyl) acetate (CAS registry number 181300-41-4) in tetrahydrofuran. The mixture was left to stir at 60 ° C. for 14 h, a further 1.02 g (0.88 mmol) of tetrakis (triphenylphosphine) palladium (0) were added and the mixture was stirred at 60 ° C.
  • Step 2 methyl [2-bromo-6-methoxy-4- (3, 3, 3 -trifluoroprop-1-en-1-yl) phenyl] acetate (example Q4.5)
  • Step 2 methyl (4-amino-2-chloro-6-methoxyphenyl) acetate
  • the reaction mixture was cooled to room temperature, filtered through Celite and washed with methanol. The filtrate was concentrated in vacuo, the residue was taken up in water and ethyl acetate and the phases were separated. The aqueous phase was extracted with ethyl acetate. The combined organic phases were washed with saturated sodium hydrogen carbonate solution and with saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated. 2.50 g (85%) of the desired intermediate compound were obtained.
  • a dusting agent is obtained by mixing 10 parts by weight of a compound of the formula (I) and / or its salts and 90 parts by weight of talc as an inert substance and comminuting it in a hammer mill.
  • a wettable powder which is easily dispersible in water is obtained by adding 25 parts by weight of a compound of the formula (I) and / or salts thereof, 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurinate mixes as a wetting agent and dispersant and grinds in a pin mill.
  • a dispersion concentrate which is easily dispersible in water is obtained by adding 20 parts by weight of a compound of the formula (I) and / or its salts with 6 parts by weight of alkylphenol polyglycol ether ((DTriton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO ) and 71 parts by weight of paraffinic mineral oil (boiling range for example approx. 255 ° C to over 277 ° C) and ground in an attrition ball mill to a fineness of less than 5 microns.
  • alkylphenol polyglycol ether ((DTriton X 207)
  • isotridecanol polyglycol ether (8 EO ) 8 EO
  • paraffinic mineral oil ground in an attrition ball mill to a fineness of less than 5 microns.
  • An emulsifiable concentrate is obtained from 15 parts by weight of a compound of Formula (I) and / or salts thereof, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.
  • a water-dispersible granulate is obtained by
  • Seeds of monocotyledonous and dicotyledonous weed or crop plants are placed in wooden fiber pots in sandy loam soil, covered with soil and grown in a greenhouse under good growth conditions.
  • the test plants are treated in the single-leaf stage 2 to 3 weeks after sowing.
  • the compounds according to the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then sprayed onto the green parts of the plant as an aqueous suspension or emulsion with a water application rate of 600 to 800 l / ha with the addition of 0.2% wetting agent .
  • WP wettable powders
  • EC emulsion concentrates
  • the compounds according to the invention have good herbicidal post-emergence activity against a broad spectrum of grass weeds and weeds.
  • the examples given show an application rate of 80 g / ha 80 - 100% effect against, among others, Alopecurus myosuroides, Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Lolium rigidum, Setaria viridis and Hordeum murinum.
  • the compounds according to the invention are therefore suitable for combating undesired vegetation by the post-emergence method.
  • Seeds of monocotyledonous or dicotyledonous weed or crop plants are laid out in wooden fiber pots in sandy loam and covered with soil.
  • the compounds according to the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then applied to the surface of the covering soil as an aqueous suspension or emulsion with a water application rate of 600 to 800 l / ha with the addition of 0.2% wetting agent .
  • Table 13 Pre-emergence effect at 80 g / ha against ALOMY in%
  • Table 14 Pre-emergence development at 80 g / ha against AVEFA in%
  • the compounds according to the invention have good herbicidal pre-emergence activity against a broad spectrum of grass weeds and weeds.
  • the compounds each show an 80-100% effect against, among others, Alopecurus myosuroides, Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Lolium rigidum, Setaria viridis, Amaranthus retroflexus, Matricaria inodora, Stellaria media, Viola tricolor, Veronica persica and Hordeum murinum.
  • the compounds according to the invention are therefore suitable in the pre-emergence method for controlling undesired vegetation.

Abstract

The invention relates to novel herbicidally active 3-phenylpyrrolin-2-ones according to general formula (I) or to agrochemically acceptable salts thereof and to the use thereof for controlling weeds and weed grasses in crops of useful plants.

Description

3-(4-ALKENYL-PHENYL)-3-PYRROLIN-2-ONE UND DEREN VERWENDUNG 3- (4-ALKENYL-PHENYL) -3-PYRROLIN-2-ONE AND THE USE OF IT
ALS HERBIZIDE AS HERBICIDES
Beschreibung description
Die vorliegende Erfindung betrifft neue herbizid wirksame 3 -Phenylpyrrolin-2-one gemäß der allgemeinen Formel (I) oder agrochemisch akzeptable Salze davon, sowie deren Verwendung zur Bekämpfung von Unkräutern und Ungräsem in Nutzpflanzenkulturen. The present invention relates to new herbicidally active 3-phenylpyrrolin-2-ones according to the general formula (I) or agrochemically acceptable salts thereof, and their use for controlling weeds and grass weeds in crops of useful plants.
Die Verbindungsklasse der 3 -Phenylpyrrolin-2-one sowie deren Herstellung und Verwendung als Herbizide sind aus dem Stand der Technik wohl bekannt. The class of compounds of the 3-phenylpyrrolin-2-ones and their production and use as herbicides are well known from the prior art.
Darüber hinaus sind aber auch zum Beispiel bicyclische 3 -Phenylpyrrolin-2-on-Derivate (EP 0355599 Al und EP 0415211 A2) sowie substituierte monocyclische 3 -Phenylpyrrolin-2-on-Derivate (EP 0377893 A2 und EP 0442077 A2) mit herbizider, insektizider oder fungizider Wirkung beschrieben. In addition, for example, bicyclic 3-phenylpyrrolin-2-one derivatives (EP 0355599 A1 and EP 0415211 A2) and substituted monocyclic 3-phenylpyrrolin-2-one derivatives (EP 0377893 A2 and EP 0442077 A2) with herbicidal, insecticidal or fungicidal effect described.
4-Alkinyl-substituierte-3-Phenylpyrrolin-2-one mit herbizider Wirkung sind ferner aus WO 98/05638 A2, WO 01/74770 Al, WO 2015/032702 Al, WO 2015/040114 Al, WO 2017/060203 Al oder WO 2019/219587 Al bekannt. Die Wirksamkeit dieser Herbizide gegen Schadpflanzen ist von zahlreichen Parametern abhängig, beispielsweise von der verwendeten Aufwandmenge, der Zubereitungsform (Formulierung), den jeweils zu bekämpfenden Schadpflanzen, dem Schadpflanzenspektrum, den Klima- und Bodenverhältnissen sowie der Dauer der Wirkung bzw. der Abbaugeschwindigkeit des Herbizids. Zahlreiche Herbizide aus der Gruppe der 3 -Phenylpyrrolin-2-one erfordern, um eine ausreichende herbizide Wirkung zu entfalten, hohe Aufwandmengen und/oder sie haben ein zu schmales Unkrautspektrun, was deren Anwendung ökonomisch unattraktiv macht. Es besteht daher der Bedarf an alternativen Herbiziden, die verbesserte Eigenschaften aufweisen sowie ökonomisch attraktiv und gleichzeitig effizient sind. 4-Alkynyl-substituted-3-phenylpyrrolin-2-ones with herbicidal action are also from WO 98/05638 A2, WO 01/74770 A1, WO 2015/032702 A1, WO 2015/040114 A1, WO 2017/060203 A1 or WO 2019/219587 Al known. The effectiveness of these herbicides against harmful plants depends on numerous parameters, for example on the application rate used, the form of preparation (formulation), the harmful plants to be controlled, the range of harmful plants, the climatic and soil conditions and the duration of the action or the rate of degradation of the herbicide. Numerous herbicides from the group of 3-phenylpyrrolin-2-ones require, in order to develop a sufficient herbicidal action, high application rates and / or their weed spectrum is too narrow, which makes their use economically unattractive. There is therefore a need for alternative herbicides which have improved properties and are economically attractive and at the same time efficient.
Aufgabe der vorliegenden Erfindung ist folglich die Bereitstellung von neuen Verbindungen, die die genannten Nachteile nicht aufweisen. The object of the present invention is therefore to provide new compounds which do not have the disadvantages mentioned.
Die vorliegende Erfindung betrifft daher neue substituierte 3 -Phenylpyrrolin-2-one der allgemeinen Formel (I),
Figure imgf000003_0002
oder ein agrochemisch akzeptables Salz davon, wobei The present invention therefore relates to new substituted 3-phenylpyrrolin-2-ones of the general formula (I),
Figure imgf000003_0002
or an agrochemically acceptable salt thereof, wherein
R1 (C1-C6)- Alkyl, Halogen-(C1-C6)-alkyl, (C1-C6)-Alkoxy, Halogen-(C1-C6)-alkoxy, (C1-C4)-R 1 (C 1 -C 6 ) -alkyl, halogen- (C 1 -C 6 ) -alkyl, (C 1 -C 6 ) -alkoxy, halogen- (C 1 -C 6 ) -alkoxy, (C 1 - C 4 ) -
Alkoxy-(C1-C4)-alkyl, Halogen-(C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C6)-Alkoxy-(C1-C4)- alkoxy, Halogen-(C1-C6)-alkoxy-(C2-C4)-alkoxy, (C3-C6)-Cycloalkyl, (C2-C6)-Alkenyloxy, Halogen-(C2-C6)-alkenyloxy, (C2-C6)-Alkinyloxy oder Cyano-(C1-C6)-alkoxy ist, Alkoxy- (C 1 -C 4 ) -alkyl, halogen- (C 1 -C 4 ) -alkoxy- (C 1 -C 4 ) -alkyl, (C 1 -C 6 ) -alkoxy- (C 1 -C 4 ) - alkoxy, halogen- (C 1 -C 6 ) -alkoxy- (C2-C4) -alkoxy, (C 3 -C 6 ) -cycloalkyl, (C 2 -C 6 ) -alkenyloxy, halogen- (C 2 - Is C 6 ) -alkenyloxy, (C 2 -C 6 ) -alkinyloxy or cyano- (C 1 -C 6 ) -alkoxy,
R2 Wasserstoff, (C1-C6)- Alkyl, (C1-C4)-Alkoxy-(C1-C4)-alkyl, Halogen-(C1-C6)-alkyl, (C3-C6)- Cycloalkyl, (C3-C6)-Cycloalkyl-(C1-C4)-alkyl, (C2-C6)-Alkenyl, (C2-C6)-Alkinyl, (C1-C6)- Alkoxy oder Halogen-(C1-C6)-alkoxy ist, R 2 hydrogen, (C 1 -C 6 ) -alkyl, (C 1 -C 4 ) -alkoxy- (C 1 -C 4 ) -alkyl, halogen- (C 1 -C 6 ) -alkyl, (C 3 - C 6 ) - Cycloalkyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 4 ) -alkyl, (C 2 -C 6 ) -alkenyl, (C 2 -C 6 ) -alkynyl, (C 1 - C 6 ) alkoxy or halogen (C 1 -C 6 ) alkoxy,
X (C1-C6)- Alkyl, Halogen-(C1-C6)-alkyl, (C3-C6)-Cycloalkyl, (C1-C6)-Alkoxy, Halogen-(C1-C6)- alkoxy, Brom, Chlor oder Fluor ist, X (C 1 -C 6 ) alkyl, halo (C 1 -C 6 ) alkyl, (C 3 -C 6 ) cycloalkyl, (C 1 -C 6 ) alkoxy, halo (C 1 -C 6 ) - is alkoxy, bromine, chlorine or fluorine,
Y (C1-C6)- Alkyl, Halogen-(C1-C6)-alkyl, (C3-C6)-Cycloalkyl, (C1-C6)-Alkoxy, Halogen-(C1-C6)- alkoxy ist, R10 Wasserstoff, Fluor, (C1-C6)- Alkyl oder Halogen-(C1-C6)-alkyl ist, Y (C 1 -C 6 ) alkyl, halo (C 1 -C 6 ) alkyl, (C 3 -C 6 ) cycloalkyl, (C 1 -C 6 ) alkoxy, halo (C 1 -C 6 ) - is alkoxy, R 10 is hydrogen, fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) alkyl,
R11 Fluor, (C1-C6)- Alkyl oder Halogen-(C1-C6)-alkyl ist, R 11 is fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) alkyl,
R12 Wasserstoff, Fluor, (C1-C6)- Alkyl oder Halogen-(C1-C6)-alkyl ist R 12 is hydrogen, fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) alkyl
G Wasserstoff, eine abspaltbare Gruppe L oder ein Kation E ist, wobei L einer der folgenden Reste ist
Figure imgf000003_0001
worin G is hydrogen, a leaving group L or a cation E, where L is one of the following radicals
Figure imgf000003_0001
wherein
R3 (Ci-C*)- Alkyl oder (C 1-C3)- Alkoxy-(C1-C4)-alkyl ist, R 3 is (Ci-C *) - alkyl or (C 1-C3) - alkoxy- (C 1 -C 4 ) -alkyl,
R4 (C1-C4)- Alkyl ist, R5 (C1-C4)- Alkyl, ein unsubstituiertes Phenyl oder ein einfach oder mehrfach mit Halogen, (Ci-R 4 is (C 1 -C 4 ) - alkyl, R 5 (C 1 -C 4 ) - alkyl, an unsubstituted phenyl or a single or multiple with halogen, (Ci-
C4)- Alkyl, Halogen-(C1-C4)-alkyl,(C1-C4)- Alkoxy, Halogen-(C1-C4)-alkoxy, Nitro oder Cyano substituiertes Phenyl ist, C4) -alkyl, halogen- (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -alkoxy, halogen- (C 1 -C 4 ) -alkoxy, nitro or cyano-substituted phenyl,
R6, R6‘ unabhängig voneinander Methoxy oder Ethoxy ist, R7' R8 jeweils unabhängig voneinander Methyl, Ethyl, Phenyl ist, oder gemeinsam mit dem Stickstoffatom, an das sre gebunden sind, einen gesättigten 5-, 6- oder 7-gliedrigen Ring bilden, wobei ein Ringkohlenstoffatom gegebenenfalls durch ein Sauerstoff- oder Schwefelatom ersetzt sein kann, E ein Alkalimetallion, ein Ionenäquivalent eines Erdalkalimetalls, ein Ionenäquivalent Aluminium, ein Ionenäquivalent eines Übergangsmetalls, ein Magnesium-Halogen-Kation oder ein Ammoniumion ist, bei dem gegebenenfalls ein, zwei, drei oder alle vier Wasserstoffatome ersetzt sind durch gleiche oder verschiedene Reste aus den Gruppen (Ci-C 10)- Alkyl oder (C3-C?)-Cy cloalkyl, die unabhängig voneinander jeweils ein- oder mehrfach mit Fluor, Chlor, Brom, Cyano, Hydroxy substituiert oder durch ein- oder mehrere Sauerstoff- oder Schwefelatome unterbrochen sein können, ein cyclisches sekundäres oder tertiäres aliphatisches oder heteroaliphatisches Ammoniumion ist, beispielsweise Morpholinium, Thiomorpholinium, Piperidinium, Pyrrolidinium oder jeweils protoniertes l,4-Diazabicyclo[1.1.2]octane (DABCO) oder l,5-Diazabicyclo[4.3.0]undec-7-en (DBU), ein heteroaromatisches Ammoniumkation ist, beispielsweise jeweils protoniertes Pyridin, 2- Methylpyridin, 3 -Methylpyridin, 4-Methylpyridin, 2,4-Dimethylpyridin, 2,5-Dimethylpyridin, 2,6- Dimethylpyridin, 5-Ethyl-2-methylpyridin, Collidin, Pyrrol, Imidazol, Chinolin, Chinoxalin, 1,2- Dimethylimidazol, 1,3-Dimethylimidazolium-methylsulfat oder weiterhin auch für ein Trimethylsulfoniumion steht. R 6 , R 6 'are independently methoxy or ethoxy, R 7 'R 8 is each independently methyl, ethyl, phenyl, or together with the nitrogen atom to which sre are bonded, form a saturated 5-, 6- or 7-membered ring, one ring carbon atom optionally being replaced by an oxygen or Sulfur atom can be replaced, E is an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent of aluminum, an ion equivalent of a transition metal, a magnesium-halogen cation or an ammonium ion, in which one, two, three or all four hydrogen atoms are optionally replaced by the same or various radicals from the groups (Ci-C 10) - alkyl or (C3-C?) - Cycloalkyl, which are each independently substituted one or more times with fluorine, chlorine, bromine, cyano, hydroxy or by one or more Oxygen or sulfur atoms can be interrupted, is a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, for example morpholinium, thiomorphole inium, piperidinium, pyrrolidinium or in each case protonated 1,4-diazabicyclo [1.1.2] octane (DABCO) or 1,5-diazabicyclo [4.3.0] undec-7-en (DBU), is a heteroaromatic ammonium cation, for example in each case protonated Pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, collidine, pyrrole, imidazole, quinoline, quinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methyl sulfate or, furthermore, also represents a trimethylsulfonium ion.
Definitionen In den Definitionen der in den obigen Formeln verwendeten Symbole wurden Sammelbegriffe verwendet, die allgemein für die folgenden Substituenten stehen: Definitions In the definitions of the symbols used in the above formulas, collective terms were used that generally stand for the following substituents:
Halogen: Fluor, Chlor, Brom oder Iod, vorzugsweise Fluor, Chlor oder Brom und besonders bevorzugt Fluor oder Chlor. Halogen: fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine and particularly preferably fluorine or chlorine.
Alkyl: gesättigter, geradkettiger oder verzweigter Kohlenwasserstoffrest mit 1 bis 6, bevorzugt 1 bis 4 Kohlenstoffatomen, zum Beispiel (jedoch nicht darauf beschränkt) C1-C6-Alkyl wie Methyl, Ethyl,Alkyl: saturated, straight-chain or branched hydrocarbon radical with 1 to 6, preferably 1 to 4 carbon atoms, for example (but not limited to) C 1 -C 6 -alkyl such as methyl, ethyl,
Propyl (n-Propyl), 1-Methylethyl (Isopropyl), Butyl (n-Butyl), 1 -Methylpropyl (sek.-Butyl), 2- Methylpropyl (Isobutyl), 1,1 -Dimethyl ethyl (tert. -Butyl), Pentyl, 1-Methylbutyl, 2-Methylbutyl, 3- Methylbutyl, 2,2-Dimethylpropyl, 1-Ethylpropyl, 1 , 1 -Dimethylpropyl, 1,2-Dimethylpropyl, Hexyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1,1-Dimethylbutyl, 1,2- Dimethylbutyl, 1,3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1- Ethylbutyl, 2-Ethylbutyl, 1,1,2-Trimethylpropyl, 1,2,2-Trimethylpropyl, 1 -Ethyl- 1 -methylpropyl und 1 -Ethyl-2-methylpropyl. Bei dieser Gruppe handelt es sich insbesondere um eine C1-C4- Alkylgruppe, z. B. eine Methyl-, Ethyl-, Propyl-, 1-Methylethyl- (Isopropyl-), Butyl-, 1 -Methylpropyl- (sek. -Butyl - ), 2-Methylpropyl- (Isobutyl-) oder 1 , 1 -Dimethy lethy 1- (tert.-Butyl-)Gruppe. Diese Definition gilt, wenn nicht anderweitig definiert, wie zum Beispiel bei Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Halogenalkyl oder Halogenalkylsulfanyl, auch für Alkyl als Teil eines zusammengesetzten Substituenten, zum Beispiel Cycloalkylalkyl oder Hydroxyalkyl. Alkenyl: ungesättigte geradkettige oder verzweigte Kohlenwasserstoffgruppen mit 2 bis 6 und bevorzugt 2 bis 4 Kohlenstoffatomen und einer Doppelbindung in einer beliebigen Position, zum Beispiel (jedoch nicht darauf beschränkt) Ca-Ce- Alkenyl, wie Vinyl, Allyl, (E)-2-Methylvinyl, (Z)- 2-Methylvinyl, Isopropenyl, Homoallyl, (E)-But-2-enyl, (Z)-But-2-enyl, (E)-But-l-enyl, (Z)-But-l- enyl, 2-Methylprop-2-enyl, l-Methylprop-2-enyl, 2-Methylprop-l-enyl, (E)- 1 -Methylprop- 1 -enyl, (Z)- 1 -Methylprop- 1 -enyl, Pent-4-enyl, (E)-Pent-3-enyl, (Z)-Pent-3-enyl, (E)-Pent-2-enyl, (Z)-Pent-Propyl (n-propyl), 1-methylethyl (isopropyl), butyl (n-butyl), 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl), 1,1-dimethyl ethyl (tert-butyl) , Pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl , 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1 1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl. This group is in particular a C1-C4 alkyl group, e.g. B. a methyl, ethyl, propyl, 1-methylethyl (isopropyl), butyl, 1 -methylpropyl (sec.Butyl - ), 2-methylpropyl (isobutyl) or 1, 1 -dimethy lethy 1- (tert-butyl) group. Unless otherwise defined, for example in the case of alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, haloalkyl or haloalkylsulfanyl, this definition also applies to alkyl as part of a compound substituent, for example cycloalkylalkyl or hydroxyalkyl. Alkenyl: unsaturated straight-chain or branched hydrocarbon groups with 2 to 6 and preferably 2 to 4 carbon atoms and a double bond in any position, for example (but not limited to) Ca-Ce-alkenyl, such as vinyl, allyl, (E) -2- Methylvinyl, (Z) -2-methylvinyl, isopropenyl, homoallyl, (E) -But-2-enyl, (Z) -But-2-enyl, (E) -But-1-enyl, (Z) -But- l-enyl, 2-methylprop-2-enyl, l-methylprop-2-enyl, 2-methylprop-l-enyl, (E) -1 -methylprop-1-enyl, (Z) -1 -methylprop-1 - enyl, Pent-4-enyl, (E) -Pent-3-enyl, (Z) -Pent-3-enyl, (E) -Pent-2-enyl, (Z) -Pent-
2-enyl, (E)-Pent-l-enyl, (Z)-Pent-l-enyl, 3 -Methylbut-3 -enyl, 2-Methylbut-3 -enyl, 1 -Methylbut- 3- enyl, 3 -Methylbut-2-enyl, (E)-2-Methylbut-2-enyl, (Z)-2-Methylbut-2-enyl, (E)-l-Methylbut-2-enyl, (Z)- 1 -Methylbut-2-enyl, (E)-3 -Methylbut- 1 -enyl, (Z)-3 -Methylbut- 1 -enyl, (E)-2-Methylbut- 1 -enyl, (Z)-2-Methylbut-l-enyl, (E)-l -Methylbut- 1 -enyl, (Z)-l -Methylbut- 1 -enyl, 1,1 -Dimethy lprop-2-enyl, 1-Ethylprop-l-enyl, 1 -Propylvinyl, 1 -Isopropylvinyl, (E)-3 ,3 -Dimethy lprop- 1 -enyl, (Z)-3,3- Dimethylprop-l-enyl, Hex-5-enyl, (E)-Hex-4-enyl, (Z)-Hex-4-enyl, (E) -Hex- 3 -enyl, (Z)-Hex-3-enyl, (E)-Hex-2-enyl, (Z)-Hex-2-enyl, (E)-Hex-l-enyl, (Z)-Hex-l-enyl, 4-Methylpent-4-enyl, 3- Methylpent-4-enyl, 2-Methylpent-4-enyl, 1 -Methylpent-4-enyl, 4-Methylpent-3-enyl, (E)-3- Methylpent-3 -enyl, (Z)-3 -Methylpent-3 -enyl, (E)-2-Methylpent-3 -enyl, (Z)-2-Methylpent-3 -enyl, (E)- 1 -Methylpent-3 -enyl, (Z)-l -Methylpent-3 -enyl, (E)-4-Methylpent-2-enyl, (Z)-4-Methylpent-2- enyl, (E)-3 -Methylpent-2-enyl, (Z)-3-Methylpent-2-enyl, (E)-2-Methylpent-2-enyl, (Z)-2- Methylpent-2-enyl, (E)- 1 -Methylpent-2-enyl, (Z)- 1 -Methylpent-2-enyl, (E)-4-Methylpent- 1 -enyl, (Z)-4-Methylpent- 1 -enyl, (E)-3 -Methylpent- 1 -enyl, (Z)-3 -Methylpent- 1 -enyl, (E)-2-Methylpent- 1 - enyl, (Z)-2-Methylpent-l-enyl, (E)- 1 -Methylpent- 1 -enyl, (Z)-l -Methylpent- 1 -enyl, 3-Ethylbut-3- enyl, 2-Ethylbut-3-enyl, l-Ethylbut-3-enyl, (E)-3-Ethylbut-2-enyl, (Z)-3-Ethylbut-2-enyl, (E)-2- Ethylbut-2-enyl, (Z)-2-Ethylbut-2-enyl, (E)-l-Ethylbut-2-enyl, (Z)-l-Ethylbut-2-enyl, (E)-3- Ethylbut-l-enyl, (Z)-3-Ethylbut-l-enyl, 2-Ethylbut-l-enyl, (E)-l-Ethylbut-l-enyl, (Z)-l-Ethylbut-l- enyl, 2-Propylprop-2-enyl, l-Propylprop-2-enyl, 2-Isopropylprop-2-enyl, 1 -Isopropylprop-2-enyl, (E)-2-Propy lprop- 1 -enyl, (Z)-2-Propy lprop- 1 -enyl, (E)- 1 -Propy lprop- 1 -enyl, (Z)- 1 -Propylprop- 1 - enyl, (E)-2-Isopropylprop-l-enyl, (Z)-2-Isopropylprop-l-enyl, (E)- 1 -Isopropy lprop- 1 -enyl, (Z)-l- Isopropylprop-l-enyl, 1 -( 1 , 1 -Dimethylethyl)ethenyl, Buta-l,3-dienyl, Penta-l,4-dienyl, Hexa-1,5- dienyl oder Methylhexadienyl. Bei der Gruppe handelt es sich insbesondere um Vinyl oder Allyl. Diese Definition gilt, wenn nicht anderweitig definiert, auch für Alkenyl als Teil eines zusammengesetzten Substituenten, zum Beispiel Halogenalkenyl. Alldnyl: geradkettige oder verzweigte Kohlenwasserstoffgruppen mit 2 bis 6 und bevorzugt 2 bis 4 Kohlenstoffatomen und einer Dreifachbindung in einer beliebigen Position, zum Beispiel (jedoch nicht darauf beschränkt) Ca-Ce-Alkinyl, wie Ethinyl, Prop-l-inyl, Prop-2-inyl, But-l-inyl, But-2-inyl, But-3-inyl, l-Methylprop-2-inyl, Pent-l-inyl, Pent-2-inyl, Pent-3-inyl, Pent-4-inyl, 2-Methylbut-3- inyl, l-Methylbut-3-inyl, 1 -Methylbut-2-inyl, 3 -Methylbut- 1 -inyl, l-Ethylprop-2-inyl, Hex-l-inyl, Hex-2-inyl, Hex-3-inyl, Hex-4-inyl, Hex-5-inyl, 3-Methylpent-4-inyl, 2-Methylpent-4-inyl, 1- Methylpent-4-inyl, 2-Methylpent-3 -inyl, 1 -Methylpent-3 -inyl, 4-Methylpent-2-inyl, 1 -Methylpent- 2-inyl, 4-Methylpent- 1 -inyl, 3 -Methylpent- 1 -inyl, 2-Ethylbut-3-inyl, l-Ethylbut-3-inyl, 1-Ethylbut- 2-inyl, 1 -Propylprop-2-inyl, 1 -Isopropylprop-2-inyl, 2,2-Dimethylbut-3 -inyl, 1 , 1 -Dimethylbut-3 - inyl, 1 , 1 -Dimethylbut-2-inyl oder 3,3-Dimethylbut-l-inyl. Bei der Alkinylgruppe handelt es sich insbesondere um Ethinyl, Prop-l-inyl oder Prop-2-inyl. Diese Definition gilt, wenn nicht anderweitig definiert, auch für Alkinyl als Teil eines zusammengesetzten Substituenten, zum Beispiel Halogenalkinyl. 2-enyl, (E) -Pent-l-enyl, (Z) -Pent-l-enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3 - Methylbut-2-enyl, (E) -2-methylbut-2-enyl, (Z) -2-methylbut-2-enyl, (E) -l-methylbut-2-enyl, (Z) -1 -methylbut- 2-enyl, (E) -3 -methylbut-1 -enyl, (Z) -3 -methylbut-1 -enyl, (E) -2-methylbut-1 -enyl, (Z) -2-methylbut-1- enyl, (E) -1 -methylbut-1-enyl, (Z) -1 -methylbut-1 -enyl, 1,1-dimethylprop-2-enyl, 1-ethylprop-1-enyl, 1-propylvinyl, 1 -Isopropylvinyl, (E) -3, 3-dimethylprop-1-enyl, (Z) -3,3-dimethylprop-1-enyl, hex-5-enyl, (E) -hex-4-enyl, (Z ) -Hex-4-enyl, (E) -hex-3-enyl, (Z) -hex-3-enyl, (E) -hex-2-enyl, (Z) -hex-2-enyl, (E. ) -Hex-l-enyl, (Z) -Hex-l-enyl, 4-methylpent-4-enyl, 3-methylpent-4-enyl, 2-methylpent-4-enyl, 1-methylpent-4-enyl, 4-methylpent-3-enyl, (E) -3-methylpent-3-enyl, (Z) -3 -methylpent-3-enyl, (E) -2-methylpent-3-enyl, (Z) -2- Methylpent-3-enyl, (E) -1 -methylpent-3-enyl, (Z) -l -methylpent-3 -enyl, (E) -4-methylpent-2-enyl, (Z) -4-methylpent- 2- enyl, (E) -3 - Methylpent-2-enyl, (Z) -3-methylpent-2-enyl, (E) -2-methylpent-2-enyl, (Z) -2-methylpent-2-enyl, (E) -1 -methylpent- 2-enyl, (Z) -1 -methylpent-2-enyl, (E) -4-methylpent-1-enyl, (Z) -4-methylpent-1-enyl, (E) -3 -methylpent-1 - enyl, (Z) -3 -methylpent-1-enyl, (E) -2-methylpent-1-enyl, (Z) -2-methylpent-1-enyl, (E) -1 -methylpent-1-enyl, (Z) -l -Methylpent-1-enyl, 3-ethylbut-3-enyl, 2-ethylbut-3-enyl, 1-ethylbut-3-enyl, (E) -3-ethylbut-2-enyl, (Z ) -3-Ethylbut-2-enyl, (E) -2-ethylbut-2-enyl, (Z) -2-ethylbut-2-enyl, (E) -l-ethylbut-2-enyl, (Z) - l-ethylbut-2-enyl, (E) -3-ethylbut-l-enyl, (Z) -3-ethylbut-l-enyl, 2-ethylbut-l-enyl, (E) -l-ethylbut-l- enyl, (Z) -l-ethylbut-l-enyl, 2-propylprop-2-enyl, l-propylprop-2-enyl, 2-isopropylprop-2-enyl, 1-isopropylprop-2-enyl, (E) - 2-propy lprop- 1 -enyl, (Z) -2-propy lprop- 1 -enyl, (E) -1-propy lprop- 1 -enyl, (Z) -1-propylprop- 1-enyl, (E) -2-Isopropylprop-1-enyl, (Z) -2-isopropylprop-1-enyl, (E) -1 -isopropylprop-1-enyl, (Z) -l-isopropylprop-1-en yl, 1 - (1, 1-dimethylethyl) ethenyl, buta-1,3-dienyl, penta-1,4-dienyl, hexa-1,5-dienyl or methylhexadienyl. The group is in particular vinyl or allyl. Unless otherwise defined, this definition also applies to alkenyl as part of a compound substituent, for example haloalkenyl. Alldnyl: straight-chain or branched hydrocarbon groups with 2 to 6 and preferably 2 to 4 carbon atoms and a triple bond in any position, for example (but not limited to) Ca-Ce-alkynyl, such as ethynyl, prop-1-ynyl, prop-2 -ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, 1-methylprop-2-ynyl, pent-1-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4 -ynyl, 2-methylbut-3-ynyl, 1-methylbut-3-ynyl, 1-methylbut-2-ynyl, 3-methylbut-1-ynyl, 1-ethylprop-2-ynyl, hex-1-ynyl, hex -2-ynyl, hex-3-ynyl, hex-4-ynyl, hex-5-ynyl, 3-methylpent-4-ynyl, 2-methylpent-4-ynyl, 1-methylpent-4-ynyl, 2-methylpent -3-ynyl, 1 -methylpent-3-ynyl, 4-methylpent-2-ynyl, 1 -methylpent-2-ynyl, 4-methylpent-1-ynyl, 3-methylpent-1-ynyl, 2-ethylbut-3 -ynyl, 1-ethylbut-3-ynyl, 1-ethylbut-2-ynyl, 1-propylprop-2-ynyl, 1-isopropylprop-2-ynyl, 2,2-dimethylbut-3-ynyl, 1,1-dimethylbut -3 - ynyl, 1,1-dimethylbut-2-ynyl or 3,3-dimethylbut-1-ynyl. The alkynyl group is in particular ethynyl, prop-1-ynyl or prop-2-ynyl. Unless otherwise defined, this definition also applies to alkynyl as part of a compound substituent, for example haloalkynyl.
Alkoxy: gesättigte, geradkettige oder verzweigte Alkoxyreste mit 1 bis 6 und bevorzugt 1 bis 4 Kohlenstoffatomen, zum Beispiel (jedoch nicht darauf beschränkt) C1-C6-Alkoxy wie Methoxy, Ethoxy, Propoxy, 1-Methylethoxy, Butoxy, 1 -Methylpropoxy , 2-Methylpropoxy, 1,1-Alkoxy: saturated, straight-chain or branched alkoxy radicals having 1 to 6 and preferably 1 to 4 carbon atoms, for example (but not limited to) C 1 -C 6 alkoxy such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy , 2-methylpropoxy, 1,1-
Dimethylethoxy, Pentoxy, 1-Methylbutoxy, 2-Methylbutoxy, 3-Methylbutoxy, 2,2-Dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-
Dimethylpropoxy, 1-Ethylpropoxy, 1 , 1 -Dimethylpropoxy, 1 ,2-Dimethylpropoxy , Hexoxy, 1- Methylpentoxy, 2-Methylpentoxy, 3 -Methylpentoxy , 4-Methylpentoxy, 1 , 1 -Dimethylbutoxy , 1,2- Dimethylbutoxy, 1,3 -Dimethylbutoxy, 2,2-Dimethylbutoxy, 2,3 -Dimethylbutoxy, 3,3-Dimethylpropoxy, 1-ethylpropoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, hexoxy, 1- methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-
Dimethylbutoxy, 1-Ethylbutoxy, 2-Ethylbutoxy, 1 , 1 ,2-Trimethylpropoxy , 1 ,2,2-T rimethylpropoxy , 1 -Ethyl- 1 -methylpropoxy und 1 -Ethyl-2-methylpropoxy . Diese Definition gilt, wenn nicht anderweitig definiert, auch für Alkoxy als Teil eines zusammengesetzten Substituenten, zum Beispiel Halogenalkoxy, Alkinylalkoxy. Cy cloalkyl: monocyclische, gesättigte Kohlenwasserstoffgruppen mit 3 bis 6Dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 1, 2-trimethylpropoxy, 1, 2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy. Unless otherwise defined, this definition also applies to alkoxy as part of a compound substituent, for example haloalkoxy, alkynylalkoxy. Cycloalkyl: monocyclic, saturated hydrocarbon groups with 3 to 6
Kohlenstoffiringgliedem, zum Beispiel (jedoch nicht darauf beschränkt) Cy clopropyl, Cyclopentyl und Cyclohexyl. Diese Definition gilt, wenn nicht anderweitig definiert, auch für Cycloalkyl als Teil eines zusammengesetzten Substituenten, zum Beispiel Cycloalkylalkyl. Carbon ring members such as (but not limited to) cyclopropyl, cyclopentyl and cyclohexyl. Unless otherwise defined, this definition also applies to cycloalkyl as part of a compound substituent, for example cycloalkylalkyl.
Halogenalkyl/Haloalkyl: geradkettige oder verzweigte Alkylgruppen mit 1 bis 6, bevorzugt 1 bis 4 Kohlenstoffatomen (wie oben beschrieben), wobei einige oder alle der Wasserstoffatome in diesen Gruppen durch wie oben beschriebene Halogenatome ersetzt sind, zum Beispiel (jedoch nicht darauf beschränkt) Ci-Cs-Halogenalkyl wie Chlormethyl, Brommethyl, Dichlormethyl, Trichlormethyl, Fluormethyl, Difluormethyl, Trifluormethyl, Chlorfluormethyl, Dichlorfluormethyl, Chlordifluormethyl, 1-Chlorethyl, 1-Bromethyl, 1-Fluorethyl, 2-Fluorethyl, 2,2-Difluorethyl, 2,2,2- Trifluorethyl, 2-Chlor-2-fluorethyl, 2-Chlor-2,2-difluorethyl, 2,2-Dichlor-2-fluorethyl, 2,2,2- Trichlorethyl, Pentafluorethyl und l,l,l-Trifluoiprop-2-yl. Diese Definition gilt, wenn nicht anderweitig definiert, auch für Halogenalkyl als Teil eines zusammengesetzten Substituenten, zum Beispiel Halogenalkylaminoalkyl. Halogenalkenyl und Halogenalkinyl sind analog zu Halogenalkyl definiert, wobei j edoch anstelle vonHaloalkyl / haloalkyl: straight-chain or branched alkyl groups with 1 to 6, preferably 1 to 4 carbon atoms (as described above), some or all of the hydrogen atoms in these groups being replaced by halogen atoms as described above, for example (but not limited to) Ci -Cs-haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2.2 , 2- Trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and l, l, l-trifluoro-prop-2- yl. Unless otherwise defined, this definition also applies to haloalkyl as part of a compound substituent, for example haloalkylaminoalkyl. Haloalkenyl and haloalkynyl are defined analogously to haloalkyl, but instead of
Alkylgruppen Alkenyl- bzw. Alkinylgruppen als Teil des Substituenten vorhanden sind. Alkyl groups, alkenyl or alkynyl groups are present as part of the substituent.
Halogenalkoxy: geradkettige oder verzweigte Alkoxy gruppen mit 1 bis 6, bevorzugt 1 bis 3 Kohlenstoffatomen (wie oben beschrieben), wobei einige oder alle der Wasserstoffatome in diesen Gruppen durch wie oben beschriebene Halogenatome ersetzt sind, zum Beispiel (jedoch nicht darauf beschränkt) C1-C3 -halogenalkoxy wie Chlormethoxy, Brommethoxy, Dichlormethoxy,Haloalkoxy: straight-chain or branched alkoxy groups having 1 to 6, preferably 1 to 3 carbon atoms (as described above), some or all of the hydrogen atoms in these groups being replaced by halogen atoms as described above, for example (but not limited to) C 1 -C 3 -haloalkoxy such as chloromethoxy, bromomethoxy, dichloromethoxy,
Trichlormethoxy, Fluormethoxy, Difluormethoxy, Trifluormethoxy, Chlorfluormethoxy, Dichlorfluormethoxy, Chlordifluormethoxy, 1 -Chlorethoxy, 1 -Bromethoxy, 1-Fluorethoxy, 2- Fluorethoxy, 2,2-Difluorethoxy, 2,2,2-Trifluorethoxy, 2-Chlor-2-fluorethoxy, 2-Chlor-2,2- difluorethoxy, 2,2-Dichlor-2-fluorethoxy, 2,2,2-T richlorethoxy , Pentafluorethoxy und 1,1,1- Trifluorprop-2-oxy. Diese Definition gilt, wenn nicht anderweitig definiert, auch für Halogenalkoxy als Teil eines zusammengesetzten Substituenten, zum Beispiel Halogenalkoxy alkyl. Trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2- fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and 1,1,1-trifluoroprop-2-oxy. Unless otherwise defined, this definition also applies to haloalkoxy as part of a compound substituent, for example haloalkoxy alkyl.
Nicht eingeschlossen sind Kombinationen, die gegen die Naturgesetze verstoßen und die der Fachmann daher aufgrund seines Fachwissens ausschließen würde. Ringstrukturen mit drei oder mehr benachbarten Sauerstoffatomen beispielsweise sind ausgeschlossen. This does not include combinations that violate the laws of nature and which the person skilled in the art would therefore exclude on the basis of his specialist knowledge. Ring structures with three or more neighboring oxygen atoms, for example, are excluded.
Die Verbindungen der Formel (I) können als geometrische und/oder optische Isomere oder Isomerengemische in unterschiedlicher Zusammensetzung vorliegen. Beispielsweise können - abhängig von der Verknüpfung des Substituenten R1 - sowohl Enantiomere als auch cis-/trans- Isomere auftreten. Letztere sind folgendermaßen definiert:
Figure imgf000007_0001
Figure imgf000008_0001
The compounds of the formula (I) can exist as geometric and / or optical isomers or isomer mixtures in various compositions. For example, depending on the linkage of the substituent R 1 , both enantiomers and cis / trans isomers can occur. The latter are defined as follows:
Figure imgf000007_0001
Figure imgf000008_0001
Die gegebenfalls bei der Synthese anfallenden Isomerengemische können mit den üblichen technischen Methoden getrennt werden. Sowohl die reinen Isomeren bzw. Tautomere als auch die Tautomeren- und Isomerengemische, derenAny mixtures of isomers obtained during the synthesis can be separated using the customary technical methods. Both the pure isomers or tautomers and the tautomer and isomer mixtures, their
Herstellung und Verwendung sowie diese enthaltende Mittel sind Gegenstand der vorliegenden Erfindung. Im Folgenden wird der Einfachheit halber jedoch stets von Verbindungen der Formel (I) gesprochen, obwohl sowohl die reinen Verbindungen als auch gegebenenfalls Gemische mit unterschiedlichen Anteilen an isomeren und tautomeren Verbindungen gemeint sind. Die erfindungsgemäßen Verbindungen sind durch die Formel (I) allgemein definiert. Bevorzugte Substituenten bzw. Bereiche der in der oben und nachstehend erwähnten Formeln aufgeführten Reste werden im Folgenden erläutert: Production and use as well as agents containing them are the subject of the present invention. For the sake of simplicity, however, compounds of the formula (I) are always referred to below, although both the pure compounds and, if appropriate, mixtures with different proportions of isomeric and tautomeric compounds are meant. The compounds according to the invention are generally defined by the formula (I). Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below:
Bevorzugt sind Verbindungen der allgemeinen Formel (I), in denen Preference is given to compounds of the general formula (I) in which
R1 (C1-C6)- Alkyl, Halogen-(C1-C6)-alkyl, (C1-C6)- Alkoxy, Halogen-(C1-C6)-alkoxy,(C1-C4)-R 1 (C 1 -C 6 ) -alkyl, halogen- (C 1 -C 6 ) -alkyl, (C 1 -C 6 ) -alkoxy, halogen- (C 1 -C 6 ) -alkoxy, (C 1 - C 4 ) -
Alkoxy-(C1-C4)-alkyl, Halogen-(C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C6)-Alkoxy-(C2-C4)- alkoxy, Halogen-(C1-C6)-alkoxy-(C2-C4)-alkoxy, (C3-C6)-Cycloalkyl, (C2-C6)-Alkenyloxy, Halogen-(C2-C6)-alkenyloxy, (C2-C6)-Alkinyloxy oder Cyano-(C1-C6)-alkoxy ist, Alkoxy- (C 1 -C 4 ) -alkyl, halogen- (C 1 -C 4 ) -alkoxy- (C 1 -C 4 ) -alkyl, (C 1 -C 6 ) -alkoxy- (C2-C4) - alkoxy, halo (C 1 -C 6 ) alkoxy (C2 -C4) alkoxy, (C 3 -C 6 ) cycloalkyl, (C 2 -C 6 ) alkenyloxy, halo (C 2 -C 6 ) -alkenyloxy, (C 2 -C 6 ) -alkinyloxy or cyano- (C 1 -C 6 ) -alkoxy,
R2 Wasserstoff, (C1-C6)- Alkyl, (C1-C4)Alkoxy-(C2-C4)-alkyl, Halogen-(C1-C6)-alkyl, (C3-C6)- Cycloalkyl, (C2-C6)-Alkenyl oder (C2-C6)-Alkinyl, ist, X (C1-C6)- Alkyl, Halogen-(C1-C6)-alkyl, (C3-C6)-Cycloalkyl, (C1-C6)-Alkoxy, Halogen-(C1-C6> alkoxy, Brom, Chlor oder Fluor ist, R 2 hydrogen, (C 1 -C 6 ) -alkyl, (C 1 -C4) alkoxy- (C 2 -C4) -alkyl, halogen- (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) - cycloalkyl, (C 2 -C 6) alkenyl or (C 2 -C 6) alkynyl, X is (C 1 -C 6) - alkyl, halo (C 1 -C 6) alkyl, (C 3 -C 6 ) -cycloalkyl, (C 1 -C 6 ) -alkoxy, halogen- (C 1 -C 6 > alkoxy, bromine, chlorine or fluorine,
Y (C1-C6)- Alkyl, Halogen-(C1-C6)-alkyl, (C3-C6)-Cycloalkyl, (C1-C6)- Alkoxy, Halogen-(C1-C6)- alkoxy ist, Y (C 1 -C 6 ) alkyl, halo (C 1 -C 6 ) alkyl, (C 3 -C 6 ) cycloalkyl, (C 1 -C 6 ) alkoxy, halo (C 1 -C 6 ) - is alkoxy,
R10 Wasserstoff, Fluor, (C1-C6)- Alkyl oder Halogen-(C1-C6)-alkyl ist, R11 Fluor, (C1-C6)- Alkyl oder Halogen-(C1-C6)-alkyl ist, R 10 is hydrogen, fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) alkyl, R 11 is fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) is -alkyl,
R12 Wasserstoff, Fluor, (C1-C6)- Alkyl oder Halogen-(C1-C6)-alkyl ist R 12 is hydrogen, fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) alkyl
G Wasserstoff, eine abspaltbare Gruppe L oder ein Kation E ist, wobei L einer der folgenden Reste ist
Figure imgf000009_0001
wonn G is hydrogen, a leaving group L or a cation E, where L is one of the following radicals
Figure imgf000009_0001
wonn
R3 (C1-C4)- Alkyl oder (C 1-C3)- Alkoxy-(C1-C4)-alkyl ist, R 3 is (C 1 -C 4 ) -alkyl or (C 1-C3) -alkoxy- (C 1 -C 4 ) -alkyl,
R4 (C1-C4)- Alkyl ist, R5(C1-C4)- Alkyl, ein unsubstituiertes Phenyl oder ein einfach oder mehrfach mit Halogen, (Ci- C4)- Alkyl, Halogen-(C1-C4)-alkyl oder(C1-C4)- Alkoxy substituiertes Phenyl ist, R 4 is (C 1 -C 4 ) - alkyl, R 5 (C 1 -C 4 ) - alkyl, an unsubstituted phenyl or a single or multiple with halogen, (Ci- C4) - alkyl, halogen (C 1 - Is C 4 ) alkyl or (C 1 -C 4 ) alkoxy substituted phenyl,
E ein Alkalimetallion, ein Ionenäquivalent eines Erdalkalimetalls, ein Ionenäquivalent Aluminium, ein Ionenäquivalent eines Übergangsmetalls, ein Magnesium-Halogen-Kation oder ein Ammoniumion ist, bei dem gegebenenfalls ein, zwei, drei oder alle vier Wasserstoff atome ersetzt sind durch gleiche oder verschiedene Reste aus den Gruppen (Ci-C 10)- Alkyl oder (C3-C?)-Cy cloalkyl, die unabhängig voneinander jeweils ein- oder mehrfach mit Fluor, Chlor, Brom, Cyano, Hydroxy substituiert oder durch ein- oder mehrere Sauerstoff- oder Schwefelatome unterbrochen sein können, ein cyclisches sekundäres oder tertiäres aliphatisches oder heteroaliphatisches Ammoniumion ist, beispielsweise Morpholinium, Thiomorpholinium, Piperidinium, Pyrrolidinium oder jeweils protoniertes l,4-Diazabicyclo[1.1.2]octane (DABCO) oder l,5-Diazabicyclo[4.3.0]undec-7-en (DBU), ein heteroaromatisches Ammoniumkation ist, beispielsweise jeweils protoniertes Pyridin, 2- Methylpyridin, 3 -Methylpyridin, 4-Methylpyridin, 2,4-Dimethylpyridin, 2,5-Dimethylpyridin, 2,6- Dimethylpyridin, 5-Ethyl-2-methylpyridin, Collidin, Pyrrol, Imidazol, Chinolin, Chinoxalin, 1,2- Dimethylimidazol, 1,3-Dimethylimidazolium-methylsulfat oder weiterhin auch für ein Trimethylsulfoniumion steht. E is an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent of aluminum, an ion equivalent of a transition metal, a magnesium-halogen cation or an ammonium ion in which one, two, three or all four hydrogen atoms are optionally replaced by identical or different radicals the groups (Ci-C 10) - alkyl or (C3-C?) - Cy cloalkyl, which are each independently substituted one or more times with fluorine, chlorine, bromine, cyano, hydroxy or by one or more oxygen or sulfur atoms may be interrupted, a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, for example morpholinium, thiomorpholinium, piperidinium, pyrrolidinium or protonated 1,4-diazabicyclo [1.1.2] octane (DABCO) or 1,5-diazabicyclo [4.3.0 ] undec-7-ene (DBU), is a heteroaromatic ammonium cation, for example in each case protonated pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-di methylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, collidine, pyrrole, imidazole, quinoline, quinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methyl sulfate or furthermore for a Trimethylsulfonium ion.
Besonders bevorzugt sind Verbindungen der allgemeinen Formel (I), in denen Particularly preferred are compounds of the general formula (I) in which
R1 (C1-C6)-Alkyl, (C1-C6)-Alkoxy, Halogen-(C1-C6)-alkoxy , (C1-C4)-Alkoxy-(C1-C4)-alkyl oder (C1-C6)- Alkoxy-(C2-C4)-alkoxy ist, R 1 (C 1 -C 6 ) -alkyl, (C 1 -C 6 ) -alkoxy, halogen- (C 1 -C 6 ) -alkoxy, (C 1 -C 4 ) -alkoxy- (C 1 -C 4 ) -alkyl or (C 1 -C 6 ) -alkoxy- (C2-C4) -alkoxy,
R2 Wasserstoff(,C1-C4)- Alkyl, Methoxyethyl , Ethoxyethyl, Halogen-(Ci-C2)-alkyl, Cyclopropyl, (C2-C4)-Alkenyl, (C2-C4)-Alkinyl, (C1-C4)- Alkoxy oder Halogen-(C1-C4)-alkoxy ist, R 2 hydrogen (, C 1 -C 4 ) - alkyl, methoxyethyl, ethoxyethyl, halogen (Ci-C2) -alkyl, cyclopropyl, (C2-C4) -alkenyl, (C2-C4) -alkynyl, (C 1 - C 4 ) -alkoxy or halogen- (C 1 -C 4 ) -alkoxy,
X (C1-C6)-Alkyl, Halogen-(C1-C6)-alkyl, (C3-C6)-Cycloalkyl, (C1-C6)-Alkoxy, Halogen-(C1-C6)- alkoxy, Brom, Chlor oder Fluor ist, X (C 1 -C 6 ) alkyl, halo (C 1 -C 6 ) alkyl, (C 3 -C 6 ) cycloalkyl, (C 1 -C 6 ) alkoxy, halo (C 1 -C 6 ) - is alkoxy, bromine, chlorine or fluorine,
Y (C1-C6)-Alkyl, Halogen-(C1-C6)-alkyl oder (C1-C6)-Alkoxy ist, Y is (C 1 -C 6 ) -alkyl, halogen- (C 1 -C 6 ) -alkyl or (C 1 -C 6 ) -alkoxy,
R10 Wasserstoff ist, R11 (C1-C6)-Alkyl oder Halogen-(C1-C6)-alkyl ist, R 10 is hydrogen, R 11 is (C 1 -C 6 ) -alkyl or halo (C 1 -C 6 ) -alkyl,
R12 Wasserstoff oder (C1-C6)-Alkyl ist G Wasserstoff, eine abspaltbare Gruppe L oder ein Kation E ist, wobei L einer der folgenden Reste ist
Figure imgf000010_0001
R 12 is hydrogen or (C 1 -C 6 ) alkyl G is hydrogen, a leaving group L or a cation E, where L is one of the following radicals
Figure imgf000010_0001
5 worin 5 in which
R3 (C1-C4)- Alkyl oder (Ci-C2>Alkoxy-(Ci-C2>Alkyl ist, R 3 (C 1 -C 4 ) - alkyl or (Ci-C2> alkoxy- (Ci-C 2 > alkyl,
R4 (C1-C4)- Alkyl ist, R 4 is (C 1 -C 4 ) alkyl,
E ein Alkalimetallion, ein Ionenäquivalent eines Erdalkalimetalls, ein Ionenäquivalent Aluminium, ein Ionenäquivalent eines Übergangsmetalls, ein Magnesium-Halogen-Kation oder ein Ammoniumion ist, bei dem gegebenenfalls ein, zwei, drei oder alle vier Wasserstoffatome ersetzt sind durch gleiche oder verschiedene Reste aus den Gruppen (Ci-C 10)- Alkyl oder (C3-C7)-Cy cloalkyl. E is an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent of aluminum, an ion equivalent of a transition metal, a magnesium-halogen cation or an ammonium ion in which one, two, three or all four hydrogen atoms are optionally replaced by identical or different radicals from the Groups (Ci-C 10) - alkyl or (C3-C7) -Cy cloalkyl.
Ganz besonders bevorzugt sind Verbindungen der allgemeinen Formel (I), in denen Compounds of the general formula (I) in which
R1 Methoxy oder Methoxy ethoxy ist, R2 Wasserstoff oder Methyl ist, R 1 is methoxy or methoxy ethoxy, R 2 is hydrogen or methyl,
X Methyl, Brom oder Chlor ist, X is methyl, bromine or chlorine,
Y Methyl, Ethyl oder Methoxy ist, Y is methyl, ethyl or methoxy,
R10 Wasserstoff ist, R 10 is hydrogen,
R11 Methyl oder Trifluoromethyl ist, R12 Wasserstoff ist, R 11 is methyl or trifluoromethyl, R 12 is hydrogen,
G Wasserstoff, eine abspaltbare Gruppe L oder ein Kation E ist, wobei G is hydrogen, a leaving group L or a cation E, where
L einer der folgenden Reste ist
Figure imgf000010_0002
worin R3 Methyl, Ethyl, i-Propyl oder t-Butyl ist, L is one of the following residues
Figure imgf000010_0002
wherein R 3 is methyl, ethyl, i-propyl or t-butyl,
R4 Methyl oder Ethyl ist, R 4 is methyl or ethyl,
E ein Natriumion oder ein Kaliumion ist. E is a sodium ion or a potassium ion.
Die Herstellung der erfindungsgemäßen Verbindungen der allgemeinen Formel (I) ist im Prinzip bekannt bzw. kann in Anlehnung an literaturbekannte Verfahren erfolgen, beispielsweise indem man a) eine Verbindung der allgemeinen Formel (II),
Figure imgf000011_0001
in welcher R1, R2, X, Y, R10, R11 und R12 die oben angegebenen Bedeutungen haben und R9 für Alkyl, bevorzugt für Methyl oder Ethyl, steht, gegebenenfalls in Anwesenheit eines geeigneten Lösungsoder Verdünnungsmittels, mit einer geeigneten Base unter formaler Abspaltung der Gruppe R9OH cyclisiert, oder b) eine Verbindung der allgemeinen Formel (Ia),
Figure imgf000011_0002
in der R1, R2, X, Y, R10, R11 und R12 die oben angegebenen Bedeutungen haben, beispielsweise mit einer Verbindung der allgemeinen Formel (III),
Figure imgf000011_0003
in der L die oben angegebene Bedeutung hat und Hai für ein Halogen, vorzugsweise Chlor oder Brom oder auch eine Sulfonsäuregruppe stehen kann, gegebenenfalls in Anwesenheit eines geeigneten Lösungs- oder Verdünnungsmittels sowie einer geeigneten Base, zur Reaktion bringt oder (c) indem man Verbindungen der allgemeinen Formel (IV),
Figure imgf000012_0001
in der R1, R2, G, X und Y die oben angegebenen Bedeutungen haben und U für eine geeignete Abgangsgruppe steht, mit einem geeigneten Alkenyl-Reagenz der allgemeinen Formel (V),The preparation of the compounds of the general formula (I) according to the invention is known in principle or can be carried out on the basis of processes known from the literature, for example by a) a compound of the general formula (II),
Figure imgf000011_0001
in which R 1 , R 2 , X, Y, R 10 , R 11 and R 12 have the meanings given above and R 9 is alkyl, preferably methyl or ethyl, optionally in the presence of a suitable solvent or diluent with a suitable Base cyclized with formal elimination of the group R 9 OH, or b) a compound of the general formula (Ia),
Figure imgf000011_0002
in which R 1 , R 2 , X, Y, R 10 , R 11 and R 12 have the meanings given above, for example with a compound of the general formula (III),
Figure imgf000011_0003
in which L has the meaning given above and Hal can stand for a halogen, preferably chlorine or bromine or a sulfonic acid group, optionally in the presence of a suitable solvent or diluent and a suitable base, or (c) by reacting compounds of general formula (IV),
Figure imgf000012_0001
in which R 1 , R 2 , G, X and Y have the meanings given above and U stands for a suitable leaving group, with a suitable alkenyl reagent of the general formula (V),
Z-CR10=CR11R12 (V) in der Z für eine geeignete Abgangsgruppe steht und R10, R11 und R12 die oben angegebene Bedeutung hat, gegebenenfalls in Gegenwart geeigneter Katalysatoren und einer geeigneten Base, umsetzt. Als Abgangsgruppe U kommen beispielsweise Halogenatome wie Chlor, Brom oder Iod, Alkylsulfonestergruppen wie beispielsweise Triflat, Mesylat oder Nonaflat in Betracht. Als Abgangsgruppe Z kommen beispielsweise Magnesiumchlorid, Magnesiumbromid, Zinkchlorid, ein Trialkylzinnrest, Carboxyl sowie Boronsäure-Reste wie -B(OH)2 oder -B(OAlkyl)2 in Betracht. Als Katalysatoren sind insbesondere Pd° Komplexe sehr gut geeignet, wobei in vielen Fällen auch der Zusatz von Cu®-Salzen sehr vorteilhaft sein kann. Auch Liganden wie etwa 1,4- Bis(diphenylphosphino)butan können verwendet werden.
Figure imgf000012_0002
Z-CR 10 = CR 11 R 12 (V) in which Z represents a suitable leaving group and R 10 , R 11 and R 12 have the meaning given above, optionally in the presence of suitable catalysts and a suitable base. As leaving group U, for example, halogen atoms such as chlorine, bromine or iodine, alkyl sulfonic ester groups such as triflate, mesylate or nonaflate are suitable. As leaving group Z, for example, magnesium chloride, magnesium bromide, zinc chloride, a trialkyltin radical, carboxyl and boronic acid radicals such as -B (OH) 2 or -B (O-alkyl) 2 come into consideration. Pd ° complexes in particular are very suitable as catalysts, and in many cases the addition of Cu® salts can also be very advantageous. Ligands such as 1,4-bis (diphenylphosphino) butane can also be used.
Figure imgf000012_0002
Die beschriebene Methodik ist Stand der Technik und im Übrigen auch unter dem Stichwort "Palladium-katalysierte Kreuzkupplung", "Sonogashira-, Negishi-, Suzuki-, Stille- oder Kumada- Kupplung" einschlägig literaturbekaimt. The methodology described is state of the art and is also relevant to the literature under the heading “Palladium-catalyzed cross-coupling”, “Sonogashira, Negishi, Suzuki, Stille or Kumada coupling”.
Die Vorstufen der allgemeinen Formel (II) können in Analogie zu bekannten Verfahren, beispielsweise durch Umsetzung eines Aminosäureesters der allgemeinen Formel (VI), in der R1, R2 und R9 die oben beschriebene Bedeutung haben, mit einer Phenylessigsäure der allgemeinen Formel (VH), in der X, Y, R10, R11 und R12 die oben beschriebene Bedeutung haben, gegebenenfalls durch Zusatz eines wasserentziehenden Mittels und gegebenenfalls in Anwesenheit eines geeigneten Lösungs- bzw. Verdünnungsmittels, hergestellt werden.
Figure imgf000013_0001
Aminoester der allgemeinen Formel (VI) sind literaturbekannt, beispielsweise aus WO 2006/000355.The precursors of the general formula (II) can be carried out in analogy to known processes, for example by reacting an amino acid ester of the general formula (VI), in which R 1 , R 2 and R 9 have the meaning described above, with a phenylacetic acid of the general formula ( VH), in which X, Y, R 10 , R 11 and R 12 have the meaning described above, optionally through Addition of a dehydrating agent and, if appropriate, in the presence of a suitable solvent or diluent, are prepared.
Figure imgf000013_0001
Amino esters of the general formula (VI) are known from the literature, for example from WO 2006/000355.
Die Herstellung der Phenylessigsäuren der allgemeinen Formel (VII) ist unten näher beschrieben. The preparation of the phenylacetic acids of the general formula (VII) is described in more detail below.
Eine weitere Variante zur Herstellung von Vorstufen der allgemeinen Formel (II) besteht unter anderem auch darin, dass man eine Verbindung mit der allgemeinen Formel (VIII), in der R1, R2· R9 X, Y und U die oben angegebene Bedeutung haben, nach der bereits beschriebenen Kreuzkupplungs- Methodik mit einer Verbindung der allgemeinen Formel (V), in der Z, R10, R11 und R12 die oben angegebene Bedeutung hat, umsetzt:
Figure imgf000013_0002
Another variant for the preparation of precursors of the general formula (II) consists, inter alia, of the fact that a compound with the general formula (VIII) in which R 1 , R 2 · R 9 X, Y and U has the meaning given above have, according to the already described cross-coupling methodology, with a compound of the general formula (V) in which Z, R 10 , R 11 and R 12 have the meaning given above:
Figure imgf000013_0002
Die benötigten Vorstufen der allgemeinen Formel (VII) können beispielsweise erhalten werden, indem man eine Verbindung mit der allgemeinen Formel (IX), in der X, Y und U die oben angegebene Bedeutung haben und R13 für Wasserstoff, Alkyl, bevorzugt für Methyl- oder Ethyl steht, nach der bereits beschriebenen Kreuzkupplungs-Methodik mit einer Verbindung der allgemeinen Formel (V), in der Z, R10, R11 und R12 die oben angegebene Bedeutung hat, zur Reaktion bringt:
Figure imgf000013_0003
Steht R13 für Alkyl, bevorzugt für Methyl- oder Ethyl, können die benötigten Vorstufen der allgemeinen Formel (VH) durch eine Spaltung des Esters der allgemeinen Formel (ΧΠ), in der X,Y, R10, R11 und R12 die oben angegebene Bedeutung hat, nach Standardmethoden erhalten werden:
Figure imgf000014_0002
Die benötigten Vorstufen der allgemeinen Formel (IX) können zum Beispiel erhalten werden, indem man nach literalurbekannten Verfahren eine Acetateinheit in Verbindungen der allgemeinen Formel (XI), in der X, Y und U die oben angegebene Bedeutung haben, einführt. The required precursors of the general formula (VII) can be obtained, for example, by adding a compound of the general formula (IX) in which X, Y and U have the meaning given above and R 13 is hydrogen, alkyl, preferably methyl or ethyl, according to the cross-coupling method already described, reacts with a compound of the general formula (V) in which Z, R 10 , R 11 and R 12 have the meaning given above:
Figure imgf000013_0003
If R 13 is alkyl, preferably methyl or ethyl, the required precursors of the general formula (VH) can be obtained by cleavage of the ester of the general formula (ΧΠ) in which X, Y, R 10 , R 11 and R 12 die has the meaning given above, can be obtained by standard methods:
Figure imgf000014_0002
The required precursors of the general formula (IX) can be obtained, for example, by introducing an acetate unit into compounds of the general formula (XI) in which X, Y and U have the meanings given above, according to processes known in the literature.
Dies kann beispielsweise analog zu den in WO 05/44796 oder in WO 10/115780 oder in W019/219587 beschriebenen Verfahren durch Meerwein- Aryli erung eines Anilins der allgemeinen Formel (XI) mit Vinylidenchlorid gefolgt von einer Hydrolyse oder Alkoholyse der Zwischenverbindung (X) geschehen:
Figure imgf000014_0001
This can be done, for example, analogously to the method described in WO 05/44796 or in WO 10/115780 or in WO19 / 219587 by Meerwein arylation of an aniline of the general formula (XI) with vinylidene chloride followed by hydrolysis or alcoholysis of the intermediate compound (X) happen:
Figure imgf000014_0001
Daneben sind auch weitere alternative Herstellungsverfahren bekannt, wie zum Beispiel die Einführung von Malonsäureestern in Halogenaromaten, wie sie zum Beispiel in WO 15/032702 beschrieben sind. Diese Phenylmalonsäureester lassen sich nach Derivatisierung in der 4-Position verseifen und zur gewünschten Phenylessigsäure der allgemeinen Formel (VII) decarboxylieren. In addition, other alternative production processes are also known, such as, for example, the introduction of malonic acid esters into haloaromatics, as described, for example, in WO 15/032702. After derivatization, these phenylmalonic acid esters can be saponified in the 4-position and decarboxylated to give the desired phenylacetic acid of the general formula (VII).
Vorstufen der allgemeinen Formel (XI) wiederum können durch gängige Standardmethoden wie Bromierung und/oder Alkylierung aus kommerziell erhältlichen Aminonitrophenolen erhalten werden. Gegenstand der vorliegenden Erfindung sind desweiteren Verbindungen der Formel (ΧΠ), worin die Reste folgende Bedeutungen auf weisen:
Figure imgf000015_0001
Precursors of the general formula (XI) can in turn be obtained from commercially available amino nitrophenols by common standard methods such as bromination and / or alkylation. The present invention also relates to compounds of the formula (ΧΠ) in which the radicals have the following meanings:
Figure imgf000015_0001
X ist Methyl, Brom oder Chlor X is methyl, bromine, or chlorine
Y ist Methyl, Ethyl oder Methoxy Y is methyl, ethyl or methoxy
R10 ist Wasserstoff R11 ist Methyl oder Trifluoromethyl R 10 is hydrogen R 11 is methyl or trifluoromethyl
R12 ist Wasserstoff R 12 is hydrogen
R 13 ist Wasserstoff, Methyl oder Ethyl. R 13 is hydrogen, methyl or ethyl.
Die erfindungsgemäßen Verbindungen der Formel (I) (und/oder deren Salze), imfolgenden zusammen als „erfindungsgemäße Verbindungen“ bezeichnet, weisen eine ausgezeichnete herbizide Wirksamkeit gegen ein breites Spektrum wirtschaftlich wichtiger mono- und dikotyler annueller Schadpflanzen auf. The compounds of the formula (I) according to the invention (and / or their salts), hereinafter referred to collectively as “compounds according to the invention”, have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous annual harmful plants.
Gegenstand der vorliegenden Erfindung ist daher auch ein Verfahren zur Bekämpfung von unerwünschten Pflanzen oder zur Wachstumsregulierung von Pflanzen, vorzugsweise in Pflanzenkulturen, worin eine oder mehrere erfindungsgemäße Veibindung(en) auf die Pflanzen (z.B. Schadpflanzen wie mono- oder dikotyle Unkräuter oder unerwünschte Kulturpflanzen), das SaatgutThe present invention therefore also relates to a method for controlling unwanted plants or for regulating the growth of plants, preferably in plant crops, in which one or more compounds according to the invention are applied to the plants (for example harmful plants such as monocotyledonous or dicotyledonous weeds or unwanted crop plants), the seed
(z.B. Körner, Samen oder vegetative Vermehrungsorgane wie Knollen oder Sprossteile mit Knospen) oder die Fläche, auf der die Pflanzen wachsen (z.B. die Anbaufläche), ausgebracht werden. Dabei können die erfindungsgemäßen Verbindungen z.B. im Vorsaat- (ggf. auch durch Einarbeitung in den Boden), Vorauf lauf- oder Nachauflaufverfahren ausgebracht werden. Im Einzelnen seien beispielhaft einige Vertreter der mono- und dikotylen Unkrautflora genannt, die durch die erfindungsgemäßen Verbindungen kontrolliert werden können, ohne dass durch die Nennung eine Beschränkung auf bestimmte Arten erfolgen soll. (e.g. grains, seeds or vegetative reproductive organs such as tubers or sprouts with buds) or the area on which the plants grow (e.g. the cultivation area). The compounds according to the invention can be applied, for example, by pre-sowing (if necessary also by incorporation into the soil), pre-emergence or post-emergence methods. Some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the compounds according to the invention, without the mentioning of them being intended to restrict to certain species, may be mentioned in detail by way of example.
Monokotyle Schadpflanzen der Gattungen: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Pani cum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum. Dikotyle Unkräuter der Gattungen: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodi um, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindemia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Phaibitis, Plantago, Polygonum, Portul aca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium. Monocotyledons harmful plants of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragloaimeter, Festylochata , Ischaemum, Leptochloa, Lolium, Monochoria, Pani cum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum. Dicot weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodi um, Emex, Erysimum,, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindemia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Phaibitis, Plantago, Polygonum, Portul aca, Ranunculus, Raphanus, Rorippa, Rotalalsola, Rumex, Rumex , Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
Werden die erfindungsgemäßen Verbindungen vor dem Keimen auf die Erdoberfläche appliziert, so wird entweder das Auflaufen der Unkrautkeimlinge vollständig verhindert oder die Unkräuter wachsen bis zum Keimblattstadium heran, stellen j edoch dann ihr Wachstum ein. If the compounds according to the invention are applied to the surface of the earth before germination, either the emergence of the weed seedlings is completely prevented or the weeds grow to the cotyledon stage, but then stop growing.
Bei Applikation der Wirkstoffe auf die grünen Pflanzenteile im Nachauflaufverfahren tritt nach der Behandlung Wachstums stop ein und die Schadpflanzen bleiben in dem zum Applikationszeitpunkt vorhandenen Wachstumsstadium stehen oder sterben nach einer gewissen Zeit ganz ab, so dass auf diese Weise eine für die Kulturpflanzen schädliche Unkrautkonkurrenz sehr früh und nachhaltig beseitigt wird. When the active ingredients are applied to the green parts of the plant using the post-emergence method, growth stops after the treatment and the harmful plants remain in the growth stage present at the time of application or die completely after a certain time, so that in this way competition from weeds that is harmful to the crop plants is very early and is permanently eliminated.
Die erfindungsgemäßen Verbindungen können in Nutzkulturen Selektivitäten auf weisen und können auch als nichtselektive Herbizide eingesetzt werden. The compounds according to the invention can have selectivities in useful crops and can also be used as nonselective herbicides.
Aufgrund ihrer herbiziden und pflanzenwachstumsregulatorischen Eigenschaften können die Wirkstoffe auch zur Bekämpfung von Schadpflanzen in Kulturen von bekannten oder noch zu entwickelnden gentechnisch veränderten Pflanzen eingesetzt werden. Die transgenen Pflanzen zeichnen sich in der Regel durch besondere vorteilhafte Eigenschaften aus, beispielsweise durch Resistenzen gegenüber bestimmten in der Agrarindustrie verwendeten Wirkstoff , vor allem bestimmten Herbiziden, Resistenzen gegenüber Pflanzenkrankheiten oder Erregern von Pflanzenkrankheiten wie bestimmten Insekten oder Mikroorganismen wie Pilzen, Bakterien oder Viren. Andere besondere Eigenschaften betreffen z.B. das Emtegut hinsichtlich Menge, Qualität, Lagerfähigkeit, Zusammensetzung und spezieller Inhaltsstoffe. So sind transgene Pflanzen mit erhöhtem Stärkegehalt oder veränderter Qualität der Stärke oder solche mit anderer Fettsäurezusammensetzung des Emteguts bekannt. Weitere besondere Eigenschaften liegen in einer Toleranz oder Resistenz gegen abiotische Stressoren z.B. Hitze, Kälte, Trockenheit, Salz und ultraviolette Strahlung. Because of their herbicidal and plant growth regulatory properties, the active compounds can also be used for controlling harmful plants in crops of known or still to be developed genetically modified plants. The transgenic plants are usually characterized by particularly advantageous properties, for example by resistance to certain active ingredients used in the agricultural industry, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties relate, for example, to the crop in terms of quantity, quality, shelf life, composition and special ingredients. Thus, transgenic plants with an increased starch content or a changed quality of the starch or those with a different fatty acid composition of the harvested material are known. Other special properties are tolerance or resistance to abiotic stressors e.g. heat, cold, drought, salt and ultraviolet radiation.
Bevorzugt ist die Anwendung der erfindungsgemäßen Verbindungen der Formel (I) oder deren Salze in wirtschaftlich bedeutenden transgenen Kulturen von Nutz-und Zierpflanzen, Die Verbindungen der Formel (I) können als Herbizide in Nutzpflanzenkulturen eingesetzt werden, welche gegenüber den phytotoxi sehen Wirkungen der Herbizide resistent sind bzw. gentechnisch resistent gemacht wurden. The use of the compounds of the formula (I) according to the invention or their salts in economically important transgenic crops of useful and ornamental plants is preferred, The compounds of the formula (I) can be used as herbicides in crops of useful plants which are resistant to the phytotoxic effects of the herbicides or which have been made resistant by genetic engineering.
Herkömmliche Wege zur Herstellung neuer Pflanzen, die im Vergleich zu bisher vorkommenden Pflanzen modifizierte Eigenschaften aufweisen, bestehen beispielsweise in klassischen Züchtungsverfahren und der Erzeugung von Mutanten. Alternativ können neue Pflanzen mit veränderten Eigenschaften mit Hilfe gentechnischer Verfahren erzeugt werden (siehe z.B. EP 0221044, EP 0131624). Beschrieben wurden beispielsweise in mehreren Fällen gentechnische Veränderungen von Kulturpflanzen zwecks Modifikation der in den Pflanzen synthetisierten Stärke (z.B. WO 92/011376 A, WO 92/014827 A, WO 91/019806 A), transgene Kulturpflanzen, welche gegen bestimmte Herbizide vom Typ Glufosinate (vgl. z.B. EP 0242236 A, EP 0242246 A) oder Glyphosate (WO 92/000377 A) oder der Sulfonylharnstoffe (EP 0257993 A, US 5,013,659) oder gegen Kombinationen oder Mischungen dieser Herbizide durch „gene stacking“ resistent sind, wie transgenen Kulturpflanzen z. B. Mais oder Soja mit dem Handelsnamen oder der Bezeichnung Optimum™ GAT™ (Glyphosate ALS Tolerant). transgene Kulturpflanzen, beispielsweise Baumwolle, mit der Fähigkeit Bacillus thuringiensis-Toxine (Bt-Toxine) zu produzieren, welche die Pflanzen gegen bestimmte Schädlinge resistent machen (EP 0142924 A, EP 0193259 A). transgene Kulturpflanzen mit modifizierter Fettsäurezusammensetzung (WO 91/013972 A). gentechnisch veränderte Kulturpflanzen mit neuen Inhalts- oder Sekundärstoffen z.B. neuen Phytoalexinen, die eine erhöhte Krankheitsresistenz verursachen (EP 0309862 A, EP 0464461Conventional ways of producing new plants that have modified properties compared to previously occurring plants consist, for example, of classic breeding processes and the creation of mutants. Alternatively, new plants with modified properties can be produced with the aid of genetic engineering (see e.g. EP 0221044, EP 0131624). For example, genetic modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/011376 A, WO 92/014827 A, WO 91/019806 A), transgenic crop plants which are resistant to certain herbicides of the glufosinate type ( See, for example, EP 0242236 A, EP 0242246 A) or glyphosate (WO 92/000377 A) or the sulfonylureas (EP 0257993 A, US 5,013,659) or are resistant to combinations or mixtures of these herbicides by “gene stacking”, such as transgenic crops e.g. . B. corn or soy with the trade name or the designation Optimum ™ GAT ™ (Glyphosate ALS Tolerant). transgenic crop plants, for example cotton, with the ability to produce Bacillus thuringiensis toxins (Bt toxins), which make the plants resistant to certain pests (EP 0142924 A, EP 0193259 A). transgenic crop plants with modified fatty acid composition (WO 91/013972 A). genetically modified crop plants with new ingredients or secondary substances, e.g. new phytoalexins, which cause increased disease resistance (EP 0309862 A, EP 0464461
A) gentechnisch veränderte Pflanzen mit reduzierter Photorespiration, die höhere Erträge und höhere Stresstoleranz aufweisen (EP 0305398 A) transgene Kulturpflanzen, die pharmazeutisch oder diagnostisch wichtige Proteine produzieren („molecular pharming“) transgene Kulturpflanzen, die sich durch höhere Erträge oder bessere Qualität auszeichnen transgene Kulturpflanzen die sich durch eine Kombinationen z.B. der o. g. neuen Eigenschaften auszeichnen („gene stacking“) Zahlreiche molekularbiologische Techniken, mit denen neue transgene Pflanzen mit veränderten Eigenschaften hergestellt werden können, sind im Prinzip bekannt; siehe z.B. I. Potrykus und G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg, oder Christou, "Trends in Plant Science" 1 (1996) 423-431). Für derartige gentechnische Manipulationen können Nucleinsäuremoleküle in Plasmide eingebracht werden, die eine Mutagenese oder eine Sequenzveränderung durch Rekombination von DNA- Sequenzen erlauben. Mit Hilfe von Standardverfahren können z.B. Basenaustausche vorgenommen, Teilsequenzen entfernt oder natürliche oder synthetische Sequenzen hinzugefügt werden. Für die Verbindung der DNA-Fragmente untereinander können an die Fragmente Adaptoren oder Linker angesetzt werden, siehe z.B. Sambrook et al., 1989, Molecular Cloning, A Laboratoiy Manual, 2. Aufl. Cold Spring Haibor Laboratoiy Press, Cold Spring Haibor, NY; oder Winnacker "Gene und Klone", VCH Weinheim 2. Auflage 1996 A) genetically modified plants with reduced photorespiration, which have higher yields and higher stress tolerance (EP 0305398 A) transgenic crops that produce pharmaceutically or diagnostically important proteins (“molecular pharming”) transgenic crops that are characterized by higher yields or better quality transgenic Cultivated plants which are characterized by a combination of, for example, the above-mentioned new properties (“gene stacking”). Numerous molecular biological techniques with which new transgenic plants with modified properties can be produced are known in principle; see, for example, I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg, or Christou, "Trends in Plant Science" 1 (1996) 423-431). For such genetic manipulations, nucleic acid molecules can be introduced into plasmids which allow mutagenesis or a sequence change by recombination of DNA sequences. With the help of standard procedures, for example, base exchanges can be carried out, partial sequences can be removed or natural or synthetic sequences can be added. To connect the DNA fragments to one another, adapters or linkers can be attached to the fragments, see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd edition. Cold Spring Haibor Laboratory Press, Cold Spring Haibor, NY; or Winnacker "Genes and Clones", VCH Weinheim 2nd edition 1996
Die Herstellung von Pflanzenzellen mit einer verringerten Aktivität eines Genprodukts kann beispielsweise erzielt werden durch die Expression mindestens einer entsprechenden antisense-RNA, einer sense-RNA zur Erzielung eines Cosuppressionseffektes oder die Expression mindestens eines entsprechend konstruierten Ribozyms, das spezifisch Transkripte des obengenannten Genprodukts spaltet. Hierzu können zum einen DNA-Moleküle verwendet werden, die die gesamte codierende Sequenz eines Genprodukts einschließlich eventuell vorhandener flankierender Sequenzen umfassen, als auch DNA-Moleküle, die nur Teile der codierenden Sequenz umfassen, wobei diese Teile lang genug sein müssen, um in den Zellen einen antisense-Effekt zu bewirken. Möglich ist auch die Verwendung von DNA-Sequenzen, die einen hohen Grad an Homologie zu den codiereden Sequenzen eines Genprodukts aufweisen, aber nicht vollkommen identisch sind. The production of plant cells with a reduced activity of a gene product can be achieved, for example, by expressing at least one corresponding antisense RNA, one sense RNA to achieve a cosuppression effect or by expressing at least one appropriately constructed ribozyme that specifically cleaves transcripts of the above-mentioned gene product. For this purpose, on the one hand, DNA molecules can be used that include the entire coding sequence of a gene product including any flanking sequences that may be present, as well as DNA molecules that only include parts of the coding sequence, these parts having to be long enough to be in the cells to bring about an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but which are not completely identical.
Bei der Expression von Nucleinsäuremolekülen in Pflanzen kann das synthetisierte Protein in jedem beliebigen Kompartiment der pflanzlichen Zelle lokalisiert sein. Um aber die Lokalisation in einem bestimmten Kompartiment zu erreichen, kann z.B. die codierende Region mit DNA-Sequenzen verknüpft werden, die die Lokalisierung in einem bestimmten Kompartiment gewährleisten. Derartige Sequenzen sind dem Fachmann bekannt (siehe beispielsweise Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Nall. Acad. Sei. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). Die Expression der Nukleinsäuremoleküle kann auch in den Organellen der Pflanzenzellen stattfinden. When nucleic acid molecules are expressed in plants, the synthesized protein can be localized in any desired compartment of the plant cell. However, in order to achieve the localization in a certain compartment, e.g. the coding region can be linked with DNA sequences that guarantee the localization in a certain compartment. Such sequences are known to the person skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Nall. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1: 95-106 (1991)). The expression of the nucleic acid molecules can also take place in the organelles of the plant cells.
Die transgenen Pflanzenzellen können nach bekannten Techniken zu ganzen Pflanzen regeneriert werden. Bei den transgenen Pflanzen kann es sich prinzipiell um Pflanzen jeder beliebigen Pflanzenspezies handeln, d.h., sowohl monokotyle als auch dikotyle Pflanzen. So sind transgene Pflanzen erhältlich, die veränderte Eigenschaften durch Überexpression, Suppression oder Inhibierung homologer (= natürlicher) Gene oder Gensequenzen oder Expression heterologer (= fremder) Gene oder Gensequenzen aufweisen. Vorzugsweise können die erfindungsgemäßen Verbindungen (I) in transgenen Kulturen eingesetzt werden, welche gegen Wuchsstoffe, wie z.B. 2,4-D, Dicamba oder gegen Herbizide, die essentielle Pflanzenenzyme, z.B. Acetolactatsynthasen (ALS), EPSP Synthasen, Glutaminsynthasen (GS) oder Hydoxyphenylpyruvat Dioxygenasen (HPPD) hemmen, respektive gegen Herbizide aus der Gruppe der Sulfonylharnstoffe, der Glyphosate, Glufosinale oder Benzoylisoxazole und analogen Wirkstoffe, oder gegen beliebige Kombinationen dieser Wirkstoffe, resistent sind. The transgenic plant cells can be regenerated into whole plants using known techniques. The transgenic plants can in principle be plants of any plant species, ie both monocotyledonous and dicotyledonous plants. In this way, transgenic plants can be obtained which have changed properties due to overexpression, suppression or inhibition of homologous (= natural) genes or gene sequences or the expression of heterologous (= foreign) genes or gene sequences. The compounds (I) according to the invention can preferably be used in transgenic crops which are effective against growth substances, such as 2,4-D, dicamba or against herbicides, the essential plant enzymes, e.g. acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydoxyphenylpyruvate Dioxygenases (HPPD) inhibit or are resistant to herbicides from the group of sulfonylureas, glyphosates, glufosinals or benzoylisoxazoles and analogous active ingredients, or to any combination of these active ingredients.
Besonders bevorzugt können die erfindungsgemäßen Verbindungen in transgenen Kulturpflanzen eingesetzt werden, die gegen eine Kombination von CHyphosaten und Ghifosinaten, Glyphosalen und Sulfonylharnstoffen oder Imidazolinonen resistent sind. Ganz besonders bevorzugt können die erfindungsgemäßen Verbindungen in transgenen Kulturpflanzen wie z. B. Mais oder Soja mit dem Handelsnamen oder der Bezeichnung OptimumTM GATTM (Glyphosate ALS Tolerant) eingesetzt werden. The compounds according to the invention can particularly preferably be used in transgenic crop plants which are resistant to a combination of CHyphosates and ghifosinates, glyphosals and sulfonylureas or imidazolinones. The compounds according to the invention can very particularly preferably be used in transgenic crop plants such as, for. B. corn or soy with the trade name or the designation OptimumTM GATTM (Glyphosate ALS Tolerant) can be used.
Bei der Anwendung der erfindungsgemäßen Wirkstoffe in transgenen Kulturen treten neben den in anderen Kulturen zu beobachtenden Wirkungen gegenüber Schadpflanzen oftmals Wirkungen auf, die für die Applikation in der jeweiligen transgenen Kultur spezifisch sind, beispielsweise ein verändertes oder speziell erweitertes Unkrautspektrum, das bekämpft werden kann, veränderte Aufwandmengen, die für die Applikation eingesetzt werden können, vorzugsweise gute Kombinierbarkeit mit den Herbiziden, gegenüber denen die transgene Kultur resistent ist, sowie Beeinflussung von Wuchs und Ertrag der transgenen Kulturpflanzen. Gegenstand der Erfindung ist deshalb auch die Verwendung der erfindungsgemäßen Verbindungen der Formel (I) als Herbizide zur Bekämpfung von Schadpflanzen in transgenen Kulturpflanzen.When the active ingredients according to the invention are used in transgenic crops, in addition to the effects on harmful plants observed in other crops, effects that are specific for the application in the respective transgenic crop, for example a modified or specially expanded weed spectrum that can be controlled, often occur Application rates that can be used for the application, preferably good compatibility with the herbicides to which the transgenic culture is resistant, and influencing the growth and yield of the transgenic crop plants. The invention therefore also relates to the use of the compounds of the formula (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
Die erfindungsgemäßen Verbindungen können in Form von Spritzpulvem, emulgierbaren Konzentraten, versprühbaren Lösungen, Stäubemitteln oder Granulaten in den üblichen Zubereitungen angewendet werden. Gegenstand der Erfindung sind deshalb auch herbizide und pflanzenwachstumsregulierende Mittel, welche die erfindungsgemäßen Verbindungen enthalten.The compounds according to the invention can be used in the customary preparations in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules. The invention therefore also relates to herbicidal and plant growth-regulating agents which contain the compounds according to the invention.
Die erfindungsgemäßen Verbindungen können auf verschiedene Art formuliert werden, je nachdem welche biologischen und/oder chemisch-physikalischen Parameter vorgegeben sind. Als Formulierungsmöglichkeiten kommen beispielsweise in Frage: Spritzpulver (WP), wasserlösliche Pulver (SP), wasserlösliche Konzentrate, emulgierbare Konzentrate (EC), Emulsionen (EW), wie Öl-in-Wasser- und Wasser-in-Öl-Emulsionen, versprühbare Lösungen, Suspensionskonzentrate (SC), Dispersionen auf Öl- oder Wasserbasis, ölmischbare Lösungen, Kapselsuspensionen (CS), Stäubemittel (DP), Beizmittel, Granulate für die Streu- und Bodenapplikation, Granulate (GR) in Form von Mikro-, Sprüh-, Aufzugs- und Adsorptionsgranulaten, wasserdispergierbare Granulate (WG), wasserlösliche Granulate (SG), UL V -F ormuli erungen, Mikrokapseln und Wachse. Diese einzelnen Formulierungstypen sind im Prinzip bekannt und werden beispielsweise beschrieben in: Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hanser Verlag München, 4. Aufl. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973, K. Martens, "Spray Diying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London. The compounds according to the invention can be formulated in various ways, depending on the prevailing biological and / or chemico-physical parameters. Possible formulation options include, for example: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions , Suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), dressings, granules for litter and soil application, granules (GR) in the form of micro, spray, lift - and adsorption granules, water-dispersible granules (WG), water-soluble granulates (SG), UL V formulations, microcapsules and waxes. These individual formulation types are known in principle and are described, for example, in: Winnacker-Küchler, "Chemische Technologie", Volume 7, C. Hanser Verlag Munich, 4th edition 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY , 1973, K. Martens, "Spray Diying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.
Die notwendigen Formulierungshilfsmittel wie Inertmaterialien, Tenside, Lösungsmittel und weitere Zusatzstoffe sind ebenfalls bekannt und werden beispielsweise beschrieben in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N.Y., C. Marsden, "Solvents Guide", 2nd Ed., Interscience, N.Y. 1963, McCutcheoris "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J., Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964, Schönfeldt, "Grenzflächenaktive Äthylenoxid-addukte", Wiss. Verlagsgesell., Stuttgart 1976, Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hanser Verlag München, 4. Aufl. 1986. Auf der Basis dieser Formulierungen lassen sich auch Kombinationen mit anderen Wirkstoffen, wie Z.B. Insektiziden, Akariziden, Herbiziden, Fungiziden, sowie mit Safenern, Düngemitteln und/oder Wachstumsregulatoren herstellen, z.B. in Form einer Fertigformulierung oder als Tankmix. The necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry," 2nd Ed., J. Wiley & Sons, N.Y., C. Marsden, "Solvents Guide," 2nd Ed., Interscience, N.Y. 1963, McCutcheori's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J., Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964, Schönfeldt, "Grenzflächenactive Äthylenoxid-addukte", Wiss. Verlagsgesell., Stuttgart 1976, Winnacker-Küchler, "Chemische Technologie", Volume 7, C. Hanser Verlag Munich, 4th edition 1986. On the basis of these formulations, combinations with other active ingredients, such as, for example, insecticides, acaricides, herbicides, can also be used , Fungicides, as well as with safeners, fertilizers and / or growth regulators, e.g. in the form of a ready-made formulation or as a tank mix.
Als Kombinationspartner für die erfindungsgemäßen Verbindungen in Mischungsformulierungen oder im Tank-Mix sind beispielsweise bekannte Wirkstoffe, die auf einer Inhibition von beispielsweise Acetolactat-Synthase, Acetyl-CoA-Carboxylase, Cellulose-Synthase, Enolpymvylshikimat-3 -phosphat- Synthase, Glutamin-Synthetase, p-Hydroxyphenylpymvat-Dioxygenase, Phytoendesaturase, Photosystem I, Photosystem Π oder Protoporphyrinogen-Oxidase beruhen, einsetzbar, wie sie z.B. aus Weed Research 26 (1986) 441-445 oder "The Pesticide Manual", 16th edition, The British Crop Protection Council und the Royal Soc. of Chemistry, 2006 und dort zitierter Literatur beschrieben sind. Nachfolgend werden beispielhaft bekannte Herbizide oder Pflanzenwachstumsregulatoren genannt, die mit den erfindungsgemäßen Verbindungen kombiniert werden können, wobei diese Wirkstoffe entweder mit ihrem "common name" in der englischsprachigen Variante gemäß International Organization fbr Standardization (ISO) oder mit dem chemischen Namen bzw. mit der Codenummer bezeichnet sind. Dabei sind stets sämtliche Anwendungsformen wie beispielsweise Säuren, Salze, Ester sowie auch alle isomeren Formen wie Stereoisomere und optische Isomere umfaßt, auch wenn diese nicht explizit erwähnt sind.As combination partners for the compounds according to the invention in mixture formulations or in the tank mix, for example, known active ingredients which act on an inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpymvylshikimate-3-phosphate synthase, glutamine synthetase, p-Hydroxyphenylpymvat-Dioxygenase, Phytoendesaturase, Photosystem I, Photosystem Π or Protoporphyrinogen-Oxidase based, can be used, as for example from Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 16th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2006 and the literature cited there. Known herbicides or plant growth regulators which can be combined with the compounds according to the invention are mentioned below by way of example, these active ingredients either with their "common name" in the English-language variant according to the International Organization fbr Standardization (ISO) or with the chemical name or code number are designated. All application forms such as acids, salts, esters and also all isomeric forms such as stereoisomers and optical isomers are always included, even if these are not explicitly mentioned.
Beispiele für solche herbiziden Mischungspartner sind: Examples of such herbicidal mixing partners are:
Acetochlor, Acifluorfen, Acifluorfen-Methyl, Acifluorfen-Natrium, Aclonifen, Alachlor, Allidochlor, Alloxydim, Alloxydim-Natrium, Ametryn, Amicarbazone, Amidochlor, Amidosulfuron, 4-Amino-3-chlor-6-(4-chlor-2-fluor-3-methylphenyl)-5-fluorpyridiii-2-carbon-säure, Aminocyclopyrachlor, Aminocyclopyrachlor-Kalium, Aminocyclopyrachlor-Methyl, Aminopyralid, Aminopyralid-Dimethylammonium, Aminopyralid-Tripromin, Amitrol, Ammoniumsulfamat, Anilofos, Asulam, Asulam-Kalium, Asulam-Natrium, Atrazin, Azafenidin, Azimsulfuron, Beflubutamid, (S)-(-)-Beflubutamid, Beflubutamid-M, Benazolin, Benazolin-Ethyl, Benazolin- Dimethylammonium, Benazolin-Kalium, Benfluralin, Benfuresat, Bensulfuron, B ensulfuron-Methyl , Bensulid, Bentazon, Bentazon-Natrium, Benzobicyclon, Benzofenap, Bicyclopyron, Bifenox, Bilanafos, Bilanafos-Natrium, Bipyrazon, Bispyribac, Bispyribac-Natrium, Bixlozon, Bromacil, Bromacil-Lithium, Bromacil-Natrium, Bromobutid, Bromofenoxim, Bromoxynil, Bromoxynil- Butyrat, -Kalium, -Heptanoat und -Octanoat, Busoxinon, Butachlor, Butafenacil, Butamifos, Butenachlor, Butralin, Butroxydim, Butylat, Cafenstrol, Cambendichlor, Carbetamid, Carfentrazon, Carfentrazon-Ethyl, Chloramben, Chloramben- Ammonium, Chloramben-Diolamin, Chlroamben- Methyl, Chloramben-Methylammonium, Chloramben-Natrium, Chlorbromuron, Chlorfenac, Chlorfenac- Ammonium, Chlorfenac -Natrium, Chlorfenprop, Chlorfenprop-Methyl, Chlorflurenol, Chlorflurenol-Methyl, Chloridazon, Chlorimuron, Chlorimuron-Ethyl, Chlorophthalim,Acetochlor, Acifluorfen, Acifluorfen-Methyl, Acifluorfen-Sodium, Aclonifen, Alachlor, Allidochlor, Alloxydim, Alloxydim-Sodium, Ametryn, Amicarbazone, Amidochlor, Amidosulfuron, 4-Amino-3-chloro-6- (4-chloro-2-fluoro-3-methylphenyl) -5-fluoropyridiii-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyrachlor potassium, aminocyclopyrachloro-methyl, aminopyralid, aminopyralid-dimethylammonium, Aminopyralid tripromine, amitrole, ammonium sulfamate, anilofos, asulam, asulam potassium, asulam sodium, atrazine, azafenidin, azimsulfuron, beflubutamide, (S) - (-) - beflubutamide, beflubutamide-M, benazolin, benazolin-ethyl, benazolin-ethyl, benazolin-ethyl Dimethylammonium, Benazolin-Potassium, Benfluralin, Benfuresat, Bensulfuron, Bensulfuron-Methyl, Bensulid, Bentazon, Bentazon-Sodium, Benzobicyclon, Benzofenap, Bicyclopyrone, Bifenox, Bilanafos, Bilanafos-Sodium, Bipyrazone, Bispyribacz-Sodium, Bipyrazone, Bispyribacz-Sodium , Bromacil lithium, bromacil sodium, bromobutide, bromofenoxime, bromoxynil, bromoxynil butyrate, potassium, heptanoate and octanoate, busoxinone, butachlor, butafenacil, butamifos, butenachlor, butraline, butroxydim, butylate, cafenichlor, cambendol Carfentrazone, carfentrazone-ethyl, Chloramben, chloramben ammonium, chloramben diolamine, chloramben methyl, chloramben methylammonium, chloramben sodium, chlorbromuron, chlorfenac, chlorfenac ammonium, chlorfenac sodium, chlorfenprop, chlorfenprop-methyl, chlorofurenol, chlorofurenol-methyl, chloridazon, Chlorimuron-ethyl, chlorophthalim,
Chlorotoluron, Chlorsulfuron, Chlorthal, Chlorthal-Dimethyl, Chlorthal-Monomethyl, Cinidon, Cinidon-Ethyl, Cinmethylin, , exo-(+)-Cinmethylin, i.e. (lR,2S,4S)-4-Isopropyl-l-methyl-2-[(2- methylbenzyl)oxy ] -7-oxabicy clo [2.2.1] -heptan, exo-(-)-Cinmethylin, i.e. (lR,2S,4S)-4-Isopropyl-l- methyl-2-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptan, Cinosulfuron, Clacyfos, Clethodim, Clodinafop, Clodinafop-Ethyl, Clodinafop-Propargyl, Clomazone, Clomeprop, Clopyralid,Chlorotoluron, Chlorsulfuron, Chlorthal, Chlorthal-Dimethyl, Chlorthal-Monomethyl, Cinidon, Cinidon-Ethyl, Cinmethylin,, exo - (+) - Cinmethylin, i.e. (lR, 2S, 4S) -4-isopropyl-l-methyl-2 - [(2-methylbenzyl) oxy] -7-oxabicy clo [2.2.1] -heptane, exo - (-) - cinmethylin, i.e. (IR, 2S, 4S) -4-isopropyl-1-methyl-2 - [(2-methylbenzyl) oxy] -7-oxabicyclo [2.2.1] heptane, cinosulfuron, Clacyfos, Clethodim, Clodinafop, Clodinafop-ethyl, Clodinafop -Propargyl, Clomazone, Clomeprop, Clopyralid,
Clopyralid-Methyl, Clopyralid-Olamin, Clopyralid-Kalium, Clopyralid-Tripomin, Cloransulam, Cloransulam-Methyl, Cumyluron, Cyanamid, Cyanazin, Cycloat, Cyclopyranil, Cyclopyrimorat, Cyclosulfamuron, Cycloxydim, Cyhalofop, Cyhalofop-Butyl, Cyprazin, 2,4-D (einschließlich des - Theammonium, -Butotyl, -Butyl, -Cholin, -Diethylammonium, -Dimethylammonium, -Diolamin, - Doboxyl, -Dodecylammonium, -Etexyl, -Ethyl, -2-Ethylhexyl, -Heptylammonium, -Isobutyl, - Isooctyl, -Isopropyl, -Isopropylammonium, -Lithium, -Meptyl, -Methyl, -Kalium, - T etradecyl ammonium, -Triethylammonium, -Triisopropanolammonium, -Tripromin und -Trolamine Salzes davon), 2,4-DB, 2,4-DB-Butyl, -Dimethylammonium, -Isooctyl, -Kalium und -Natrium, Daimuron (Dymron), Dalapon, Dalapon-Calcium, Dalapon-Magnesium, Dalapon-Natrium, Dazomet, Dazomet-Natrium, n-Decanol, 7-Deoxy-D-Sedoheptulose, Desmedipham, Detosyl- pyrazolate (DTP), Dicamba und seine Salze, z.B. Dicamba-Biproamin, Dicamba-N,N-Bis(3- aminopropyl)methylamin, Dicamba-butotyl, Dicamba-Cholin, Dicamba-Diglycolamin, Dicamba- Dimethylammonium, Dicamba-Diethanolaminemmonium, Dicamba-Diethylammonium, Dicamba- Isopropy 1 ammonium, Dicamba-Methyl, Dicamba-Monoethanolaminedicamba-Olamin, Dicamba- Kalium, Dicamba-Natrium, Dicamba-Triethanolamin, Dichlobenil, 2-(2,5-Dichlorobenzyl)-4,4- dimethyl-l,2-oxazolidin-3-on, Dichlorprop, Dichlorprop-Butotyl, Dichlroprop-Dimethylammonium, Dichhlorprop-Etexyl, Dichlorprop-Ethylammonium, Dichlorprop-Isoctyl, Dichlorprop-Methyl, Dichlorprop-Kalium, Dichlorprop-Natrium, Dichlorprop-P, Dichlorprop-P-Dimethylammonium, Dichlorprop-P-Etexyl, Dichlorprop-P-Kalium, Dichlorprop-Natrium, Diclofop, Diclofop-Methyl, Diclofop-P, Diclofop-P-Methyl, Diclosulam, Difenzoquat, Difenzoquat-Metilsulfat, Diflufenican, Diflufenzopyr, Diflufenzopyr-Natrium, Dimefuron, Dimepiperate, Dimesulfazet, Dimethachlor, Dimethametryn, Dimethenamid, Dimethenamid-P, Dimetrasulfuron, Dinitramine, Dinoterb, Dinoteib-Acetate, Diphenamid, Diquat, Diquat-Dibromid, Diquat-Dichloride, Dithiopyr, Diuron, DNOC, DNOC-Ammonium, DNOC-Kalium, DNOC-Natrium, Endothal, Endothal-Diammonium, Endothal -Dikalium, Endothal -Dinatri um, Epyrifenacil (S-3100), EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron, Ethametsulfuron-Methyl, Ethiozin, Ethofumesate, Ethoxyfen, Ethoxyfen-Ethyl, Ethoxysulfüron, Etobenzanid, F-5231, i.e. N-[2-Chlor-4-fluor-5-[4-(3-fluorpropyl)-4,5-dihydn>-5- oxo-lH-tetrazol-l-yl]-phenyl]-ethansulfonamid, F-7967, i.e. 3-[7-Chlor-5-fluor-2-(trifluormethyl)- lH-benzimidazol-4-yl]-l-methyl-6-(trifluormethyl)pyrimidin-2,4(lH,3H)-dion, ΡβηοχίφΓορ,Clopyralid-Methyl, Clopyralid-Olamin, Clopyralid-Kalium, Clopyralid-Tripomin, Cloransulam, Cloransulam-Methyl, Cumyluron, Cyanamid, Cyanazin, Cycloat, Cyclopyranil, Cyclopyrimorat, Cyclosulfamuron, Cycloxydim, Cyhalofypofop-2,4-Butyl, Cyhalofypofop-butzin D (including des - Theammonium, -Butotyl, -Butyl, -Cholin, -Diethylammonium, -Dimethylammonium, -Diolamine, -Doboxyl, -Dodecylammonium, -Etexyl, -Ethyl, -2-Ethylhexyl, -Heptylammonium, -Isobutyl, -Isooctyl , -Isopropyl, -Isopropylammonium, -Lithium, -Meptyl, -Methyl, -potassium, -Tetradecylammonium, -triethylammonium, -Triisopropanolammonium, -tripromine and -Trolamine salt thereof), 2,4-DB, 2,4-DB -Butyl, -dimethylammonium, -isooctyl, -potassium and -sodium, daimuron (Dymron), dalapon, dalapon calcium, dalapon magnesium, dalapon sodium, dazomet, dazomet sodium, n-decanol, 7-deoxy-D- Sedoheptulose, Desmedipham, Detosylpyrazolate (DTP), Dicamba and its salts, for example dicamba-biproamine, dicamba-N, N-bis (3-aminopropyl) methylamine, dicamba-bu totyl, dicamba-choline, dicamba-diglycolamine, dicamba-dimethylammonium, dicamba-diethanolamine-ammonium, dicamba-diethylammonium, dicamba-isopropy 1 ammonium, dicamba-methyl, dicamba-monoethanolamine, dicamba-olefinium, dicamba-olamine, sodium, dicamba-olefin Dichlobenil, 2- (2,5-dichlorobenzyl) -4,4-dimethyl-1,2-oxazolidin-3-one, dichlorprop, dichlorprop-butotyl, dichlroprop-dimethylammonium, Dichlorprop-Etexyl, Dichlorprop-Ethylammonium, Dichlorprop-Isoctyl, Dichlorprop-Methyl, Dichlorprop-Potassium, Dichlorprop-Sodium, Dichlorprop-P, Dichlorprop-P-Dimethylammonium, Dichlorprop-P-Etexyl, Dichlorprop-P-Potassium, dichloro Diclofop, Diclofop-Methyl, Diclofop-P, Diclofop-P-Methyl, Diclosulam, Difenzoquat, Difenzoquat-Metilsulfat, Diflufenican, Diflufenzopyr, Diflufenzopyr-Sodium, Dimefuron, Dimepiperamido, Dimethenamid-P-methyl, Dimetrethenulfazet, Dimetrethuron Dinitramine, Dinoterb, Dinoteib-Acetate, Diphenamid, Diquat, Diquat-Dibromid, Diquat-Dichloride, Dithiopyr, Diuron, DNOC, DNOC-Ammonium, DNOC-Potassium, DNOC-Sodium, Endothal, Endothal-Diammonium, Endothal-Dipotassium, Endothal - Dinatrium, Epyrifenacil (S-3100), EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron, Ethametsulfuron-Methyl, Ethiozin, Ethofumesate, Ethoxyfen, Ethoxyfen-Ethyl, Ethoxysulfüron, Etobenzanid, F-5231, ie N- [2-chloro-4- fluoro-5- [4- (3-fluoropropyl) -4,5-dihydric> -5-oxo -lH-tetrazol-l-yl] -phenyl] -ethanesulfonamide, F-7967, ie 3- [7-chloro-5-fluoro-2- (trifluoromethyl) - lH-benzimidazol-4-yl] -l-methyl- 6- (trifluoromethyl) pyrimidine-2,4 (lH, 3H) -dione, ΡβηοχίφΓορ,
Fenoxaprop-P, Fenoxaprop-Ethyl, Fenoxaprop-P-Ethyl, Fenoxasulfone, Fenpyrazone, Fenquinotrione, Fentrazamid, Flamprop, Flamprop-Isoproyl, Flamprop-Methyl, Flamprop-M-Fenoxaprop-P, Fenoxaprop-Ethyl, Fenoxaprop-P-Ethyl, Fenoxasulfone, Fenpyrazone, Fenquinotrione, Fentrazamid, Flamprop, Flamprop-Isoproyl, Flamprop-Methyl, Flamprop-M-
Isopropyl, Flamprop-M-Methyl, Flazasulfuron, Florasulam, Florpyrauxifen, Florpyrauxifen-benzyl, Fluazifop, Fluazifop-Butyl, Fluazifop-Methyl, Fluazifop-P, Fluazifop-P-Butyl, Flucaibazone, Flucarbazone-sodium, Flucetosulfuron, Fluchloralin, Flufenacet, Flufenpyr, Flufenpyr-Ethyl, Flumetsulam, Flumiclorac, Flumiclorac-Pentyl, Flumioxazin, Fluometuron, Flurenol, Flurenol- Butyl, -Dimethylammonium und -Methyl, Fluoroglycofen, Fluoroglycofen-Ethyl, Flupropanat,Isopropyl, Flamprop-M-Methyl, Flazasulfuron, Florasulam, Florpyrauxifen, Florpyrauxifen-benzyl, Fluazifop, Fluazifop-Butyl, Fluazifop-Methyl, Fluazifop-P, Fluazifop-P-Butyl, Flucaibazone, Flucarbazone-sodium, Flucetosulfuron, Flufenpyr, Flufenpyr-Ethyl, Flumetsulam, Flumiclorac, Flumiclorac-Pentyl, Flumioxazin, Fluometuron, Flurenol, Flurenol-Butyl, -Dimethylammonium und -Methyl, Fluoroglycofen, Fluoroglycofen-Ethyl, Flupropanat,
Flupropanat-Natrium, Flupyrsulfuron, Flupyrsulfuron-Methyl, Flupyrsulfuron-Methyl-Natrium, Fluridon, Flurochloridon, Fluroxypyr, Fluroxypyr-Butometyl, Fluroxypyr-Meptyl, Flurtamon, Fluthiacet, Fluthiacet-Methyl, Fomesafen, Fomesafen-Natrium, Foramsulfuron, Foramsulfuron- Natrium, Fosamine, Fosamine- Ammonium, CHufosinate, Gl ufosinate- Ammonium, CHufosinate- Natrium, L-CHufosinat-Ammonium, L-Glufosiant-Natrium, Glufosinat-P-Natrium, Glufosinate-P-Flupropanat-Sodium, Flupyrsulfuron, Flupyrsulfuron-Methyl, Flupyrsulfuron-Methyl-Sodium, Fluridone, Flurochloridon, Fluroxypyr, Fluroxypyr-Butometyl, Fluroxypyr-Meptyl, Flurtamon, Fluthiacetomes, Fluthiacet-Methyl, Fulfuronsodium, Sodium Fosamine, Fosamine- ammonium, CHufosinate, Glufosinate- ammonium, CHufosinate- sodium, L-CHufosinate-ammonium, L-glufosinate-sodium, glufosinate-P-sodium, glufosinate-P-
Ammonium, Glyphosat, Glyphosat-Ammonium, -IsopropylAmmonium, -Diammonium, - Dimethylammonium, -Kalium, -Natrium, -Sesquinatrium und -Trimesium, H-9201, i.e. 0-(2,4- Dimethyl-6-nitrophenyl)-0-ethyl-isopropylphosphoramidothioat, Halauxifen, Halauxifen-methyl, Halosafen, Halosulfuron, Halosulfuron-Methyl, Haloxyfop, Haloxyfop-P, Haloxyfop-Ethoxyethyl, Haloxyfop-P-Ethoxyethyl, Haloxyfop-Methyl, Haloxyfop-P-Methyl, Haloxifop-Natrium,Ammonium, glyphosate, glyphosate-ammonium, -isopropyl-ammonium, -diammonium, -dimethylammonium, -potassium, -sodium, -sesquinodium and -trimesium, H-9201, i.e. 0- (2,4-dimethyl-6-nitrophenyl) -0-ethyl-isopropylphosphoramidothioate, halauxifen, halauxifen-methyl, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, Haloxyfop-methyl, haloxyfop-P-methyl, haloxifop sodium,
Hexazinon, HNPC-A8169, i.e. Prop-2-yn-l-yl (2S)-2-{3-[(5-tert-butylpyridin-2- yl)oxy ]phenoxy } propanoat, HW-02, i.e. 1 -(Dimethoxyphosphoryl)-ethyl-(2,4- dichlorphenoxy)acetat, Hydantocidin, Imazamethabenz, Imazamethabenz-Methyl, Imazamox, Imazamox- Ammonium, Imazapic, Imazapic-Ammonium, Imazapyr, Imazapyr-Isopropylammonium, Imazaquin, Imazaquin- Ammonium, Imazaquin-Methyl , Imazethapyr, Imazethapyr- Ammonium, Imazosulfuron, Indanofan, Indaziflam, Iodosulfuron, Iodosulfuron-Methyl, Iodosulfuron-Methyl- Natrium, Ioxynil, Ioxynil -Lithium, -Octanoat, -Kalium und Natrium, Ipfencarbazon, Isoproturon, Isouron, Isoxaben, Isoxaflutole, Kaibutilat, KUH- 043, i.e. 3 -( { [5 -(Difluormethyl)- 1 -methyl-3 - (trifluormethyl)-lH-pyrazol-4-yl]methyl}sulfonyl)-5,5-dimethyl-4,5-dihydro-l,2-oxazol, Ketospiradox, Ketospiradox-Kalium, Lactofen, Lenacil, Linuron, MCPA, MCPA-Butotyl, -Butyl, - Dimethylammonium, -Diolamin, -2-Ethylhexyl, -Ethyl, -Isobutyl, Isoctyl, -Isopropyl, - Isopropylammonium, -Methyl, Olamin, -Kalium, -Natrium und -Trolamin, MCPB, MCPB- Methyl, -Ethyl und -Natrium, Mecoprop, Mecoprop-Butotyl, Mecoprop- dimethylammonium, Mecoprop-Diolamin, Mecoprop-Etexyl, Mecoprop-Ethadyl, Mecoprop-Isoctyl, Mecoprop-Methyl, Mecoprop-Kalium, Mecoprop-Natrium, und Mecoprop-Trolamin, Mecoprop-P, Mecoprop-P- Butotyl, -Dimethylammonium, -2-Ethylhexyl und -Kalium, Mefenacet, Mefluidid, Mefluidid- Diolamin, Mefluidid-Kalium, Mesosulfuron, Mesosulfuron-Methyl, Mesosulfuron-Natrium, Mesotrion, Methabenzthiazuron, Metam, Metamifop, Metamitron, Metazachlor, Metazosulfuron, Methabenzthi azuron, Methiopyrsulfuron, Methiozolin, Methyl isothiocyanat, Metobromuron, Metolachlor, S-Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron, Metsulfuron-Methy 1 , Molinat, Monolinuron, Monosulfuron, Monosulfuron-Methyl, MT-5950, i.e. N-[3-Chlor-4-(l- methylethyl)-phenyl]-2-methylpentanamid, NGGC-011, Napropamid, NC-310, i.e. 4-(2,4- Dichlorbenzoyl)- 1 -methyl-5-benzyloxypyrazol, NC-656, i.e. 3-[(Isopropylsulfonyl)methyl]-N-(5- methyl-l,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)[l,2,4]triazolo-[4,3-a]pyridin-8-caiboxamid, Neburon, Nicosulfuron, Nonansäure (Pelargonsäure), Norflurazon, Ölsäure (Fettsäuren), Orbencarb, Orthosulfamuron, Oiyzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefone, Oxyfluorfen,Hexazinone, HNPC-A8169, ie prop-2-yn-l-yl (2S) -2- {3 - [(5-tert-butylpyridin-2- yl) oxy] phenoxy} propanoate, HW-02, ie 1 - (Dimethoxyphosphoryl) -ethyl- (2,4-dichlorophenoxy) acetate, hydantocidin, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin-methyl, imaza , Imazethapyr, imazethapyr- ammonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron-methyl, iodosulfuron-methyl- Sodium, ioxynil, ioxynil lithium, octanoate, potassium and sodium, ipfencarbazon, isoproturon, isouron, isoxaben, isoxaflutole, kaibutilat, KUH-043, ie 3 - ({[5 - (difluoromethyl) -1 -methyl-3 - (trifluoromethyl) -1H-pyrazol-4-yl] methyl} sulfonyl) -5,5-dimethyl-4,5-dihydro-1,2-oxazole, ketospiradox, ketospiradox potassium, lactofen, lenacil, linuron, MCPA, MCPA -Butotyl, -Butyl, -Dimethylammonium, -Diolamine, -2-Ethylhexyl, -Ethyl, -Isobutyl, Isoctyl, -Isopropyl, -Isopropylammonium, -Methyl, Olamine, -potassium, -sodium and -Trolamine, MCPB, MCPB-methyl , Ethyl and sodium, mecoprop, mecoprop-butotyl, mecoprop-dimethylammonium, mecoprop-diolamine, mecoprop-etexyl, mecoprop-ethadyl, mecoprop-isoctyl, mecoprop-methyl, mecoprop-potassium, mecoprop-sodium, and mecoprop-trolamine, Mecoprop-P, mecoprop-P-butotyl, -dimethylammonium, -2-ethylhexyl and -potassium, mefenacet, mefluidid, mefluidid-diolamine, mefluidid-potassium, mesosulfuron, mesosulfuron-methyl, mesosulfuron-sodium, mesotrione, methabenzthiazthiaz n, Metam, Metamifop, Metamitron, Metazachlor, Metazosulfuron, Methabenzthi azuron, Methiopyrsulfuron, Methiozolin, Methyl isothiocyanate, Metobromuron, Metolachlor, S-Metolachlor, Metosulam, Metoxuron, Metribuzin, Monosulfuron, Monosulfuron, Monosulfuron, Metsulfuron, -Metsulfuron, Monosulfuron, Monosulfuron, Metsulfuron -Methyl, MT-5950, ie N- [3-chloro-4- (l-methylethyl) -phenyl] -2-methylpentanamide, NGGC-011, napropamid, NC-310, ie 4- (2,4-dichlorobenzoyl) - 1-methyl-5-benzyloxypyrazole, NC-656, ie 3 - [(isopropylsulfonyl) methyl] -N- (5-methyl-1,3,4-oxadiazol-2-yl) -5- (trifluoromethyl) [I. , 2,4] triazolo- [4,3-a] pyridine-8-caiboxamid, neburon, nicosulfuron, nonanoic acid (pelargonic acid), norflurazon, oleic acid (fatty acids), orbencarb, orthosulfamuron, oiyzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, Oxyfluorfen,
Paraquat, Paraquat-dichlorid, Paraquat-Dimethylsulfat, Pebulat, Pendimethalin, Penoxsulam, Pentachlorphenol, Pentoxazon, Pethoxamid, Petroleumöl, Phenmedipham, Hienmedipham-Ethyl, Picloram, Picloram-dimethylammonium, Picloram-Etexyl, Picloram-Isoctyl, Picloram-Methyl, Picloram-Olamin, Picloram-Kalium, Picloram-Triethylammonium, Picloram-Tripromin, Picloram- Trolamin, Picolinafen, Pinoxaden, Piperophos, Pretilachlor, Primisulfuron, Primisulfuron-Methyl, Prodiamine, Profoxydim, Prometon, Prometryn, Propachlor, Propanil, Propaquizafop, Propazine, Propham, Propisochlor, Propoxycarbazone, Propoxycarbazone-Natrium, Propyrisulfuron, Propyzamid, Prosulfocarb, Prosulfuron, Pyraclonil, Pyraflufen, Pyraflufen-Ethyl, Pyrasulfotol, Pyrazolynat (Pyrazolat), PyrazosulftuOn, Pyrazosulfuron-Ethyl, Pyrazoxyfen, Pyribambenz, Pyribambenz-Isopropyl, Pyribambenz-Propyl, Pyribenzoxim, Pyributicaib, Pyridafol, Pyridat,Paraquat, Paraquat-dichlorid, Paraquat-Dimethylsulfat, Pebulat, Pendimethalin, Penoxsulam, Pentachlorphenol, Pentoxazon, Pethoxamid, Petroleum Oil, Phenmedipham, Hienmedipham-Ethyl, Picloram, Picloram-dimethylammonium, Picloram-dimethylammonium, Picloramlor-Etexyl, Picloramlor-Etexyl, Picloram-Etexyl, Picloram-Etexyl, Picloram-Etexyl, Methyl Olamine, Picloram-Kalium, Picloram-Triethylammonium, Picloram-Tripromin, Picloram- Trolamin, Picolinafen, Pinoxaden, Piperophos, Pretilachlor, Primisulfuron, Primisulfuron-Methyl, Prodiamine, Profoxydim, Prometon, Prometryn, Propachlor, Propanil, Propisochlor, propoxycarbazone, propoxycarbazone sodium, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotol, pyrazolynate (pyrazolate), pyrazambenz, propyrisulfuron, pyrazambenzoxy , Pyributicaib, pyridafol, pyridate,
Pyriftalid, Pyriminobac, Pyriminobac-Methyl, Pyrimisulfan, Pyrithiobac, Pyrithiobac-Natrium, Pyroxasulfon, Pyroxsulam, Quinclorac, Quinclorac -Dimethylammonium, Quinclorac-Methyl, Quinmerac, Quinoclamin, Quizalofop, Quizalofop-Ethyl, Quizalofop-P, Quizalofop-P-Ethyl, Quizalofop-P-T efuryl, QYM201, i.e. l-{2-Chloro-3-[(3-cyclopropyl-5-hydroxy-l-methyl-lH- pyrazol-4-yl)caibonyl]-6-(trifluoromethyl)phe-nyl}piperidin-2-on, Rimsulfuron, Saflufenacil,Pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfon, pyroxsulam, quinclorac, quinclorac -dimethylammonium, quinclorac-methyl, quinmerac, quinoclamin, quizopalofop, quizopylof, Quizalofop-PT efuryl, QYM201, ie 1- {2-Chloro-3 - [(3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazol-4-yl) caibonyl] -6- (trifluoromethyl) phenyl} piperidin-2-one, rimsulfuron , Saflufenacil,
Sethoxydim, Siduron, Simazine, Simetryn, SL-261, Sulcotrione, Sulfentrazone, Sulfometuron, Sulfometuron-Methyl, Sulfosulfuron, , SYP-249, i.e. 1 -Ethoxy-3 -methyl- 1 -oxobut-3 -en-2-yl-5 - [2- chlor-4-(trifluormethyl)phenoxy]-2-nitrobenzoat, SYP-300, i.e. l-[7-Fluor-3-oxo-4-(prop-2-in-l-yl)- 3 ,4-dihy dro-2H- 1 ,4-benzoxazin-6-yl]-3 -propyl-2-thioxoimidazolidin-4,5-dion, 2,3 ,6-TB A, TC A (Trichloressigsäure) und seine Salze, z.B. T C A-ammonium, TCA-Calcium, TCA-Ethyl, TCA- Magnesium, TCA-Natrium, Tebuthiuron, Tefüiyltrione, Tembotrion, Tepraloxydim, Teibacil, Teibucaib, Teibumeton, Terbuthylazine, Teibutiyn, Tetflupyrolimet, Thaxtomin, Thenylchlor, Thiazopyr, Thiencarbazone, Thiencarbazon-Methyl, Thifensulfuron, Thifensulfuron-Methyl, Thiobencarb, Tiafenacil, Tolpyralat, Topramezon, Tralkoxydim, Triafamon, Tri-allat, Triasulfuron, Triaziflam, Tribenuron, Tribenuron-Methyl, Triclopyr, Triclopyr-Butotyl, Triclopyr-Cholin, Triclopyr-Ethyl, Triclopyr-Triethylammonium, Trietazine, T rifloxy sulfuron, T rifloxy sulfuron- Natrium, Trifludimoxazin, Trifluralin, Triflusulfuron, Triflusulfuron-Methyl, Tritosulfuron, Hamstoffsulfat, Vemolat, XDE-848, ZJ-0862, i.e. 3,4-Dichlor-N-{2-[(4,6-dimethoxypyrimidin-2- yl)oxy]benzyl} anilin, 3-(2-Chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6- dihydropyrimidin-l-(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazol-5-carbonsäureethylester, 3- Chloro-2-[3-(difluoromethyl)isoxazolyl-5-yl]phenyl-5-chloropyrimidin-2-yl-ether, 2-(3,4-Sethoxydim, Siduron, Simazine, Simetryn, SL-261, Sulcotrione, Sulfentrazone, Sulfometuron, Sulfometuron-methyl, Sulfosulfuron,, SYP-249, ie 1 -ethoxy-3-methyl-1-oxobut-3-en-2-yl-5 - [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoate , SYP-300, ie l- [7-fluoro-3-oxo-4- (prop-2-yn-l-yl) -3, 4-dihydro-2H-1, 4-benzoxazin-6-yl] -3-propyl-2-thioxoimidazolidine-4,5-dione, 2,3,6-TB A, TC A (trichloroacetic acid) and its salts, for example TC A-ammonium, TCA-calcium, TCA-ethyl, TCA-magnesium , TCA-sodium, tebuthiuron, Tefüiyltrione, tembotrione, tepraloxydim, Teibacil, Teibucaib, Teibumeton, Terbuthylazine, Teibutiyn, Tetflupyrolimet, thaxtomin, thenylchlor, thiazopyr, thiencarbazone, Thiencarbazon-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, Tiafenacil, Tolpyralat, topramezone , Tralkoxydim, Triafamon, Tri-allat, Triasulfuron, Triaziflam, Tribenuron, Tribenuron-Methyl, Triclopyr, Triclopyr-Butotyl, Triclopyr-Choline, Triclopyr-Ethyl, Triclopyr-Triethylammonium, Trietazine, T rifloxy-sulfurifludon, T rifazin , Trifluralin, triflusulfuron, triflusulf uron-methyl, tritosulfuron, urea sulfate, vemolate, XDE-848, ZJ-0862, ie 3,4-dichloro-N- {2 - [(4,6-dimethoxypyrimidin-2- yl) oxy] benzyl} aniline, 3- (2-Chloro-4-fluoro-5- (3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1- (2H) -yl) phenyl) -5-methyl-4,5 -dihydroisoxazole-5-carboxylic acid ethyl ester, 3- chloro-2- [3- (difluoromethyl) isoxazolyl-5-yl] phenyl-5-chloropyrimidin-2-yl ether, 2- (3,4-
Dimethoxyphenyl)-4-[(2-hydroxy-6-oxocyclohex-l-en-l-yl)carbonyl]-6-methylpyridazin-3(2//)-on, 2-( {2-[(2-Methoxyethoxy)methyl]-6-methylpyridin-3-yl} carbonyl)cyclohexan- 1 ,3-dion, (5-Dimethoxyphenyl) -4 - [(2-hydroxy-6-oxocyclohex-1-en-1-yl) carbonyl] -6-methylpyridazin-3 (2 //) - one, 2- ({2 - [(2-methoxyethoxy ) methyl] -6-methylpyridin-3-yl} carbonyl) cyclohexane-1,3-dione, (5-
Hydroxy- 1 -methyl- lH-pyrazol-4-yl)(3 ,3 ,4-trimethyl- 1 , 1 -dioxido-2,3 -dihydro- 1 -benzothiophen-5- yl)methanon, 1 -Methyl-4-[(3 ,3 ,4-trimethyl- 1 , 1 -dioxido-2,3 -dihydro- 1 -benzothiophen-5- yl)caibonyl]-lH-pyrazol-5-yl-propan-l-sulfonat, 4- {2-Chloro-3 - [(3 , 5 -dimethyl- 1 H-pyrazol- 1 - yl)methyl]-4-(methylsulfonyl)benzoyl}-l-methyl-lH-pyrazol-5-yl-l,3-dimethyl-lH-pyrazole-4- carboxylat; Cyanomethyl-4-amino-3-chloro-5-fluoro-6-(7-fluoro-lH-indol-6-yl)pyridin-2- carboxylat, Prop-2-yn-l-yl-4-amino-3-chloro-5-fluoro-6-(7-fluoro-lH-indol-6-yl)pyridin-2- carboxylat, Methyl-4-amino-3 -chloro-5-fluoro-6-(7-fluoro- lH-indol-6-yl)pyridin-2-carboxylat, 4- Amino-3-chlor-5-fluor-6-(7-fluor-lH-indol-6-yl)pyridin-2-carbonsäure, Benzyl-4-amino-3-chlor-5- fluor-6-(7-fluor-lH-indol-6-yl)pyridin-2-carboxylat, Ethyl-4-amin-3-chlor-5-fluor-6-(7-fluor-lH- indol-6-yl)pyridin-2-carboxylat, Methyl-4-amino-3-chlor-5-fluor-6-(7-fluor-l-isobutyiyl-lH-indol- 6-yl)pyridin-2-carboxylat, Methyl-6-(l-acetyl-7-fluor-lH-mdol-6-yl)-4-amino-3-chloro-5- fluoropyridine-2-carboxylat, Methyl-4-amino-3-chlor-6-[l-(2,2-dimethylpropa-noyl)-7-fluor-lH- indol-6-yl]-5-fluoropyridin-2-carboxylat, Methyl-4-amino-3 -chlor-5 -fluor-6- [7-fluor- 1 - (methoxyacetyl)-lH-indol-6-yl]pyridin-2-carboxylat, Kalium 4-amino-3-chlor-5-fluor-6-(7-fluor- lH-indol-6-yl)pyridin-2-carboxylat, Natrium 4-amino-3 -chlor-5 -fluor-6-(7-fluor- 1 H-indol-6- yl)pyridin-2-carboxylat, Butyl-4-amino-3-chlor-5-fluor-6-(7-fluor-lH-indol-6-yl)pyridin-2- carboxylat, 4-Hydroxy-l-methyl-3-[4-(trifluormethyl)pyridin-2-yl]imidazolidin-2-on, 3-(5-tert- butyl- 1 ,2-oxazol-3 -yl)-4-hydroxy- 1 -methylimidazolidin-2-on. Beispiele für Pflanzenwachstumsregulatoren als mögliche Mischungspartner sind:Hydroxy-1-methyl-1 H -pyrazol-4-yl) (3, 3, 4-trimethyl-1, 1-dioxido-2,3-dihydro-1-benzothiophen-5-yl) methanone, 1 -methyl-4 - [(3, 3, 4-trimethyl- 1, 1-dioxido-2,3-dihydro- 1 -benzothiophen-5-yl) caibonyl] -lH-pyrazol-5-yl-propane-1-sulfonate, 4- {2-Chloro-3 - [(3, 5 -dimethyl-1H-pyrazol-1-yl) methyl] -4- (methylsulfonyl) benzoyl} -1-methyl-1H-pyrazol-5-yl-1,3 -dimethyl-1H-pyrazole-4-carboxylate; Cyanomethyl 4-amino-3-chloro-5-fluoro-6- (7-fluoro-1H-indol-6-yl) pyridin-2-carboxylate, prop-2-yn-1-yl-4-amino-3 -chloro-5-fluoro-6- (7-fluoro-1H-indol-6-yl) pyridine-2-carboxylate, methyl-4-amino-3-chloro-5-fluoro-6- (7-fluoro-1H -indol-6-yl) pyridine-2-carboxylate, 4- amino-3-chloro-5-fluoro-6- (7-fluoro-1H-indol-6-yl) pyridine-2-carboxylic acid, benzyl-4- amino-3-chloro-5- fluoro-6- (7-fluoro-1H-indol-6-yl) pyridine-2-carboxylate, ethyl-4-amine-3-chloro-5-fluoro-6- (7- fluoro-1H-indol-6-yl) pyridine-2-carboxylate, methyl-4-amino-3-chloro-5-fluoro-6- (7-fluoro-1-isobutyiyl-1H-indol-6-yl) pyridine -2-carboxylate, methyl 6- (1-acetyl-7-fluoro-1H-mdol-6-yl) -4-amino-3-chloro-5-fluoropyridine-2-carboxylate, methyl-4-amino-3 -chloro-6- [1- (2,2-dimethylpropa-noyl) -7-fluoro-1H-indol-6-yl] -5-fluoropyridine-2-carboxylate, methyl-4-amino-3-chloro-5 -fluoro-6- [7-fluoro-1 - (methoxyacetyl) -lH-indol-6-yl] pyridine-2-carboxylate, potassium 4-amino-3-chloro-5-fluoro-6- (7-fluoro- 1H-indol-6-yl) pyridine-2-carboxylate, sodium 4-amino-3-chloro-5-fluor-6- (7-fl uor- 1 H-indol-6- yl) pyridine-2-carboxylate, butyl-4-amino-3-chloro-5-fluoro-6- (7-fluoro-1H-indol-6-yl) pyridin-2- carboxylate, 4-hydroxy-1-methyl-3- [4- (trifluoromethyl) pyridin-2-yl] imidazolidin-2-one, 3- (5-tert-butyl-1,2-oxazol-3-yl) - 4-hydroxy-1-methylimidazolidin-2-one. Examples of plant growth regulators as possible mixing partners are:
Abscisinsäure, Acibenzolar, Acibenzol ar- S -methyl , 1 -Aminocyclopro-l -yl-carbonsäure undAbscisic acid, acibenzolar, acibenzol ar-S -methyl, 1-aminocyclopro-1-yl-carboxylic acid and
Derivate davon, 5-Aminolävulinsäure, Ancymidol, 6-Benzylaminopurin, Brassinolid, Brassinolid- ethyl, Catechin, Chitooligosaccharide (CO; COs unterscheiden sich von LCOs dadurch, dass ihnen die anhängende Fettsäurekette fehlt, die charakteristisch für LCOs ist. COs, manchmal auch als N- Acetylchitooligosaccharide bezeichnet, bestehen ebenfalls aus GlcNAc -Resten, haben aber Seitenkettendekorationen, die sie von Chitinmolekülen [(CeHnNOsJn, CAS-Nr. 1398-61-4] und Chitosanmolekülen [(CsHiiN04)n, CAS-Nr. 9012-76-4]), Chitinverbindungen, Chlormequatchlorid, Cloprop, Cyclanilid, 3 -(Cy cloprop- 1 -eny l)propionsäure, Daminozid, Dazomet, Dazomet-Natrium, n- Decanol, Dikegulac, Dikegulac-Natrium, Endothal, Endothal-Dikalium, Dinatrium und Mono(N,N- dimethylalkylammonium), Ethephon, Flumetralin, Flurenol, Flurenol-Butyl, Flurenol-Methyl, Flurprimidol, Forchlorfenuron, Gibberellinsäure, Inabenfid, Indol-3 -Essigsäure (IAA), 4-Indol-3- ylbuttersäure, Isoprothiolan, Probenazol, Jasmonsäure, Jasmonsäure oder Derivate davon (z. B. Jasmonsäuremethylester), Lipo-Chitooligosaccharide (LCO, manchmal auch als symbiotische Nodulations-(Nod-)Signale (oder Nod-Faktoren) oder als Myc-Faktoren bezeichnet), bestehen aus einem Oligosaccharid-Grundgerüst aus ß 1,4-verknüpften N-Acetyl-D-Glucosamin (" GlcNAc" )- Resten mit einer N-verknüpften Fettacylkette, die am nicht reduzierenden Ende kondensiert ist. Wie in der Fachwelt bekannt, unterscheiden sich LCOs in der Anzahl der CHcNAc-Reste im Rückgrat, in der Länge und dem Sättigungsgrad der Fettacylkette und in den Substitutionen von reduzierenden und nicht reduzierenden Zuckerresten), Linolsäure oder Derivate davon, Linolensäure oder Derivate davon, Maleinsäurehydrazid, Mepiquatchlorid, Mepiquatpentaborat, 1 -Methyl cyclopropen, 3'- Methylabscisinsäure, 2-(l -Naphthyl)acetamid, 1-Naphthylessigsäure, 2-Naphthyloxyessigsäure, Nitrophenolat-Gemisch, 4-Oxo-4[(2-Phenylethyl)amino]buttersäure, Paclobutrazol, 4- Phenylbuttersäure, N-Phenylphthal aminsäure, Prohexadion, Prohexadion-Calcium, Prohydrojasmon, Salicylsäure, Salicylsäuremethylester, Strigolacton, Tecnazen, Thidiazuron, Triacontanol, Trinexapac, Trinexapac-ethyl, Tsitodef, Uniconazol, Uniconazol-P, 2-Fluor-N-(3-methoxyphenyl)- 9H-purin-6-amin. Derivatives thereof, 5-aminolevulinic acid, ancymidol, 6-benzylaminopurine, brassinolide, brassinolide ethyl, catechin, chitooligosaccharides (CO; COs differ from LCOs in that they lack the pendant fatty acid chain that is characteristic of LCOs. COs, sometimes also as N-acetylchitooligosaccharides, also made up of GlcNAc residues, but have side chain decorations that are derived from chitin molecules [(CeHnNOsJn, CAS No. 1398-61-4] and chitosan molecules [(CsHiiN04) n, CAS No. 9012-76- 4]), chitin compounds, chlormequat chloride, cloprop, cyclanilide, 3 - (cycloprop- 1 -eny l) propionic acid, daminocide, dazomet, dazomet sodium, n-decanol, dikegulac, dikegulac sodium, endothal, endothal dipotassium, disodium and mono (N, N-dimethylalkylammonium), ethephon, flumetralin, flurenol, flurenol-butyl, flurenol-methyl, flurprimidol, forchlorfenuron, gibberellic acid, inabenfid, indol-3-acetic acid (IAA), 4-indol-3-ylbutyric acid, isoprothiol-3-ylbutyric acid , Probenazole, jasmonic acid, jasmone acid or derivatives thereof (e.g. B. jasmonic acid methyl ester), lipo-chitooligosaccharides (LCO, sometimes also referred to as symbiotic nodulation (Nod) signals (or Nod factors) or as Myc factors), consist of an oligosaccharide skeleton of ß 1,4-linked N -Acetyl-D-glucosamine ("GlcNAc") - residues with an N-linked fatty acyl chain condensed at the non-reducing end. As known in the art, LCOs differ in the number of CHcNAc residues in the backbone, in the length and the degree of saturation of the fatty acyl chain and in the substitutions of reducing and non-reducing sugar residues), linoleic acid or derivatives thereof, linolenic acid or derivatives thereof, maleic hydrazide , Mepiquat chloride, mepiquat pentaborate, 1-methyl cyclopropene, 3'-methylabscisic acid, 2- (1-naphthyl) acetamide, 1-naphthylacetic acid, 2-naphthyloxyacetic acid, nitrophenolate mixture, 4-oxo-4 [(2-phenylethyl) amino] butyric acid , Paclobutrazole, 4-phenylbutyric acid, N-phenylphthalamic acid, Prohexadione, Prohexadione-Calcium, Prohydrojasmone, Salicylic acid, Salicylic acid methyl ester, Strigolactone, Tecnazen, Thidiazuron, Triacontanol, Trinexapac, Trinexapac-ethyl, Trinexapac-ethyl, Tsitodef, Uniconxapac-ethyl, Tsitodef, Uniconxapac-ethyl, Tsitodef, N- (3-methoxyphenyl) - 9H-purine-6-amine.
Safener, die in Kombination mit den erfindungsgemäßen Verbindungen der Formel (I) und ggf. in Kombinationen mit weiteren Wirkstoffen wie z.B. Insektiziden, Akariziden, Herbiziden, Fungiziden wie oben aufgelistet, eingesetzt werden können, sind vorzugsweise ausgewählt aus der Gruppe bestehend aus: Safeners, which can be used in combination with the compounds of the formula (I) according to the invention and optionally in combinations with other active ingredients such as insecticides, acaricides, herbicides, fungicides as listed above, are preferably selected from the group consisting of:
Sl) Verbindungen der Formel (Sl),
Figure imgf000026_0001
wobei die Symbole und Indizes folgende Bedeutungen haben: Sl) compounds of the formula (Sl),
Figure imgf000026_0001
where the symbols and indices have the following meanings:
ΠΑ ist eine natürliche Zahl von 0 bis 5, vorzugsweise 0 bis 3; ΠΑ is a natural number from 0 to 5, preferably 0 to 3;
RA ist Halogen, (C1-C4)-Alkyl, (C1-C4)A- lkoxy, Nitro oder Halogen-(C1-C4)-alkyl; WA ist ein unsubstituierter oder substituierter divalenter heterocyclischer Rest aus der Gruppe der teilungesättigten oder aromatischen Fünfring-Heterocyclen mit 1 bis 3 Heteroringatomen aus der Gruppe N und O, wobei mindestens ein N-Atom und höchstens ein O-Atom im Ring enthalten ist, vorzugsweise ein Rest aus der Gruppe (WA1) bis (WA4),
Figure imgf000026_0002
nu ist 0 oder 1; RA is halogen, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) alkoxy, nitro or halo (C 1 -C 4 ) -alkyl; WA is an unsubstituted or substituted divalent heterocyclic radical from the group of partially unsaturated or aromatic five-membered ring heterocycles with 1 to 3 hetero ring atoms from the group N and O, with at least one N atom and at most one O atom in the ring, preferably one Remainder from group (WA 1 ) to (WA 4 ),
Figure imgf000026_0002
nu is 0 or 1;
RA2 ist ORA3, SRA3 oder NRA3RA4 oder ein gesättigter oder ungesättigter 3- bis 7-gliedriger Heterocyclus mit mindestens einem N-Atom und bis zu 3 Heteroatomen, vorzugsweise aus der Gruppe O und S, der über das N-Atom mit der Carbonylgruppe in (Sl) verbunden ist und unsubstituiert oder durch Reste aus der Gruppe (C1-C4)-Alkyl, (C1-C4)A- lkoxy oder gegebenenfalls substituiertes Phenyl substituiert ist, vorzugsweise ein Rest der Formel ORA3, NHRA4 oder N(CH3)2, insbesondere der Formel ORA3; RA 2 is ORA 3 , SRA 3 or NRA 3 RA 4 or a saturated or unsaturated 3 to 7-membered heterocycle with at least one N atom and up to 3 heteroatoms, preferably from the group O and S, which has the N- Atom is connected to the carbonyl group in (S1) and is unsubstituted or substituted by radicals from the group (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) alkoxy or optionally substituted phenyl, preferably a radical of the formula ORA 3 , NHRA 4 or N (CH3) 2, in particular of the formula ORA 3 ;
RA3 ist Wasserstoff oder ein unsubstituierter oder substituierter aliphatischer Kohlenwasserstoffrest, vorzugsweise mit insgesamt 1 bis 18 C- Atomen; RA 3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably with a total of 1 to 18 carbon atoms;
RA4 ist Wasserstoff, (C1-C6)- Alkyl, (C1-C6)-Alkoxy oder substituiertes oder unsubstituiertes Phenyl; RA 4 is hydrogen, (C 1 -C 6) - alkyl, (C 1 -C 6) -alkoxy or substituted or unsubstituted phenyl;
RA5 ist H, (C1-C6)-Alkyl, Halogen-(C1-C6)-alkyl, (C 1-C4)- Alkoxy-(C i-Cs)-alkyl, Cyano oder COORA9, worin RA9 Wasserstoff, (Ci-Cs)- Alkyl, Halogen-(C1-C6)-alkyl, (C1-C4A)-lkoxy-(C1-C4)- alkyl, (C1-C6)-Hydroxyalkyl, (C3-Ci2)-Cycloalkyl oder Tri-(C1-C4)-alkyl-silyl ist; RA6, RA7, RA8 sind gleich oder verschieden Wasserstoff, (C1-C6)- Alkyl, Halogen-(C1-C6)-alkyl, (Cs- Ci2)-Cy cloalkyl oder substituiertes oder unsubstituiertes Phenyl; vorzugsweise: a) Verbindungen vom Typ der Dichlorpheny lpyrazolin-3 -carbonsäure (Sla), vorzugsweise Verbindungen wie l-(2,4-Dichlorphenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazolin-3-carbonsäure, 1 -(2,4-Dichlorphenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazolin-3 -carbonsäur eethylester (Sl-1)RA 5 is H, (C 1 -C 6 ) -alkyl, halogen- (C 1 -C 6 ) -alkyl, (C 1-C4) -alkoxy- (C i-Cs) -alkyl, cyano or COORA 9 , wherein RA 9 is hydrogen, (Ci-Cs) - alkyl, halogen (C 1 -C 6 ) alkyl, (C 1 -C 4 A) alkoxy (C 1 -C 4 ) - alkyl, (C 1 - C 6 ) -hydroxyalkyl, (C3-Ci2) -cycloalkyl or tri- (C 1 -C 4 ) -alkyl-silyl; RA 6, RA 7, RA 8 are identical or different hydrogen, (C 1 -C 6) - alkyl, halo (C 1 -C 6) alkyl, (Cs-Ci2) -Cy cloalkyl or substituted or unsubstituted phenyl; preferably: a) compounds of the dichloropheny lpyrazoline-3-carboxylic acid type (Sl a ), preferably compounds such as 1- (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylic acid, 1 - (2,4-Dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylic acid ethyl ester (Sl-1)
("Mefenpyr-diethyl"), und verwandte Verbindungen, wie sie in der WO-A-91/07874 beschrieben sind; b) Derivate der Dichlorphenylpyrazolcarbonsäure (Slb), vorzugsweise Verbindungen wie 1 -(2, 4-Dichlorphenyl)-5-methyl-pyrazol-3-carbonsäur eethylester (Sl-2), l-(2,4-Dichlorphenyl)-5-isopropyl-pyrazol-3-carbonsäureethylester (Sl-3),("Mefenpyr-diethyl"), and related compounds as described in WO-A-91/07874; b) Derivatives of dichlorophenylpyrazole carboxylic acid (Sl b ), preferably compounds such as 1- (2,4-dichlorophenyl) -5-methyl-pyrazole-3-carboxylic acid ethyl ester (Sl-2), 1- (2,4-dichlorophenyl) -5 -isopropyl-pyrazole-3-carboxylic acid ethyl ester (Sl-3),
1 -(2,4-Dichlorphenyl)-5-(l , 1 -dimethyl-ethyl)pyrazol-3 -carbonsäureethyl-ester (S 1 -4) und verwandte Verbindungen, wie sie in EP-A-333 131 und EP-A-269806 beschrieben sind; c) Derivate der l,5-Diphenylpyrazol-3-carbonsäure (Slc), vorzugsweise Verbindungen wie 1 -(2, 4-Dichlorphenyl)-5-phenylpyrazol-3-carbonsäur eethylester (Sl-5), l-(2-Chlorphenyl)-5-phenylpyrazol-3-carbonsäuremethylester (Sl-6) und verwandte Verbindungen wie sie beispielsweise in der EP-A-268554 beschrieben sind; d) Verbindungen vom Typ der Triazolcarbonsäuren (Sld), vorzugsweise Verbindungen wie Fenchlorazol(-ethylester), d.h. l-(2,4-Dichlorphenyl)-5-trichlormethyl-(lH)-l,2,4-triazol-3-carbon- säureethylester (Sl-7), und verwandte Verbindungen wie sie in EP-A-174562 und EP-A-346620 beschrieben sind; e) Verbindungen vom Typ der 5 -Benzyl- oder 5-Phenyl-2-isoxazolin-3- carbonsäure oder der 5,5-1- (2,4-Dichlorophenyl) -5- (l, 1 -dimethyl-ethyl) pyrazole-3-carboxylic acid ethyl ester (S 1 -4) and related compounds, as described in EP-A-333 131 and EP- A-269806; c) Derivatives of l, 5-diphenylpyrazole-3-carboxylic acid (Sl c ), preferably compounds such as 1- (2, 4-dichlorophenyl) -5-phenylpyrazole-3-carboxylic acid ethyl ester (Sl-5), 1- (2- Chlorophenyl) -5-phenylpyrazole-3-carboxylic acid methyl ester (S1-6) and related compounds as described, for example, in EP-A-268554; d) Compounds of the triazole carboxylic acid type (Sl d ), preferably compounds such as fenchlorazole (ethyl ester), ie l- (2,4-dichlorophenyl) -5-trichloromethyl- (lH) -l, 2,4-triazole-3- carboxylic acid ethyl ester (Sl-7), and related compounds as described in EP-A-174562 and EP-A-346620; e) Compounds of the 5-benzyl or 5-phenyl-2-isoxazoline-3-carboxylic acid type or the 5,5-
Diphenyl-2-isoxazolin-3 -carbonsäure (Sle), vorzugsweise Verbindungen wieDiphenyl-2-isoxazoline-3-carboxylic acid (Sl e ), preferably compounds such as
5-(2,4-Dichlorbenzyl)-2-isoxazolin-3-carbonsäureethylester (Sl-8) oder 5 -Phenyl -2-isoxazolin-3 - carbonsäureethylester (Sl-9) und verwandte Verbindungen, wie sie in WO-A-91/08202 beschrieben sind, bzw. 5 , 5 -Diphenyl-2-isoxazolin-3 -carbonsäure (Sl-10) oder 5 , 5 -Diphenyl-2-isoxazolin-3 - carbonsäureethylester (Sl-11) ("Isoxadifen-ethyl") oder -n-propylester (Sl-12) oder der 5-(4-Fluorphenyl)-5-phenyl-2-isoxazolin-3-carbonsäureethylester (Sl-13), wie sie in der Patentanmeldung WO-A-95/07897 beschrieben sind. S2) Chinolinderivate der Formel (S2),
Figure imgf000028_0001
wobei die Symbole und Indizes folgende Bedeutungen haben: 5- (2,4-dichlorobenzyl) -2-isoxazoline-3-carboxylic acid ethyl ester (Sl-8) or 5-phenyl -2-isoxazoline-3-carboxylic acid ethyl ester (Sl-9) and related compounds, as described in WO-A- 91/08202, or 5, 5-diphenyl-2-isoxazoline-3-carboxylic acid (S1-10) or 5, 5-diphenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-11) ("Isoxadifen-ethyl ") or -n-propyl ester (S1-12) or the 5- (4-fluorophenyl) -5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-13), as described in the patent application WO-A-95 / 07897 are described. S2) quinoline derivatives of the formula (S2),
Figure imgf000028_0001
where the symbols and indices have the following meanings:
RB 1 ist Halogen, (C1-C4)-Alkyl, (C1-C4) A- lkoxy, Nitro oder Halogen-(C1-C4)-alkyl; ns ist eine natürliche Zahl von 0 bis 5, vorzugsweise 0 bis 3; RB 1 is halogen, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) alkoxy, nitro or halo (C 1 -C 4 ) -alkyl; ns is a natural number from 0 to 5, preferably 0 to 3;
RB2 ist ORB3, SRB3 oder NRB3RB4 oder ein gesättigter oder ungesättigter 3- bis 7-gliedriger Heterocyclus mit mindestens einem N-Atom und bis zu 3 Heteroatomen, vorzugsweise aus der Gruppe O und S, der über das N-Atom mit der Carbonylgruppe in (S2) verbunden ist und unsubstituiert oder durch Reste aus der Gruppe (C1-C4)- Alkyl, (C1-C4)- Alkoxy oder gegebenenfalls substituiertes Phenyl substituiert ist, vorzugsweise ein Rest der Formel ORB3, NHRB4 oder N(CH3)2, insbesondere der Formel ORB3; RB3 ist Wasserstoff oder ein unsubstituierter oder substituierter aliphatischer Kohlenwasserstoffrest, vorzugsweise mit insgesamt 1 bis 18 C- Atomen; RB 2 is ORB 3 , SRB 3 or NRB 3 RB 4 or a saturated or unsaturated 3- to 7-membered heterocycle with at least one N atom and up to 3 heteroatoms, preferably from the group O and S, which has the N- Atom is connected to the carbonyl group in (S2) and is unsubstituted or substituted by radicals from the group (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -alkoxy or optionally substituted phenyl, preferably a radical of the formula ORB 3 , NHRB 4 or N (CH3) 2, in particular of the formula ORB 3 ; RB 3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably with a total of 1 to 18 carbon atoms;
RB4 ist Wasserstoff, (C1-C6)- Alkyl, (C1-C6)- Alkoxy oder substituiertes oder unsubstituiertes Phenyl; RB 4 is hydrogen, (C 1 -C 6 ) -alkyl, (C 1 -C 6 ) -alkoxy or substituted or unsubstituted phenyl;
TB ist eine (Ci oder C2)-Alkandiylkette, die unsubstituiert oder mit einem oder zwei (Ci- C4)Alkylresten oder mit [(C 1-C3)- Alkoxy ] -carbony 1 substituiert ist; vorzugsweise: a) Verbindungen vom Typ der 8-Chinolinoxyessigsäure (S2a), vorzugsweise (5-Chlor-8-chinolinoxy)essigsäure-(l-methylhexyl)ester ("Cloquintocet-mexyl") (S2-1), (5-Chlor-8-chinolinoxy)essigsäure-(l,3 -dimethyl-but- 1 -yl)ester (S2-2), (5-Chlor-8-chinolinoxy)essigsäure-4-allyloxy-butylester (S2-3),TB is a (Ci or C2) -alkanediyl chain which is unsubstituted or substituted with one or two (Ci- C4) alkyl radicals or with [(C 1-C3) -alkoxy] -carbony 1; preferably: a) compounds of the 8-quinolinoxyacetic acid type (S2 a ), preferably (5-chloro-8-quinolinoxy) acetic acid (l-methylhexyl) ester ("Cloquintocet-mexyl") (S2-1), (5- Chloro-8-quinolinoxy) acetic acid (1,3-dimethyl-but-1 -yl) ester (S2-2), (5-chloro-8-quinolinoxy) acetic acid 4-allyloxy-butyl ester (S2-3),
(5-Chlor-8-chinolinoxy)essigsäure-l-allyloxy-prop-2-ylester (S2-4), (5-Chlor-8-chinolinoxy)essigsäureethylester (S2-5), (5-Chlor-8-chinolinoxy)essigsäuremethylester (S2-6), (5-Chlor-8-chinolinoxy)essigsäureallylester (S2-7), (5-Chlor-8-chinolinoxy)essigsäure-2-(2-propyliden-iminoxy)-l-ethylester (S2-8), (5-Chlor-8- chinolinoxy)essigsäure-2-oxo-prop- 1 -ylester (S2-9) und verwandte Verbindungen, wie sie in EP-A-86750, EP-A-94349 und EP-A-191 736 oder ΕΡ-Α-0 492 366 beschrieben sind, sowie (5- Chlor-8-chinolinoxy)essigsäure (S2-10), deren Hydrate und Salze, beispielsweise deren Lithium-, Natrium- Kalium-, Kalzium-, Magnesium-, Aluminium-, Eisen-, Ammonium-, quartäre Ammonium-, Sulfonium-, oder Phosphoni umsalze wie sie in der WO-A-2002/34048 beschrieben sind; b) Verbindungen vom Typ der (5-Chlor-8-chinolinoxy)malonsäure (S2b), vorzugsweise Verbindungen wie (5-Chlor-8-chinolinoxy)malonsäurediethylester,(5-Chloro-8-quinolinoxy) -acetic acid-1-allyloxy-prop-2-yl ester (S2-4), (5-chloro-8-quinolinoxy) -acetic acid ethyl ester (S2-5), (5-chloro-8-quinolinoxy ) methyl acetate (S2-6), (5-chloro-8-quinolinoxy) allyl acetate (S2-7), 2- (2-propylidene-iminoxy) -l-ethyl (5-chloro-8-quinolinoxy) acetic acid (S2 -8), (5-chloro-8-quinolinoxy) acetic acid 2-oxo-prop-1 -yl ester (S2-9) and related compounds, as described in EP-A-86750, EP-A-94349 and EP-A-191 736 or ΕΡ-Α-0 492 366 are described, as well as (5-chloro-8-quinolinoxy) acetic acid (S2-10), its hydrates and salts , for example their lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts as described in WO-A-2002/34048; b) Compounds of the (5-chloro-8-quinolinoxy) malonic acid type (S2 b ), preferably compounds such as (5-chloro-8-quinolinoxy) diethyl malonate,
(5-Chlor-8-chinolinoxy)malonsäurediallylester, (S-Chlor-S-chinolin- oxy)malonsäure-methyl-ethylester und verwandte Verbindungen, wie sie in EP-A-0 582 198 beschrieben sind. S3) Verbindungen der Formel (S3)
Figure imgf000029_0001
wobei die Symbole und Indizes folgende Bedeutungen haben: Diallyl (5-chloro-8-quinolinoxy) malonic acid, methyl-ethyl (S-chloro-S-quinolinoxy) malonic acid and related compounds, as described in EP-A-0 582 198. S3) compounds of the formula (S3)
Figure imgf000029_0001
where the symbols and indices have the following meanings:
Rc 1 ist(C1-C4)- Alkyl, Halogen-(C1-C4)-alkyl, (C2-C4)-Alkenyl, Halogen-(C2-C4)-alkenyl, (C3-C7)- Cycloalkyl, vorzugsweise Dichlormethyl; Rc2, Rc3 sind gleich oder verschieden Wasserstoff, (C1-C4)A-lkyl, (C2-C4)-Alkenyl, (C2-C4)-Alkinyl,Rc 1 is (C 1 -C 4 ) -alkyl, halo- (C 1 -C 4 ) -alkyl, (C2-C4) -alkenyl, halo- (C2-C4) -alkenyl, (C3-C7) -cycloalkyl , preferably dichloromethyl; Rc 2 , Rc 3 are identically or differently hydrogen, (C 1 -C 4 ) A-alkyl, (C2-C4) -alkenyl, (C2-C4) -alkynyl,
Halogen-(C1-C4)-alkyl, Halogen-(C2-C4)-alkenyl, (C1-C4)-Alkylcaibamoyl-(C1-C4)-alkyl, (C2-C4)- Alkenylcarbamoyl-(C1-C4)-alkyl, (C 1-C4)- Alkoxy-(C1-C4)-alkyl, Dioxolanyl-(C1-C4)-alkyl,Halo- (C 1 -C 4 ) -alkyl, halo- (C2-C4) -alkenyl, (C 1 -C 4 ) -alkylcaibamoyl- (C 1 -C 4 ) -alkyl, (C2-C4) -alkenylcarbamoyl- (C 1 -C 4 ) -alkyl, (C 1-C4) -alkoxy- (C 1 -C 4 ) -alkyl, dioxolanyl- (C 1 -C 4 ) -alkyl,
Thiazolyl, Furyl, Furylalkyl, Thienyl, Piperidyl, substituiertes oder unsubstituiertes Phenyl, oder Rc2 und Rc3 bilden zusammen einen substituierten oder unsubstituierten heterocyclischen Ring, vorzugsweise einen Oxazolidin-, Thiazolidin-, Piperidin-, Morpholin-, Hexahydropyrimidin- oder Benzoxazinring; vorzugsweise: Thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or Rc 2 and Rc 3 together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine, piperidine, morpholine, hexahydropyrimidine or benzoxazine ring; preferably:
Wirkstoffe vom Typ der Dichloracetamide, die häufig als Vorauflaufsafener (bodenwirksameActive ingredients of the dichloroacetamide type, which are often used as pre-emergence safeners (soil-effective
Safener) angewendet werden, wie z. B. "Dichlormid" (N,N-Diallyl-2,2-dichloracetamid) (S3-1),Safener) are used, such as. B. "Dichlormid" (N, N-diallyl-2,2-dichloroacetamide) (S3-1),
"R-29148" (3-Dichloracetyl-2,2,5-trimethyl-l,3-oxazolidin) der Firma Stauffer (S3-2), "R-28725" (3 -Dichloracetyl-2, 2, -dimethyl- 1,3 -oxazolidin) der Firma Stauffer (S3-3),"R-29148" (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer (S3-2), "R-28725" (3-dichloroacetyl-2,2, -dimethyl- 1,3-oxazolidine) from Stauffer (S3-3),
"Benoxacor" (4-Dichloracetyl-3 ,4-dihy dro-3 -methy 1-2H- 1 ,4-benzoxazin) (S3-4),"Benoxacor" (4-dichloroacetyl-3, 4-dihydro-3-methy 1-2H-1, 4-benzoxazine) (S3-4),
"PPG-1292" (N-Allyl-N-[(l,3-dioxolan-2-yl)-methyl]-dichloracetamid) der Firma PPG Industries (S3-5), "PPG-1292" (N-Allyl-N - [(1,3-dioxolan-2-yl) methyl] dichloroacetamide) from PPG Industries (S3-5),
"DKA-24" (N-Allyl-N-[(allylaminocarbonyl)methyl]-dichloracetamid) der Firma Sagro-Chem (S3-6), "DKA-24" (N-Allyl-N - [(allylaminocarbonyl) methyl] dichloroacetamide) from Sagro-Chem (S3-6),
"AD-67" oder "MON 4660" (3 -Dichloracetyl- 1 -oxa-3 -aza-spiro [4,5] decan) der Firma Nitrokemia bzw. Monsanto (S3-7),"AD-67" or "MON 4660" (3-dichloroacetyl-1-oxa-3-aza-spiro [4,5] decane) from Nitrokemia or Monsanto (S3-7),
"Ή-35" (1 -Dichloracetyl-azepan) der Firma TRI-Chemical RT (S3-8),"Ή-35" (1-dichloroacetyl-azepane) from TRI-Chemical RT (S3-8),
"Diclonon" (Dicyclonon) oder "BAS145138" oder "LAB145138" (S3-9)"Diclonon" (Dicyclonon) or "BAS145138" or "LAB145138" (S3-9)
((RS)- 1 -Dichloracetyl-3 ,3 , 8a-trimethy lperhy dropyrrolo [ 1 ,2-a]pyrimidin-6-on) der Firma BASF, "Furilazol" oder "MON 13900" ((RS)-3-Dichloracetyl-5-(2-furyl)-2,2-dimethyloxazolidin) (S3-10); sowie dessen (R)-Isomer (S3-11). ((RS) -1-dichloroacetyl-3, 3, 8a-trimethy lperhy dropyrrolo [1, 2-a] pyrimidin-6-one) from BASF, "Furilazol" or "MON 13900" ((RS) -3- Dichloroacetyl-5- (2-furyl) -2,2-dimethyloxazolidine) (S3-10); as well as its (R) -isomer (S3-11).
S4) N-Acylsulfonamide der Formel (S4) und ihre Salze,
Figure imgf000030_0001
worin die Symbole und Indizes folgende Bedeutungen haben: S4) N-acylsulfonamides of the formula (S4) and their salts,
Figure imgf000030_0001
where the symbols and indices have the following meanings:
AD ist S02-NRD3-C0 oder CO-NRD3-SC>2 XD ist CH oder N; AD is SO2-NRD 3 -C0 or CO-NRD 3 -SC> 2 XD is CH or N;
RD1 ist CO-NRD5RD6 oder NHCO-RD7; RD 1 is CO-NRD 5 RD 6 or NHCO-RD 7 ;
RD2 ist Halogen, Halogen-(C1-C4)-alkyl, Halogen-(C1-C4)-alkoxy, Nitro, (C1-C A4)l-kyl, (C1-C4)- Alkoxy, (C1-C4)-Alkylsulfonyl, (C1-C4)-Alkoxy carbony 1 oder (C 1-C4)- Alkyl carbonyl; RD 2 is halogen, halogen- (C 1 -C 4 ) -alkyl, halogen- (C 1 -C 4 ) -alkoxy, nitro, (C 1 -CA 4 ) l-alkyl, (C 1 -C 4 ) - Alkoxy, (C 1 -C 4 ) -alkylsulfonyl, (C 1 -C 4 ) -alkoxy carbony 1 or (C 1 -C4) -alkyl carbonyl;
RD3 ist Wasserstoff, (Ci-C*)- Alkyl, (C2-C4)-Alkenyl oder (C2-C4)-Alkinyl; RD4 ist Halogen, Nitro, (C1-C4)- Alkyl, Halogen-(C1-C4)-alkyl, Halogen-(C1-C4)-alkoxy, (C3-C6)- Cycloalkyl, Phenyl,(C1-C4)- Alkoxy, Cyano, (C1-C4)- Alkylthio, (C1-C4)-Alkylsulfinyl, (C1-C4)- Alkylsulfonyl, (C1-C4)-Alkoxy carbonyl oder (C1-CA4)l-kylcaibonyl; RD 3 is hydrogen, (Ci-C *) -alkyl, (C2-C4) -alkenyl or (C2-C4) -alkynyl; RD 4 is halogen, nitro, (C 1 -C 4) - alkyl, halo (C 1 -C 4) alkyl, halo (C 1 -C 4) alkoxy, (C 3 -C 6) - cycloalkyl , Phenyl, (C 1 -C 4 ) alkoxy, cyano, (C 1 -C 4 ) alkylthio, (C 1 -C 4 ) alkylsulfinyl, (C 1 -C 4 ) alkylsulfonyl, (C 1 -C 4 ) -alkoxy carbonyl or (C 1 -CA 4 ) l-kylcaibonyl;
RD5 ist Wasserstoff, (C1-C6)- Alkyl, (C3-C6)-Cycloalkyl, (C2-C6)-Alkenyl, (C2-C6)-Alkinyl, (Cs- CeJ-Cycloalkenyl, Phenyl oder 3- bis 6-gliedriges Heterocyclyl enthaltend VD Heteroatome aus der Gruppe Stickstoff, Sauerstoff und Schwefel, wobei die sieben letztgenannten Reste durch VD Substituenten aus der Gruppe Halogen, (C1-C6)-Alkoxy, Halogen-(C1-C6)-alkoxy, (C1-C2)- Alkylsulfinyl, (C1-C2)-Alkylsulfonyl, (C3-C6)-Cycloalkyl, (C1-C4)- Alkoxy carbonyl, (C1-C4)- Alkylcaibonyl und Phenyl und im Falle cyclischer Reste auch (C1-C4)-Alkyl und Halogen-(C1-C4)- alkyl substituiert sind; RD 5 is hydrogen, (C 1 -C 6 ) alkyl, (C 3 -C 6 ) cycloalkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (Cs- CeJ- Cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl containing VD heteroatoms from the group nitrogen, oxygen and sulfur, the last seven radicals being replaced by VD substituents from the group halogen, (C 1 -C 6 ) -alkoxy, halogen- (C 1 -C 6 ) -alkoxy, (C1-C2) -alkylsulfinyl, (C 1 -C 2 ) -alkylsulfonyl, (C 3 -C 6 ) -cycloalkyl, (C 1 -C 4 ) -alkoxy carbonyl, (C 1 -C 4 ) - Alkylcaibonyl and phenyl and, in the case of cyclic radicals, also (C 1 -C 4) alkyl and halo (C 1 -C 4) - alkyl are substituted;
RD6 ist Wasserstoff, (C1-C6)-Alkyl, (C2-C6)-Alkenyl oder (C2-C6)-Alkinyl, wobei die drei letztgenannten Reste durch VD Reste aus der Gruppe Halogen, Hydroxy, (C1-C4)-Alkyl, (C1-C4)- Alkoxy und (C1-C4)-Alkylthio substituiert sind, oder RD 6 is hydrogen, (C 1 -C 6 ) -alkyl, (C 2 -C 6 ) -alkenyl or (C 2 -C 6 ) -alkynyl, the last three radicals being replaced by VD radicals from the group halogen, hydroxy, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -alkoxy and (C 1 -C 4 ) -alkylthio are substituted, or
RD5 und RD6 gemeinsam mit dem dem sie tragenden Stickstoffatom einen Pyrrolidinyl- oder Piperidinyl-Rest bilden; RD 5 and RD 6 together with the nitrogen atom carrying them form a pyrrolidinyl or piperidinyl radical;
RD7 ist Wasserstoff,(C1-C4)- Alkylamino, Di-(C1-C4)-alkylamino, (C1-C6)-Alkyl, (C3-C6)- Cycloalkyl, wobei die 2 letztgenannten Reste durch VD Substituenten aus der Gruppe Halogen, (Ci- C4)-Alkoxy, Halogen-(C1-C6)-alkoxy und (C1-C4)A- lkylthio und im Falle cyclischer Reste auch (Ci- C4)- Alkyl und Halogen-(C1-C4)-alkyl substituiert sind; nD ist 0, 1 oder 2; mD ist 1 oder 2; RD 7 is hydrogen, (C 1 -C 4 ) -alkylamino, di- (C 1 -C 4 ) -alkylamino, (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, where the 2 last-mentioned radicals by VD substituents from the group halogen, (Ci- C4) -alkoxy, halogen- (C 1 -C 6 ) -alkoxy and (C 1 -C 4 ) alkylthio and in the case of cyclic radicals also (Ci- C 4 ) alkyl and halo (C 1 -C 4 ) alkyl are substituted; nD is 0, 1 or 2; mD is 1 or 2;
VD ist 0, 1, 2 oder 3; davon bevorzugt sind Verbindungen vom Typ der N-Acylsulfonamide, z.B. der nachfolgenden Formel (S4a), die z. B. bekannt sind aus WO-A-97/45016
Figure imgf000031_0001
worin VD is 0, 1, 2 or 3; Preferred of these are compounds of the N-acylsulfonamide type, for example of the following formula (S4 a ), which z. B. are known from WO-A-97/45016
Figure imgf000031_0001
wherein
RD7 (C1-C6)-Alkyl, (C3-C6)-Cycloalkyl, wobei die 2 letztgenannten Reste durch VD Substituenten aus der Gruppe Halogen, (C1-C4)-Alkoxy, Halogen-(C1-C6)-alkoxy und (C1-C4)A-lkylthio und im Falle cyclischer Reste auch (C1-C4)- Alkyl und Halogen-(C1-C4)-alkyl substituiert sind; RD 7 (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, where the 2 last-mentioned radicals are replaced by VD substituents from the group halogen, (C 1 -C 4 ) -alkoxy, halogen- (C 1 -C 6 ) -alkoxy and (C 1 -C 4 ) A-alkylthio and, in the case of cyclic radicals, also (C 1 -C 4 ) -alkyl and halogen- (C 1 -C 4 ) -alkyl are substituted;
RD4 Halogen, (Ci-C4>Alkyl, (C1-C4)-Alkoxy, CF3; mo 1 oder 2; RD 4 halogen, (Ci-C4> alkyl, (C 1 -C 4 ) -alkoxy, CF 3; mo 1 or 2;
VD ist 0, 1, 2 oder 3 bedeutet; sowie Acylsulfamoylbenzoesäureamide, z.B. der nachfolgenden Formel (S4b), die z.B. bekannt sind aus WO-A-99/16744,
Figure imgf000032_0002
VD is 0, 1, 2 or 3; as Acylsulfamoylbenzoic acid amides, for example of the following formula (S4 b ), which are known, for example, from WO-A-99/16744,
Figure imgf000032_0002
Z.B. solche worin RD5 = Cyclopropyl und (RD4) = 2-OMe ist ("Cyprosulfamide", S4-1), For example, those in which RD 5 = cyclopropyl and (RD 4 ) = 2-OMe ("Cyprosulfamide", S4-1),
RD5 = Cyclopropyl und (RD4) = 5-Cl-2-OMe ist (S4-2), RD 5 = cyclopropyl and (RD 4 ) = 5-Cl-2-OMe is (S4-2),
RD5 = Ethyl und (RD4) = 2-OMe ist (S4-3), RD 5 = ethyl and (RD 4 ) = 2-OMe is (S4-3),
RD5 = Isopropyl und (RD4) = 5-Cl-2-OMe ist (S4-4) und RD 5 = isopropyl and (RD 4 ) = 5-Cl-2-OMe is (S4-4) and
RD5 = Isopropyl und (RD4) = 2-OMe ist (S4-5). sowie RD 5 = isopropyl and (RD 4 ) = 2-OMe is (S4-5). as
Verbindungen vom Typ der N-Acylsulfamoylphenylhamstoffe der Formel (S4C), die z.B. bekannt sind aus der EP- A-365484,
Figure imgf000032_0001
worin Compounds of the N-acylsulfamoylphenylureas type of the formula (S4 C ), which are known, for example, from EP-A-365484,
Figure imgf000032_0001
wherein
RD8 und RD9unabhängig voneinander Wasserstoff, (C1-C8)- Alkyl, (C3-C6)-Cycloalkyl, (C3-C6)- Alkenyl, (C3-C6)-Alkinyl, RD RD 8 and 9 are independently hydrogen, (C 1 -C 8) - alkyl, (C 3 -C 6) -cycloalkyl, (C 3 -C 6) - alkenyl, (C 3 -C 6) -alkynyl,
RD4 Halogen,(C1-C4)-Alkyl, (C1-C4)-Alkoxy, CF3 mD 1 oder 2 bedeutet; beispielsweise l-[4-(N-2-Methoxybenzoylsulfamoyl)phenyl]-3-methylhamstoff, l-[4-(N-2-Methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylhamstoff, l-[4-(N-4,5-Dimethylbenzoylsulfamoyl)phenyl]-3-methylhamstoff, sowie RD 4 is halogen, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -alkoxy, CF 3 mD 1 or 2; for example 1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3-methylurea, 1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3,3-dimethylurea, 1- [4- (N-4 , 5-dimethylbenzoylsulfamoyl) phenyl] -3-methylurea, as
N-Phenylsulfonylterephthalamide der Formel (S411), die z.B. bekannt sind aus CN 101838227,
Figure imgf000033_0001
N-phenylsulfonylterephthalamides of the formula (S4 11 ), which are known, for example, from CN 101838227,
Figure imgf000033_0001
Z.B. solche worin RD4 Halogen,(C1-C4)-Alkyl, (C1-C4)A- lkoxy, CF3; mn 1 oder 2; For example those in which RD 4 is halogen, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) alkoxy, CF 3; mn 1 or 2;
RD5 Wasserstoff, (C1-C6)-Alkyl, (C3-C6)-Cycloalkyl, (Ca-GO-Alkenyl, (C2-C6)-Alkinyl, (C3-C6)- Cycloalkenyl bedeutet. RD 5 hydrogen, (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (Ca-GO-alkenyl, (C 2 -C 6 ) -alkynyl, (C 3 -C 6 ) -cycloalkenyl means.
S5) Wirkstoffe aus der Klasse der Hydroxyaromaten und der aromatisch-aliphatischen Caibonsäurederivate (S5), Z.B. S5) Active ingredients from the class of hydroxyaromatics and the aromatic-aliphatic caibonic acid derivatives (S5), e.g.
3 ,4, 5 -T riacetoxybenzoesäureethylester, 3,5-Dimethoxy-4-hydroxybenzoesäure, 3,5- Dihydroxybenzoesäure, 4-Hydroxysalicylsäure, 4-Fluorsalicyclsäure, 2 -Hydroxy zimtsäure, 2,4- Dichlorzimtsäure, wie sie in der WO-A-2004/084631, WO-A-2005/015994, WO-A-2005/016001 beschrieben sind. S6) Wirkstoffe aus der Klasse der l,2-Dihydrochinoxalin-2-one (S6), z.B. 3, 4, 5-triacetoxybenzoic acid ethyl ester, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicylic acid, 2-hydroxy cinnamic acid, 2,4-dichlorocinnamic acid, as described in WO A-2004/084631, WO-A-2005/015994, WO-A-2005/016001. S6) Active ingredients from the class of the 1,2-dihydroquinoxalin-2-ones (S6), e.g.
1 -Methyl -3 -(2-thienyl)- 1 ,2-dihy drochinoxalin-2-on, 1 -Methyl-3 -(2-thienyl)- 1 ,2-dihy drochinoxalin- 2-thion, 1 -(2- Aminoethy l)-3 -(2-thienyl)- 1 ,2-dihy dro-chinoxalin-2-on-hy drochlorid, l-(2-1 -Methyl -3 - (2-thienyl) -1, 2-dihydroquinoxalin-2-one, 1-methyl-3 - (2-thienyl) -1, 2-dihydroquinoxalin-2-thione, 1 - (2 - Aminoethy l) -3 - (2-thienyl) - 1, 2-dihydro-quinoxalin-2-one hydrochloride, l- (2-
Methylsulfonylaminoethyl)-3-(2-thienyl)-l,2-dihydro-chinoxalin-2-on, wie sie in der WO-A- 2005/112630 beschrieben sind. S7) Verbindungen der Formel (S7),wie sie in der WO-A-1998/38856 beschrieben sind
Figure imgf000033_0002
worin die Symbole und Indizes folgende Bedeutungen haben: Methylsulfonylaminoethyl) -3- (2-thienyl) -1, 2-dihydro-quinoxalin-2-one, as described in WO-A-2005/112630. S7) Compounds of the formula (S7), as described in WO-A-1998/38856
Figure imgf000033_0002
where the symbols and indices have the following meanings:
RE1, RE2 sind unabhängig voneinander Halogen,(C1-C4)- Alkyl, (C1-C4)- Alkoxy, Halogen- (C1-C4)- alkyl, (C1-C4)-Alkylamino, Di-(C1-C4)-Alkylamino, Nitro; AE ist COORE3 oder COSRE4 RE 1 , RE 2 are independently halogen, (C 1 -C 4 ) - alkyl, (C 1 -C 4 ) - alkoxy, halogen (C 1 -C 4 ) - alkyl, (C 1 -C 4 ) - Alkylamino, di (C 1 -C 4 ) alkylamino, nitro; AE is COORE 3 or COSRE 4
RE3, RE4 sind unabhängig voneinander Wasserstoff,(C1-C4)- Alkyl, (C2-C6)-Alkenyl, (C2-C4)- Alkinyl, Cyanoalkyl, Halogen-(C1-C4)-alkyl, Phenyl, Nitrophenyl, Benzyl, Halobenzyl, Pyridinylalkyl und Alkylammonium, ns 1 ist 0 oder 1 RE 3 , RE 4 are independently hydrogen, (C 1 -C 4 ) -alkyl, (C 2 -C 6 ) -alkenyl, (C2-C4) -alkynyl, cyanoalkyl, halogen- (C 1 -C 4 ) - alkyl, phenyl, nitrophenyl, benzyl, halobenzyl, pyridinylalkyl and alkylammonium, ns 1 is 0 or 1
2 3 2 3
ΠΕ , ΠΕ sind unabhängig voneinander 0, 1 oder 2, vorzugsweise: ΠΕ, ΠΕ are independently 0, 1 or 2, preferably:
Diphenylmethoxyessigsäure, Diphenylmethoxyacetic acid,
Diphenylmethoxyessigsäureethylester, Diphenylmethoxyessigsäuremethylester (CAS-Reg.Nr. 41858-19-9) (S7-1). Ethyl diphenyl methoxyacetate, methyl diphenylmethoxyacetate (CAS Reg. No. 41858-19-9) (S7-1).
S8) Verbindungen der Formel (S8),wie sie in der WO-A-98/27049 beschrieben sind
Figure imgf000034_0001
worin S8) Compounds of the formula (S8), as described in WO-A-98/27049
Figure imgf000034_0001
wherein
XF CH oder N, nF für den Fall, dass XF=N ist, eine ganze Zahl von 0 bis 4 und für den Fall, dass XF=CH ist, eine ganze Zahl von 0 bis 5 , XF CH or N, nF for the case that XF = N, an integer from 0 to 4 and for the case that XF = CH, an integer from 0 to 5,
RF1 Halogen,(C1-C4)- Alkyl, Halogen-(C1-C4)-alkyl, (C1-C4)- Alkoxy, Halogen-(C1-C4)-alkoxy, Nitro,(C1-C4)-Alkylthio, (C1-C4)-Alkylsulfonyl, (C1-C4) A-lkoxy carbonyl, ggf. substituiertes. Phenyl, ggf. substituiertes Phenoxy, RF2 Wasserstoff oder (C1-C4)-Alkyl RF 1 halogen, (C 1 -C 4 ) -alkyl, halogen- (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -alkoxy, halogen- (C 1 -C 4 ) -alkoxy, nitro, (C 1 -C 4 ) -alkylthio, (C 1 -C 4 ) -alkylsulfonyl, (C 1 -C 4 ) A-alkoxy carbonyl, optionally substituted. Phenyl, optionally substituted phenoxy, RF 2 hydrogen or (C 1 -C 4 ) -alkyl
RF3 Wasserstoff, (C1-C6)- Alkyl, (C2-C4)-Alkenyl, (C2-C4)— Alkinyl, oder Aryl, wobei jeder der vorgenannten C-haltigen Reste unsubstituiert oder durch einen oder mehrere, vorzugsweise bis zu drei gleiche oder verschiedene Reste aus der Gruppe, bestehend aus Halogen und Alkoxy substituiert ist; bedeuten, oder deren Salze, vorzugsweise Verbindungen worin XF CH, nF eine ganze Zahl von 0 bis 2 , RF 3 is hydrogen, (C 1 -C 6 ) -alkyl, (C2-C4) -alkenyl, (C2-C4) -alkynyl, or aryl, where each of the aforementioned C-containing radicals is unsubstituted or by one or more, preferably up to is substituted to three identical or different radicals from the group consisting of halogen and alkoxy; mean, or their salts, preferably compounds in which XF CH, nF is an integer from 0 to 2,
RF1 Halogen,(C1-C4)- Alkyl, Halogen-(C1-C4)-alkyl, (C1-CA4)l-koxy, Halogen-(C1-C4)-alkoxy , RF 1 halogen, (C 1 -C 4 ) -alkyl, halogen- (C 1 -C 4 ) -alkyl, (C 1 -CA 4 ) l-koxy, halogen- (C 1 -C 4 ) -alkoxy,
RF2 Wasserstoff oder(C1-C4)- Alkyl, RF3 Wasserstoff, (C1-C6)- Alkyl, (C2-C4)-Alkenyl, (C2-C4)-Alkinyl, oder Aryl, wobei jeder der vorgenannten C-haltigen Reste unsubstituiert oder durch einen oder mehrere, vorzugsweise bis zu drei gleiche oder verschiedene Reste aus der Gruppe, bestehend aus Halogen und Alkoxy substituiert ist, bedeuten, oder deren Salze. RF 2 is hydrogen or (C 1 -C 4 ) -alkyl, RF 3 is hydrogen, (C 1 -C 6 ) -alkyl, (C2-C4) -alkenyl, (C2-C4) -alkynyl, or aryl, where any of the The aforementioned C-containing radicals are unsubstituted or substituted by one or more, preferably up to three, identical or different radicals from the group consisting of halogen and alkoxy, or their salts.
S9) Wirkstoffe aus der Klasse der 3-(5-Tetrazolylcaibonyl)-2-chinolone (S9), z.B. 1 ,2-Dihydro-4-hydroxy- 1 -ethyl-3 -(5-tetrazolylcarbonyl)-2-chinolon (C AS-Reg.Nr. 219479- 18-2), 1 ,2-Dihy dro-4-hy droxy- 1 -methy 1-3 -(5 -tetrazoly 1-carbony l)-2-chinolon (CAS-Reg.Nr. 95855-00-8), wie sie in der WO- A- 1999/000020 beschrieben sind. S9) Active ingredients from the class of the 3- (5-tetrazolylcaibonyl) -2-quinolones (S9), for example 1,2-dihydro-4-hydroxy-1-ethyl-3 - (5-tetrazolylcarbonyl) -2-quinolone (C. AS-Reg.Nr. 219479-18-2), 1, 2-Dihydro-4-Hydroxy- 1 -methy 1-3 - (5 -tetrazoly 1-carbony l) -2-quinolone (CAS-Reg. No. 95855-00-8), as described in WO-A-1999/000020.
S10) Verbindungen der Formeln (S108) oder (SIO6) wie sie in der WO- A-2007/023719 und WO-A-2007/023764 beschrieben sind
Figure imgf000035_0001
worin S10) Compounds of the formulas (S10 8 ) or (SIO 6 ) as described in WO-A-2007/023719 and WO-A-2007/023764
Figure imgf000035_0001
wherein
RG1 Halogen,(C1-C4)- Alkyl, Methoxy, Nitro, Cyano, CF3, OCF3 RG 1 halogen, (C 1 -C 4 ) - alkyl, methoxy, nitro, cyano, CF3, OCF3
YG, ZG unabhängig voneinander O oder S, no eine ganze Zahl von 0 bis 4, YG, ZG independently of one another O or S, no an integer from 0 to 4,
RG2 (Ci-Cie)- Alkyl, (C2-C6)-Alkenyl, (C3-C6)-Cycloalkyl, Aryl; Benzyl, Halogenbenzyl, RG 2 (Ci-Cie) -alkyl, (C 2 -C 6 ) -alkenyl, (C 3 -C 6 ) -cycloalkyl, aryl; Benzyl, halobenzyl,
RG3 Wasserstoff oder (C1-C6)- Alkyl bedeutet. Sil) Wirkstoffe vom Typ der Oxyimino-Verbindungen (Sil), die als Saatbeizmittel bekannt sind, wie z. B.RG 3 is hydrogen or (C 1 -C 6 ) - alkyl. Sil) Active ingredients of the type of oxyimino compounds (Sil), which are known as seed dressings, such as. B.
"Oxabetrinil" ((Z)-l,3-Dioxolan-2-ylmethoxyimino(phenyl)acetonitril) (Sll-1), das als Saatbeiz- Safener für Hirse gegen Schäden von Metolachlor bekannt ist, "Fluxofenim" (l-(4-Chlorphenyl)-2,2,2-trifluor-l-ethanon-0-(l,3-dioxolan-2-ylmethyl)-oxim) (Sll-2), das als Saatbeiz-Safener für Hirse gegen Schäden von Metolachlor bekannt ist, und"Oxabetrinil" ((Z) -l, 3-Dioxolan-2-ylmethoxyimino (phenyl) acetonitril) (Sll-1), which is known as a seed dressing safener for millet against damage from metolachlor, "Fluxofenim" (l- (4 -Chlorophenyl) -2,2,2-trifluoro-l-ethanon-0- (l, 3-dioxolan-2-ylmethyl) oxime) (Sll-2), which is known as a seed dressing safener for millet against damage from metolachlor is and
"Cyometrinil" oder "CGA-43089" ((Z)-Cyanomethoxyimino(phenyl)acetonitril) (Sll-3), das als Saatbeiz-Safener für Hirse gegen Schäden von Metolachlor bekannt ist. "Cyometrinil" or "CGA-43089" ((Z) -Cyanomethoxyimino (phenyl) acetonitrile) (Sll-3), which is known as a seed dressing safener for millet against damage from metolachlor.
S12) Wirkstoffe aus der Klasse der Isothiochromanone (S12), wie z.B. Methyl- [(3 -oxo-lH-2- benzothiopyran-4(3H)-yliden)methoxy]acetat (CAS-Reg.Nr. 205121-04-6) (S12-1) und verwandte Verbindungen aus WO-A-1998/13361. S12) Active ingredients from the class of isothiochromanones (S12), such as methyl [(3 -oxo-lH-2-benzothiopyran-4 (3H) -ylidene) methoxy] acetate (CAS reg. No. 205121-04-6 ) (S12-1) and related compounds from WO-A-1998/13361.
S13) Eine oder mehrere Verbindungen aus Gruppe (S13): S13) One or more compounds from group (S13):
"Naphthalic anhydrid" ( 1 ,8-Naphthalindicarbonsäureanhydrid) (S13-1), das als Saatbeiz-Safener für Mais gegen Schäden von Thiocarbamatherbiziden bekannt ist, "Fenclorim" (4,6-Dichlor-2-phenylpyrimidin) (S13-2), das als Safener für Pretilachlor in gesätem Reis bekannt ist, "Naphthalic anhydride" (1,8-naphthalenedicarboxylic acid anhydride) (S13-1), which is known as a seed dressing safener for maize against damage from thiocarbamate herbicides, "Fenclorim" (4,6-dichloro-2-phenylpyrimidine) (S13-2) known as a safener for pretilachlor in sown rice,
"Flurazole" (Benzyl-2-chlor-4-trifluormethyl-l,3-thiazol-5-carboxylat) (S13-3), das als Saatbeiz- Safener für Hirse gegen Schäden von Alachlor und Metolachlor bekannt ist, "Flurazole" (benzyl-2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (S13-3), which is known as a seed dressing safener for millet against damage from alachlor and metolachlor,
"CL 304415" (CAS-Reg.Nr. 31541-57-8) (4-Carboxy-3 ,4-dihy dro-2H- 1 -benzopyran-4-essigsäure) (S13-4) der Firma American Cyanamid, das als Safener für Mais gegen Schäden von Imidazolinonen bekannt ist, "CL 304415" (CAS Reg. No. 31541-57-8) (4-carboxy-3, 4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4) from American Cyanamid, the is known as a safener for maize against damage by imidazolinones,
"MG 191" (CAS-Reg.Nr. 96420-72-3) (2-Dichlormethyl-2-methyl- 1 ,3 -dioxolan) (S13-5) der Firma Nitrokemia, das als Safener für Mais bekannt ist, "MG 191" (CAS-Reg.Nr. 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia, which is known as a safener for maize,
"MG 838" (CAS-Reg.Nr. 133993-74-5) (2-propenyl l-oxa-4-azaspiro[4.5]decan-4-carbodithioat) (S13-6) der Firma Nitrokemia,"MG 838" (CAS Reg. No. 133993-74-5) (2-propenyl l-oxa-4-azaspiro [4.5] decane-4-carbodithioate) (S13-6) from Nitrokemia,
"Disulfoton" (0,0-Diethyl S-2-ethylthioethyl phosphordithioat) (S13-7), "Disulfoton" (0,0-diethyl S-2-ethylthioethyl phosphorodithioate) (S13-7),
"Dietholate" (0,0-Diethyl-O-phenylphosphorothioat) (S13-8), "Dietholate" (0,0-diethyl-O-phenylphosphorothioate) (S13-8),
"Mephenate" (4-Chlorphenyl-methylcarbamat) (S13-9). S14) Wirkstoffe, die neben einer herbiziden Wirkung gegen Schadpflanzen auch Safenerwirkung an Kulturpflanzen wie Reis aufweisen, wie z. B."Mephenate" (4-chlorophenyl methyl carbamate) (S13-9). S14) Active ingredients which, in addition to a herbicidal effect against harmful plants, also have a safener effect on crop plants such as rice, such as. B.
"Dimepiperate" oder "MY 93" (S- 1 -Methyl- 1 -phenyl ethyl -piperidin- 1 -carbothioat), das als Safener für Reis gegen Schäden des Herbizids Molinate bekannt ist, "Daimuron" oder "SK 23" (1 -(1 -Methyl- 1 -phenylethyl)-3 -p-tolyl-hamstoff), das als Safener für Reis gegen Schäden des Herbizids Imazosulfuron bekannt ist, "Dimepiperate" or "MY 93" (S-1 -methyl-1-phenyl ethyl -piperidine-1-carbothioate), which is known as a safener for rice against damage by the herbicide Molinate, "Daimuron" or "SK 23" (1 - (1 -Methyl- 1 -phenylethyl) -3 -p-tolyl-urea), which is known as a safener for rice against damage by the herbicide imazosulfuron,
"Cumyluron" = "JC 940" (3-(2-Chlorphenylmethyl)-l-(l-methyl-l-phenyl-ethyl)hamstoff, siehe JP- A-60087254), das als Safener für Reis gegen Schäden einiger Herbizide bekannt ist, "Cumyluron" = "JC 940" (3- (2-chlorophenylmethyl) -l- (l-methyl-l-phenyl-ethyl) urea, see JP-A-60087254), which is known as a safener for rice against damage of some herbicides is,
" Methoxyphenon" oder "NK 049" (3 ,3 '-DimethyM-methoxy-benzophenon), das als Safener für Reis gegen Schäden einiger Herbizide bekannt ist, "Methoxyphenon" or "NK 049" (3, 3 '-DimethyM-methoxy-benzophenone), which is known as a safener for rice against the damage of some herbicides,
"CSB" (l-Brom-4-(chlormethylsulfonyl)benzol) von Kumiai, (CAS-Reg.Nr. 54091-06-4), das als Safener gegen Schäden einiger Herbizide in Reis bekannt ist. "CSB" (1-bromo-4- (chloromethylsulfonyl) benzene) from Kumiai, (CAS Reg. No. 54091-06-4), which is known as a safener against damage from some herbicides in rice.
S15) Verbindungen der Formel (S15) oder deren Tautomere
Figure imgf000037_0001
wie sie in der WO-A-2008/131861 und WO-A-2008/131860 beschrieben sind, worin S15) Compounds of the formula (S15) or their tautomers
Figure imgf000037_0001
as described in WO-A-2008/131861 and WO-A-2008/131860, wherein
RH1 einen Halogen-(C1-C6)-alkylrest bedeutet und RH 1 denotes a halogen (C 1 -C 6 ) alkyl radical and
RH2 Wasserstoff oder Halogen bedeutet und RH 2 is hydrogen or halogen and
RH3, RH4 unabhängig voneinander Wasserstoff, (Ci-Ci6)-Alkyl, (C2-Cie)-Alkenyl oder (Ca-Cie)- Alkinyl, wobei jeder der letztgenannten 3 Reste unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, Hydroxy, Cyano, (C1-C4)-Alkoxy, halogen-(C1-C4)-alkoxy, (C1-C4)-Alkylthio,(C1-C4)- Alkylamino, Di[(C1-C4)-alkyl]-amino, [(C 1-C4)- Alkoxy ] -carbonyl, [Halogen-(C1-C4)- alkoxy ] -carbonyl, (C3-C6)-Cycloalkyl, das unsubstituiert oder substituiert ist, Phenyl, das unsubstituiert oder substituiert ist, und Heterocyclyl, das unsubstituiert oder substituiert ist, substituiert ist, oder (C3-C6)-Cycloalkyl, (C4-C6)-Cycloalkenyl, (C3-C6)-Cycloalkyl, das an einer Seite des Rings mit einem 4 bis 6-gliedrigen gesättigten oder ungesättigten caibocyclischen Ring kondensiert ist, oder (C4-C6)-Cycloalkenyl, das an einer Seite des Rings mit einem 4 bis 6-gliedrigen gesättigten oder ungesättigten caibocyclischen Ring kondensiert ist, wobei jeder der letztgenannten 4 Reste unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, Hydroxy, Cyano, (C1-C4)- Alkyl, Halogen-(C1-C4)-alkyl, (C1-CA4l)k-oxy, Halogen-(C1-C4)- alkoxy, (C1-C4)-Alkylthio, (C1-C4)A-lkylamino, Di[(C1-C4)-alkyl]-amino, [(C1-C4)-Alkoxy]- caibonyl, [Halogen-(Ci-C4)-alkoxy]-carbonyl, (C3-C6)-Cycloalkyl, das unsubstituiert oder substituiert ist, Phenyl, das unsubstituiert oder substituiert ist, und Heterocyclyl, das unsubstituiert oder substituiert ist, substituiert ist, bedeutet oder RH 3 , RH 4 independently of one another are hydrogen, (Ci-Ci6) -alkyl, (C2-Cie) -alkenyl or (Ca-Cie) -alkynyl, each of the last-mentioned 3 radicals being unsubstituted or by one or more radicals from the group consisting of halogen , Hydroxy, cyano, (C 1 -C 4 ) -alkoxy, halogen- (C 1 -C 4 ) -alkoxy, (C 1 -C 4 ) -alkylthio, (C 1 -C 4 ) -alkylamino, di [( C 1 -C 4 alkyl] amino, [(C 1 -C 4) alkoxy] carbonyl, [halo (C 1 -C 4 ) alkoxy] carbonyl, (C 3 -C 6 ) cycloalkyl that is unsubstituted or substituted, phenyl that is unsubstituted or substituted, and heterocyclyl that is unsubstituted or substituted, is substituted, or (C 3 -C 6 ) -cycloalkyl, (C4-C6) -cycloalkenyl, (C 3 -C 6 ) -cycloalkyl, which is condensed on one side of the ring with a 4 to 6-membered saturated or unsaturated caibocyclic ring, or (C4-C6) -cycloalkenyl, which is condensed on one side of the ring with a 4 to 6-membered saturated or unsaturated caibocyclic ring, each of the last-mentioned 4 radicals being unsubstituted or by one or more radicals from the group consisting of halogen, hydroxy, Cyano, (C 1 -C 4 ) alkyl, halo (C 1 -C 4 ) alkyl, (C 1 CA 4 l) k-oxy, halo (C 1 -C 4 ) alkoxy, (C 1 -C 4 ) alkylthio, (C 1 -C 4 ) A -alkylamino, di [(C 1 -C 4 ) alkyl] amino, [(C 1 -C 4 ) alkoxy] caibonyl, [halogen - (Ci-C4) -alkoxy] -carbonyl, (C 3 -C 6 ) -cycloalkyl, which is unsubstituted or substituted, phenyl, which is unsubstituted or substituted, and heterocyclyl, which is unsubstituted or substituted, is substituted, or
RH3 (C1-C4)- Alkoxy, (C2-C4)-Alkenyloxy, (C2-C6)-Alkinyloxy oder Halogen-(C2-C4)-alkoxy bedeutet und RH 3 is (C 1 -C 4 ) -alkoxy, (C2-C4) -alkenyloxy, (C 2 -C 6 ) -alkinyloxy or halogen- (C2-C4) -alkoxy and
RH4 Wasserstoff oder (C1-C4)- Alkyl bedeutet oder RH 4 denotes hydrogen or (C 1 -C 4 ) -alkyl or
RH3 und RH4 zusammen mit dem direkt gebundenen N-Atom einen vier- bis achtgliedrigen heterocyclischen Ring, der neben dem N-Atom auch weitere Heteroringatome, vorzugsweise bis zu zwei weitere Heteroringatome aus der Gruppe N, O und S enthalten kann und der unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, Cyano, Nitro, (C1-C4)- Alkyl, Halogen-(C1-C4)- alkyl, (C1-C4)- Alkoxy, Halogen-(C1-C4)-alkoxy und (C1-C4)-Alkylthio substituiert ist, bedeutet. RH 3 and RH 4 together with the directly bonded N atom form a four- to eight-membered heterocyclic ring which, in addition to the N atom, can also contain further hetero-ring atoms, preferably up to two further hetero-ring atoms from the group N, O and S and which is unsubstituted or by one or more radicals from the group consisting of halogen, cyano, nitro, (C 1 -C 4 ) alkyl, halogen (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, halogen ( C 1 -C 4 ) -alkoxy and (C 1 -C 4 ) -alkylthio is substituted.
S16) Wirkstoffe, die vorrangig als Herbizide eingesetzt werden, jedoch auch Safenerwirkung auf Kulturpflanzen aufweisen, z.B. S16) Active ingredients that are primarily used as herbicides, but also have a safener effect on crops, e.g.
(2,4-Dichlorphenoxy)essigsäure (2,4-D),(2,4-dichlorophenoxy) acetic acid (2,4-D),
(4-Chlorphenoxy)essigsäure, (R,S)-2-(4-Chlor-o-tolyloxy)propionsäure (Mecoprop), 4-(2,4-Dichlorphenoxy)buttersäure (2,4-DB), (4-Chlor-o-tolyloxy)essigsäure (MCPA), 4-(4-Chlor-o-tolyloxy)buttersäure, 4-(4-Chlorphenoxy)buttersäure, 3,6-Dichlor-2-methoxybenzoesäure (Dicamba), 1 -(Ethoxycarbonyl)ethyl-3 ,6-dichlor-2-methoxybenzoat (Lactidichlor-ethyl). (4-chlorophenoxy) acetic acid, (R, S) -2- (4-chloro-o-tolyloxy) propionic acid (mecoprop), 4- (2,4-dichlorophenoxy) butyric acid (2,4-DB), (4- Chloro-o-tolyloxy) acetic acid (MCPA), 4- (4-chloro-o-tolyloxy) butyric acid, 4- (4-chlorophenoxy) butyric acid, 3,6-dichloro-2-methoxybenzoic acid (Dicamba), 1 - (ethoxycarbonyl) ethyl 3, 6-dichloro-2-methoxybenzoate (lactidichloro-ethyl).
Besonders bevorzugte Safener sind Mefenpyr-diethyl, Cyprosulfamid, Isoxadifen-ethyl, Cloquintocet-mexyl, Dichlormid und Metcamifen. Spritzpulver sind in Wasser gleichmäßig dispergierbare Präparate, die neben dem Wirkstoff außer einem Verdünnungs- oder Inertstoff noch Tenside ionischer und/oder nichtionischer Art (Netzmittel, Dispergiermittel), z.B. polyoxyethylierte Alkylphenole, polyoxethylierte Fettalkohole, polyoxethylierte Fettamine, Fettalkoholpolyglykolether-sulfate, Alkansulfonate,Particularly preferred safeners are Mefenpyr-diethyl, Cyprosulfamid, Isoxadifen-ethyl, Cloquintocet-Mexyl, Dichlormid and Metcamifen. Wettable powders are preparations that are uniformly dispersible in water, which in addition to the active ingredient, in addition to a diluent or inert substance, also ionic and / or nonionic surfactants (wetting agents, dispersants), e.g. polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkane sulfonates,
Alkylbenzolsulfonate, ligninsulfonsaures Natrium, 2,2'-dinaphthylmethan-6,6'-disulfonsaures Natrium, dibutylnaphthalin-sulfonsaures Natrium oder auch oleoylmethyltaurinsaures Natrium enthalten. Zur Herstellung der Spritzpulver werden die herbiziden Wirkstoffe beispielsweise in üblichen Apparaturen wie Hammermühlen, Gebläsemühlen und Luftstrahlmühlen feingemahlen und gleichzeitig oder anschließend mit den Formulierungshilfsmitteln vermischt. Alkylbenzenesulfonates, sodium lignosulfonic acid, sodium 2,2'-dinaphthylmethane-6,6'-disulfonic acid, sodium dibutylnaphthalene-sulfonic acid or sodium oleoylmethyltaurinate. To produce the wettable powders, the herbicidally active ingredients are finely ground, for example, in customary apparatus such as hammer mills, blower mills and air jet mills and simultaneously or subsequently mixed with the formulation auxiliaries.
Emulgierbare Konzentrate werden durch Auflösen des Wirkstoffes in einem organischen Lösungsmittel z.B. Butanol, Cyclohexanon, Dimethylformamid, Xylol oder auch höhersiedenden Aromaten oder Kohlenwasserstoffen oder Mischungen der organischen Lösungsmittel unter Zusatz von einem oder mehreren Tensiden ionischer und/oder nichtionischer Art (Emulgatoren) hergestellt. Als Emulgatoren können beispielsweise verwendet werden: Alkylarylsulfonsaure Calzium-Salze wie Ca-Dodecylbenzolsulfonat oder nichtionische Emulgatoren wie Fettsäurepoly-glykolester, Alkylarylpolyglykolether, Fettalkoholpolyglykolether, Propylenoxid-Ethylen- oxid-Kondensationsprodukte, Alkylpolyether, Sorbitanester wie z.B. Sorbitanfett-säureester oder Polyoxethylensorbitanester wie z.B. Polyoxyethylensorbitan-fettsäureester. Emulsifiable concentrates are produced by dissolving the active ingredient in an organic solvent, e.g. butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of an ionic and / or nonionic type (emulsifiers). Examples of emulsifiers that can be used are: alkylarylsulphonic acid calcium salts such as calcium dodecylbenzenesulphonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers such as sorbitan oxyethane fatty esters, eg sorbitan oxyethyl fatty esters, sorbitan oxyethyl esters such as sorbitan oxyethyl fatty esters, eg sorbitan oxyethyl fatty esters, sorbitan oxyethylene fatty esters, sorbitan oxyethylene fatty esters, sorbitan oxyethyl esters such as sorbitan oxyethyl fatty esters, sorbitan oxyethyl esters, sorbitan oxyethyl esters such as calcium dodecylbenzenesulfonate .
Stäubemittel erhält man durch Vermahlen des Wirkstoffes mit fein verteilten festen Stoffen, z.B. Talkum, natürlichen Tonen, wie Kaolin, Bentonit und Ityrophyllit, oder Diatomeenerde. Suspensionskonzentrate können auf Wasser- oder Ölbasis sein. Sie können beispielsweise durch Naß-Vermahlung mittels handelsüblicher Perlmühlen und gegebenenfalls Zusatz von Tensiden, wie sie z.B. oben bei den anderen Formulierungstypen bereits aufgeführt sind, hergestellt werden. Dusting agents are obtained by grinding the active ingredient with finely divided solid substances, e.g. talc, natural clays such as kaolin, bentonite and ityrophyllite, or diatomaceous earth. Suspension concentrates can be water or oil based. They can be produced, for example, by wet grinding using commercially available bead mills and, if necessary, the addition of surfactants, such as those already listed above for the other types of formulation.
Emulsionen, z.B. Öl-in-Wasser-Emulsionen (EW), lassen sich beispielsweise mittels Rührern, Kolloidmühlen und/oder statischen Mischern unter Verwendung von wäßrigen organischen Lösungsmitteln und gegebenenfalls Tensiden, wie sie z.B. oben bei den anderen Formulierungstypen bereits aufgeführt sind, herstellen. Granulate können entweder durch Verdüsen des Wirkstoffes auf adsorptionsfähiges, granuliertes Inertmalerial hergestellt werden oder durch Aufbringen von Wirkstoffkonzentraten mittels Klebemitteln, z.B. Polyvinylalkohol, polyaciylsaurem Natrium oder auch Mineralölen, auf die Oberfläche von Trägerstoffen wie Sand, Kaolinite oder von granuliertem Inertmaterial. Auch können geeignete Wirkstoffe in der für die Herstellung von Düngemittelgranulaten üblichen Weise - gewünschtenfalls in Mischung mit Düngemitteln - granuliert werden. Emulsions, for example oil-in-water emulsions (EW), can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as those already listed above for the other types of formulation. Granules can be produced either by spraying the active ingredient onto adsorptive, granulated inert material or by applying active ingredient concentrates using adhesives, e.g. polyvinyl alcohol, sodium polyacylate or mineral oils, to the surface of carrier materials such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules - if desired as a mixture with fertilizers.
Wasserdispergierbare Granulate werden in der Regel nach den üblichen Verfahren wieWater-dispersible granules are usually by the usual methods such as
Sprühtrocknung, Wirbelbett-Granulierung, Teller-Granulierung, Mischung mitSpray drying, fluidized bed granulation, plate granulation, mixing with
Hochgeschwindigkeitsmischem und Extrusion ohne festes Inertmaterial hergestellt. High speed mixing and extrusion made without solid inert material.
Zur Herstellung von Teller-, Fließbett-, Extruder- und Sprühgranulate siehe z.B. Verfahren in "Spray-Diying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London, J.E. Browning, "Agglomeration", Chemical and Engineering 1967, Seiten 147 ff, "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, S. 8-57. For the production of plate, fluidized bed, extruder and spray granules, see, for example, the method in "Spray-Diying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London, J.E. Browning, "Agglomeration", Chemical and Engineering 1967, pp. 147 ff, "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.
Für weitere Einzelheiten zur Formulierung von Pflanzenschutzmitteln siehe z.B. G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, Seiten 81-96 und J.D. Frey er, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, Seiten 101-103. For further details on the formulation of plant protection products see e.g. G.C. Klingman, "Weed Control as a Science," John Wiley and Sons, Inc., New York, 1961, pp. 81-96 and J.D. Frey er, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.
Die agrochemischen Zubereitungen enthalten in der Regel 0.1 bis 99 Gew.-%, insbesondere 0.1 bis 95 Gew.-%, erfindungsgemäße Verbindungen. In Spritzpulvem beträgt die Wirkstoff-konzentrationThe agrochemical preparations generally contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of compounds according to the invention. The active ingredient concentration in wettable powder is
Z.B. etwa 10 bis 90 Gew.-%, der Rest zu 100 Gew.-% besteht aus üblichen Formulierungsbestandteilen. Bei emulgierbaren Konzentraten kann die Wirkstoffkonzentration etwa 1 bis 90, vorzugsweise 5 bis 80 Gew.-% betragen. Staubförmige Formulierungen enthalten 1 bis 30 Gew.-% Wirkstoff, vorzugsweise meistens 5 bis 20 Gew.-% an Wirkstoff, versprühbare Lösungen enthalten etwa 0.05 bis 80, vorzugsweise 2 bis 50 Gew.-% Wirkstoff. Bei wasser-dispergierbaren Granulaten hängt der Wirkstoffgehalt zum Teil davon ab, ob die wirksame Verbindung flüssig oder fest vorliegt und welche Granulierhilfsmittel, Füllstoffe usw. verwendet werden. Bei den in Wasser dispergierbaren Granulaten liegt der Gehalt an Wirkstoff beispielsweise zwischen 1 und 95 Gew.-%, vorzugsweise zwischen 10 und 80 Gew.-%. Daneben enthalten die genannten Wirkstofformulierungen gegebenenfalls die j eweils üblichen Haft-,For example about 10 to 90% by weight, the remainder to 100% by weight consists of conventional formulation components. In the case of emulsifiable concentrates, the active ingredient concentration can be about 1 to 90, preferably 5 to 80% by weight. Dust-like formulations contain 1 to 30% by weight of active ingredient, preferably mostly 5 to 20% by weight of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50% by weight of active ingredient. In the case of water-dispersible granules, the active ingredient content depends in part on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used. In the case of the water-dispersible granules, the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight. In addition, the active ingredient formulations mentioned contain, where appropriate, the usual adhesive,
Netz-, Dispergier-, Emulgier-, Penetrations-, Konservierungs-, Frostschutz- und Lösungsmittel, Füll-, Träger- und Farbstoffe, Entschäumer, Verdunstungshemmer und den pH-Wert und die Viskosität beeinflussende Mittel. Auf der Basis dieser Formulierungen lassen sich auch Kombinationen mit anderen pestizid wirksamen Stoffen, wie z.B. Insektiziden, Akariziden, Herbiziden, Fungiziden, sowie mit Safenern, Düngemitteln und/oder Wachstumsregulatoren herstellen, z.B. in Form einer Fertigformulierung oder als Tankmix. Zur Anwendung werden die in handelsüblicher Form vorliegenden Formulierungen gegebenenfalls in üblicher Weise verdünnt z.B. bei Spritzpulvem, emulgierbaren Konzentraten, Dispersionen und wasserdispergierbaren Granulaten mittels Wasser. Staubförmige Zubereitungen, Boden- bzw. Streugranulate sowie versprühbare Lösungen werden vor der Anwendung üblicherweise nicht mehr mit weiteren inerten Stoffen verdünnt. Mit den äußeren Bedingungen wie Temperatur, Feuchtigkeit, der Art des verwendeten Herbizids, u.a. variiert die erforderliche Aufwandmenge der Verbindungen der Formel (I) und deren Salze. Sie kann innerhalb weiter Grenzen schwanken, z.B. zwischen 0,001 und 10,0 kg/ha oder mehr Aktivsubstanz, vorzugsweise liegt sie jedoch zwischen 0,005 bis 5 kg/ha, weiter bevorzugt im Bereich von 0,01 bis 1,5 kg/ha, insbesondere bevorzugt im Bereich von 0,05 bis 1 kg/ha g/ha. Dies gilt sowohl für die Anwendung im Vorauflauf oder im Nachauflauf. Wetting agents, dispersing agents, emulsifying agents, penetration agents, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and agents that influence pH and viscosity. On the basis of these formulations, combinations with other pesticidally active substances, such as insecticides, acaricides, herbicides, fungicides, and with safeners, fertilizers and / or growth regulators, for example in the form of a finished formulation or as a tank mix, can also be produced. For use, the formulations present in commercially available form are, if appropriate, diluted in the customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules using water. Preparations in the form of dust, soil granules or granules as well as sprayable solutions are usually no longer diluted with other inert substances before use. The required application rate of the compounds of the formula (I) and their salts varies with the external conditions such as temperature, humidity and the type of herbicide used. It can fluctuate within wide limits, for example between 0.001 and 10.0 kg / ha or more of active substance, but is preferably between 0.005 and 5 kg / ha, more preferably in the range from 0.01 to 1.5 kg / ha, in particular preferably in the range from 0.05 to 1 kg / ha g / ha. This applies to both pre-emergence and post-emergence use.
Trägerstoflf bedeutet eine natürliche oder synthetische, organische oder anorganische Substanz, mit welchen die Wirkstoffe zur besseren Anwendbarkeit, v.a. zum Aufbringen auf Pflanzen oder Pflanzenteile oder Saatgut, gemischt oder verbunden sind. Der Trägerstoflf, welcher fest oder flüssig sein kann, ist im Allgemeinen inert und sollte in der Landwirtschaft verwendbar sein. Als feste oder flüssige Trägerstoffe kommen infrage: z.B. Ammoniumsalze und natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und natürliche oder synthetische Silikate, Harze, Wachse, feste Düngemittel, Wasser, Alkohole, besonders Butanol, organische Solventien, Mineral- und Pflanzenöle sowie Derivate hiervon. Mischungen solcher Trägerstoflfe können ebenfalls verwendet werden. Als feste Trägerstoflfe für Granulate kommen infrage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnussschalen, Maiskolben und Tabakstängel. Als verflüssigte gasförmige Streckmittel oder Trägerstoflfe kommen solche Flüssigkeiten infrage, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z.B. Aerosol-Treibgase, wie Halogenkohlenwasserstoffe, sowie Butan, Propan, Stickstoff und Kohlendioxid. Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulverige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabikum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine, und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein. Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im Wesentlichen infrage: Aromaten, wie Xylol, Toluol oder Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Dichlormethan, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, mineralische und pflanzliche Öle, Alkohole, wie Butanol oder Glykol sowie deren Ether und Ester, Ketone, wie Aceton, Methyl- ethylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser. Carrier material means a natural or synthetic, organic or inorganic substance with which the active ingredients are mixed or combined for better applicability, especially for application to plants or parts of plants or seeds. The carrier, which can be solid or liquid, is generally inert and should be agriculturally useful. Suitable solid or liquid carriers are: for example ammonium salts and natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals such as highly disperse silica, aluminum oxide and natural or synthetic silicates, resins, waxes, solid Fertilizers, water, alcohols, especially butanol, organic solvents, mineral and vegetable oils and derivatives thereof. Mixtures of such carriers can also be used. Solid carriers for granules are: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours and granules made from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. Liquefied gaseous extenders or carriers are liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. Adhesives such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and also natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Further additives can be mineral and vegetable oils. If water is used as an extender, it is also possible, for example, to use organic solvents as auxiliary solvents. The following liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylene or dichloromethane, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, mineral and vegetable oils, alcohols such as Butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
Die erfindungsgemäßen Mittel können zusätzlich weitere Bestandteile enthalten, wie z.B. oberflächenaktive Stoffe. Als oberflächenaktive Stoffe kommen Emulgier- und/oder Schaum erzeugende Mittel, Dispergiermittel oder Benetzungsmittel mit ionischen oder nicht-ionischen Eigenschaften oder Mischungen dieser oberflächenaktiven Stoffe infrage. Beispiele hierfür sind Salze von Polyacrylsäure, Salze von Lignosulphonsäure, Salze von Phenolsulphonsäure oder Naphthalinsulphonsäure, Polykondensate von Ethylenoxid mit Fettalkoholen oder mit Fettsäuren oder mit Fettaminen, substituierten Phenolen (vorzugsweise Alkylphenole oder Arylphenole), Salze von Sulphobemsteinsäureestem, Taurinderivate (vorzugsweise Alkyltaurate), Phosphorsäureester von polyethoxylierten Alkoholen oder Phenole, Fettsäureester von Polyolen, und Derivate der Verbindungen enthaltend Sulphate, Sulphonate und Phosphate, z.B. Alkylarylpolyglycolether, Alkylsulfonate, Alkylsulfate, Arylsulfonate, Eiweißhydrolysate, Lignin-Sulfitablaugen und Methylcellulose. Die Anwesenheit einer oberflächenaktiven Substanz ist notwendig, wenn einer der Wirkstoff und/oder einer der inerten Trägerstoffe nicht in Wasser löslich ist und wenn die Anwendung in Wasser erfolgt. Der Anteil an oberflächenaktiven Stoffen liegt zwischen 5 und 40 Gewichtsprozent des erfindungsgemäßen Mittels. Es können Farbstoffe wie anorganische Pigmente, Z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metall- phthalocyaninfarbstoffe und Spurennährstoffe, wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden. The agents according to the invention can additionally contain further components, such as, for example, surface-active substances. Suitable surface-active substances are emulsifiers and / or foam-generating agents, dispersants or wetting agents with ionic or non-ionic properties or mixtures of these surface-active substances. Examples of these are salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (preferably alkylphenols or arylphenols), salts of sulfosulfinic acid esters (preferably alkylphenols, tauric acid esters) polyethoxylated alcohols or phenols, fatty acid esters of polyols, and derivatives of the compounds containing sulphates, sulphonates and phosphates, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, protein hydrolysates, lignin sulphite waste liquors and methyl cellulose. The presence of a surface-active substance is necessary if one of the active substances and / or one of the inert carriers is not soluble in water and if the application takes place in water. The proportion of surface-active substances is between 5 and 40 percent by weight of the agent according to the invention. Dyes such as inorganic pigments, e.g. iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
Gegebenenfalls können auch andere zusätzliche Komponenten enthalten sein, z.B. schützende Kolloide, Bindemittel, Klebstoffe, Verdicker, thixotrope Stoffe, Penetrationsförderer, Stabilisatoren, Sequestiermittel, Komplexbildner. Im Allgemeinen können die Wirkstoffe mit jedem festen oder flüssigen Additiv, welches für Formulierungszwecke gewöhnlich verwendet wird, kombiniert werden. Im Allgemeinen enthalten die erfindungsgemäßen Mittel und Formulierungen zwischen 0,05 und 99 Gew.-%, 0,01 und 98 Gew.-%, vorzugsweise zwischen 0,1 und 95 Gew.-%, besonders bevorzugt zwischen 0,5 und 90 % Wirkstoff, ganz besonders bevorzugt zwischen 10 und 70 Gewichtsprozent. Die erfindungsgemäßen Wirkstoffe bzw. Mittel können als solche oder in Abhängigkeit von ihren j eweiligen physikalischen und/oder chemischen Eigenschaften in Form ihrer Formulierungen oder den daraus bereiteten Anwendungsformen, wie Aerosole, Kipseisuspensionen, Kaltnebelkonzentrate, Heißnebelkonzentrate, verkapselte Granulate, Feingranulate, fließfähige Konzentrate für die Behandlung von Saatgut, gebrauchsfertige Lösungen, verstäubbare Pulver, emulgierbare Konzentrate, Öl-in-Wasser-Emulsionen, Wasser-in-Öl-Emulsionen, Makrogranulate, Mikrogra- nulate, Öl dispergieibare Pulver, Öl mischbare fließfähige Konzentrate, Öl mischbare Flüssigkeiten, Schäume, Pasten, Pestizid ummanteltes Saatgut, Suspensionskonzentrate, Suspensions-Emulsions- Konzentrate, lösliche Konzentrate, Suspensionen, Spritzpulver, lösliche Pulver, Stäubemittel und Granulate, wasserlösliche Granulate oder Tabletten, wasserlösliche Pulver für Saatgut-behandlung, benetzbare Pulver, Wirkstoff-imprägnierte Natur- und synthetische Stoffe sowie Feinstverkapse- hingen in polymeren Stoffen und in Hüllmassen für Saatgut, sowie ULV-Kalt- und Warmnebel- Formulierungen eingesetzt werden. If necessary, other additional components can also be included, for example protective colloids, binders, adhesives, thickeners, thixotropic substances, penetration promoters, stabilizers, sequestering agents, complexing agents. In general, the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes will. In general, the agents and formulations according to the invention contain between 0.05 and 99% by weight, 0.01 and 98% by weight, preferably between 0.1 and 95% by weight, particularly preferably between 0.5 and 90% Active ingredient, very particularly preferably between 10 and 70 percent by weight. The active ingredients or agents according to the invention can be used as such or depending on their respective physical and / or chemical properties in the form of their formulations or the use forms prepared therefrom, such as aerosols, Kipseisuspensions, cold mist concentrates, hot mist concentrates, encapsulated granules, fine granules, flowable concentrates for the Treatment of seeds, ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, macrogranulates, microgranulates, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, foams, Pastes, pesticide-coated seeds, suspension concentrates, suspension-emulsion concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, dusts and granulates, water-soluble granulates or tablets, water-soluble powders for seed treatment, wettable powders, active ingredient-impregnated natural and synthetic ical substances as well as finest encapsulation can be used in polymeric substances and in coating compounds for seeds, as well as ULV cold and warm mist formulations.
Die genannten Formulierungen können in an sich bekannter Weise hergestellt werden, z.B. durch Vermischen der Wirkstoffe mit mindestens einem üblichen Streckmittel, Lösungs- bzw. Verdünnungsmittel, Emulgator, Dispergier- und/oder Binde- oder Fixiermittels, Netzmittel, Wasser- Repellent, gegebenenfalls Sikkative und UV-Stabilisatoren und gegebenenfalls Farbstoffen und Pigmenten, Entschäumer, Konservierungsmittel, sekundäre Verdickungsmittel, Kleber, Gibberelline sowie weiteren Verarbeitungshilfsmitteln. The formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one customary extender, solvent or diluent, emulsifier, dispersant and / or binding or fixing agent, wetting agent, water repellant, optionally siccatives and UV stabilizers and optionally dyes and pigments, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and other processing aids.
Die erfindungsgemäßen Mittel umfassen nicht nur Formulierungen, welche bereits anwendungsfertig sind und mit einer geeigneten Apparatur auf die Pflanze oder das Saatgut ausgebracht werden können, sondern auch kommerzielle Konzentrate, welche vor Gebrauch mit Wasser verdünnt werden müssen. The agents according to the invention not only include formulations which are already ready to use and can be applied to the plant or seed with a suitable apparatus, but also commercial concentrates which have to be diluted with water before use.
Die erfindungsgemäßen Wirkstoffe können als solche oder in ihren (handelsüblichen) Formulierungen sowie in den aus diesen Formulierungen bereiteten Anwendungsformen in Mischung mit anderen (bekannten) Wirkstoffen, wie Insektiziden, Lockstoffen, Sterilantien, Bakteriziden, Akariziden, Nematiziden, Fungiziden, Wachstumsregulatoren, Herbiziden, Düngemitteln, Safener bzw. Semiochemicals vorliegen. The active compounds according to the invention can be used as such or in their (commercially available) formulations and in the use forms prepared from these formulations as a mixture with other (known) active compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, fertilizers , Safeners or semiochemicals are present.
Die erfindungsgemäße Behandlung der Pflanzen und Pflanzenteile mit den Wirkstoffen bzw. Mitteln erfolgt direkt oder durch Einwirkung auf deren Umgebung, Lebensraum oder Lagerraum nach den üblichen Behandlungsmethoden, z.B. durch Tauchen, (Ver-)Spritzen, (Ver-)Sprühen, Berieseln, Verdampfen, Zerstäuben, Vernebeln, (Ver-)Streuen, Verschäumen, Bestreichen, Verstreichen, Gießen (drenchen), Tröpfchenbewässerung und bei Vermehrungsmaterial, insbesondere bei Samen, weiterhin durch Trockenbeizen, Nassbeizen, Schlämmbeizen, Inkrustieren, ein- oder mehrschichtiges Umhüllen usw. Es ist ferner möglich, die Wirkstoffe nach dem Ultra-Low- V olume-V erfahren auszubringen oder die Wirkstoffzubereitung oder den Wirkstoff selbst in den Boden zu injizieren. The treatment according to the invention of the plants and plant parts with the active ingredients or agents is carried out directly or by acting on their surroundings, living space or storage room using the customary treatment methods, for example by dipping, spraying, spraying, sprinkling, Evaporation, atomization, misting, (scattering) scattering, foaming, brushing, spreading, watering (drenching), drip irrigation and, in the case of propagation material, especially seeds, by dry dressing, wet dressing, slurry dressing, encrusting, single or multi-layer coating, etc. It it is also possible to apply the active ingredients according to the ultra-low volume method or to inject the active ingredient preparation or the active ingredient itself into the soil.
Wie auch weiter unten beschrieben, ist die Behandlung von transgenem Saatgut mit den erfindungsgemäßen Wirkstoffen bzw. Mitteln von besonderer Bedeutung. Dies betrifft das Saatgut von Pflanzen, die wenigstens ein heterologes Gen enthalten, das die Expression eines Polypeptids oder Proteins mit insektiziden Eigenschaften ermöglicht. Das heterologe Gen in transgenem Saatgut kann Z.B. aus Mikroorganismen der Arten Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, CHomus oder CHiocladium stammen. Bevorzugt stammt dieses heterologe Gen aus Bacillus sp., wobei das Genprodukt eine Wirkung gegen den Maiszünsler (European com borer) und/oder Western Com Rootworm besitzt. Besonders bevorzugt stammt das heterologe Gen aus Bacillus thuringiensis. Im Rahmen der vorliegenden Erfindung wird das erfindungsgemäße Mittel alleine oder in einer geeigneten Formulierung auf das Saatgut aufgebracht. Vorzugsweise wird das Saatgut in einem Zustand behandelt, in dem so stabil ist, dass keine Schäden bei der Behandlung auftreten. Im Allgemeinen kann die Behandlung des Saatguts zu jedem Zeitpunkt zwischen der Ernte und der Aussaat erfolgen. Üblicherweise wird Saatgut verwendet, das von der Pflanze getrennt und von Kolben, Schalen, Stängeln, Hülle, Wolle oder Fruchtfleisch befreit wurde. So kann zum Beispiel Saatgut verwendet werden, das geerntet, gereinigt und bis zu einem Feuchtigkeitsgehalt von unter 15 Gew.-% getrocknet wurde. Alternativ kann auch Saatgut verwendet werden, das nach dem Trocknen z.B. mit Wasser behandelt und dann erneut getrocknet wurde. As also described further below, the treatment of transgenic seeds with the active ingredients or agents according to the invention is of particular importance. This concerns the seeds of plants which contain at least one heterologous gene which enables the expression of a polypeptide or protein with insecticidal properties. The heterologous gene in transgenic seed can originate, for example, from microorganisms of the species Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, CHomus or CHiocladium. This heterologous gene preferably originates from Bacillus sp., The gene product having an effect against the European corn borer and / or Western Com Rootworm. The heterologous gene is particularly preferably derived from Bacillus thuringiensis. In the context of the present invention, the agent according to the invention is applied to the seed alone or in a suitable formulation. The seed is preferably treated in a state in which it is so stable that no damage occurs during the treatment. In general, the seed can be treated at any point between harvest and sowing. Usually seeds are used that have been separated from the plant and freed from cobs, peels, stems, husks, wool or pulp. For example, seeds can be used that have been harvested, cleaned and dried to a moisture content of less than 15% by weight. As an alternative, seeds can also be used which, after drying, have been treated with water, for example, and then dried again.
Im Allgemeinen muss bei der Behandlung des Saatguts darauf geachtet werden, dass die Menge des auf das Saatgut aufgebrachten erfindungsgemäßen Mittels und/oder weiterer Zusatzstoffe so gewählt wird, dass die Keimung des Saatguts nicht beeinträchtigt bzw. die daraus hervorgehende Pflanze nicht geschädigt wird. Dies ist vor allem bei Wirkstoffen zu beachten, die in bestimmten Aufwandmengen phytotoxische Effekte zeigen können. In general, when treating the seed, care must be taken to ensure that the amount of the agent according to the invention and / or further additives applied to the seed is selected so that the germination of the seed is not impaired or the plant resulting therefrom is not damaged. This is especially important for active ingredients that can show phytotoxic effects when applied in certain amounts.
Die erfindungsgemäßen Mittel können unmittelbar aufgebracht werden, also ohne weitere Komponenten zu enthalten und ohne verdünnt worden zu sein. In der Regel ist es vorzuziehen, die Mittel in Form einer geeigneten Formulierung auf das Saatgut aufzubringen. Geeignete Formulierungen und Verfahren für die Saatgutbehandlung sind dem Fachmann bekannt und werden ζ,Β. in den folgenden Dokumenten beschrieben: US 4,272,417 A, US 4,245,432 A, US 4,808,430, US 5,876,739, US 2003/0176428 Al, WO 2002/080675 Al, WO 2002/028186 A2. The agents according to the invention can be applied immediately, that is to say without containing further components and without having been diluted. As a rule, it is preferable to apply the agents to the seed in the form of a suitable formulation. Suitable formulations and methods for seed treatment are and will be known to the person skilled in the art ζ, Β. described in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430, US 5,876,739, US 2003/0176428 A1, WO 2002/080675 A1, WO 2002/028186 A2.
Die erfindungsgemäßen Wirkstoffe können in die üblichen Beizmittel-Formulierungen überführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Schäume, Slurries oder andere Hüllmassen für Saatgut, sowie ULV-Formulierungen. The active compounds according to the invention can be converted into the customary seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other coating compositions for seeds, and also ULV formulations.
Diese Formulierungen werden in bekannter Weise hergestellt, indem man die Wirkstoffe mit üblichen Zusatzstoffen vermischt, wie zum Beispiel übliche Streckmittel sowie Lösungs- oder Verdünnungsmittel, Farbstoffe, Netzmittel, Dispergiermittel, Emulgatoren, Entschäumer, Konservierungsmittel, sekundäre Verdickungsmittel, Kleber, Gibberelline und auch Wasser. Als Farbstoffe, die in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen enthalten sein können, kommen alle für derartige Zwecke üblichen Farbstoffe in Betracht. Dabei sind sowohl in Wasser wenig lösliche Pigmente als auch in Wasser lösliche Farbstoffe verwendbar. Als Beispiele genannt seien die unter den Bezeichnungen Rhodamin B, C.I. Pigment Red 112 und C.I. Solvent Red 1 bekannten Farbstoffe. Als Netzmittel, die in den erfindungsgemäß verwendbaren Beizmittel-Formulienmgen enthalten sein können, kommen alle zur Formulierung von agrochemischen Wirkstoffen üblichen, die Benetzung fördernden Stoffe in Frage. Vorzugsweise verwendbar sind Alkylnaphthalin-Sulfonate, wie Diiso- propyl- oder Diisobutyl-naphthalin-Sulfonate. These formulations are prepared in a known manner by mixing the active ingredients with customary additives, such as customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also water. Suitable dyes which can be contained in the seed dressing formulations which can be used according to the invention are all dyes customary for such purposes. Both pigments which are sparingly soluble in water and dyes which are soluble in water can be used here. Examples are those under the names Rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1 known dyes. Suitable wetting agents which can be contained in the seed dressing formulations which can be used according to the invention are all substances which are customary for the formulation of agrochemical active ingredients and which promote wetting. Alkylnaphthalene sulfonates, such as diisopropyl or diisobutyl naphthalene sulfonates, can preferably be used.
Als Dispergiermittel und/oder Emulgatoren, die in den erfindungsgemäß verwendbaren Beizmittel- Formulierungen enthalten sein können, kommen alle zur Formulierung von agrochemischen Wirkstoffen üblichen nichtionischen, anionischen und kationischen Dispergiermittel in Betracht. Vorzugsweise verwendbar sind nichtionische oder anionische Dispergiermittel oder Gemische von nichtionischen oder anionischen Dispergiermitteln. Als geeignete nichtionische Dispergiermittel sind insbesondere Ethylenoxid-Propylenoxid Blockpolymere, Alkylphenolpolyglykolether sowie Tri- stryrylphenolpolyglykolether und deren phosphatierte oder sulfatierte Derivate zu nennen. Geeignete anionische Dispergiermittel sind insbesondere Ligninsulfonate, Polyacrylsäuresalze und Aryl- sulfonat-Formaldehydkondensate. Suitable dispersants and / or emulsifiers which can be contained in the seed dressing formulations which can be used according to the invention are all nonionic, anionic and cationic dispersants customary for the formulation of agrochemical active ingredients. Nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants can preferably be used. Suitable nonionic dispersants are, in particular, ethylene oxide-propylene oxide block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ethers and their phosphated or sulfated derivatives. Suitable anionic dispersants are, in particular, lignosulfonates, polyacrylic acid salts and arylsulfonate-formaldehyde condensates.
Als Entschäumer können in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen alle zur Formulierung von agrochemischen Wirkstoffen üblichen schaumhemmenden Stoffe enthalten sein. Vorzugsweise verwendbar sind Silikonentschäumer und Magnesiumstearat. Als Konservierungsmittel können in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen alle für derartige Zwecke in agrochemischen Mitteln einsetzbaren Stoffe vorhanden sein. Beispielhaft genannt seien Dichlorophen und Benzylalkoholhemiformal. All foam-inhibiting substances customary for the formulation of agrochemical active ingredients can be contained as defoamers in the seed dressing formulations which can be used according to the invention. Silicone defoamers and magnesium stearate can preferably be used. All substances which can be used in agrochemical agents for such purposes can be present as preservatives in the seed dressing formulations which can be used according to the invention. Examples are dichlorophene and benzyl alcohol hemiformal.
Als sekundäre Verdickungsmittel, die in den erfindungsgemäß verwendbaren Beizmittel-Formu- lierungen enthalten sein können, kommen alle für derartige Zwecke in agrochemischen Mitteln einsetzbaren Stoffe in Frage. Vorzugsweise in Betracht kommen Cellulosederivate, Acrylsäurederivate, Xanthan, modifizierte Tone und hochdisperse Kieselsäure. Secondary thickeners which can be contained in the seed dressing formulations which can be used according to the invention are all substances which can be used in agrochemical compositions for such purposes. Cellulose derivatives, acrylic acid derivatives, xanthan gum, modified clays and highly disperse silicic acid are preferred.
Als Kleber, die in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen enthalten sein können, kommen alle üblichen in Beizmitteln einsetzbaren Bindemittel in Frage. Vorzugsweise genannt seien Polyvinylpyrrolidon, Polyvinylacetat, Polyvinylalkohol und Tylose. As adhesives which can be contained in the seed dressing formulations which can be used according to the invention, all conventional binders which can be used in seed dressings are suitable. Polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose may be mentioned as preferred.
Die erfindungsgemäß verwendbaren Beizmittel-Formulierungen können entweder direkt oder nach vorherigem Verdünnen mit Wasser zur Behandlung von Saatgut der verschiedensten Art, auch von Saatgut transgener Pflanzen, eingesetzt werden. Dabei können im Zusammenwirken mit den durch Expression gebildeten Substanzen auch zusätzliche synergistische Effekte auftreten. Zur Behandlung von Saatgut mit den erfindungsgemäß verwendbaren Beizmittel-Formulierungen oder den daraus durch Zugabe von Wasser hergestellten Zubereitungen kommen alle üblicherweise für die Beizung einsetzbaren Mischgeräte in Betracht. Im einzelnen geht man bei der Beizung so vor, dass man das Saatgut in einen Mischer gibt, die jeweils gewünschte Menge an Beizmittel-Formu- lierungen entweder als solche oder nach vorherigem Verdünnen mit Wasser hinzufügt und bis zur gleichmäßigen Verteilung der Formulierung auf dem Saatgut mischt. Gegebenenfalls schließt sich ein Trocknungsvorgang an. The seed dressing formulations which can be used according to the invention can be used either directly or after prior dilution with water for the treatment of seeds of the most varied of types, including seeds of transgenic plants. In this context, additional synergistic effects can also occur in cooperation with the substances formed by expression. For the treatment of seeds with the seed dressing formulations which can be used according to the invention or the preparations produced therefrom by adding water, all mixing devices which can customarily be used for dressing are suitable. In detail, the procedure for dressing is to put the seed in a mixer, add the desired amount of dressing formulations either as such or after prior dilution with water and mix until the formulation is evenly distributed on the seed . If necessary, this is followed by a drying process.
Die erfindungsgemäßen Wirkstoffe eignen sich bei guter Pflanzenverträglichkeit, günstiger Warmblütertoxizität und guter Umweltverträglichkeit zum Schutz von Pflanzen und Pflanzenorganen, zur Steigerung der Emteerträge, Verbesserung der Qualität des Emtegutes. Sie können vorzugsweise als Pflanzenschutzmittel eingesetzt werden. Sie sind gegen normal sensible und resistente Arten sowie gegen alle oder einzelne Entwicklungsstadien wirksam. The active compounds according to the invention are suitable for protecting plants and plant organs, for increasing crop yields and improving the quality of the crop, given good plant tolerance, favorable warm-blooded toxicity and good environmental compatibility. They can preferably be used as crop protection agents. They are effective against normally sensitive and resistant species and against all or individual stages of development.
Als Pflanzen, welche erfindungsgemäß behandelt werden können, seien folgende Hauptanbaupflanzen erwähnt: Mais, Sojabohne, Baumwolle, Brassica Ölsaaten wie Brassica napus (z.B. Canola), Brassica rapa, B. juncea (z.B. (Acker-)Senf) und Brassica carinata, Reis, Weizen Zuckerrübe, Zurckerrohr, Hafer, Roggen, Gerste, Hirse, Triticale, Flachs, Wein und verschiedene Früchte und Gemüse von verschiedenen botanischen Taxa wie z.B. Rosaceae sp. (beispielsweise Kernfrüchte wie Apfel und Birne, aber auch Steinfrüchte wie Aprikosen, Kirschen, Mandeln und Pfirsiche und Beerenfrüchte wie Erdbeeren), Ribesioidae sp., Juglandaceae sp., Betul aceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (beispielsweise Bananenbäume und -plantagen), Rubiaceae sp. (beispielsweise Kaffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (beispielsweise Zitronen, Organen und Grapefruit); Solanaceae sp. (beispielsweise Tomaten, Kartoffeln, Pfeffer, Auberginen), Liliaceae sp., Compositae sp. (beispielsweise Salat, Artischocke and Chicoree - einschließlich Wurzelchicoree, Endivie oder gemeinen Chicoree), Umbelliferae sp. (beispielsweise Karrotte, Petersilie, Stangensellerie und Knollensellerie), Cucurbitaceae sp. (beispielsweise Gurke - einschließlich Gewürzgurke, Kürbis, Wassermelone, Flaschenkürbis und Melonen), Alliaceae sp. (beispielsweise Lauch und Zwiebel), Cruciferae sp. (beispielsweise Weißkohl, Rotkohl, Brokkoli, Blumenkohl, Rosenkohl, Pak Choi, Kohlrabi, Radieschen, Meerrettich, Kresse und Chinakohl), Leguminosae sp. (beispielsweise Erdnüsse, Erbsen, und Bohnen - wie z.B. Stangenbohne und Ackerbohne), Chenopodiaceae sp. (beispielsweise Mangold, Futterrübe, Spinat, Rote Rübe), Malvaceae (beispielsweise Okra), Asparagaceae (beispielsweise Spargel); Nutzpflanzen und Zierpflanzen in Garten und Wald; sowie jeweils genetisch modifizierte Arten dieser Pflanzen. The following main crops may be mentioned as plants which can be treated according to the invention: maize, soybeans, cotton, Brassica oil seeds such as Brassica napus (e.g. canola), Brassica rapa, B. juncea (e.g. (field) mustard) and Brassica carinata, rice, Wheat, sugar beet, sugar cane, oats, rye, barley, millet, triticale, flax, wine and various fruits and vegetables from various botanical taxa such as Rosaceae sp. (For example pome fruits like apple and pear, but also stone fruits like apricots, cherries, almonds and Peaches and berries such as strawberries), Ribesioidae sp., Juglandaceae sp., Betul aceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (e.g. banana trees and plantations), Rubiaceae sp. (e.g. coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (e.g. lemons, organs and grapefruit); Solanaceae sp. (for example tomatoes, potatoes, pepper, eggplant), Liliaceae sp., Compositae sp. (e.g. lettuce, artichoke and chicory - including root chicory, endive or common chicory), Umbelliferae sp. (e.g., carrot, parsley, celery and celeriac), Cucurbitaceae sp. (e.g., cucumber - including pickles, squash, watermelon, bottle gourd, and melons), Alliaceae sp. (e.g. leek and onion), Cruciferae sp. (for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes, horseradish, cress and Chinese cabbage), Leguminosae sp. (for example peanuts, peas, and beans - such as runner bean and field bean), Chenopodiaceae sp. (for example Swiss chard, fodder beet, spinach, beetroot), Malvaceae (for example okra), Asparagaceae (for example asparagus); Useful plants and ornamental plants in gardens and forests; as well as genetically modified species of these plants.
Wie oben erwähnt, können erfindungsgemäß alle Pflanzen und deren Teile behandelt werden. In einer bevorzugten Ausführungsform werden wild vorkommende oder durch konventionelle biologische Zuchtmethoden, wie Kreuzung oder Protoplastenfusion erhaltenen Pflanzenarten und Pflanzensorten sowie deren Teile behandelt. In einer weiteren bevorzugten Ausführungsform werden transgene Pflanzen und Pflanzensorten, die durch gentechnologische Methoden gegebenenfalls in Kombination mit konventionellen Methoden erhalten wurden (Genetically Modified Organisms) und deren Teile behandelt. Der Begriff „Teile“ bzw. „Teile von Pflanzen“ oder „Pflanzenteile“ wurde oben erläutert. Besonders bevorzugt werden erfindungsgemäß Pflanzen der jeweils handelsüblichen oder in Gebrauch befindlichen Pflanzensorten behandelt. Unter Pflanzensorten versteht man Pflanzen mit neuen Eigenschaften („Traits“), die sowohl durch konventionelle Züchtung, durch Mutagenese oder durch rekombinante DNA-T echniken gezüchtet worden sind. Dies können Sorten, Rassen, Bio- und Genotypen sein. As mentioned above, all plants and their parts can be treated according to the invention. In a preferred embodiment, plant species and plant cultivars occurring in the wild or obtained by conventional biological breeding methods such as crossing or protoplast fusion, as well as their parts, are treated. In a further preferred embodiment, transgenic plants and plant cultivars which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetically modified organisms), and their parts are treated. The term “parts” or “parts of plants” or “plant parts” has been explained above. According to the invention, it is particularly preferred to treat plants of the plant varieties which are commercially available or in use. Plant cultivars are understood to be plants with new properties (“traits”) that have been bred by conventional breeding, by mutagenesis or by recombinant DNA technology. These can be varieties, races, bio and genotypes.
Das erfindungsgemäße Behandlungsverfahren kann für die Behandlung von genetisch modifizierten Organismen (GMOs), z. B. Pflanzen oder Samen, verwendet werden. Genetisch modifizierte Pflanzen (oder transgene Pflanzen) sind Pflanzen, bei denen ein heterologes Gen stabil in das Genom integriert worden ist. Der Begriff "heterologes Gen" bedeutet im wesentlichen ein Gen, das außerhalb der Pflanze bereitgestellt oder assembliert wird und das bei Einführung in das Zellkemgenom, das Chloroplastengenom oder das Mitochondriengenom der transformierten Pflanze dadurch neue oder verbesserte agronomische oder sonstige Eigenschaften verleiht, dass es ein interessierendes Protein oder Polypeptid exprimiert oder dass es ein anderes Gen, das in der Pflanze vorliegt bzw. andere Gene, die in der Pflanze vorliegen, herunterreguliert oder abschaltet (zum Beispiel mittels Antisense- Technologie, Cosuppressionstechnologie oder RNAi-T echnologie [RNA Interference]). Ein heterologes Gen, das im Genom voriiegt, wird ebenfalls als Transgen bezeichnet Ein Transgen, das durch sein spezifisches Voriiegen im Pflanzengenom definiert ist, wird als Transformations- bzw. transgenes Event bezeichnet. The treatment method according to the invention can be used for the treatment of genetically modified organisms (GMOs), e.g. B. plants or seeds can be used. Genetically modified plants (or transgenic plants) are plants in which a heterologous gene has been stably integrated into the genome. The term "heterologous gene" means essentially a gene which is provided or assembled outside the plant and which when introduced into the cell nucleus genome, the chloroplast genome or the mitochondrial genome of the transformed plant gives new or improved agronomic or other properties that it gives an interesting Protein or polypeptide expressed or that it is another gene that is present in the plant or others Genes that are present in the plant are downregulated or switched off (for example by means of antisense technology, cosuppression technology or RNAi technology [RNA interference]). A heterologous gene that is present in the genome is also called a transgene. A transgene that is defined by its specific presence in the plant genome is called a transformation or transgenic event.
In Abhängigkeit von den Pflanzenarten oder Pflanzensorten, ihrem Standort und ihren Wachstumsbedingungen (Böden, Klima, Vegetationsperiode, Ernährung) kann die erfindungsgemäße Behandlung auch zu überadditiven (" synergistischen") Effekten führen. So sind zum Beispiel die folgenden Effekte möglich, die über die eigentlich zu erwartenden Effekte hinausgehen: verringerte Aufwandmengen und/oder erweitertes Wirkungsspektrum und/oder erhöhte Wirksamkeit der Wirkstoffe und Zusammensetzungen, die erfindungsgemäß eingesetzt werden können, besseres Pflanzenwachstum, erhöhte Toleranz gegenüber hohen oder niedrigen Temperaturen, erhöhte Toleranz gegenüber Trockenheit oder Wasser- oder Bodensalzgehalt, erhöhte Blühleistung, Emteerleichterung, Reifebeschleunigung, höhere Erträge, größere Früchte, größere Pflanzenhöhe, intensiver grüne Farbe des Blatts, frühere Blüte, höhere Qualität und/oder höherer Nährwert der Emteprodukte, höhere Zuckerkonzentration in den Früchten, bessere Lagerfähigkeit und/oder Verarbeitbarkeit der Emteprodukte. Depending on the plant species or plant cultivars, their location and their growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention can also lead to superadditive (“synergistic”) effects. For example, the following effects are possible that go beyond the effects that are actually to be expected: reduced application rates and / or expanded spectrum of activity and / or increased effectiveness of the active ingredients and compositions that can be used according to the invention, better plant growth, increased tolerance to high or low levels Temperatures, increased tolerance to drought or water or soil salt content, increased flowering capacity, easier harvesting, accelerated ripening, higher yields, larger fruits, higher plant height, more intense green color of the leaves, earlier flowering, higher quality and / or higher nutritional value of the harvested products, higher sugar concentration in the fruits, better storability and / or processability of the harvest products.
Zu Pflanzen und Pflanzensorten, die vorzugsweise erfindungsgemäß behandelt werden, zählen alle Pflanzen, die über Erbgut verfügen, das diesen Pflanzen besonders vorteilhafte, nützliche Merkmale verleiht (egal, ob dies durch Züchtung und/oder Biotechnologie erzielt wurde). Plants and plant cultivars which are preferably treated according to the invention include all plants which have genetic material which gives these plants particularly advantageous, useful characteristics (regardless of whether this was achieved by breeding and / or biotechnology).
Beispiele für Nematoden-resistente Pflanzen sind z.B. folgenden US Patentanmeldungen beschrieben: 11/765,491, 11/765,494, 10/926,819, 10/782,020, 12/032,479, 10/783,417, 10/782,096, 11/657,964, 12/192,904, 11/396,808, 12/166,253, 12/166,239, 12/166,124, 12/166,209, 11/762,886, 12/364,335, 11/763,947, 12/252,453, 12/209,354, 12/491,396 und 12/497,221. Examples of nematode-resistant plants are described, for example, in the following US patent applications: 11 / 765,491, 11 / 765,494, 10 / 926,819, 10 / 782,020, 12 / 032,479, 10 / 783,417, 10 / 782,096, 11 / 657,964, 12 / 192,904, 11 / 396,808, 12 / 166,253, 12 / 166,239, 12 / 166,124, 12 / 166,209, 11 / 762,886, 12 / 364,335, 11 / 763,947, 12 / 252,453, 12 / 209,354, 12 / 491,396 and 12 / 497,221.
Pflanzen, die erfindungsgemäß behandelt werden können, sind Hybridpflanzen, die bereits die Eigenschaften der Heterosis bzw. des Hybrideffekts exprimieren, was im Allgemeinen zu höherem Ertrag, höherer Wüchsigkeit, besserer Gesundheit und besserer Resistenz gegen biotische und abiotische Stressfaktoren führt. Solche Pflanzen werden typischerweise dadurch erzeugt, dass man eine ingezüchtete pollensterile Eltemlinie (den weiblichen Kreuzungspartner) mit einer anderen ingezüchteten pollenfertilen Eltemlinie (dem männlichen Kreuzungspartner) kreuzt. Das Hybridsaatgut wird typischerweise von den pollensterilen Pflanzen geerntet und an Vermehrer verkauft. Pollensterile Pflanzen können manchmal (z. B. beim Mais) durch Entf ahnen (d.h. mechanischem Entfernen der männlichen Geschlechtsorgane bzw. der männlichen Blüten), produziert werden; es ist jedoch üblicher, dass die Pollensterilität auf genetischen Determinanten im Pflanzengenom beruht. In diesem Fall, insbesondere dann, wenn es sich bei dem gewünschten Produkt, da man von den Hybridpflanzen ernten will, um die Samen handelt, ist es üblicherweise günstig, sicherzustellen, dass die Pollenfertilität in Hybridpflanzen, die die für die Pollensterilität verantwortlichen genetischen Determinanten enthalten, völlig restoriert wird. Dies kann erreicht werden, indem sichergestellt wird, dass die männlichen Kreuzungspartner entsprechende Fertilitätsrestorergene besitzen, die in der Lage sind, die Pollenfertilität in Hybridpflanzen, die die genetischen Determinanten, die für die Pollensterilität verantwortlich sind, enthalten, zu restorieren. Genetische Determinanten für Pollensterilität können im Cytoplasma lokalisiert sein. Beispiele für cytoplasmatische Pollensterilität (CMS) wurden zum Beispiel für Brassica-Arten beschrieben. Genetische Determinanten für Pollensterilität können jedoch auch im Zellkemgenom lokalisiert sein. Pollensterile Pflanzen können auch mit Methoden der pflanzlichen Biotechnologie, wie Gentechnik, erhalten werden. Ein besonders günstiges Mittel zur Erzeugung von pollensterilen Pflanzen ist in WO 89/10396 beschrieben, wobei zum Beispiel eine Ribonuklease wie eine Bamase selektiv in denPlants which can be treated according to the invention are hybrid plants which already express the properties of heterosis or the hybrid effect, which generally leads to higher yields, higher vigor, better health and better resistance to biotic and abiotic stress factors. Such plants are typically created by crossing an inbred male sterile parent line (the female cross partner) with another inbred male fertile parent line (the male cross partner). The hybrid seeds are typically harvested from the male-sterile plants and sold to propagators. Male-sterile plants can sometimes (e.g. in the case of maize) by detaching (ie mechanical removal of the male genital organs or the male flowers); however, it is more common that male sterility is due to genetic determinants in the plant genome. In this case, especially if the desired product, since one wishes to harvest from the hybrid plants, is the seeds, it is usually beneficial to ensure that the male fertility in hybrid plants which contain the genetic determinants responsible for male sterility , will be completely restored. This can be achieved by ensuring that the male crossing partners have appropriate fertility restorer genes capable of restoring male fertility in hybrid plants that contain the genetic determinants responsible for male sterility. Genetic determinants of male sterility can be located in the cytoplasm. Examples of cytoplasmic male sterility (CMS) have been described for Brassica species, for example. However, genetic determinants for male sterility can also be located in the cell nucleus genome. Male-sterile plants can also be obtained using methods of plant biotechnology, such as genetic engineering. A particularly favorable means for the production of male sterile plants is described in WO 89/10396, for example a ribonuclease such as a Bamase selectively in the
Tapetumzellen in den Staubblättern exprimiert wird. Die Fertilität kann dann durch Expression eines Ribonukleasehemmers wie Barstar in den Tapetumzellen restoriert werden. Tapetum cells is expressed in the stamens. Fertility can then be restored by expressing a ribonuclease inhibitor such as barstar in the tapetum cells.
Pflanzen oder Pflanzensorten (die mit Methoden der Pflanzenbiotechnologie, wie der Gentechnik, erhalten werden), die erfindungsgemäß behandelt werden können, sind herbizidtolerante Pflanzen, d. h. Pflanzen, die gegenüber einem oder mehreren vorgegebenen Herbiziden tolerant gemacht worden sind. Solche Pflanzen können entweder durch genetische Transformation oder durch Selektion von Pflanzen, die eine Mutation enthalten, die solch eine Herbizidtoleranz verleiht, erhalten werden. Plants or plant cultivars (which are obtained using methods of plant biotechnology, such as genetic engineering) which can be treated according to the invention are herbicide-tolerant plants; H. Plants that have been made tolerant to one or more specified herbicides. Such plants can be obtained either by genetic transformation or by selection of plants which contain a mutation which confers such herbicide tolerance.
Herbizidtolerante Pflanzen sind zum Beispiel glyphosatetolerante Pflanzen, d. h. Pflanzen, die gegenüber dem Herbizid CHyphosate oder dessen Salzen tolerant gemacht worden sind. Pflanzen können mit verschiedenen Methoden tolerant gegenüber CHyphosate gemacht werden. So können zum Beispiel glyphosatetolerante Pflanzen durch Transformation der Pflanze mit einem Gen, das für das Enzym S-Enolpyruvylshikimat-3-phosphatsynthase (EPSPS) kodiert, erhalten werden. Beispiele für solche EPSPS-Gene sind das AroA-Gen (Mutante CT7) des Bakterium Salmonella typhimurium (Comai et al., 1983, Science 221, 370-371), das CP4-Gen des Bakteriums Agrobacterium sp. (Barry et al., 1992, Curr. Topics Plant Physiol. 7, 139-145), die Gene, die für eine EPSPS aus der Petunie (Shah et al., 1986, Science 233, 478-481), für eine EPSPS aus der Tomate (Gasser et al., 1988, J. Biol. Chem. 263, 4280-4289) oder für eine EPSPS aus Eleusine (WO 01/66704) kodieren. Es kann sich auch um eine mutierte EPSPS handeln. (Hyphosate-tolerante Pflanzen können auch dadurch erhalten werden, dass man ein Gen exprimiert, das für ein CHyphosate- Oxidoreduktase-Enzym kodiert. (Hyphosate-tolerante Pflanzen können auch dadurch erhalten werden, dass man ein Gen exprimiert, das für ein Glyphosate-acetyltransferase-Enzym kodiert. Glyphosatetolerante Pflanzen können auch dadurch erhalten werden, dass man Pflanzen, die natürlich vorkommende Mutationen der oben erwähnten Gene enthalten, selektiert. Pflanzen, die EPSPS Gene, welche Glyphosate- Toleranz verleihen, exprimieren, sind beschrieben. Pflanzen, welche andere Gene, die Glyphosate- Toleranz verleihen, z.B. Decarboxylase-Gene, sind beschrieben. Herbicide-tolerant plants are, for example, glyphosate-tolerant plants, ie plants which have been made tolerant to the herbicide CHyphosate or its salts. Plants can be made tolerant to CHyphosate using various methods. For example, glyphosate-tolerant plants can be obtained by transforming the plant with a gene that codes for the enzyme S-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonella typhimurium (Comai et al., 1983, Science 221, 370-371), the CP4 gene of the bacterium Agrobacterium sp. (Barry et al., 1992, Curr. Topics Plant Physiol. 7, 139-145), the genes necessary for a petunia EPSPS (Shah et al., 1986, Science 233, 478-481) for an EPSPS from the tomato (Gasser et al., 1988, J. Biol. Chem. 263, 4280-4289) or for an EPSPS from Eleusine (WO 01/66704). It can also be a mutated EPSPS. (Hyphosate-tolerant plants can also be obtained by expressing a gene that codes for a CHyphosate oxidoreductase enzyme. (Hyphosate-tolerant plants can also be obtained by expressing a gene which codes for a glyphosate acetyltransferase enzyme. Glyphosate-tolerant plants can also be obtained by selecting plants which contain naturally occurring mutations of the genes mentioned above. Plants expressing EPSPS genes that confer glyphosate tolerance are described. Plants which confer other genes that confer glyphosate tolerance, e.g., decarboxylase genes, are described.
Sonstige heibizidresistente Pflanzen sind zum Beispiel Pflanzen, die gegenüber Herbiziden, die das Enzym CHutaminsynthase hemmen, wie Bialaphos, Phosphinotricin oder Ghifosinale, tolerant gemacht worden sind. Solche Pflanzen können dadurch erhalten werden, dass man ein Enzym exprimiert, das das Herbizid oder eine Mutante des Enzyms Glutaminsynthase, das gegenüber Hemmung resistent ist, entgiftet. Solch ein wirksames entgiftendes Enzym ist zum Beispiel ein Enzym, das für ein Phosphinotricin-acetyltransferase kodiert (wie zum Beispiel das bar- oder pat- Protein aus Streptomyces- Arten). Pflanzen, die eine exogene Phosphinotricin-acetyltransferase exprimieren, sind beschrieben. Other heat-resistant plants are, for example, plants that have been made tolerant to herbicides which inhibit the enzyme CHutamine synthase, such as bialaphos, phosphinotricin or ghifosinale. Such plants can be obtained by expressing an enzyme that detoxifies the herbicide or a mutant of the enzyme glutamine synthase that is resistant to inhibition. Such an effective detoxifying enzyme is, for example, an enzyme which codes for a phosphinotricin acetyltransferase (such as the bar or pat protein from Streptomyces species). Plants expressing an exogenous phosphinotricin acetyltransferase have been described.
Weitere heibizidtolerante Pflanzen sind auch Pflanzen, die gegenüber den Herbiziden, die das Enzym Hydroxyphenylpyruvatdioxygenase (HPPD) hemmen, tolerant gemacht worden sind. Bei den Hydroxyphenylpyruvatdioxygenasen handelt es sich um Enzyme, die die Reaktion, in der para- Hydroxyphenylpyruvat (HPP) zu Homogentisat umgesetzt wird, katalysieren. Pflanzen, die gegenüber HPPD-Hemmem tolerant sind, können mit einem Gen, das für ein natürlich vorkommendes resistentes HPPD-Enzym kodiert, oder einem Gen, das für ein mutiertes oder chimäres HPPD-Enzym kodiert, transformiert werden, wie in WO 96/38567, WO 99/24585, WO 99/24586, WO 2009/144079, WO 2002/046387 oder US 6,768,044 beschrieben. Eine Toleranz gegenüber HPPD-Hemmem kann auch dadurch erzielt werden, dass man Pflanzen mit Genen transformiert, die für gewisse Enzyme kodieren, die die Bildung von Homogentisat trotz Hemmung des nativen HPPD-Enzyms durch den HPPD-Hemmer ermöglichen. Solche Pflanzen sind in WO 99/34008 und WO 02/36787 beschrieben. Die Toleranz von Pflanzen gegenüber HPPD-Hemmem kann auch dadurch verbessert werden, dass man Pflanzen zusätzlich zu einem Gen, das für ein HPPD- tolerantes Enzym kodiert, mit einem Gen transformiert, das für ein Prephenatdehydrogenase-Enzym kodiert, wie in WO 2004/024928 beschrieben ist. Außerdem können Pflanzen noch toleranter gegen HPPD-Hemmem gemacht werden, indem man ein Gen in ihr Genom einfügt, welches für ein Enzym kodiert, das HPPD-Hemmer metabolisiert oder abbaut, wie z.B. CYP450 Enzyme (siehe WO 2007/103567 und WO 2008/150473). Other herbicide-tolerant plants are also plants that have been made tolerant of herbicides which inhibit the enzyme hydroxyphenylpyruvate dioxygenase (HPPD). The hydroxyphenylpyruvate dioxygenases are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is converted to homogenate. Plants tolerant to HPPD inhibitors can be transformed with a gene encoding a naturally occurring resistant HPPD enzyme or a gene encoding a mutated or chimeric HPPD enzyme, as in WO 96/38567 , WO 99/24585, WO 99/24586, WO 2009/144079, WO 2002/046387 or US 6,768,044. Tolerance to HPPD inhibitors can also be achieved by transforming plants with genes which code for certain enzymes which enable the formation of homogenate despite the inhibition of the native HPPD enzyme by the HPPD inhibitor. Such plants are described in WO 99/34008 and WO 02/36787. The tolerance of plants to HPPD inhibitors can also be improved by transforming plants, in addition to a gene that codes for an HPPD-tolerant enzyme, with a gene that codes for a prephenate dehydrogenase enzyme, as in WO 2004/024928 is described. In addition, plants can be made even more tolerant of HPPD inhibitors by inserting a gene into their genome which codes for an enzyme that metabolizes or degrades HPPD inhibitors, such as CYP450 enzymes (see WO 2007/103567 and WO 2008/150473 ).
Weitere heibizidresistente Pflanzen sind Pflanzen, die gegenüber Acetolactatsynthase (ALS)- Hemmem tolerant gemacht worden sind. Zu bekannten ALS-Hemmem zählen zum Beispiel Sulfonylharnstoff, Imidazolinon, Triazolopyrimidine, Pyrimidinyloxy(thio)benzoate und/oder Sulfonylaminocarbonyltriazolinon-Herbizide. Es ist bekannt, dass verschiedene Mutationen im Enzym ALS (auch als Acetohydroxysäure-Synthase, AHAS, bekannt) eine Toleranz gegenüber unterschiedlichen Herbiziden bzw. Gruppen von Herbiziden verleihen wie z.B. in Tranel und Wright (Weed Science 2002, 50, 700-712) beschrieben ist. Die Herstellung von sulfonylhamstofftoleranten Pflanzen und imidazolinontoleranten Pflanzen ist beschrieben. Weitere Sulfonylharnstoff- und imidazolinontolerante Pflanzen sind auch beschrieben. Other plants resistant to herbicides are plants which have been made tolerant to acetolactate synthase (ALS) inhibitors. Known ALS inhibitors include, for example, sulfonylurea, imidazolinone, triazolopyrimidines, pyrimidinyloxy (thio) benzoates and / or Sulfonylaminocarbonyltriazolinone herbicides. It is known that various mutations in the enzyme ALS (also known as acetohydroxy acid synthase, AHAS) confer tolerance to different herbicides or groups of herbicides, as described, for example, in Tranel and Wright (Weed Science 2002, 50, 700-712) is. The production of sulfonylurea tolerant plants and imidazolinone tolerant plants is described. Other sulfonylurea and imidazolinone tolerant plants are also described.
Weitere Pflanzen, die gegenüber Imidazolinonen und/oder Sulfonylharnstoffen tolerant sind, können durch induzierte Mutagenese, Selektion in Zellkulturen in Gegenwart des Herbizids oder durch Mutationszüchtung erhalten werden (vgl. z.B. für Sojabohne US 5,084,082, für Reis WO 97/41218, für Zuckerrübe US 5,773,702 und WO 99/057965, für Salat US 5,198,599 oder für Sonnenblume WO 01/065922). Further plants that are tolerant of imidazolinones and / or sulfonylureas can be obtained by induced mutagenesis, selection in cell cultures in the presence of the herbicide or by mutation breeding (cf., for example, US Pat. No. 5,084,082 for soybeans, WO 97/41218 for rice, US Pat. No. 5,773,702 for sugar beet and WO 99/057965, for lettuce US 5,198,599 or for sunflower WO 01/065922).
Pflanzen oder Pflanzensorten (die nach Methoden der pflanzlichen Biotechnologie, wie der Gentechnik, erhalten wurden), die ebenfalls erfindungsgemäß behandelt werden können, sind gegenüber abiotischen Stressfaktoren tolerant. Solche Pflanzen können durch genetische Transformation oder durch Selektion von Pflanzen, die eine Mutation enthalten, die solch eine Stressresistenz verleiht, erhalten werden. Zu besonders nützlichen Pflanzen mit Stresstoleranz zählen folgende: a. Pflanzen, die ein Transgen enthalten, das die Expression und/oder Aktivität des Gens für die Poly(ADP-ribose)polymerase (PARP) in den Pflanzenzellen oder Pflanzen zu reduzieren vermag. b. Pflanzen, die ein stresstoleranzfordemdes Transgen enthalten, das die Expression und/oder Aktivität der für PARC kodierenden Gene der Pflanzen oder Pflanzenzellen zu reduzieren vermag; c. Pflanzen, die ein stresstoleranzfordemdes Transgen enthalten, das für ein in Pflanzen funktionelles Enzym des Nicotinamidadenindinukleotid-Salvage-Biosynthesewegs kodiert, darunter Nicotinamidase, Nicotinatphosphoribosyltransferase, Nicotinsäuremononukleotidadenyltransferase, Nicotinantidadenindinukleotidsynthetase oder Nicotinamidphosphoribosyltransferase. Plants or plant cultivars (which were obtained by methods of plant biotechnology, such as genetic engineering), which can also be treated according to the invention, are tolerant of abiotic stress factors. Such plants can be obtained by genetic transformation or by selection of plants which contain a mutation which confers such stress resistance. Particularly useful plants with stress tolerance include the following: a. Plants which contain a transgene which is able to reduce the expression and / or activity of the gene for the poly (ADP-ribose) polymerase (PARP) in the plant cells or plants. b. Plants which contain a stress tolerance-promoting transgene which is able to reduce the expression and / or activity of the genes of the plants or plant cells coding for PARC; c. Plants which contain a stress tolerance-promoting transgene which codes for an enzyme of the nicotinamide adenine dinucleotide salvage biosynthetic pathway that is functional in plants, including nicotinamidase, nicotinate phosphoribosyl transferase, nicotinic acid mononucleotide adenyl transferase or nicotinic antide adenine dinucleotide transferase.
Pflanzen oder Pflanzensorten (die nach Methoden der pflanzlichen Biotechnologie, wie der Gentechnik, erhalten wurden), die ebenfalls erfindungsgemäß behandelt werden können, weisen eine veränderte Menge, Qualität und/oder Lagerfähigkeit des Emteprodukts und/oder veränderte Eigenschaften von bestimmten Bestandteilen des Emteprodukts auf, wie zum Beispiel: 1) Transgene Pflanzen, die eine modifizierte Stärke synthetisieren, die bezüglich ihrer chemisch-physikalischen Eigenschaftei, insbesondere des Amylosegehalts oder des Amylose/Amylopektin- Verhältnisses, des Verzweigungsgrads, der durchschnittlichen Kettenlänge, der Verteilung der Seitenketten, des Viskositätsverhaltens, der Gelfestigkeit, der Stäikekomgröße und/oder Stärkekommorphologje im Vergleich mit der synthetisierten Stärke in Wildtyppflanzenzellen oder - pflanzen verändert ist, so dass sich diese modifizierte Stärke besser für bestimmte Anwendungen eignet 2) Transgene Pflanzen, die Nichtstärkekohlenhydratpolymere synthetisieren, oderPlants or plant varieties (which were obtained by methods of plant biotechnology, such as genetic engineering), which can also be treated according to the invention, have a changed amount, quality and / or shelf life of the harvested product and / or changed properties of certain components of the harvested product, such as: 1) Transgenic plants that synthesize a modified starch which, in terms of their chemical-physical properties, in particular the amylose content or the amylose / amylopectin The ratio, the degree of branching, the average chain length, the distribution of the side chains, the viscosity behavior, the gel strength, the starch size and / or starch commorphology is changed in comparison with the synthesized starch in wild-type plant cells or plants, so that this modified starch is better for certain applications suitable 2) transgenic plants that synthesize non-starch carbohydrate polymers, or
Nichtstärkekohlenhydratpolymere, deren Eigenschaften im Vergleich zu Wildtyppflanzen ohne genetische Modifikation verändert sind. Beispiele sind Pflanzen, die Polyfructose, insbesondere des Inulin- und Levantyps, produzieren, Pflanzen, die alpha- 1 ,4-Glucane produzieren, Pflanzen, die alpha- 1 ,6-verzweigte alpha- 1 ,4-Glucane produzieren und Pflanzen, die Alteman produzieren. 3) Transgene Pflanzen, die Hyaluronan produzieren. Non-starch carbohydrate polymers whose properties are changed compared to wild-type plants without genetic modification. Examples are plants that produce polyfructose, in particular of the inulin and levan type, plants that produce alpha-1,4-glucans, plants that produce alpha-1,6-branched alpha-1,4-glucans and plants that produce Alteman produce. 3) Transgenic Plants That Produce Hyaluronan.
4) Transgene Pflanzen oder Hybridpflanzen wie Zwiebeln mit bestimmten Eigenschaften wie , hohem Anteil an löslichen Feststoffen“ (,high soluble solids content’), geringe Schärfe (,low pungency’, LP) und/oder lange Lagerfähigkeit (,long storage’, LS). 4) Transgenic plants or hybrid plants such as onions with certain properties such as "high soluble solids content", low heat ("low pungency", LP) and / or long storage life ("long storage", LS ).
Pflanzen oder Pflanzensorten (die nach Methoden der pflanzlichen Biotechnologie, wie der Gentechnik, erhalten wurden), die ebenfalls erfindungsgemäß behandelt werden können, sind Pflanzen wie Baumwollpflanzen mit veränderten Fasereigenschaften. Solche Pflanzen können durch genetische Transformation oder durch Selektion von Pflanzen, die eine Mutation enthalten, die solche veränderten Fasereigenschaften verleiht, erhalten werden; dazu zählen: a) Pflanzen wie Baumwollpflanzen, die eine veränderte Form von Cellulosesynthasegenen enthalten, b) Pflanzen wie Baumwollpflanzen, die eine veränderte Form von rsw2- oder rsw3 -homologen Nukleinsäuren enthalten, wie Baumwollpflanzen mit einer erhöhten Expression der Saccharosephosphat- synthase; c) Pflanzen wie Baumwollpflanzen mit einer erhöhten Expression der Saccharose synthase; d) Pflanzen wie Baumwollpflanzen bei denen der Zeitpunkt der Durchlaßsteuerung der Plasmodesmen an der Basis der Faserzelle verändert ist, z. B. durch Herunterregulieren der faserselektiven ß-l,3-Glucanase; e) Pflanzen wie Baumwollpflanzen mit Fasern mit veränderter Reaktivität, z. B. durch Expression des N-Acetylglucosamintransferasegens, darunter auch nodC, und von Chitinsynthasegenen. Pflanzen oder Pflanzensorten (die nach Methoden der pflanzlichen Biotechnologie, wie der Gentechnik, erhalten wurden), die ebenfalls erfindungsgemäß behandelt werden können, sind Pflanzen wie Raps oder verwandte Brassica-Pflanzen mit veränderten Eigenschaften der Ölzusammensetzung. Solche Pflanzen können durch genetische Transformation oder durch Selektion von Pflanzen, die eine Mutation enthalten, die solche veränderten Öleigenschaften verleiht, erhalten werden; dazu zählen: a) Pflanzen wie Rapspflanzen, die Öl mit einem hohen Ölsäuregehalt produziere; b) Pflanzen wie Rapspflanzen, die Öl mit einem niedrigen Linolensäuregehalt produzieren. c) Pflanzen wie Rapspflanzen, die Öl mit einem niedrigen gesättigten Fettsäuregehalt produzieren. Pflanzen oder Pflanzensorten (die nach Methoden der pflanzlichen Biotechnologie, wie der Gentechnik, erhalten werden können), die ebenfalls erfindungsgemäß behandelt werden können, sind Pflanzen wie Kartoffeln, welche Virus-resistent sind z.B. gegen den Kartoffelvirus Y (Event SY230 und SY233 von Tecnoplant, Argentinien), oder welche resistent gegen Krankheiten wie die Kraut- und Knollenfäule (potato late blight) (z.B. RB Gen), oder welche eine verminderte kälteinduzierte Süße zeigen (welche die Gene Nt-Inh, Π-INV tragen) oder welche den Zwerg-Phänotyp zeigen (Gen A-20 Oxidase). Plants or plant cultivars (which were obtained by methods of plant biotechnology, such as genetic engineering), which can likewise be treated according to the invention, are plants such as cotton plants with modified fiber properties. Such plants can be obtained by genetic transformation or by selection of plants which contain a mutation which confers such altered fiber properties; these include: a) plants such as cotton plants which contain a modified form of cellulose synthase genes, b) plants such as cotton plants which contain a modified form of rsw2- or rsw3 -homologous nucleic acids, such as cotton plants with an increased expression of sucrose phosphate synthase; c) Plants such as cotton plants with an increased expression of sucrose synthase; d) Plants such as cotton plants in which the timing of the flow control of the plasmodesmata is changed at the base of the fiber cell, e.g. B. by downregulating the fiber-selective β-1,3-glucanase; e) Plants such as cotton plants with fibers with altered reactivity, e.g. B. by expression of the N-acetylglucosamine transferase gene, including nodC, and of chitin synthase genes. Plants or plant cultivars (which were obtained by methods of plant biotechnology, such as genetic engineering), which can likewise be treated according to the invention, are plants such as rapeseed or related Brassica plants with modified properties of the oil composition. Such plants can be obtained by genetic transformation or by selection of plants which contain a mutation which confers such altered oil properties; these include: a) Plants such as rape plants that produce oil with a high oleic acid content; b) Plants such as rape plants that produce oil with a low linolenic acid content. c) Plants such as rapeseed that produce oil with a low content of saturated fat. Plants or plant varieties (which can be obtained by methods of plant biotechnology, such as genetic engineering), which can also be treated according to the invention, are plants such as potatoes, which are virus-resistant, e.g. against the potato virus Y (Event SY230 and SY233 from Tecnoplant, Argentina), or which are resistant to diseases such as late blight (potato late blight) (e.g. RB gene), or which show a reduced sweetness induced by cold (which carry the genes Nt-Inh, Π-INV) or which the dwarf Show phenotype (gene A-20 oxidase).
Pflanzen oder Pflanzensorten (die nach Methoden der pflanzlichen Biotechnologie, wie der Gentechnik, erhalten wurden), die ebenfalls erfindungsgemäß behandelt werden können, sind Pflanzen wie Raps oder verwandte Brassica-Pflanzen mit veränderten Eigenschaften im Samenausfall (seed shattering). Solche Pflanzen können durch genetische Transformation oder durch Selektion von Pflanzen, die eine Mutation enthalten, die solche veränderten Eigenschaften verleihen, und umfassen Pflanzen wie Raps mit verzögertem oder vermindertem Samenausfall. Plants or plant cultivars (which were obtained by methods of plant biotechnology, such as genetic engineering), which can also be treated according to the invention, are plants such as rapeseed or related Brassica plants with changed properties in the case of seed shattering. Such plants can, by genetic transformation or by selection of plants containing a mutation, confer such altered traits and include plants such as oilseed rape with delayed or reduced seed loss.
Besonders nützliche transgene Pflanzen, die erfindungsgemäß behandelt werden können, sind Pflanzen mit Transformationsevents oder Kombinationen von Transformationsevent, welche in den USA beim Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA) Gegenstand von erteilten oder anhängigen Petitionen für den nicht-regulierten Status sind. Die Information hierzu ist j ederzeit beim APHIS (4700 River Road Riverdale, MD 20737, USA) erhältlich, z.B. über die Intemetseite http://www.aphis.usda.gov/brs/not_reg.html. Am Anmeldetag dieser Anmeldung waren beim APHIS die Petitionen mit folgenden Informationen entweder erteilt oder anhängig: - Petition: Identifikationsnummer der Petition. Die Technische Beschreibung des Transformationsevents kann im einzelnen Petitionsdokument erhältlich von APHIS auf der Website über die Petitionsnummer gefunden werden. Diese Beschreibungen sind hiermit per Referenz offenbart. Particularly useful transgenic plants that can be treated according to the invention are plants with transformation events or combinations of transformation events which are the subject of petitions issued or pending in the USA at the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA) are for the non-regulated status. The information on this is available at any time from APHIS (4700 River Road Riverdale, MD 20737, USA), eg via the Internet site http://www.aphis.usda.gov/brs/not_reg.html. On the filing date of this application, the petitions with the following information were either granted or pending at APHIS: - Petition: identification number of the petition. The technical description of the transformation event can be found in the individual petition document available from APHIS on the website via the petition number. These descriptions are hereby disclosed by reference.
- Erweiterung einer Petition: Referenz zu einer frühere Petition, für die eine Erweiterung oder Verlängerung beantragt wird. - Extension of a petition: reference to a previous petition for which an extension or extension is requested.
Institution: Name der die Petition einreichenden Person. Institution: Name of the person submitting the petition.
Regulierter Artikel: die betroffen Pflanzenspecies. Regulated article: the affected plant species.
- Transgener Phänotyp: die Eigenschaft („Trait“), die der Pflanze durch das Transformationsevent verliehen wird. - Transgenic phenotype: the trait given to the plant by the transformation event.
- Transformationevent oder -linie: der Name des oder der Events (manchmal auch als Linie(n) bezeichnet), für die der nicht-regulierte Status beantragt ist. - Transformation event or line: the name of the event or events (sometimes referred to as line (s)) for which non-regulated status is requested.
- APHIS Documente: verschiedene Dokumente, die von APHIS bzgl. der Petition veröffentlicht warden oder von APHIS auf Anfrage erhalten werden können. Besonders nützliche transgene Pflanzen, die erfindungsgemäß behandelt werden können, sind Pflanzen mit einem oder mehreren Genen, die für ein oder mehrere Toxine kodieren, sind die transgenen Pflanzen, die unter den folgenden Handelsbezeichnungen angeboten werden: YIELD GARD® (zum Beispiel Mais, Baumwolle, Sojabohnen), KnockOut® (zum Beispiel Mais), BiteGard® (zum Beispiel Mais), BT-Xtra® (zum Beispiel Mais), StarLink® (zum Beispiel Mais), Bollgard® (Baumwolle), Nucotn® (Baumwolle), Nucotn 33B® (Baumwolle), NatureGard® (zum Beispiel Mais), Protecta® und NewLeaf® (Kartoffel). Herbizidtolerante Pflanzen, die zu erwähnen sind, sind zum Beispiel Maissorten, Baumwollsorten und Sojabohnensorten, die unter den folgenden Handelsbezeichnungen angeboten werden: Roundup Ready® (Glyphosatetoleranz, zum Beispiel Mais, Baumwolle, Sojabohne), Liberty Link® (Phosphinotricintoleranz, zum Beispiel Rips), IMI® (Imidazolinontoleranz) und SCS® (Sylfonylhamstoflftoleranz), zum Beispiel Mais. Zu den herbizidresistenten Pflanzen (traditionell auf Herbizidtoleranz gezüchtete Pflanzen), die zu erwähnen sind, zählen die unter der Bezeichnung Clearfield® angebotenen Sorten (zum Beispiel Mais). - APHIS documents: various documents that are published by APHIS regarding the petition or that can be obtained from APHIS on request. Particularly useful transgenic plants which can be treated according to the invention are plants with one or more genes which code for one or more toxins, are the transgenic plants which are sold under the following trade names: YIELD GARD® (for example maize, cotton, Soybeans), KnockOut® (e.g. corn), BiteGard® (e.g. corn), BT-Xtra® (e.g. corn), StarLink® (e.g. corn), Bollgard® (cotton), Nucotn® (cotton), Nucotn 33B® (cotton), NatureGard® (e.g. maize), Protecta® and NewLeaf® (potato). Herbicide-tolerant plants to be mentioned are, for example, maize varieties, cotton varieties and soybean varieties, which are sold under the following trade names: Roundup Ready® (glyphosate tolerance, e.g. corn, cotton, soybean), Liberty Link® (phosphinotricintolerance, e.g. rips) , IMI® (imidazolinone tolerance) and SCS® (sylphonyl urea tolerance), for example corn. The herbicide-resistant plants (plants traditionally bred for herbicide tolerance) that should be mentioned include the varieties sold under the name Clearfield® (e.g. maize).
Die nachfolgenden Beispiele erläutern die vorliegende Erfindung. Chemische Beispiele The following examples illustrate the present invention. Chemical examples
Bei der Auswertung von NMR-Signalen werden folgende Abkürzungen verwendet: s (Singulett), d (Dublett), t (Triplett), q (Quartett), quint (Quintett), sext (Sextett), sept (Septett), m (Multiple#), mc (Multiple# centered) NMR-Peak-Listenverfahren The following abbreviations are used when evaluating NMR signals: s (singlet), d (doublet), t (triplet), q (quartet), quint (quintet), sext (sextet), sept (septet), m (multiple #), mc (Multiple # centered) NMR peak list method
Die 1H-NMR-Daten ausgewählter Beispiele weiden in Form von 1H-NMR-Peaklisten notiert. Zu jedem Signalpeak wird erst der δ-Wert in ppm und dann die Signalintensität in runden Klammem aufgefuhrt. Die δ-Wert - Signalintensitäts- Zahlenpaare von verschiedenen Signalpeaks werden durch Semikolons voneinander getrennt aufgelistet. Die Peakliste eines Beispieles hat daher die Form: δι (Intensität1*; δ2 (Intensitäti); ; δi (Intensität^; . ; δn (Intensität,,) The 1H-NMR data of selected examples are noted in the form of 1H-NMR peak lists. For each signal peak, first the δ value in ppm and then the signal intensity is listed in round brackets. The δ-value - signal intensity number pairs of different signal peaks are listed separated from each other by semicolons. The peak list of an example therefore has the form: δι (intensity 1 *; δ 2 (intensity i );; δ i (intensity ^;.; Δ n (intensity ,,)
Die Intensität scharfer Signale korreliert mit der Höhe der Signale in einem gedruckten Beispiel eines NMR-Spektrums in cm und zeigt die wirklichen Verhältnisse der Signalintensitäten. Bei breiten Signalen können mehrere Peaks oder die Mitte des Signals und ihre relative Intensität im Vergleich zum intensivsten Signal im Spektrum gezeigt weiden. The intensity of sharp signals correlates with the height of the signals in a printed example of an NMR spectrum in cm and shows the real relationships between the signal intensities. Broad signals may show multiple peaks or the center of the signal and their relative intensity compared to the most intense signal in the spectrum.
Zur Kalibrierung der chemischen Verschiebung von 1H-NMR-Spektren benutzen wir Tetramethylsilan und/oder die chemische Verschiebung des Lösungsmittels, be sondern im Falle von Spektren, die in DMSO gemessen weiden. Daher kann in NMR-Peaklisten der Tetramethylsilan-Peak Vorkommen, muss es aber nicht. Die Listen der 1H-NMR-Peaks sind ähnlich den klassischen 1H-NMR-Ausdrucken und enthalten somit gewöhnlich alle Peaks, die bei einer klassischen NMR-Inteipretation aufgefuhrt weiden. To calibrate the chemical shift of 1H-NMR spectra, we use tetramethylsilane and / or the chemical shift of the solvent, but in the case of spectra measured in DMSO. The tetramethylsilane peak can therefore appear in NMR peak lists, but does not have to be. The lists of the 1H-NMR peaks are similar to the classic 1H-NMR printouts and therefore usually contain all peaks that are listed in a classic NMR interpretation.
Darüber hinaus können sie wie klassische 1 H-NMR- Ausdrucke Lösungsmittelsignale, Signale von Stereoisomeren der Zielverbindungen, die ebenfalls Gegenstand der Erfindung sind, und/oder Peaks von Verunreinigungen zeigen. Bei der Angabe von Veibindungssignalen im Delta-Bereich von Lösungsmitteln und/oder Wasser sind in unseren Listen von 1H-NMR-Peaks die gewöhnlichen Lösungsmittelpeaks, zum Beispiel Peaks von DMSO in DMSO-De und der Peak von Wasser, gezeigt, die gewöhnlich im Durchschnitt eine hohe Intensität aufweisen. Die Peaks von Stereoisomeren der Targetverbindungen und/oder Peaks von Verunreinigungen haben gewöhnlich im Durchschnitt eine geringere Intensität als die Peaks der Zielverbindungen (zum Beispiel mit einer Reinheit von >90%). In addition, like classic 1 H-NMR printouts, they can show solvent signals, signals of stereoisomers of the target compounds, which are also the subject of the invention, and / or peaks of impurities. When specifying connection signals in the delta range of solvents and / or water, our lists of 1H-NMR peaks show the usual solvent peaks, for example peaks from DMSO in DMSO-De and the peak from water, which are usually on average have a high intensity. The peaks of stereoisomers of the target compounds and / or peaks of impurities usually have, on average, a lower intensity than the peaks of the target compounds (for example with a purity of> 90%).
Solche Stereoisomere und/oder Verunreinigungen können typisch für das jeweilige Herstellungsverfahren sein. Ihre Peaks können somit dabei helfen, die Reproduktion unseres Herstellungsverfahrens anhand von “Nebenprodukt-Fingerabdrücken” zu erkennen. Such stereoisomers and / or impurities can be typical of the particular manufacturing process. Your peaks can thus help to identify the reproduction of our manufacturing process based on “by-product fingerprints”.
Einem Experten, der die Peaks der Zielverbindungen mit bekannten Verfahren (MestreC, ACD- Simulation, aber auch mit empirisch ausgewerteten Erwartungswerten) berechnet, kann je nach Bedarf die Peaks der Zielverbindungen isolieren, wobei gegebenenfalls zusätzliche Intensitätsfilter eingesetzt werden. Diese Isolierung wäre ähnlich dem betreffenden Peak-Picking bei der klassischen 1H-NMR- Interpretation. An expert who calculates the peaks of the target compounds with known methods (MestreC, ACD simulation, but also with empirically evaluated expected values) can isolate the peaks of the target compounds as required, with additional intensity filters being used if necessary. This isolation would be similar to the relevant peak picking in the classical 1H-NMR interpretation.
Weitere Details zu 1H-NMR-Peaklisten können der Research Disclosure Database Number 564025 entnommen weiden. Further details on 1H NMR peak lists can be found in Research Disclosure Database Number 564025.
Beispiel D2.1: 3-[2-Ethyl-6-methyl-4-(prop-l-en-l-yl)phenyl]-4-hydroxy-8-methoxy-l-azaspiro[4.5]dec-3-en-2-on
Figure imgf000056_0001
Example D2.1: 3- [2-Ethyl-6-methyl-4- (prop-l-en-l-yl) phenyl] -4-hydroxy-8-methoxy-l-azaspiro [4.5] dec-3- en-2-on
Figure imgf000056_0001
1.00 g (2.58 mmol) Methyl-l-{2-[2-ethyl-6-methyl-4-(prop-l-en-l-yl)phenyl]acetamido}-4- methoxycyclohexancarboxylat wurden in 4.6 ml Dimethylformamid bei Raumtemperatur vorgelegt und portionsweise mit 0.64 g (5.70 mmol) Kalium-t-butylat versetzt. Nach beendeter Zugabe wurde das Reaktionsgemisch 1 h lang bei Raumtemperatur nachgerührt. 1.00 g (2.58 mmol) of methyl l- {2- [2-ethyl-6-methyl-4- (prop-l-en-l-yl) phenyl] acetamido} -4-methoxycyclohexanecarboxylate were in 4.6 ml of dimethylformamide at room temperature and 0.64 g (5.70 mmol) of potassium t-butoxide are added in portions. After the addition had ended, the reaction mixture was stirred at room temperature for 1 hour.
Die Reaktionsmischung wurde im Vakuum zur Trockne eingeengt, mit Wasser versetzt und mit Dichlormethan gewaschen. Die wäßrige Phase wurde mit 2M Salzsäure sauer gestellt. Der ausgefallene Niederschlag wurde abgesaugt und getrocknet. Man erhielt 0.87 g (94 %) der gewünschten Titelveibindung.
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Beispiel S2J: The reaction mixture was concentrated to dryness in vacuo, water was added and the mixture was washed with dichloromethane. The aqueous phase was acidified with 2M hydrochloric acid. The deposited precipitate was filtered off with suction and dried. 0.87 g (94%) of the desired title compound were obtained.
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Example S2J:
Natrium-3-[2-ethyl-6-methyl-4-(prop-l-en-l-yl)phenyl]-8-methoxy-2-oxo-l-azaspiro[4.5]dec-3-en-Sodium 3- [2-ethyl-6-methyl-4- (prop-l-en-l-yl) phenyl] -8-methoxy-2-oxo-l-azaspiro [4.5] dec-3-en-
4-olat
Figure imgf000061_0001
4-olat
Figure imgf000061_0001
0.13 g (0.37 mmol) 3 - [2-Ethyl-6-methyl-4-(prop- 1 -en- 1 -yl)phenyl] -4-hy droxy-8-methoxy- 1 - azaspiro[4.5 ] dec-3 -en-2-on wurden bei Raumtemperatur in 0.12 ml Methanol gelöst und mit 0.08 ml einer 25%igen methanolischen Natriummethanolat-Lösung versetzt. Nach beendeter Zugabe wurde das Reaktionsgemisch 15 min lang bei Raumtemperatur nachgerührt. 0.13 g (0.37 mmol) 3 - [2-ethyl-6-methyl-4- (prop- 1-en-1 -yl) phenyl] -4-hydroxy-8-methoxy-1-azaspiro [4.5] dec- 3-en-2-one were dissolved in 0.12 ml of methanol at room temperature, and 0.08 ml of a 25% strength methanolic sodium methoxide solution was added. After the addition had ended, the reaction mixture was stirred at room temperature for 15 minutes.
Die Reaktionsmischung wurde im Vakuum zur Trockne eingeengt. The reaction mixture was concentrated to dryness in vacuo.
Man erhielt 0.14 g (100 %) der gewünschten Titelverbindung. 0.14 g (100%) of the desired title compound was obtained.
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000066_0001
Ul Beispiel P2.1: Ul Example P2.1:
3-[2-Ethyl-6-methyl-4-(prop- 1 -en- 1 -yl)phenyl]-8-methoxy-2-oxo- 1 -azaspiro[4.5]dec-3 -en-4-yl-2- methylpropanoat
Figure imgf000067_0001
0.30 g (0.84 mmol) 3 - [2-Ethyl-6-methyl-4-(prop- 1 -en- 1 -yl)phenyl] -4-hy droxy-8-methoxy- 1 - azaspiro[4.5]dec-3-en-2-on wurden mit 0.35 ml Triethylamin in 1.0 ml Dichlormethan vorgelegt und 10 min bei Raumtemperatur gerührt. Anschließend tropfte man 0.18 g (1.69 mmol) 2- Methylpropanoyl chlorid in 0.5 ml Dichlormethan langsam zu und ließ anschließend 2 Tage bei Raumtemperatur rühren. Danach wurde mit Wasser gewaschen, getrocknet und im Vakuum eingeengt. Die Reinigung des Rohprodukts erfolgte durch Chromatographie auf Kieselgel (Ethylacetat /n-Heptan). 3- [2-Ethyl-6-methyl-4- (prop-1-en-1-yl) phenyl] -8-methoxy-2-oxo-1-azaspiro [4.5] dec-3-en-4-yl -2-methyl propanoate
Figure imgf000067_0001
0.30 g (0.84 mmol) 3 - [2-ethyl-6-methyl-4- (prop- 1-en-1 -yl) phenyl] -4-hydroxy-8-methoxy-1-azaspiro [4.5] dec- 3-en-2-one were initially charged with 0.35 ml of triethylamine in 1.0 ml of dichloromethane and stirred for 10 min at room temperature. 0.18 g (1.69 mmol) of 2-methylpropanoyl chloride in 0.5 ml of dichloromethane were then slowly added dropwise and the mixture was then left to stir at room temperature for 2 days. It was then washed with water, dried and concentrated in vacuo. The crude product was purified by chromatography on silica gel (ethyl acetate / n-heptane).
Man erhielt 0.14 g (38 %) der gewünschten Titelverbindung. 0.14 g (38%) of the desired title compound were obtained.
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
erstellung von Ausgangsmaterialien eispiel Q2.1: ethyl-l-{2-[2-ethyl-6-methyl-4-(prop-l-en-l-yl)phenyl]acetamido}-4-methoxycyclohexancarboxylat
Figure imgf000072_0001
70 g (3.21 mmol) [2-Ethyl-6-methyl-4-(prop- 1 -en- 1 -yl)phenyl]essigsäure wurden in 15 ml chlormethan gelöst und mit zwei Tropfen Dimethylformamid versetzt. Man gab 0.81 g (6.41 mmol) xalylchlorid tropfenweise hinzu und erhitzte 1 h lang bis zum Ende der Gasentwicklung unter Rückfluss m Sieden. Anschließend engte man die Reaktionslösung zur Trockne ein und nahm in 10 ml chlormethan auf. (Lösung 1). einem separaten Kolben wurden 0.72 g (3.21 mmol) 4-Methoxy-l- methoxycarbonyl)cyclohexanaminiumchlorid sowie 1.79 ml Triethylamin in 50 ml Dichlormethan rgelegt und unter Rühren Lösung 1 zugetropft. Nach 1 h Rühren bei Raumtemperatur wurde mit asser gewaschen, die organische Phase abgetrennt, das Lösungsmittel im Vakuum entfernt und der ückstand säulenchromatographisch (Silicagel, Gradient Ethylacetat/n-Heptan) gereinigt. an erhielt 1.00 g (80%) der gewünschten Zwischenstufe. nalog wurden folgende Zwischenstufen hergestellt:
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Preparation of Starting Materials Example Q2.1: ethyl l- {2- [2-ethyl-6-methyl-4- (prop-l-en-l-yl) phenyl] acetamido} -4-methoxycyclohexane carboxylate
Figure imgf000072_0001
70 g (3.21 mmol) of [2-ethyl-6-methyl-4- (prop-1-en-1-yl) phenyl] acetic acid were dissolved in 15 ml of chloromethane and two drops of dimethylformamide were added. 0.81 g (6.41 mmol) of xalyl chloride were added dropwise and the mixture was heated under reflux for 1 h until the evolution of gas had ceased. The reaction solution was then concentrated to dryness and taken up in 10 ml of chloromethane. (Solution 1). 0.72 g (3.21 mmol) of 4-methoxy-1-methoxycarbonyl) cyclohexanaminium chloride and 1.79 ml of triethylamine in 50 ml of dichloromethane were placed in a separate flask and solution 1 was added dropwise with stirring. After stirring for 1 h at room temperature, the mixture was washed with water, the organic phase was separated off, the solvent was removed in vacuo and the residue was purified by column chromatography (silica gel, gradient ethyl acetate / n-heptane). an received 1.00 g (80%) of the desired intermediate. nalog the following intermediate stages were produced:
Figure imgf000073_0001
Figure imgf000074_0001
Beispiel Q3.1:
Figure imgf000073_0001
Figure imgf000074_0001
Example Q3.1:
[2-Ethyl-6-methyl-4-(prop- 1-en-l -yl)phenyl] essigsäure [2-Ethyl-6-methyl-4- (prop-1-en-1-yl) phenyl] acetic acid
Schritt 1: Methyl- [2-ethyl-6-methyl-4-(prop- 1-en-l -yl)phenyl] acetat (Beispiel Q4.1)
Figure imgf000075_0001
Step 1: methyl- [2-ethyl-6-methyl-4- (prop-1-en-l -yl) phenyl] acetate (example Q4.1)
Figure imgf000075_0001
3.62 g (26.55 mmol) Zinkchlorid und 1.13 g (26.55 mmol) Lititiumchlorid wurden bei 140°C im Hochvakuum 3 h lang getrocknet. Man ließ auf Raumtemperatur abkühlen, belüftete mit Argon, löste in 57 ml Tetrahydrofuran und kühlte die Lösung auf 0°C. Bei dieser Temperatur wurden unter Rühren 53 ml (26.55 mmol) einer käuflichen 0.5M Lösung von 1 -Propenylmagnesi umbromid in Tetrahydrofuran zugetropft. Man ließ auf Raumtemperatur kommen, rührte 1 h nach, versetzte mit 1.02 g (0.88 mmol) Tetrakis(triphenylphosphm)palladium(0) und tropfte dann eine Lösung von 4.00 g (14.75 mmol) Methyl-(4-brom-2-ethyl-6-methylphenyl)acetat (CAS Registry Nummer 181300-41- 4) in T etrahy drofuran zu. Man ließ 14 h bei 60°C rühren, versetzte mit weiteren 1.02 g (0.88 mmol) Tetrakis(triphenylphosphin)palladium(0) und ließ weitere 14 h bei 60°C rühren. Nach dem Abkühlen auf Raumtemperatur gab man auf Wasser und extrahierte mehrmals mit Ethylacetat. Die vereinigten organischen Phasen wurden getrocknet und im Vakuum eingeengt. Der Rückstand wurde an Kieselgel (Ethyl acetat/Hexan) chromatographiert. 3.62 g (26.55 mmol) of zinc chloride and 1.13 g (26.55 mmol) of lithium chloride were dried at 140 ° C. in a high vacuum for 3 hours. The mixture was allowed to cool to room temperature, vented with argon, dissolved in 57 ml of tetrahydrofuran and the solution was cooled to 0 ° C. At this temperature, 53 ml (26.55 mmol) of a commercially available 0.5M solution of 1-propenyl magnesia bromide in tetrahydrofuran were added dropwise with stirring. The mixture was allowed to come to room temperature, stirred for 1 h, admixed with 1.02 g (0.88 mmol) of tetrakis (triphenylphosphine) palladium (0) and then a solution of 4.00 g (14.75 mmol) of methyl (4-bromo-2-ethyl- 6-methylphenyl) acetate (CAS registry number 181300-41-4) in tetrahydrofuran. The mixture was left to stir at 60 ° C. for 14 h, a further 1.02 g (0.88 mmol) of tetrakis (triphenylphosphine) palladium (0) were added and the mixture was stirred at 60 ° C. for a further 14 h. After cooling to room temperature, the mixture was poured into water and extracted several times with ethyl acetate. The combined organic phases were dried and concentrated in vacuo. The residue was chromatographed on silica gel (ethyl acetate / hexane).
Man erhielt 1.00 g (29%) der gewünschten Zwischenstufe. Schritt 2: [2-Ethyl-6-methyl-4-(prop- 1 -en-1 -yl)phenyl] essigsäure (Beispiel Q3.1)
Figure imgf000075_0002
1.00 g (29%) of the desired intermediate was obtained. Step 2: [2-Ethyl-6-methyl-4- (prop- 1 -en-1 -yl) phenyl] acetic acid (example Q3.1)
Figure imgf000075_0002
Zu einer Lösung von 1.00 g (4.30 mmol) Methyl- [2-ethyl-6-methyl-4-(prop- 1-en-l -yl)phenyl] acetat in 12 ml 2-Propanol wurden 0.85 g (12.9 mmol) 85%iges Kaliumhydroxid gegeben und unter Rückfluß bis zur vollständigen Verseifung erhitzt. Man engte ein, nahm in Wasser auf, wusch mit Dichlormethan, säuerte die wäßrige Phase mit Salzsäure bis pH=3 an und extrahierte die wäßrige Phase mehrmals mit Dichlormethan. Die vereinigten organischen Phasen wurden getrocknet und eingeengt Man erhielt 0.70 g (74%) der gewünschten Zwischenstufe. 0.85 g (12.9 mmol) were added to a solution of 1.00 g (4.30 mmol) of methyl [2-ethyl-6-methyl-4- (prop-1-en-l -yl) phenyl] acetate in 12 ml of 2-propanol 85% potassium hydroxide added and heated under reflux until complete saponification. It was concentrated, taken up in water, washed with dichloromethane, the aqueous phase was acidified with hydrochloric acid to pH = 3 and the aqueous phase was extracted several times with dichloromethane. The combined organic phases were dried and concentrated 0.70 g (74%) of the desired intermediate was obtained.
Beispiel Q4.5: Example Q4.5:
Methyl-[2-brom-6-methoxy-4-(3 ,3,3 -trifluorprop- 1 -en- 1 -yl)phenyl] acetat Methyl [2-bromo-6-methoxy-4- (3,3,3-trifluoroprop-1-en-1 -yl) phenyl] acetate
Schritt 1: Methyl-(2-brom-4-formyl-6-methoxyphenyl)acetat (Beispiel Q4.7)
Figure imgf000076_0001
Step 1: methyl (2-bromo-4-formyl-6-methoxyphenyl) acetate (example Q4.7)
Figure imgf000076_0001
Zu einer Lösung von 2.00 g (5.20 mmol) Methyl-(2-brom-4-iod-6-methoxyphenyl)acetat (Synthese siehe in WO2019219587) in 20 ml trockenem Tetrahydrofuran wurden unter Argon bei 0°C 2.8 ml (5.56 mmol) einer 2.0M Lösung von 2-Propylmagnesiumchlorid in Tetrahydrofuran getropft. Das Reaktionsgemisch wurde sich auf Raumtemperatur erwärmen gelassen. Nach 1 h wurde auf 0°C gekühlt und mit 1,20 ml (15.60 mmol) Dimethylformamid versetzt. To a solution of 2.00 g (5.20 mmol) of methyl (2-bromo-4-iodo-6-methoxyphenyl) acetate (for synthesis see in WO2019219587) in 20 ml of dry tetrahydrofuran were added under argon at 0 ° C 2.8 ml (5.56 mmol) a 2.0M solution of 2-propylmagnesium chloride in tetrahydrofuran was added dropwise. The reaction mixture was allowed to warm to room temperature. After 1 h, the mixture was cooled to 0 ° C. and 1.20 ml (15.60 mmol) of dimethylformamide were added.
Das Lösungsmittel wurde im Vakuum entfert, der Rückstand mit Dichlormethan aufgenommen, mit gesättigter Ammoniumchlorid-Lösung gewaschen und eingeengt. The solvent was removed in vacuo, the residue was taken up in dichloromethane, washed with saturated ammonium chloride solution and concentrated.
Man erhielt 0.72 g (Ausbeute 48 %) der gewünschten Zwischenstufe. 0.72 g (yield 48%) of the desired intermediate were obtained.
Schritt 2: Methyl-[2-brom-6-methoxy-4-(3 ,3 ,3 -trifluorprop- 1 -en- 1 -yl)phenyl]acetat (Beispiel Q4.5)
Figure imgf000076_0002
Step 2: methyl [2-bromo-6-methoxy-4- (3, 3, 3 -trifluoroprop-1-en-1-yl) phenyl] acetate (example Q4.5)
Figure imgf000076_0002
Zu einer Lösung von 0.40 g (1.39 mmol) Methyl-(2-brom-4-formyl-6-methoxyphenyl)acetat imd 0.63 g (1.27 mmol) Triphenyl(2,2,2-trifluorethyl)phosphomumtrifluormethansulfonat (CAS Registry Nummer 135654-55-6, T. Hanamoto, N. Morita imd K. Shindo in Eur. J Org. Chem. 2003, 4279-4285, DOI: 10.1002/ejoc.200300395) in 11 ml Dimethylformamid wurden bei Raumtemperatur portionsweise insgesamt 0.44 g (2.91 mmol) Caesiumfluorid gegeben und 20 h bei Raumtemperatur nachrühren gelassen. Man versetzte mit weiteren 0.63 g (1.27 mmol) Triphenyl(2,2,2-trifluorethyl)phosphoniumtrifluormethansulfonat sowie 0.44 g (2.91 mmol) Caesiumfluorid und rührte weitere 4 h bei Raumtemperatur und weitere 4 Tage bei 30°C nach. Man gab auf Wasser, extrahierte die wäßrige Phase mehrmals mit Ethylacetat. Die vereinigten organischen Phasen wurden getrocknet und eingeengt. To a solution of 0.40 g (1.39 mmol) methyl (2-bromo-4-formyl-6-methoxyphenyl) acetate and 0.63 g (1.27 mmol) triphenyl (2,2,2-trifluoroethyl) phosphomum trifluoromethanesulfonate (CAS registry number 135654- 55-6, T. Hanamoto, N. Morita and K. Shindo in Eur. J Org. Chem. 2003, 4279-4285, DOI: 10.1002 / ejoc.200300395) in 11 ml of dimethylformamide a total of 0.44 g (2.91 mmol) given cesium fluoride and allowed to stir at room temperature for 20 h. A further 0.63 g (1.27 mmol) of triphenyl (2,2,2-trifluoroethyl) phosphonium trifluoromethanesulfonate and 0.44 g (2.91 mmol) were added Cesium fluoride and stirred for a further 4 hours at room temperature and a further 4 days at 30 ° C. It was added to water and the aqueous phase was extracted several times with ethyl acetate. The combined organic phases were dried and concentrated.
Man erhielt 0.41 g (Ausbeute 59 %) der gewünschten Zwischenstufe. 0.41 g (yield 59%) of the desired intermediate was obtained.
Beispiel Q4.2: Example Q4.2:
Methyl- [2-chlor-6-methoxy-4-(prop- 1-en- l-yl)phenyl] acetat Schritt 1: Methyl-(2-chlor-6-methoxy-4-nitrophenyl)acetat
Figure imgf000077_0001
6.10 g (59.2 mmol) tert-Butylnitrit und 5.97 g (44.4 mmol) Kupfer(II)-chlorid wurden in 60 mlMethyl [2-chloro-6-methoxy-4- (prop-1-en-l-yl) phenyl] acetate Step 1: Methyl (2-chloro-6-methoxy-4-nitrophenyl) acetate
Figure imgf000077_0001
6.10 g (59.2 mmol) tert-butyl nitrite and 5.97 g (44.4 mmol) copper (II) chloride were in 60 ml
Acetonitril suspendiert und auf 0°C gekühlt. Dann wurden 40.20 g (415 mmol) Vinylidenchlorid langsam zugetropft und 1 h nachgerüht, bevor auf 40°C erwärmt wurde. Bei dieser Temperatur wurden portionsweise insgesamt 6.00 g (29.6 mmol) 2-Chlor-6-methoxy-4-nitroanilin (CAS Registry Nummer 41956-18-7) zugegeben. Nach beendeter Zugabe wurde noch 20 h bei 40°C gerührt. Unter Eiskühlung wurde langsam mit IM Salzsäure versetzt, mit Ethylacetat extrahiert, mit Wasser und gesättigter Kochsalzlösung gewaschen und über Natriumsulfat getrocknet und eingeengt. Suspended acetonitrile and cooled to 0 ° C. 40.20 g (415 mmol) of vinylidene chloride were then slowly added dropwise and the mixture was stirred for 1 hour before the mixture was heated to 40.degree. At this temperature, a total of 6.00 g (29.6 mmol) of 2-chloro-6-methoxy-4-nitroaniline (CAS registry number 41956-18-7) were added in portions. After the addition had ended, the mixture was stirred at 40 ° C. for a further 20 h. 1M hydrochloric acid was added slowly while cooling with ice, the mixture was extracted with ethyl acetate, washed with water and saturated sodium chloride solution, dried over sodium sulfate and concentrated.
Man erhielt 9.40 g des Rohprodukts l-Chlor-3-methoxy-5-nitro-2-(2,2,2-trichlorethyl)benzol, welches direkt in der folgenden Reaktion eingesetzt wurde. 9.40 g of the crude product 1-chloro-3-methoxy-5-nitro-2- (2,2,2-trichloroethyl) benzene, which was used directly in the following reaction, were obtained.
9.40 g (29.5 mmol) dieses rohen Zwischenproduktes wurden in 50 ml Methanol gelöst, auf 0°C gekühlt und langsam mit 21.2 g (118.0 mmol) einer 30%igen methanolischer Natriummethanolat- Lösung versetzt. Anschließend wurde 20 h lang unter Rückfluß erhitzt. Man kühlte auf 0°C, versetzte vorsichtig mit 3.47 g (35.40 mmol) konzentrierter Schwefelsäure und erhitzte weitere 2 h bis zum vollständigen Umsatz unter Rückfluß. 9.40 g (29.5 mmol) of this crude intermediate product were dissolved in 50 ml of methanol, cooled to 0 ° C. and slowly mixed with 21.2 g (118.0 mmol) of a 30% strength methanolic sodium methoxide solution. The mixture was then refluxed for 20 hours. The mixture was cooled to 0 ° C., 3.47 g (35.40 mmol) of concentrated sulfuric acid were carefully added and the mixture was refluxed for a further 2 h until conversion was complete.
Nach dem Abkühlen wurde mit Wasser versetzt, mit Ethylacetat extrahiert, und die organische Phase wurde mit gesättigter Kochsalzlösung gewaschen, über Natriumsulfat getrocknet und nach Abdestillieren des Lösungsmittel an Kieselgel mit Hexan/Essigester chromatographiert. Ausbeute 3.20 g (42% über zwei Schritte) After cooling, water was added, the mixture was extracted with ethyl acetate, and the organic phase was washed with saturated sodium chloride solution, dried over sodium sulfate and, after the solvent had been distilled off, chromatographed on silica gel with hexane / ethyl acetate. Yield 3.20 g (42% over two steps)
Schritt 2: Methyl-(4-amino-2-chlor-6-methoxyphenyl)acetat
Figure imgf000078_0002
Step 2: methyl (4-amino-2-chloro-6-methoxyphenyl) acetate
Figure imgf000078_0002
3.20 g (12.3 mmol) Methyl-(2-chlor-6-methoxy-4-nitrophenyl)acetat wurden in 40 ml eines Tetrahydrofuran-Wasser-Gemisches (V/V= 4/1) gelöst und portionsweise jeweils mit insgesamt 5.27 g (98.60 mmol) festem Ammoniumchlorid gefolgt von 2.75 g (49.3 mmol) Eisenpulver versetzt. Nach beendeter Zugabe wurde die Reaktionsmischung 21 h lang bei 70°C gerührt. 3.20 g (12.3 mmol) of methyl (2-chloro-6-methoxy-4-nitrophenyl) acetate were dissolved in 40 ml of a tetrahydrofuran-water mixture (V / V = 4/1) and each with a total of 5.27 g ( 98.60 mmol) of solid ammonium chloride followed by 2.75 g (49.3 mmol) of iron powder. After the addition had ended, the reaction mixture was stirred at 70 ° C. for 21 hours.
Das Reaktionsgemisch wurde auf Raumtemperatur gekühlt, über Celite filtriert und mit Methanol nachgewaschen. Das Filtrat wurde im Vakuum eingeengt, der Rückstand mit Wasser und Ethylacetat aufgenommen und die Phasen getrennt. Die wäßrige Phase wurde noch mit Ethylacetat extrahiert. Die vereinigten organischen Phasen wurden mit gesättigter Natriumhydrogencarbonat-Lösung und mit gesättigter Kochsalzlösung gewaschen, über Natriumsulfat getrocknet, filtriert und eingeengt. Man erhielt 2.50 g (85%) der gewünschten Zwischenverbindung. The reaction mixture was cooled to room temperature, filtered through Celite and washed with methanol. The filtrate was concentrated in vacuo, the residue was taken up in water and ethyl acetate and the phases were separated. The aqueous phase was extracted with ethyl acetate. The combined organic phases were washed with saturated sodium hydrogen carbonate solution and with saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated. 2.50 g (85%) of the desired intermediate compound were obtained.
Ή-ΝΜΚ (600 MHz, δ in ppm, CDCh): δ = 3.70 (s, 3H), 3.75 (s, 2H), 3.80 (s, 3H), 6.15 (s, 1H), 6.35 (s, 1H) Ή-ΝΜΚ (600 MHz, δ in ppm, CDCh): δ = 3.70 (s, 3H), 3.75 (s, 2H), 3.80 (s, 3H), 6.15 (s, 1H), 6.35 (s, 1H)
Schritt 3: Methyl-(2-chlor-4-iod-6-methoxyphenyl)acetat (Beispiel Q4.6)
Figure imgf000078_0001
Step 3: methyl (2-chloro-4-iodo-6-methoxyphenyl) acetate (example Q4.6)
Figure imgf000078_0001
Zu einer Lösung von 15 ml (170 mmol) konzentrierter Salzsäure in 50 ml Wasser wurden zwischen -5°C und 0°C insgesamt 6.50 g (28.3 mmol) Methyl-(4-amino-2-chlor-6-methoxyphenyl)acetat gegeben. Anschließend wurde eine Lösung von 2.05 g (29.7 mmol) Natriumnitrit in 10 ml Wasser tropfenweise zwischen -5°C und 0°C zugegeben und nach erfolgter Zugabe für weitere 30 min nachgerührt. Dann wurden 35 ml Ethylacetat zugegeben, bevor tropfenweise zwischen -5°C und 0°C eine Lösung von 7.05 g (42.4 mmol) Kaliumiodid in 15 ml Wasser zugegeben wurde. Nach der Zugabe wurde die Reaktionsmischung 2 h unter 0°C nachgerührt. Das Reaktionsgemisch wurde dann dreimal mit jeweils 60 ml Ethylacetat extrahiert. Die vereinigten organischen Phasen wurden mit gesättigter Natriumthiosulfat-Lösung, gesättigter Natriumhydrogencarbonat-Lösung, gesättigter Kochsalz-Lösung gewaschen, über Natriumsulfat getrocknet und eingeengt. Das Rohprodukt wurde durch Chromatographie an Kieselgel (Ethylacetat/Hexan) gereinigt. Man erhielt 6.00 g (60%) des gewünschten Zwischenproduktes. A total of 6.50 g (28.3 mmol) of methyl (4-amino-2-chloro-6-methoxyphenyl) acetate were added to a solution of 15 ml (170 mmol) of concentrated hydrochloric acid in 50 ml of water between -5 ° C. and 0 ° C. . A solution of 2.05 g (29.7 mmol) of sodium nitrite in 10 ml of water was then added dropwise between -5 ° C. and 0 ° C. and, after the addition, the mixture was stirred for a further 30 min. 35 ml of ethyl acetate were then added before a solution of 7.05 g (42.4 mmol) of potassium iodide in 15 ml of water was added dropwise between -5 ° C. and 0 ° C. After the addition, the reaction mixture was stirred below 0 ° C. for 2 h. The reaction mixture was then extracted three times with 60 ml of ethyl acetate each time. The combined organic phases were washed with saturated sodium thiosulphate solution, saturated sodium hydrogen carbonate solution, saturated sodium chloride solution, dried over sodium sulphate and concentrated. The crude product was purified by chromatography on silica gel (ethyl acetate / hexane). 6.00 g (60%) of the desired intermediate were obtained.
Ή-ΝΜΒ (600 MHz, δ in ppm, CDCh): δ = 3.70 (s, 3H), 3.75-3.85 (m, 5H), 7.10 (s, 1H), 7.40 (s,Ή-ΝΜΒ (600 MHz, δ in ppm, CDCh): δ = 3.70 (s, 3H), 3.75-3.85 (m, 5H), 7.10 (s, 1H), 7.40 (s,
1H) 1H)
Schritt 4: Methyl-[2-chlor-6-methoxy-4-(prop-l-en-l-yl)phenyl]acetat (Beispiel Q4.2)
Figure imgf000079_0002
Step 4: methyl [2-chloro-6-methoxy-4- (prop-l-en-l-yl) phenyl] acetate (Example Q4.2)
Figure imgf000079_0002
0.72 g (5.29 mmol) Zinkchlorid und 0.22 g (5.29 mmol) Lithiumchlorid wurden in 8 ml Tetrahydrofuran gelöst, und die entstandene Lösung wurde auf 0°C gekühlt. Bei dieser Temperatur tropfte man unter Rühren insgesamt 10.5 ml (5.29 mmol) einer käuflichen 0.5M Lösung von 1-Propenylmagnesiumbromid in Tetrahydrofuran zu. Man ließ auf Raumtemperatur kommen, rührte 1 h nach, versetzte mit 0.20 g (0.18 mmol) Tetrakis(triphenylphosphm)palladium(0) und tropfte dann eine Lösung von 1.00 g (2.94 mmol) Methyl-(2-chlor-4-iod-6-methoxyphenyl)acetat in 2 ml Tetrahydrofuran langsam zu. Man ließ 2 h bei 70°C nachrühren. Das Lösungsmittel wurde im Vakuum entfernt und der Rückstand in Dichlormethan aufgenommen. Man wusch die organische Phase mit IM Salzsäure und gesättigter Kochsalzlösung, trocknete und engte im Vakuum ein. Der Rückstand wurde an Kieselgel (Ethylacetat/Hexan) chromatographiert. Man erhielt 0.42 g (54%) der gewünschten Zwischenstufe. Beispiel Q3.8 0.72 g (5.29 mmol) of zinc chloride and 0.22 g (5.29 mmol) of lithium chloride were dissolved in 8 ml of tetrahydrofuran, and the resulting solution was cooled to 0 ° C. At this temperature, a total of 10.5 ml (5.29 mmol) of a commercially available 0.5M solution of 1-propenylmagnesium bromide in tetrahydrofuran were added dropwise with stirring. The mixture was allowed to come to room temperature, stirred for 1 h, treated with 0.20 g (0.18 mmol) of tetrakis (triphenylphosphine) palladium (0) and then a solution of 1.00 g (2.94 mmol) of methyl (2-chloro-4-iodo- 6-methoxyphenyl) acetate in 2 ml of tetrahydrofuran slowly. The mixture was left to stir at 70 ° C. for 2 h. The solvent was removed in vacuo and the residue was taken up in dichloromethane. The organic phase was washed with 1M hydrochloric acid and saturated sodium chloride solution, dried and concentrated in vacuo. The residue was chromatographed on silica gel (ethyl acetate / hexane). 0.42 g (54%) of the desired intermediate was obtained. Example Q3.8
Methyl- [2-chlor-6-methoxy-4-(2-methylprop- 1-en- l-yl)phenyl] acetat
Figure imgf000079_0001
Methyl [2-chloro-6-methoxy-4- (2-methylprop-1-en-1-yl) phenyl] acetate
Figure imgf000079_0001
Durch eine Lösung von 1.500 g (4.40 mmol) Methyl-(2-chlor-4-iod-6-methoxyphenyl)acetat, 0.57 g (5.70 mmol) (2-Methylprop-l-en-l-yl)boronsäure und 3.65 g (26.43 mmol) Kaliumcarbonat in 8 ml Wasser und 30 ml 1 ,2-Dimethoxyethan wurde 30 min lang Argon geleitet. Through a solution of 1,500 g (4.40 mmol) of methyl (2-chloro-4-iodo-6-methoxyphenyl) acetate, 0.57 g (5.70 mmol) of (2-methylprop-l-en-l-yl) boronic acid and 3.65 g (26.43 mmol) potassium carbonate in 8 ml of water and 30 ml of 1,2-dimethoxyethane were passed in argon for 30 minutes.
Anschließend wurden 0.26 g (0.22 mmol) Tetrakis(triphenylphoshine)palladium(0) zu dieser Lösung gegeben, und es wurde 6 h zum Rückfluß erhitzt. Das Lösungsmittel wurde im Vakuum entfernt, der Rückstand in Wasser aufgenommen und mit Ethylacetat extrahiert. Die organische Phase wurde getrocknet und eingeengt. Then 0.26 g (0.22 mmol) of tetrakis (triphenylphoshine) palladium (0) were added to this solution, and the mixture was refluxed for 6 h. The solvent was removed in vacuo, the residue was taken up in water and extracted with ethyl acetate. The organic phase was dried and concentrated.
Der Rückstand wurde an Kieselgel (Ethylacetat/Heptan) chromatographiert. The residue was chromatographed on silica gel (ethyl acetate / heptane).
Man erhielt 0.93 g (79%) der gewünschten Zwischenstufe. Analog wurden folgende Verbindungen hergestelt 0.93 g (79%) of the desired intermediate was obtained. The following connections were made analogously
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
A. Formulierungsbeispiele a) Ein Stäubemittel wird erhalten, indem man 10 Gew. Teile einer Verbindung der Formel (I) und/oder deren Salze und 90 Gew. Teile Talkum als Inertstoff mischt und in einer Schlagmühle zerkleinert. b) Ein in Wasser leicht dispergierbares, benetzbares Pulver wird erhalten, indem man 25 Gewichtsteile einer Verbindung der Formel (I) und/oder deren Salze, 64 Gew. Teile kaolinhaltigen Quarz als Inertstoff, 10 Gewichtsteile ligninsulfonsaures Kalium und 1 Gew. Teil oleoylmethyltaurinsaures Natrium als Netz und Dispergiermittel mischt und in einer Stiftmühle mahlt. c) Ein in Wasser leicht dispergierbares Dispersionskonzentrat wird erhalten, indem man 20 Gew. Teile einer Verbindung der Formel (I) und/oder deren Salze mit 6 Gew. Teilen Alkylphenolpolyglykolether ((DTriton X 207), 3 Gew. Teilen Isotridecanolpolyglykolether (8 EO) und 71 Gew. Teilen paraffinischem Mineralöl (Siedebereich z.B. ca. 255°C bis über 277° C) mischt und in einer Reibkugelmühle auf eine Feinheit von unter 5 Mikron vermahlt d) Ein emulgierbares Konzentrat wird erhalten aus 15 Gew. Teilen einer Verbindung der Formel (I) und/oder deren Salze, 75 Gew. Teilen Cyclohexanon als Lösungsmittel und 10 Gew. Teilen oxethyliertes Nonylphenol als Emulgator. e) Ein in Wasser dispergierbares Granulat wird erhalten indem man
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
A. Formulation Examples a) A dusting agent is obtained by mixing 10 parts by weight of a compound of the formula (I) and / or its salts and 90 parts by weight of talc as an inert substance and comminuting it in a hammer mill. b) A wettable powder which is easily dispersible in water is obtained by adding 25 parts by weight of a compound of the formula (I) and / or salts thereof, 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurinate mixes as a wetting agent and dispersant and grinds in a pin mill. c) A dispersion concentrate which is easily dispersible in water is obtained by adding 20 parts by weight of a compound of the formula (I) and / or its salts with 6 parts by weight of alkylphenol polyglycol ether ((DTriton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO ) and 71 parts by weight of paraffinic mineral oil (boiling range for example approx. 255 ° C to over 277 ° C) and ground in an attrition ball mill to a fineness of less than 5 microns. d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of Formula (I) and / or salts thereof, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier. e) A water-dispersible granulate is obtained by
75 Gew. Teile einer Verbindung der Formel (I) und/oder deren Salze, 10 Gew. Teile ligninsulfonsaures Calcium, 75 parts by weight of a compound of the formula (I) and / or salts thereof, 10 parts by weight of calcium lignosulfonate,
5 Gew. Teile Natriumlaurylsulfat, 5 parts by weight of sodium lauryl sulfate,
3 Gew. Teile Polyvinylalkohol und 3 parts by weight of polyvinyl alcohol and
7 Gew. Teile Kaolin mischt auf einer Stiftmühle mahlt und das Pulver in einem Wirbelbett durch Aufsprühen von Wasser als Granulierflüssigkeit granuliert. f) Ein in Wasser dispergierbares Granulat wird auch erhalten, indem man 7 parts by weight of kaolin is mixed on a pin mill and the powder is granulated in a fluidized bed by spraying on water as a granulating liquid. f) A water-dispersible granulate is also obtained by
25 Gew. Teile einer Verbindung der Formel (I) und/oder deren Salze, 5 Gew. Teile 2,2' Dinaphthylmethan 6,6' disulfonsaures Natrium, 25 parts by weight of a compound of the formula (I) and / or its salts, 5 parts by weight of 2,2 'dinaphthylmethane 6,6' disulfonic acid sodium,
2 Gew. Teile oleoylmethyltaurinsaures Natrium, 2 parts by weight of sodium oleoylmethyltaurinate,
1 Gew. Teil Polyvinylalkohol, 1 part by weight of polyvinyl alcohol,
17 Gew. Teile Calciumcarbonat und 50 Gew. Teile Wasser auf einer Kolloidmühle homogenisiert und vorzerkleinert, anschließend auf einer Perlmühle mahlt und die so erhaltene Suspension in einem Sprühturm mittels einer Einstoffdüse zerstäubt und trocknet. 17 parts by weight of calcium carbonate and 50 parts by weight of water are homogenized and pre-comminuted in a colloid mill, then ground in a bead mill and the suspension thus obtained is atomized in a spray tower using a single-fluid nozzle and dried.
B. Biologische Daten 1. Herbizide Wirkung bzw. Kulturpflanzenverträglichkeit im Nachauflauf B. Biological data 1. Post-emergence herbicidal activity or crop plant tolerance
Samen von mono- bzw. dikotylen Unkraut- bzw. Kulturpflanzen werden in Holzfasertöpfen in sandigem Lehmboden ausgelegt, mit Erde abgedeckt und im Gewächshaus unter guten Wachstumsbedingungen angezogen. 2 bis 3 Wodien nach der Aussaat werden die Versuchspflanzen im Einblattstadium behandelt. Die in Form von benetzbaren Pulvern (WP) oder als Emulsionskonzentrate (EC) formulierten erfindungsgemäßen Verbindungen werden dann als wässrige Suspension bzw. Emulsion mit einer Wasseraufwandmenge von umgerechnet 600 bis 800 1/ha unter Zusatz von 0,2% Netzmittel auf die grünen Pflanzenteile gesprüht. Nach ca. 3 Wochen Standzeit der Versuchspflanzen im Gewächshaus unter optimalen Wachstumsbedingungen wird die Wirkung der Präparate visuell im Vergleich zu unbehandelten Kontrollen bonitiert (herbizide Wirkung in Prozent (%): 100% Wirkung = Pflanzen sind abgestorben, 0 % Wirkung = wie Kontrollpflanzen). Seeds of monocotyledonous and dicotyledonous weed or crop plants are placed in wooden fiber pots in sandy loam soil, covered with soil and grown in a greenhouse under good growth conditions. The test plants are treated in the single-leaf stage 2 to 3 weeks after sowing. The compounds according to the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then sprayed onto the green parts of the plant as an aqueous suspension or emulsion with a water application rate of 600 to 800 l / ha with the addition of 0.2% wetting agent . After the test plants have stood in the greenhouse for about 3 weeks under optimal growth conditions, the effect of the preparations is rated visually in comparison to untreated controls (herbicidal effect in percent (%): 100% effect = plants have died, 0% effect = like control plants).
Unerwünschte Pflanzen / Weeds:
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Unwanted Plants / Weeds:
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Wie die Ergebnisse aus Tabelle 1-12 zeigen, weisen die erfindungsgemäßen Verbindungen eine gute herbizide Nachauflaufwirksamkeit gegen ein breites Spektrum von Ungräsem und Unkräutern auf. Beispielsweise zeigen die aufgeführten Beispiele bei einer Aufwandmenge von 80 g/ha eine 80 - 100%-ige Wirkung unter anderem gegen Alopecurus myosuroides, Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Lolium rigidum, Setaria viridis und Hordeum murinum. Die erfindungsgemäßen Verbindungen eignen sich deshalb im Nachauflaufverfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs. As the results from Table 1-12 show, the compounds according to the invention have good herbicidal post-emergence activity against a broad spectrum of grass weeds and weeds. For example, the examples given show an application rate of 80 g / ha 80 - 100% effect against, among others, Alopecurus myosuroides, Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Lolium rigidum, Setaria viridis and Hordeum murinum. The compounds according to the invention are therefore suitable for combating undesired vegetation by the post-emergence method.
2. Herbizide Wirkung bzw. Kulturpflanzenverträglichkeit im Vorauflauf 2. Herbicidal action or crop plant tolerance in pre-emergence
Samen von mono- bzw. dikotylen Unkraut- bzw. Kulturpflanzen werden in Holzfasertöpfen in sandiger Lehmerde ausgelegt und mit Erde abgedeckt. Die in Form von benetzbaren Pulvern (WP) oder als Emulsionskonzentrate (EC) formulierten erfindungsgemäßen Verbindungen werden dann als wässrige Suspension bzw. Emulsion mit einer Wasseraufwandmenge von umgerechnet 600 bis 8001/ha unter Zusatz von 0,2% Netzmittel auf die Oberfläche der Abdeckerde appliziert. Seeds of monocotyledonous or dicotyledonous weed or crop plants are laid out in wooden fiber pots in sandy loam and covered with soil. The compounds according to the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then applied to the surface of the covering soil as an aqueous suspension or emulsion with a water application rate of 600 to 800 l / ha with the addition of 0.2% wetting agent .
Nach der Behandlung werden die Töpfe im Gewächshaus aufgestellt und unter guten Wachstumsbedingungen für die Testpflanzen gehalten. Die visuelle Bonitur der Schäden an dm Versuchspflanzen erfolgt nach einer Versuchszeit von 3 Wochen im Vergleich zu unbehandelten Kontrollen (herbizide Wirkung in Prozent (%): 100% Wirkung = Pflanzen sind abgestorben, 0 % Wirkung = wie Kontrollpflanzen). After the treatment, the pots are placed in the greenhouse and kept under good growth conditions for the test plants. The visual assessment of the damage to the test plants takes place after a test period of 3 weeks in comparison with untreated controls (herbicidal effect in percent (%): 100% effect = plants have died, 0% effect = like control plants).
Tabelle 13: Vorauflaufwirkung bei 80 g/ha gegen ALOMY in %
Figure imgf000092_0001
Tabelle 14: Vorauflaufwiikung bei 80 g/ha gegen AVEFA in % Table 13: Pre-emergence effect at 80 g / ha against ALOMY in%
Figure imgf000092_0001
Table 14: Pre-emergence development at 80 g / ha against AVEFA in%
< <
BeispielDosierung nummer [g/ha] I Example dosage number [g / ha] I
D1.2 80 90 D1.2 80 90
D2.1 80 80 D2.1 80 80
D2.2 80 90 D2.2 80 90
D2.4 80 90 D2.4 80 90
D2.5 80 90 D2.5 80 90
P1.2 80 100 P1.2 80 100
P2.2 80 80 P2.2 80 80
P2.3 80 80 P2.3 80 80
P2.5 80 100 P2.5 80 100
Sl.l 80 80 Sl.l 80 80
S2.4 80 90 S2.4 80 90
Tabelle 15: Vorauflaufwiikung bei 80 g/ha gegen DIGSA in % Table 15: Pre-emergence development at 80 g / ha against DIGSA in%
< <
Beispiel- Dosierung C/3 mimmer O Example dosage C / 3 always O
[g/ha] NN [g / ha] NN
Q Q
D1.2 80 100 D1.2 80 100
D2.3 80 90 D2.3 80 90
D2.4 80 100 D2.4 80 100
D2.5 80 100 D2.5 80 100
D2.6 80 90 D2.6 80 90
P1.2 80 100 P1.2 80 100
P2.3 80 100 P2.3 80 100
P2.4 80 100 P2.4 80 100
P2.5 80 100 P2.5 80 100
P2.6 80 100 P2.6 80 100
P2.7 80 100 P2.7 80 100
S2.2 80 90 S2.2 80 90
S2.4 80 100 S2.4 80 100
S2.5 80 100 S2.5 80 100
S2.6 80 100 Tabelle 16: Vorauflaufwiikung bei 80 g/ha gegen ECHCG in %S2.6 80 100 Table 16: Pre-emergence development at 80 g / ha against ECHCG in%
BeispielDosierung U nummer [g/ha] U Example dosage U number [g / ha] U
W W.
D2.1 80 100 D2.1 80 100
D2.4 80 80 D2.4 80 80
D2.5 80 100 D2.5 80 100
D2.6 80 100
Figure imgf000094_0001
Figure imgf000095_0001
mimmfir [g/ha] 2
Figure imgf000096_0001
Figure imgf000097_0001
D2.6 80 100
Figure imgf000094_0001
Figure imgf000095_0001
mimmfir [g / ha] 2
Figure imgf000096_0001
Figure imgf000097_0001
Wie die Ergebnisse aus der Tabelle 13-27 zeigen, weisen die erfindungsgemäßen Verbindungen eine gute herbizide Vorauflaufwirksamkeit gegen ein breites Spektrum von Ungräsem und Unkräutern auf. Beispielsweise zeigen die Verbindungen bei einer Aufwandmenge von 80 g/ha jeweils eine 80 - 100%-ige Wirkung unter anderem gegen Alopecurus myosuroides, Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Lolium rigidum, Setaria viridis, Amaranthus retroflexus, Matricaria inodora, Stellaria media, Viola tricolor, Veronica persica und Hordeum murinum. Die erfindungsgemäßen Verbindungen eignen sich deshalb im Vorauflaufverfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs. As the results from Table 13-27 show, the compounds according to the invention have good herbicidal pre-emergence activity against a broad spectrum of grass weeds and weeds. For example, at an application rate of 80 g / ha, the compounds each show an 80-100% effect against, among others, Alopecurus myosuroides, Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Lolium rigidum, Setaria viridis, Amaranthus retroflexus, Matricaria inodora, Stellaria media, Viola tricolor, Veronica persica and Hordeum murinum. The compounds according to the invention are therefore suitable in the pre-emergence method for controlling undesired vegetation.

Claims

Patentansprüche Claims
1. 3 -Phenylpyrrolin-2one der allgemeinen Formel (I) oder ein agrochemisch akzeptables Salz davon,
Figure imgf000098_0002
wobei 1. 3-phenylpyrrolin-2ones of the general formula (I) or an agrochemically acceptable salt thereof,
Figure imgf000098_0002
whereby
R1 (C1-C6)- Alkyl, Halogen-(Ci-C6>alkyl, (C1-C6)-Alkoxy, Halogen-(Ci-C6>alkox(yC,1-C4)- Alkoxy-(C1-C4)-alkyl, Halogen-(C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C6)- Alkoxy-(C 1-C4)- alkoxy, Halogen-(C1-C6)-alkoxy-(C2-C4)-alkoxy , (C3-C6)-Cycloalkyl, (C1-C6)- Alkenyloxy, Halogen-(C2-C6)-alkenyloxy, (C1-C6)-Alkinyloxy oder Cyano-(C1-C6)-alkoxy ist, R 1 (C 1 -C 6 ) alkyl, halogen (Ci-C6> alkyl, (C 1 -C 6 ) alkoxy, halogen (Ci-C6> alkox (yC, 1 -C 4 ) alkoxy) (C 1 -C 4 ) -alkyl, halo- (C 1 -C 4 ) -alkoxy- (C 1 -C 4 ) -alkyl, (C 1 -C 6 ) -alkoxy- (C 1-C4) -alkoxy , Halogen- (C 1 -C 6 ) -alkoxy- (C2-C4) -alkoxy, (C 3 -C 6 ) -cycloalkyl, (C 1 -C 6 ) -alkenyloxy, halogen- (C 2 -C 6 ) -alkenyloxy, (C 1 -C 6 ) -alkinyloxy or cyano- (C 1 -C 6 ) -alkoxy,
R2 Wasserstoff, (C1-C6)- Alkyl, (C 1-C4)- Alkoxy-(C1-C4)-alkyl, Halogen-(C1-C6)-alkyl, (C3-C6)-R 2 is hydrogen, (C 1 -C 6 ) -alkyl, (C 1-C4) -alkoxy- (C 1 -C 4 ) -alkyl, halogen- (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -
Cy cloalkyl, (C3-C6)-Cycloalkyl-(C1-C4)-alkyl, (C2-C6)-Alkenyl, (C2-C6)-Alkmyl, (C1-C6)- Alkoxy oder Halogen-(C1-C6)-alkoxy ist, Cycloalkyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 4 ) -alkyl, (C 2 -C 6 ) -alkenyl, (C 2 -C 6 ) -alkmyl, (C 1 -C 6 ) - is alkoxy or halogen (C 1 -C 6 ) alkoxy,
X (C1-C6)- Alkyl, Halogen-(C1-C6)-alkyl, (C3-Cö)-Cycloalkyl, (C1-C6)-Alkoxy, Halogen-(C1- C6)-alkoxy, Brom, Chlor oder Fluor ist, X (C 1 -C 6) - alkyl, halo (C 1 -C 6) alkyl, (C3-COE) cycloalkyl, (C 1 -C 6) alkoxy, halo (C 1 - C 6) -alkoxy, bromine, chlorine or fluorine,
Y (C1-C6)- Alkyl, Halogen-(C1-C6)-alkyl, (C3-C6>Cycloalkyl, (C1-C6)- Alkoxy, Halogen-(C1- C6)-alkoxy ist, Y is (C 1 -C 6) - alkyl, halo (C 1 -C 6) alkyl, (C3-C6> cycloalkyl, (C 1 -C 6) - alkoxy, halo (C 1 - C 6) - is alkoxy,
R10 Wasserstoff, Fluor, (C1-C6)- Alkyl oder Halogen-(C1-C6)-alkyl ist, R 10 is hydrogen, fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) alkyl,
R11 Fluor, (C1-C6)- Alkyl oder Halogen-(C1-C6)-alkyl ist, R12 Wasserstoff, Fluor, (C1-C6)-Alkyl oder Halogen-(C1-C6)-alkyl ist R 11 is fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) alkyl, R 12 is hydrogen, fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) -alkyl
G Wasserstoff, eine abspaltbare Gruppe L oder ein Kation E ist, wobei L einer der folgenden Reste ist
Figure imgf000098_0001
worin G is hydrogen, a leaving group L or a cation E, where L is one of the following radicals
Figure imgf000098_0001
wherein
R3 (C1-C4)- Alkyl oder (C 1-C3)- Alkoxy-(C1-C4)-alkyl ist, R 3 is (C 1 -C 4 ) -alkyl or (C 1-C3) -alkoxy- (C 1 -C 4 ) -alkyl,
R*(C1-C4)- Alkyl ist, R5 (C1-C4)- Alkyl, ein unsubstituiertes Phenyl oder ein einfach oder mehrfach mit Halogen, (Ci- C4)-Alkyl, Halogen-(C1-C4)-alkyl, (C1-C4)A-lkoxy, Halogen-(C1-C4)-alkoxy , Nitro oder Cyano substituiertes Phenyl ist, R * is (C 1 -C 4 ) alkyl, R 5 (C 1 -C 4 ) - alkyl, an unsubstituted phenyl or a single or multiple with halogen, (Ci- C4) -alkyl, halogen- (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) A-alkoxy, halogen- (C 1 -C 4 ) -alkoxy, nitro or cyano-substituted phenyl,
R6, R6‘ unabhängig voneinander Methoxy oder Ethoxy ist, R7· R8 jeweils unabhängig voneinander Methyl, Ethyl, Phenyl ist, oder gemeinsam mit demR 6 , R 6 'are independently methoxy or ethoxy, R 7 · R 8 are each independently methyl, ethyl, phenyl, or together with the
Stickstoffatom, an das sie gebunden sind, emen gesättigten 5-, 6- oder 7-gliedrigen Ring bilden, wobei ein Ringkohlenstoffatom gegebenenfalls durch ein Sauerstoff- oder Schwefelatom ersetzt sein kann, Nitrogen atom to which they are bonded form a saturated 5-, 6- or 7-membered ring, where a ring carbon atom can optionally be replaced by an oxygen or sulfur atom,
E ein Alkalimetallion, ein Ionenäquivalent eines Erdalkalimetalls, ein Ionenäquivalent Aluminium, ein Ionenäquivalent eines Übergangsmetalls, ein Magnesium-Halogen-Kation oder ein Ammoniumion ist, bei dem gegebenenfalls ein, zwei, drei oder alle vier Wasserstoffatome ersetzt sind durch gleiche oder verschiedene Reste aus den Gruppen (Ci-Cio)-Alkyl oder (C3-C7)- Cycloalkyl, die unabhängig voneinander jeweils ein- oder mehrfach mit Fluor, Chlor, Brom, Cyano, Hydroxy substituiert oder durch ein- oder mehrere Sauerstoff- oder Schwefelatome unterbrochen sein können, ein cyclisches sekundäres oder tertiäres aliphatisches oder heteroaliphatisches Ammoniumion ist, beispielsweise Morpholinium, Thiomorpholinium, Piperidinium, Pyrrolidinium oder jeweils protoniertes l,4-Diazabicyclo[1.1.2]octane (DABCO) oder l,5-Diazabicyclo[4.3.0]undec-7-en (DBU), ein heteroaromatisches Ammoniumkation ist, beispielsweise jeweils protoniertes fyridin, 2-Methylpyridin, 3 -Methylpyridin, 4-Methylpyridin, 2,4-Dimethylpyridin, 2,5-Dimethylpyridin, 2,6-Dimethylpyridin, 5-Ethyl-2-methylpyridin, Collidin, Pyrrol, Imidazol, Chinolin, Chinoxalin, 1 ,2-Dimethylimidazol, 1,3- Dimethylimidazolium-methylsulfat oder weiterhin auch für ein Trimethylsulfoniumion steht. E is an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent of aluminum, an ion equivalent of a transition metal, a magnesium-halogen cation or an ammonium ion in which one, two, three or all four hydrogen atoms are optionally replaced by identical or different radicals from the Groups (Ci-Cio) -alkyl or (C3-C7) -cycloalkyl, which, independently of one another, can be substituted one or more times with fluorine, chlorine, bromine, cyano, hydroxyl or interrupted by one or more oxygen or sulfur atoms, is a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, for example morpholinium, thiomorpholinium, piperidinium, pyrrolidinium or in each case protonated 1,4-diazabicyclo [1.1.2] octane (DABCO) or 1,5-diazabicyclo [4.3.0] undec-7 -en (DBU), is a heteroaromatic ammonium cation, for example protonated fyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimeth in each case ylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, collidine, pyrrole, imidazole, quinoline, quinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methyl sulfate or furthermore for a Trimethylsulfonium ion.
2. Verbindungen der Formel (I) gemäß Anspruch 1 oder ein agrochemisch akzeptables Salz davon, worin R1 (C1-C6)- Alkyl, Halogen-(Ci-C6>alkyl, (C1-C6)-Alkoxy, Halogen-(Ci-C6>alkoxy, (C1-C4)-2. Compounds of formula (I) according to claim 1 or an agrochemically acceptable salt thereof, wherein R 1 is (C 1 -C 6) - alkyl, halo (Ci-C6> alkyl, (C 1 -C 6) alkoxy, Halogen- (Ci-C6> alkoxy, (C 1 -C 4 ) -
Alkoxy-(C1-C4)-alkyl, Halogen-(C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C6)- Alkoxy-CCi-C*)- alkoxy, Halogen-(C1-C6)-alkoxy-(C2-C4)-alkoxy , (C1-C6)C-y cloalkyl, (C1-C6)A-lkenyloxy, Halogen-(C>C6)-alkenyloxy, (C2-C6)-Alkinyloxy oder Cyano-(C1-C6)-alkoxy ist, Alkoxy- (C 1 -C 4 ) -alkyl, halogen- (C 1 -C 4 ) -alkoxy- (C 1 -C 4 ) -alkyl, (C 1 -C 6 ) - alkoxy-CCi-C *) - alkoxy, halo (C 1 -C 6 ) alkoxy (C 2 -C 4 ) alkoxy, (C 1 -C 6 ) cycloalkyl, (C 1 -C 6 ) A-lkenyloxy, halo (C> Is C6) -alkenyloxy, (C 2 -C 6 ) -alkinyloxy or cyano- (C 1 -C 6 ) -alkoxy,
R2 Wasserstoff, (C1-C6)- Alkyl, (C1-CA4)l-koxy-(C2-C4)-alkyl, Halogen-(C1-C6)-alkyl, (C3-C6)- Cycloalkyl, (C2-C6)-Alkenyl oder (C2-C6)-Alkinyl, ist, R 2 is hydrogen, (C 1 -C 6 ) -alkyl, (C 1 -CA 4 ) l-koxy- (C 2 -C 4 ) -alkyl, halogen- (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (C 2 -C 6 ) -alkenyl or (C 2 -C 6 ) -alkynyl,
X (C1-C6)- Alkyl, Halogen-(C1-C6)-alkyl, (C3-C6)-Cycloalkyl, (Ci-G>)-Alkoxy, Halogen-(C1-X (C 1 -C 6 ) -alkyl, halogen- (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (Ci-G > ) -alkoxy, halogen- (C 1 -
C6)-alkoxy, Brom, Chlor oder Fluor ist, C 6 ) alkoxy, bromine, chlorine or fluorine,
Y(C1-C6)- Alkyl, Halogen-(C1-C6)-alkyl, (C3-C6)-Cycloalkyl, (C1-C6)-Alkoxy, Halogen-(C1- C6)-alkoxy ist, R10 Wasserstoff, Fluor, (C1-C6)- Alkyl oder Halogen-(C1-C6)-alkyl ist, R11 Fluor, (C1-C6)- Alkyl oder Halogen-(C1-C6)-alkyl ist, Y is (C 1 -C 6) - alkyl, halo (C 1 -C 6) alkyl, (C 3 -C 6) -cycloalkyl, (C 1 -C 6) alkoxy, halo (C 1 - C 6 ) is -alkoxy, R 10 is hydrogen, fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) alkyl, R 11 is fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) is -alkyl,
R12 Wasserstoff, Fluor, (C1-C6)- Alkyl oder Halogen-(C1-C6)-alkyl ist G Wasserstoff, eine abspaltbare Gruppe L oder ein Kation E ist, wobei L einer der folgenden Reste ist R 12 is hydrogen, fluorine, (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) alkyl, G is hydrogen, a removable group L or a cation E, where L is one of the following radicals
A, Ar R4 A, Ar R 4
~~S o rS worin ~~ S o rS in what
R3 (C1-C4)- Alkyl oder (C 1-C3)- Alkoxy-(C1-C4)-alkyl ist, R4 (Ci-C4>Alkyl ist, R 3 is (C 1 -C 4 ) -alkyl or (C 1-C3) -alkoxy- (C 1 -C 4 ) -alkyl, R 4 is (Ci-C4> alkyl,
R5 (C1-C4)- Alkyl, ein imsubstituiertes Phenyl oder ein einfach oder mehrfach mit Halogen, (Ci- C4)-Alkyl, Halogen-(C1-C4)-alkyl oder (C1-CA4)lk-oxy substituiertes Phenyl ist, R 5 (C 1 -C 4 ) - alkyl, an unsubstituted phenyl or one or more times with halogen, (Ci- C4) -alkyl, halogen- (C 1 -C 4 ) -alkyl or (C 1 -CA 4 ) is lk-oxy substituted phenyl,
E ein Alkalimetallion, ein Ionenäquivalent eines Erdalkalimetalls, ein Ionenäquivalent Aluminium, ein Ionenäquivalent eines Übergangsmetalls, ein Magnesium-Halogen-Kation oder ein Ammoniumion ist, bei dem gegebenenfalls ein, zwei, drei oder alle vier Wasserstoffatome ersetzt sind durch gleiche oder verschiedene Reste aus den Grippen (Ci-C 10)- Alkyl oder (C3-C7)- Cycloalkyl, die unabhängig voneinander jeweils ein- oder mehrfach mit Fluor, Chlor, Brom, Cyano, Hydroxy substituiert oder durch ein- oder mehrere Sauerstoff- oder Schwefelatome unterbrochen sein können, ein cyclisches sekundäres oder tertiäres aliphatisches oder heteroaliphatisches Ammoniumion ist, beispielsweise Morpholinium, Thiomorpholinium, Piperidinium, Pyrrolidinium oder jeweils protoniertes l,4-Diazabicyclo[1.1.2]octane (DABCO) oder l,5-Diazabicyclo[4.3.0]undec-7-en (DBU), ein heteroaromatisdies Ammoniumkation ist, beispielsweise jeweils protoniertes Pyridin, 2-Methylpyridin, 3-Methylpyridin, 4-Methylpyridin, 2,4-Dimethylpyridin, 2,5-Dimethylpyridin, 2,6-Dimethylpyridin, 5-Ethyl-2-methylpyridin, Collidin, Pyrrol, Imidazol, Chinolin, Chinoxalin, 1 ,2-Dimethylimidazol, 1,3-E is an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent of aluminum, an ion equivalent of a transition metal, a magnesium-halogen cation or an ammonium ion in which one, two, three or all four hydrogen atoms are optionally replaced by identical or different radicals from the Flu (Ci-C 10) - alkyl or (C3-C7) - cycloalkyl, which, independently of one another, can each be substituted one or more times with fluorine, chlorine, bromine, cyano, hydroxy or interrupted by one or more oxygen or sulfur atoms , is a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, for example morpholinium, thiomorpholinium, piperidinium, pyrrolidinium or protonated 1,4-diazabicyclo [1.1.2] octane (DABCO) or 1,5-diazabicyclo [4.3.0] undec- 7-ene (DBU), is a heteroaromatic ammonium cation, for example protonated pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimet hylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, collidine, pyrrole, imidazole, quinoline, quinoxaline, 1,2-dimethylimidazole, 1,3-
Dimetiiytimidazolium-methylsulfat oder weiterhin auch für ein Trimethylsulfoniumion steht.Dimetiiytimidazolium-methylsulfat or also stands for a trimethylsulfoniumion.
3. Verbindungen der Formel (I) gemäß Anspruch 1 oder 2 oder ein agrochemisch akzeptables Salz davon, worin R1 (C1-C6)- Alkyl, (C1-C6)-Alkoxy, Halogen-(C1-C6)-alkoxy, (Ci-C4>-Alkoxy-(C1-C4)-alkyl oder (C1-C6)-Alkoxy-(C2-C4)-alkoxy ist, R2 Wasserstoff, (C1-C4)- Alkyl, Methoxyethyl , Ethoxyethyl, Halogen-(Ci-C2)-alkyl, Cyclopropyl, (C2-C4)-Alkenyl, (C2-C4)-Alkinyl, (C1-CA4)l-koxy oder Halogen-(C1-C4)- alkoxy ist, 3. Compounds of formula (I) according to claim 1 or 2, or an agrochemically acceptable salt thereof, wherein R 1 is (C 1 -C 6) - alkyl, (C 1 -C 6) alkoxy, halo (C 1 -C 6 ) -alkoxy, (Ci-C4> -alkoxy- (C 1 -C 4 ) -alkyl or (C 1 -C 6 ) -alkoxy- (C2-C4) -alkoxy, R 2 is hydrogen, (C 1 -C 4 ) -alkyl, methoxyethyl, ethoxyethyl, halogen- (Ci-C2) -alkyl, cyclopropyl, (C2-C4) -alkenyl, (C2-C4) -alkynyl, (C 1 - CA 4 ) is l-koxy or halo (C 1 -C 4 ) alkoxy,
X (C1-C6)- Alkyl, Halogen-(C1-C6)-alkyl, (C3-C6)-Cycloalkyl, (C1-C6)-Alkoxy, Halogen-(Ci-X (C 1 -C 6 ) -alkyl, halogen- (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (C 1 -C 6 ) -alkoxy, halogen- (Ci-
C6)-alkoxy, Brom, Chlor oder Fluor ist, C6) alkoxy, bromine, chlorine or fluorine,
Y (C1-C6)-Alkyl, Halogen-(C1-C6)-alkyl oder (C1-C6)-Alkoxy ist, Y is (C 1 -C 6 ) -alkyl, halogen- (C 1 -C 6 ) -alkyl or (C 1 -C 6 ) -alkoxy,
R10 Wasserstoff ist, R 10 is hydrogen,
R11 (C1-C6)-Alkyl oder Halogen-(C1-C6)-alkyl ist, R 11 is (C 1 -C 6 ) alkyl or halo (C 1 -C 6 ) alkyl,
R12 Wasserstoff oder (C1-C6)-Alkyl ist R 12 is hydrogen or (C 1 -C 6 ) alkyl
G Wasserstoff, eine abspaltbare Gruppe L oder ein Kation E ist, wobei L einer der folgenden Reste ist
Figure imgf000101_0001
R3 (C1-C4)- Alkyl oder (C1-C2) Alkoxy-(C1-C2)-Alkyl ist, G is hydrogen, a leaving group L or a cation E, where L is one of the following radicals
Figure imgf000101_0001
R 3 is (C 1 -C 4 ) -alkyl or (C 1 -C 2 ) alkoxy- (C 1 -C 2 ) -alkyl,
R4(C1-C4)- Alkyl ist, R 4 is (C 1 -C 4 ) alkyl,
E ein Alkalimetallion, ein Ionenäquivalent eines Erdalkalimetalls, ein Ionenäquivalent Aluminium, ein Ionenäquivalent eines Übergangsmetalls, ein Magnesium-Halogen-Kation oder ein Ammoniumion ist, bei dem gegebenenfalls ein, zwei, drei oder alle vier Wasserstoffatome ersetzt sind durch gleiche oder verschiedene Reste aus den Gruppen (Ci-Cio)-Alkyl oder (C3-C7)- Cy cloalkyl. E is an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent of aluminum, an ion equivalent of a transition metal, a magnesium-halogen cation or an ammonium ion in which one, two, three or all four hydrogen atoms are optionally replaced by identical or different radicals from the Groups (Ci-Cio) -alkyl or (C3-C7) -cycloalkyl.
4. Verbindungen der Formel (I) gemäß einem der Ansprüche 1 bis 3 oder ein agrochemisch akzeptables Salz davon, worin 4. Compounds of formula (I) according to any one of claims 1 to 3 or an agrochemically acceptable salt thereof, in which
R1 Methoxy oder Methoxy ethoxy ist, R 1 is methoxy or methoxy ethoxy,
R2 Wasserstoff oder Methyl ist, R 2 is hydrogen or methyl,
X Methyl, Brom oder Chlor ist, X is methyl, bromine or chlorine,
Y Methyl, Elhyl oder Methoxy ist, R10 Wasserstoff ist, Y is methyl, ethyl or methoxy, R 10 is hydrogen,
R11 Methyl oder Trifluoromethyl ist R 11 is methyl or trifluoromethyl
R12 Wasserstoff ist, R 12 is hydrogen,
G Wasserstoff, eine abspaltbare Gruppe L oder ein Kation E ist, wobei L einer der folgenden Reste ist
Figure imgf000102_0001
worin G is hydrogen, a leaving group L or a cation E, where L is one of the following radicals
Figure imgf000102_0001
wherein
R3 Methyl, Ethyl, i-Propyl oder t-Butyl ist, R 3 is methyl, ethyl, i-propyl or t-butyl,
R4 Methyl oder Ethyl ist, E ein Natriumion oder ein Kaliumion ist R 4 is methyl or ethyl, E is a sodium ion or a potassium ion
5. Verfahren zur Herstellung der Verbindungen der Formel (I) oder ein agrochemisch akzeptables Salz davon gemäß einem der Ansprüche 1 bis 4, indem eine Verbindung der allgemeinen Formel (II) 5. A process for the preparation of the compounds of the formula (I) or an agrochemically acceptable salt thereof according to any one of claims 1 to 4, by using a compound of the general formula (II)
1 1
R R.
S £9 CR1°=CR11R12 S £ 9 CR 1 ° = CR 11 R 12
(Π) (Π)
R in welcher R1, R2, X, Y, R10, R11 und R12 die oben angegebenen Bedeutungen haben und R9 für Alkyl, bevorzugt für Methyl oder Ethyl, steht, gegebenenfalls in Anwesenheit eines geeigneten Lösungs- oder Verdünnungsmittels, mit einer geeigneten Base unter formaler Abspaltung der Gruppe R9OH cyclisiert wird. R in which R 1 , R 2 , X, Y, R 10 , R 11 and R 12 have the meanings given above and R 9 is alkyl, preferably methyl or ethyl, optionally in the presence of a suitable solvent or diluent, is cyclized with a suitable base with formal elimination of the group R 9 OH.
6. Verbindung der Formel (ΧΠ)
Figure imgf000103_0001
wobei 6. Compound of the formula (ΧΠ)
Figure imgf000103_0001
whereby
X Methyl, Brom oder Chlor ist, X is methyl, bromine or chlorine,
Y Methyl, Ethyl oder Methoxy ist, Y is methyl, ethyl or methoxy,
R10 Wasserstoff ist, R 10 is hydrogen,
R11 Methyl oder Trifluoromethyl ist, R 11 is methyl or trifluoromethyl,
R12 Wasserstoff ist, R 12 is hydrogen,
R 13 Wasserstoff, Methyl oder Ethyl ist. R 13 is hydrogen, methyl or ethyl.
7. Agrochemisches Mittel, enthaltend a) mindestens eine Verbindung der Formel (I) oder ein agrochemisch akzeptables Salz davon, wie in einem oder mehreren der Ansprüche 1 bis 4 definiert, und b) im Pflanzenschutz übliche Hilfs- und Zusatzstoffe. 7. Agrochemical agent containing a) at least one compound of the formula (I) or an agrochemically acceptable salt thereof, as defined in one or more of claims 1 to 4, and b) auxiliaries and additives customary in crop protection.
8. Agrochemisches Mittel, enthaltend a) mindestens eine Verbindung der Formel (I) oder ein agrochemisch akzeptables Salz davon, wie in einem oder mehreren der Ansprüche 1 bis 4 definiert, b) einen oder mehrere von Komponente a) verschiedene agrochemische Wirkstoffe, und optional c) im Pflanzenschutz übliche Hilfs- und Zusatzstoffe. 8. Agrochemical composition containing a) at least one compound of the formula (I) or an agrochemically acceptable salt thereof, as defined in one or more of claims 1 to 4, b) one or more agrochemical active ingredients different from component a), and optionally c) auxiliaries and additives customary in plant protection.
9. Verfahren zur Bekämpfung von unerwünschten Pflanzen oder zur Wachstumsregulierung von Pflanzen, wobei eine wirksame Menge mindestens einer Verbindung der Formel (I) oder ein agrochemisch akzeptables Salz davon, wie in einem oder mehreren der Ansprüche 1 bis 4 definiert, auf die Pflanzen, das Saatgut oder die Fläche, auf der die Pflanzen wachsen, appliziert wird. 9. A method for controlling undesired plants or for regulating the growth of plants, wherein an effective amount of at least one compound of the formula (I) or an agrochemically acceptable salt thereof, as defined in one or more of claims 1 to 4, is applied to the plants, the Seed or the area on which the plants grow is applied.
10. Verwendung von Verbindungen der Formel (I) oder ein agrochemisch akzeptables Salz davon, wie in einem oder mehreren der Ansprüche 1 bis 4 definiert, als Herbizide oder Pflanzenwachstumsregulatoren. 10. Use of compounds of the formula (I) or an agrochemically acceptable salt thereof, as defined in one or more of claims 1 to 4, as herbicides or plant growth regulators.
11. Verwendung nach Anspruch 10, wobei die Verbindungen der Formel (I) oder ein agrochemisch akzeptables Salz davon zur Bekämpfung von Schadpflanzen oder zur Wachstumsregulierung in Pflanzenkulturen eingesetzt werden. 11. Use according to claim 10, wherein the compounds of the formula (I) or an agrochemically acceptable salt thereof are used for combating harmful plants or for regulating growth in plant crops.
12. Verwendung nach Anspruch 11, wobei die Kulturpflanzen transgene oder nicht transgene Kulturpflanzen sind. 12. Use according to claim 11, wherein the crop plants are transgenic or non-transgenic crop plants.
13. Saatgut, dadurch charakterisiert, dass es mit Verbindungen der allgemeinen Formel (I) oder ein agrochemisch akzeptables Salz davon, wie in einem oder mehreren der Ansprüche 1 bis 4 definiert oder einem agrochemischen Mittel gemäß einem der Ansprüche 7 oder 8, beschichtet wird. 13. Seed, characterized in that it is coated with compounds of the general formula (I) or an agrochemically acceptable salt thereof, as defined in one or more of claims 1 to 4 or an agrochemical composition according to one of claims 7 or 8.
PCT/EP2021/059077 2020-04-09 2021-04-07 3-(4-alkenyl-phenyl)-3-pyrrolin-2-ones and their use as herbicides WO2021204884A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20169156.5 2020-04-09
EP20169156 2020-04-09

Publications (1)

Publication Number Publication Date
WO2021204884A1 true WO2021204884A1 (en) 2021-10-14

Family

ID=70285562

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2021/059077 WO2021204884A1 (en) 2020-04-09 2021-04-07 3-(4-alkenyl-phenyl)-3-pyrrolin-2-ones and their use as herbicides

Country Status (2)

Country Link
AR (1) AR121820A1 (en)
WO (1) WO2021204884A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023274869A1 (en) * 2021-06-29 2023-01-05 Bayer Aktiengesellschaft 3-(4-alkenyl-phenyl)-3-pyrrolino-2-ones and their use as herbicides

Citations (85)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4245432A (en) 1979-07-25 1981-01-20 Eastman Kodak Company Seed coatings
US4272417A (en) 1979-05-22 1981-06-09 Cargill, Incorporated Stable protective seed coating
EP0086750A2 (en) 1982-02-17 1983-08-24 Ciba-Geigy Ag Use of quinoline derivatives in the protection of crop plants
EP0094349A2 (en) 1982-05-07 1983-11-16 Ciba-Geigy Ag Use of quinoline derivatives for the protection of cultivated plants
EP0131624A1 (en) 1983-01-17 1985-01-23 Monsanto Co Plasmids for transforming plant cells.
JPS6087254A (en) 1983-10-19 1985-05-16 Japan Carlit Co Ltd:The Novel urea compound and herbicide containing the same
EP0142924A2 (en) 1983-09-26 1985-05-29 Mycogen Plant Science, Inc. Insect resistant plants
EP0174562A2 (en) 1984-09-11 1986-03-19 Hoechst Aktiengesellschaft Plant protecting agents based on 1,2,4 - triazole derivatives as well as 1,2,4-triazole derivatives
EP0191736A2 (en) 1985-02-14 1986-08-20 Ciba-Geigy Ag Use of quinoline derivatives for the protection of crop plants
EP0193259A1 (en) 1985-01-18 1986-09-03 Plant Genetic Systems N.V. Modifying plants by genetic engineering to combat or control insects
EP0221044A1 (en) 1985-10-25 1987-05-06 Monsanto Company Novel plant vectors
EP0242246A1 (en) 1986-03-11 1987-10-21 Plant Genetic Systems N.V. Plant cells resistant to glutamine synthetase inhibitors, made by genetic engineering
EP0257993A2 (en) 1986-08-26 1988-03-02 E.I. Du Pont De Nemours And Company Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase
EP0268554A2 (en) 1986-10-22 1988-05-25 Ciba-Geigy Ag 1,5-Diphenyl pyrazole-3-carbonic-acid derivatives for the protection of cultured plants
EP0269806A1 (en) 1986-10-04 1988-06-08 Hoechst Aktiengesellschaft Phenylpyrazole carbonic acid derivatives, their preparation and use as plant growth regulators and antidotes
US4808430A (en) 1987-02-27 1989-02-28 Yazaki Corporation Method of applying gel coating to plant seeds
EP0305398A1 (en) 1986-05-01 1989-03-08 Honeywell Inc Multiple integrated circuit interconnection arrangement.
EP0309862A1 (en) 1987-09-30 1989-04-05 Bayer Ag Stilbene synthase gene
EP0333131A1 (en) 1988-03-17 1989-09-20 Hoechst Aktiengesellschaft Plant protective agent based on pyrazolecarboxylic acid derivatives
WO1989010396A1 (en) 1988-04-28 1989-11-02 Plant Genetic Systems N.V. Plants with modified stamen cells
EP0346620A1 (en) 1988-05-20 1989-12-20 Hoechst Aktiengesellschaft Plant protection agents containing 1,2,4-triazole derivatives, and the 1,2,4-triazole derivatives
EP0355599A1 (en) 1988-08-20 1990-02-28 Bayer Ag 3-Aryl-pyrrolidine-2,4-diones
EP0365484A1 (en) 1988-10-20 1990-04-25 Ciba-Geigy Ag Sulfamoyl phenyl ureas
EP0377893A2 (en) 1989-01-07 1990-07-18 Bayer Ag 3-Aryl-pyrrolidine-2,4-dione derivatives
EP0415211A2 (en) 1989-09-01 1991-03-06 Bayer Ag 3-Aryl-pyrrolidin-2,4-dione derivatives
US5013659A (en) 1987-07-27 1991-05-07 E. I. Du Pont De Nemours And Company Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase
WO1991008202A1 (en) 1989-11-25 1991-06-13 Hoechst Aktiengesellschaft Isoxazolines, method of preparation thereof, and their use as plant-protection agents
WO1991007874A1 (en) 1989-11-30 1991-06-13 Hoechst Aktiengesellschaft Pyrazolines for the protection of crops against herbicides
EP0442077A2 (en) 1990-02-14 1991-08-21 Bayer Ag 3-Aryl-pyrrolidine-2,4-dione derivatives as insecticides and herbicides
WO1991013972A1 (en) 1990-03-16 1991-09-19 Calgene, Inc. Plant desaturases - compositions and uses
WO1991019806A1 (en) 1990-06-18 1991-12-26 Monsanto Company Increased starch content in plants
EP0464461A2 (en) 1990-06-29 1992-01-08 Bayer Ag Stilbensynthase gene of grapevine
WO1992000377A1 (en) 1990-06-25 1992-01-09 Monsanto Company Glyphosate tolerant plants
US5084082A (en) 1988-09-22 1992-01-28 E. I. Du Pont De Nemours And Company Soybean plants with dominant selectable trait for herbicide resistance
EP0492366A2 (en) 1990-12-21 1992-07-01 Hoechst Schering AgrEvo GmbH New 5-chloroquinolin-8-oxyalkanecarbonic acid derivatives, process for their preparation and their use as antidotes for herbicides
WO1992011376A1 (en) 1990-12-21 1992-07-09 Amylogene Hb Genetically engineered modification of potato to form amylopectin-type starch
WO1992014827A1 (en) 1991-02-13 1992-09-03 Institut Für Genbiologische Forschung Berlin Gmbh Plasmids containing dna-sequences that cause changes in the carbohydrate concentration and the carbohydrate composition in plants, as well as plant cells and plants containing these plasmids
US5198599A (en) 1990-06-05 1993-03-30 Idaho Resarch Foundation, Inc. Sulfonylurea herbicide resistance in plants
EP0582198A2 (en) 1992-08-01 1994-02-09 Hoechst Schering AgrEvo GmbH Substituted (hetero-)aryle compounds, process for their preparation, those containing compositions and their use as safeners
WO1995007897A1 (en) 1993-09-16 1995-03-23 Hoechst Schering Agrevo Gmbh Substituted isoxazolines, process for producing them, agents containing them and their use as safeners
WO1996038567A2 (en) 1995-06-02 1996-12-05 Rhone-Poulenc Agrochimie Dna sequence of a gene of hydroxy-phenyl pyruvate dioxygenase and production of plants containing a gene of hydroxy-phenyl pyruvate dioxygenase and which are tolerant to certain herbicides
WO1997041218A1 (en) 1996-04-29 1997-11-06 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Herbicide resistant rice
WO1997045016A1 (en) 1996-05-29 1997-12-04 Hoechst Schering Agrevo Gmbh Novel n-acyl sulphonamides, novel mixtures of herbicides and antidotes and their use
WO1998005638A2 (en) 1996-08-05 1998-02-12 Bayer Aktiengesellschaft 2- and 2,5-substituted phenylketoenols
WO1998013361A1 (en) 1996-09-26 1998-04-02 Novartis Ag Herbicidal composition
WO1998027049A1 (en) 1996-12-19 1998-06-25 Hoechst Schering Agrevo Gmbh Novel 2-fluoroacrylic acid derivatives, novel mixtures of herbicides and antidotes and the use thereof
US5773702A (en) 1996-07-17 1998-06-30 Board Of Trustees Operating Michigan State University Imidazolinone herbicide resistant sugar beet plants
WO1998038856A1 (en) 1997-03-04 1998-09-11 Zeneca Limited Compositions for safening rice against acetochlor
WO1999000020A1 (en) 1997-06-27 1999-01-07 Hoechst Schering Agrevo Gmbh 3-(5-tetrazolyl carbonyl)-2-quinolones and products for protecting useful plants containing the same
US5876739A (en) 1996-06-13 1999-03-02 Novartis Ag Insecticidal seed coating
WO1999016744A1 (en) 1997-09-29 1999-04-08 Aventis Cropscience Gmbh Acylsulfamoyl benzoic acid amides, plant protection agents containing said acylsulfamoyl benzoic acid amides, and method for producing the same
WO1999024586A1 (en) 1997-11-07 1999-05-20 Aventis Cropscience S.A. Chimeric hydroxy-phenyl pyruvate dioxygenase, dna sequence and method for obtaining plants containing such a gene, with herbicide tolerance
WO1999034008A1 (en) 1997-12-24 1999-07-08 Aventis Cropscience S.A. Method for enzymatic preparation of homogentisate
WO1999057965A1 (en) 1998-05-14 1999-11-18 Aventis Cropscience Gmbh Sulfonylurea-tolerant sugar beet mutants
WO2001066704A2 (en) 2000-03-09 2001-09-13 Monsanto Technology Llc Methods for making plants tolerant to glyphosate and compositions thereof
WO2001065922A2 (en) 2000-03-09 2001-09-13 E. I. Du Pont De Nemours And Company Sulfonylurea-tolerant sunflower plants
WO2001074770A1 (en) 2000-04-03 2001-10-11 Bayer Cropscience Ag C2 phenyl-substituted cyclic keto-enols used as pesticides and herbicides
WO2002028186A2 (en) 2000-10-06 2002-04-11 Monsanto Technology, Llc Seed treatment with combinations of insecticides
WO2002034048A1 (en) 2000-10-23 2002-05-02 Syngenta Participations Ag Agrochemical compositions with quinoline safeners
WO2002036787A2 (en) 2000-10-30 2002-05-10 Bayer Cropscience S.A. Herbicide-tolerant plants through bypassing metabolic pathway
WO2002046387A2 (en) 2000-12-07 2002-06-13 Syngenta Limited Plant derived hydroxy phenyl pyruvate dioxygenases (hppd) resistant against triketone herbicides and transgenic plants containing these dioxygenases
WO2002080675A1 (en) 2001-03-21 2002-10-17 Monsanto Technology, Llc Treated plant seeds with controlled release of active agents
US20030176428A1 (en) 1998-11-16 2003-09-18 Schneidersmann Ferdinand Martin Pesticidal composition for seed treatment
WO2004024928A2 (en) 2002-09-11 2004-03-25 Bayer Cropscience S.A. Transformed plants with enhanced prenylquinone biosynthesis
US6768044B1 (en) 2000-05-10 2004-07-27 Bayer Cropscience Sa Chimeric hydroxyl-phenyl pyruvate dioxygenase, DNA sequence and method for obtaining plants containing such a gene, with herbicide tolerance
WO2004084631A1 (en) 2003-03-26 2004-10-07 Bayer Cropscience Gmbh Use of aromatic hydroxy compounds as safeners
WO2005016001A1 (en) 2003-08-05 2005-02-24 Bayer Cropscience Gmbh Safener based on aromatic-aliphatic carboxylic acid derivatives
WO2005015994A1 (en) 2003-08-05 2005-02-24 Bayer Cropscience Gmbh Use of aromatic compounds as safeners
WO2005044796A1 (en) 2003-11-05 2005-05-19 Bayer Cropscience Aktiengesellschaft 2-halogen-6-alkyl-phenyl substituted spirocyclic tetramic acid derivatives
WO2005112630A1 (en) 2004-05-12 2005-12-01 Bayer Cropscience Gmbh Quinoxalin-2-one derivatives crop protection agents comprising the same and method for production and use therof
WO2006000355A1 (en) 2004-06-25 2006-01-05 Bayer Cropscience Aktiengesellschaft 3'-alkoxy spirocyclic tetramic and tetronic acids
WO2007023764A1 (en) 2005-08-26 2007-03-01 Kumiai Chemical Industry Co., Ltd. Agent for reduction of harmful effect of herbicide and herbicide composition having reduced harmful effect
WO2007023719A1 (en) 2005-08-22 2007-03-01 Kumiai Chemical Industry Co., Ltd. Agent for reducing chemical injury and herbicide composition with reduced chemical injury
WO2007103567A2 (en) 2006-03-09 2007-09-13 E. I. Dupont De Nemours & Company Polynucleotide encoding a maize herbicide resistance gene and methods for use
WO2008131861A1 (en) 2007-04-30 2008-11-06 Bayer Cropscience Ag Use of pyridine-2-oxy-3-carbonamides as safeners
WO2008131860A2 (en) 2007-04-30 2008-11-06 Bayer Cropscience Ag Pyridonecarboxamides crop protection agents containing the same method for production and use thereof
WO2008150473A2 (en) 2007-05-30 2008-12-11 Syngenta Participations Ag Cytochrome p450 genes conferring herbicide resistance
WO2009144079A1 (en) 2008-04-14 2009-12-03 Bayer Bioscience N.V. New mutated hydroxyphenylpyruvate dioxygenase, dna sequence and isolation of plants which are tolerant to hppd inhibitor herbicides
CN101838227A (en) 2010-04-30 2010-09-22 孙德群 Safener of benzamide herbicide
WO2010115780A1 (en) 2009-04-08 2010-10-14 Syngenta Participations Ag Spiroheterocyclic pyrrolidine dione derivatives used as pesticides
WO2015032702A1 (en) 2013-09-06 2015-03-12 Syngenta Limited Herbicidally active 2-halogen-4-alkynyl- phenyl-pyrazolidine-dione or pyrrolidine-dione derivatives
WO2015040114A1 (en) 2013-09-20 2015-03-26 Syngenta Limited Herbicidally active 2-halogen-4-alkynyl-phenyl-pyrazolidine-dione or pyrrolidine-dione derivatives
WO2017060203A1 (en) 2015-10-06 2017-04-13 Bayer Cropscience Aktiengesellschaft New alkynyl-substituted 3-phenylpyrrolidine-2,4-diones and use thereof as herbicides
US20180230102A1 (en) * 2015-09-02 2018-08-16 Sunshine Lake Pharma Co., Ltd. Carboxy substituted (hetero) aromatic ring derivatives and preparation method and uses thereof
WO2019219587A1 (en) 2018-05-15 2019-11-21 Bayer Aktiengesellschaft 2-bromo-6-alkoxyphenyl-substituted pyrrolin-2-ones and their use as herbicides

Patent Citations (87)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4272417A (en) 1979-05-22 1981-06-09 Cargill, Incorporated Stable protective seed coating
US4245432A (en) 1979-07-25 1981-01-20 Eastman Kodak Company Seed coatings
EP0086750A2 (en) 1982-02-17 1983-08-24 Ciba-Geigy Ag Use of quinoline derivatives in the protection of crop plants
EP0094349A2 (en) 1982-05-07 1983-11-16 Ciba-Geigy Ag Use of quinoline derivatives for the protection of cultivated plants
EP0131624A1 (en) 1983-01-17 1985-01-23 Monsanto Co Plasmids for transforming plant cells.
EP0142924A2 (en) 1983-09-26 1985-05-29 Mycogen Plant Science, Inc. Insect resistant plants
JPS6087254A (en) 1983-10-19 1985-05-16 Japan Carlit Co Ltd:The Novel urea compound and herbicide containing the same
EP0174562A2 (en) 1984-09-11 1986-03-19 Hoechst Aktiengesellschaft Plant protecting agents based on 1,2,4 - triazole derivatives as well as 1,2,4-triazole derivatives
EP0193259A1 (en) 1985-01-18 1986-09-03 Plant Genetic Systems N.V. Modifying plants by genetic engineering to combat or control insects
EP0191736A2 (en) 1985-02-14 1986-08-20 Ciba-Geigy Ag Use of quinoline derivatives for the protection of crop plants
EP0221044A1 (en) 1985-10-25 1987-05-06 Monsanto Company Novel plant vectors
EP0242246A1 (en) 1986-03-11 1987-10-21 Plant Genetic Systems N.V. Plant cells resistant to glutamine synthetase inhibitors, made by genetic engineering
EP0242236A1 (en) 1986-03-11 1987-10-21 Plant Genetic Systems N.V. Plant cells resistant to glutamine synthetase inhibitors, made by genetic engineering
EP0305398A1 (en) 1986-05-01 1989-03-08 Honeywell Inc Multiple integrated circuit interconnection arrangement.
EP0257993A2 (en) 1986-08-26 1988-03-02 E.I. Du Pont De Nemours And Company Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase
EP0269806A1 (en) 1986-10-04 1988-06-08 Hoechst Aktiengesellschaft Phenylpyrazole carbonic acid derivatives, their preparation and use as plant growth regulators and antidotes
EP0268554A2 (en) 1986-10-22 1988-05-25 Ciba-Geigy Ag 1,5-Diphenyl pyrazole-3-carbonic-acid derivatives for the protection of cultured plants
US4808430A (en) 1987-02-27 1989-02-28 Yazaki Corporation Method of applying gel coating to plant seeds
US5013659A (en) 1987-07-27 1991-05-07 E. I. Du Pont De Nemours And Company Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase
EP0309862A1 (en) 1987-09-30 1989-04-05 Bayer Ag Stilbene synthase gene
EP0333131A1 (en) 1988-03-17 1989-09-20 Hoechst Aktiengesellschaft Plant protective agent based on pyrazolecarboxylic acid derivatives
WO1989010396A1 (en) 1988-04-28 1989-11-02 Plant Genetic Systems N.V. Plants with modified stamen cells
EP0346620A1 (en) 1988-05-20 1989-12-20 Hoechst Aktiengesellschaft Plant protection agents containing 1,2,4-triazole derivatives, and the 1,2,4-triazole derivatives
EP0355599A1 (en) 1988-08-20 1990-02-28 Bayer Ag 3-Aryl-pyrrolidine-2,4-diones
US5084082A (en) 1988-09-22 1992-01-28 E. I. Du Pont De Nemours And Company Soybean plants with dominant selectable trait for herbicide resistance
EP0365484A1 (en) 1988-10-20 1990-04-25 Ciba-Geigy Ag Sulfamoyl phenyl ureas
EP0377893A2 (en) 1989-01-07 1990-07-18 Bayer Ag 3-Aryl-pyrrolidine-2,4-dione derivatives
EP0415211A2 (en) 1989-09-01 1991-03-06 Bayer Ag 3-Aryl-pyrrolidin-2,4-dione derivatives
WO1991008202A1 (en) 1989-11-25 1991-06-13 Hoechst Aktiengesellschaft Isoxazolines, method of preparation thereof, and their use as plant-protection agents
WO1991007874A1 (en) 1989-11-30 1991-06-13 Hoechst Aktiengesellschaft Pyrazolines for the protection of crops against herbicides
EP0442077A2 (en) 1990-02-14 1991-08-21 Bayer Ag 3-Aryl-pyrrolidine-2,4-dione derivatives as insecticides and herbicides
WO1991013972A1 (en) 1990-03-16 1991-09-19 Calgene, Inc. Plant desaturases - compositions and uses
US5198599A (en) 1990-06-05 1993-03-30 Idaho Resarch Foundation, Inc. Sulfonylurea herbicide resistance in plants
WO1991019806A1 (en) 1990-06-18 1991-12-26 Monsanto Company Increased starch content in plants
WO1992000377A1 (en) 1990-06-25 1992-01-09 Monsanto Company Glyphosate tolerant plants
EP0464461A2 (en) 1990-06-29 1992-01-08 Bayer Ag Stilbensynthase gene of grapevine
WO1992011376A1 (en) 1990-12-21 1992-07-09 Amylogene Hb Genetically engineered modification of potato to form amylopectin-type starch
EP0492366A2 (en) 1990-12-21 1992-07-01 Hoechst Schering AgrEvo GmbH New 5-chloroquinolin-8-oxyalkanecarbonic acid derivatives, process for their preparation and their use as antidotes for herbicides
WO1992014827A1 (en) 1991-02-13 1992-09-03 Institut Für Genbiologische Forschung Berlin Gmbh Plasmids containing dna-sequences that cause changes in the carbohydrate concentration and the carbohydrate composition in plants, as well as plant cells and plants containing these plasmids
EP0582198A2 (en) 1992-08-01 1994-02-09 Hoechst Schering AgrEvo GmbH Substituted (hetero-)aryle compounds, process for their preparation, those containing compositions and their use as safeners
WO1995007897A1 (en) 1993-09-16 1995-03-23 Hoechst Schering Agrevo Gmbh Substituted isoxazolines, process for producing them, agents containing them and their use as safeners
WO1996038567A2 (en) 1995-06-02 1996-12-05 Rhone-Poulenc Agrochimie Dna sequence of a gene of hydroxy-phenyl pyruvate dioxygenase and production of plants containing a gene of hydroxy-phenyl pyruvate dioxygenase and which are tolerant to certain herbicides
WO1997041218A1 (en) 1996-04-29 1997-11-06 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Herbicide resistant rice
WO1997045016A1 (en) 1996-05-29 1997-12-04 Hoechst Schering Agrevo Gmbh Novel n-acyl sulphonamides, novel mixtures of herbicides and antidotes and their use
US5876739A (en) 1996-06-13 1999-03-02 Novartis Ag Insecticidal seed coating
US5773702A (en) 1996-07-17 1998-06-30 Board Of Trustees Operating Michigan State University Imidazolinone herbicide resistant sugar beet plants
WO1998005638A2 (en) 1996-08-05 1998-02-12 Bayer Aktiengesellschaft 2- and 2,5-substituted phenylketoenols
WO1998013361A1 (en) 1996-09-26 1998-04-02 Novartis Ag Herbicidal composition
WO1998027049A1 (en) 1996-12-19 1998-06-25 Hoechst Schering Agrevo Gmbh Novel 2-fluoroacrylic acid derivatives, novel mixtures of herbicides and antidotes and the use thereof
WO1998038856A1 (en) 1997-03-04 1998-09-11 Zeneca Limited Compositions for safening rice against acetochlor
WO1999000020A1 (en) 1997-06-27 1999-01-07 Hoechst Schering Agrevo Gmbh 3-(5-tetrazolyl carbonyl)-2-quinolones and products for protecting useful plants containing the same
WO1999016744A1 (en) 1997-09-29 1999-04-08 Aventis Cropscience Gmbh Acylsulfamoyl benzoic acid amides, plant protection agents containing said acylsulfamoyl benzoic acid amides, and method for producing the same
WO1999024585A1 (en) 1997-11-07 1999-05-20 Aventis Cropscience S.A. Mutated hydroxy-phenyl pyruvate dioxygenase, dna sequence and method for obtaining herbicide-tolerant plants containing such gene
WO1999024586A1 (en) 1997-11-07 1999-05-20 Aventis Cropscience S.A. Chimeric hydroxy-phenyl pyruvate dioxygenase, dna sequence and method for obtaining plants containing such a gene, with herbicide tolerance
WO1999034008A1 (en) 1997-12-24 1999-07-08 Aventis Cropscience S.A. Method for enzymatic preparation of homogentisate
WO1999057965A1 (en) 1998-05-14 1999-11-18 Aventis Cropscience Gmbh Sulfonylurea-tolerant sugar beet mutants
US20030176428A1 (en) 1998-11-16 2003-09-18 Schneidersmann Ferdinand Martin Pesticidal composition for seed treatment
WO2001066704A2 (en) 2000-03-09 2001-09-13 Monsanto Technology Llc Methods for making plants tolerant to glyphosate and compositions thereof
WO2001065922A2 (en) 2000-03-09 2001-09-13 E. I. Du Pont De Nemours And Company Sulfonylurea-tolerant sunflower plants
WO2001074770A1 (en) 2000-04-03 2001-10-11 Bayer Cropscience Ag C2 phenyl-substituted cyclic keto-enols used as pesticides and herbicides
US6768044B1 (en) 2000-05-10 2004-07-27 Bayer Cropscience Sa Chimeric hydroxyl-phenyl pyruvate dioxygenase, DNA sequence and method for obtaining plants containing such a gene, with herbicide tolerance
WO2002028186A2 (en) 2000-10-06 2002-04-11 Monsanto Technology, Llc Seed treatment with combinations of insecticides
WO2002034048A1 (en) 2000-10-23 2002-05-02 Syngenta Participations Ag Agrochemical compositions with quinoline safeners
WO2002036787A2 (en) 2000-10-30 2002-05-10 Bayer Cropscience S.A. Herbicide-tolerant plants through bypassing metabolic pathway
WO2002046387A2 (en) 2000-12-07 2002-06-13 Syngenta Limited Plant derived hydroxy phenyl pyruvate dioxygenases (hppd) resistant against triketone herbicides and transgenic plants containing these dioxygenases
WO2002080675A1 (en) 2001-03-21 2002-10-17 Monsanto Technology, Llc Treated plant seeds with controlled release of active agents
WO2004024928A2 (en) 2002-09-11 2004-03-25 Bayer Cropscience S.A. Transformed plants with enhanced prenylquinone biosynthesis
WO2004084631A1 (en) 2003-03-26 2004-10-07 Bayer Cropscience Gmbh Use of aromatic hydroxy compounds as safeners
WO2005016001A1 (en) 2003-08-05 2005-02-24 Bayer Cropscience Gmbh Safener based on aromatic-aliphatic carboxylic acid derivatives
WO2005015994A1 (en) 2003-08-05 2005-02-24 Bayer Cropscience Gmbh Use of aromatic compounds as safeners
WO2005044796A1 (en) 2003-11-05 2005-05-19 Bayer Cropscience Aktiengesellschaft 2-halogen-6-alkyl-phenyl substituted spirocyclic tetramic acid derivatives
WO2005112630A1 (en) 2004-05-12 2005-12-01 Bayer Cropscience Gmbh Quinoxalin-2-one derivatives crop protection agents comprising the same and method for production and use therof
WO2006000355A1 (en) 2004-06-25 2006-01-05 Bayer Cropscience Aktiengesellschaft 3'-alkoxy spirocyclic tetramic and tetronic acids
WO2007023719A1 (en) 2005-08-22 2007-03-01 Kumiai Chemical Industry Co., Ltd. Agent for reducing chemical injury and herbicide composition with reduced chemical injury
WO2007023764A1 (en) 2005-08-26 2007-03-01 Kumiai Chemical Industry Co., Ltd. Agent for reduction of harmful effect of herbicide and herbicide composition having reduced harmful effect
WO2007103567A2 (en) 2006-03-09 2007-09-13 E. I. Dupont De Nemours & Company Polynucleotide encoding a maize herbicide resistance gene and methods for use
WO2008131860A2 (en) 2007-04-30 2008-11-06 Bayer Cropscience Ag Pyridonecarboxamides crop protection agents containing the same method for production and use thereof
WO2008131861A1 (en) 2007-04-30 2008-11-06 Bayer Cropscience Ag Use of pyridine-2-oxy-3-carbonamides as safeners
WO2008150473A2 (en) 2007-05-30 2008-12-11 Syngenta Participations Ag Cytochrome p450 genes conferring herbicide resistance
WO2009144079A1 (en) 2008-04-14 2009-12-03 Bayer Bioscience N.V. New mutated hydroxyphenylpyruvate dioxygenase, dna sequence and isolation of plants which are tolerant to hppd inhibitor herbicides
WO2010115780A1 (en) 2009-04-08 2010-10-14 Syngenta Participations Ag Spiroheterocyclic pyrrolidine dione derivatives used as pesticides
CN101838227A (en) 2010-04-30 2010-09-22 孙德群 Safener of benzamide herbicide
WO2015032702A1 (en) 2013-09-06 2015-03-12 Syngenta Limited Herbicidally active 2-halogen-4-alkynyl- phenyl-pyrazolidine-dione or pyrrolidine-dione derivatives
WO2015040114A1 (en) 2013-09-20 2015-03-26 Syngenta Limited Herbicidally active 2-halogen-4-alkynyl-phenyl-pyrazolidine-dione or pyrrolidine-dione derivatives
US20180230102A1 (en) * 2015-09-02 2018-08-16 Sunshine Lake Pharma Co., Ltd. Carboxy substituted (hetero) aromatic ring derivatives and preparation method and uses thereof
WO2017060203A1 (en) 2015-10-06 2017-04-13 Bayer Cropscience Aktiengesellschaft New alkynyl-substituted 3-phenylpyrrolidine-2,4-diones and use thereof as herbicides
WO2019219587A1 (en) 2018-05-15 2019-11-21 Bayer Aktiengesellschaft 2-bromo-6-alkoxyphenyl-substituted pyrrolin-2-ones and their use as herbicides

Non-Patent Citations (27)

* Cited by examiner, † Cited by third party
Title
"Springer Lab Manual", 1995, SPRINGER VERLAG BERLIN, article "Gene Transfer to Plants"
"The Pesticide Manual", 2006, THE BRITISH CROP PROTECTION COUNCIL UND THE ROYAL SOC. OF CHEMISTRY
BARRY ET AL., CURR. TOPICS PLANT PHYSIOL., vol. 7, 1992, pages 139 - 145
BRAUN ET AL., EMBO J, vol. 11, 1992, pages 3219 - 3227
CAS , no. 135654-55-6
CAS, no. 133993-74-5
COMAI ET AL., SCIENCE, vol. 221, 1983, pages 370 - 371
G.C. KLINGMAN: "Weed Control as a Science", 1961, JOHN WILEY AND SONS, pages: 81 - 96
GASSER ET AL., J. BIOL. CHEM., vol. 263, 1988, pages 4280 - 4289
H.V. OLPHEN: "Handbook of Insecticide Dust Diluents and Carriers", 1963, J. WILEY & SONS
HEIDELBERGCHRISTOU, TRENDS IN PLANT SCIENCE, vol. 1, 1996, pages 423 - 431
J.D. FREYERS.A. EVANS: "Weed Control Handbook", 1968, BLACKWELL SCIENTIFIC PUBLICATIONS, pages: 101 - 103
J.E. BROWNING: "Chemical and Engineering", 1967, article "Agglomeration", pages: 147
JOHNSON ET AL.: "Lentil (Lens culinarisL.): A prebiotic-rich whole food legume", FOOD RESEARCH INTERNATIONAL, vol. 51, no. 1, 29 November 2012 (2012-11-29), pages 107 - 113, XP028995420, ISSN: 0963-9969, DOI: 10.1016/J.FOODRES.2012.11.025 *
K. MARTENS: "Spray-Drying Handbook", 1979, G. GOODWIN LTD.
NAGEL: "Pflanzenschutzmittelrückstände in Bio-Saatgut - Ergebnisse aus 5 Jahren Ökomonitoring", JOURNAL FÜR VERBRAUCHERSCHUTZ UND LEBENSMITTELSICHERHEIT, vol. 13, no. 1, 21 December 2017 (2017-12-21), pages 49 - 61, XP036444133, ISSN: 1661-5751, [retrieved on 20171221], DOI: 10.1007/S00003-017-1145-6 *
SAMBROOK ET AL.: "Molecular Cloning, A Laboratory Manual", 1989, COLD SPRING HARBOR LABORATORY PRESS
SCHÖNFELDT: "Grenzflächenaktive Äthylenoxid-addukte", 1976, WISS. VERLAGSGESELL.
SHAH ET AL., SCIENCE, vol. 233, 1986, pages 478 - 481
SISLEYWOOD: "McCutcheon's ''Detergents and Emulsifiers Annual", 1964, CHEM. PUBL. CO. INC.
SONNEWALD ET AL., PLANT J, vol. 1, 1991, pages 95 - 106
T. HANAMOTON. MORITAK. SHINDO, EUR../. ORG. CHEM., 2003, pages 4279 - 4285
TRANELWRIGHT, WEED SCIENCE, vol. 50, 2002, pages 700 - 712
WADE VAN VALKENBURG: "Perry's Chemical Engineer's Handbook", 1973, MARCEL DEKKER, pages: 8 - 57
WEED RESEARCH, vol. 26, 1986, pages 441 - 445
WINNACKER: "Gene und Klone", 1996, VCH WEINHEIM
WOLTER ET AL., PROC. NATL. ACAD. SCI. USA, vol. 85, 1988, pages 846 - 850

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023274869A1 (en) * 2021-06-29 2023-01-05 Bayer Aktiengesellschaft 3-(4-alkenyl-phenyl)-3-pyrrolino-2-ones and their use as herbicides

Also Published As

Publication number Publication date
AR121820A1 (en) 2022-07-13

Similar Documents

Publication Publication Date Title
EP3793977A1 (en) 2-bromo-6-alkoxyphenyl-substituted pyrrolin-2-ones and their use as herbicides
WO2019219584A1 (en) New spiro cyclohexyl pyrrolin-2-ones and their use as herbicides
WO2021204884A1 (en) 3-(4-alkenyl-phenyl)-3-pyrrolin-2-ones and their use as herbicides
EP3759105B1 (en) Herbicidally active substituted bicyclic benzoylamides
EP4075979A1 (en) 1,5-diphenylpyrazolyl-3-oxyalkyl acids and 1-phenyl-5-thienylpyrazolyl-3-oxyalkyl acids and the use thereof for control of undesired plant growth
WO2020187627A1 (en) Novel 3-(2-brom-4-alkynyl-6-alkoxyphenyl)-3-pyrrolin-2-ones and their use as herbicides
WO2019228787A1 (en) Specifically substituted 2-alkyl-6-alkoxyphenyl-3-pyrrolin-2-ones and their use as herbicides
WO2019228788A1 (en) 2-bromo-6-alkoxyphenyl-substituted pyrrolin-2-ones and their use as herbicides
EP3713417A1 (en) Herbicidally active bicyclic benzamides
EP4157851A1 (en) Substituted pyrroline-2-ones and their use as herbicides
WO2021209486A1 (en) Specifically substituted pyrroline-2-ones and their use as herbicides
WO2023280772A1 (en) N-(1,3,4-oxadiazol-2-yl)phenylcarboxamides as herbicides
EP3938349A1 (en) Specifically substituted 3-(2-alkoxy-6-alkyl-4-propinylphenyl)-3-pyrrolin-2-ones and their use as herbicides
WO2020187626A1 (en) Specifically substituted 3-phenyl-5-spirocyclopentyl-3-pyrrolin-2-ones and their use as herbicides
WO2020187629A1 (en) 3-(2-brom-4-alkynyl-6-alkoxyphenyl)-substituted 5-spirocyclohexyl-3-pyrrolin-2-ones and their use as herbicides
EP3938346A1 (en) Specifically substituted 3-(2-halogen-6-alkyl-4-propinylphenyl)-3-pyrrolin-2-ones and to the use thereof as herbicides
WO2023274869A1 (en) 3-(4-alkenyl-phenyl)-3-pyrrolino-2-ones and their use as herbicides
WO2022253700A1 (en) Specifically substituted pyrroline-2-ones and their use as herbicides
WO2019219588A1 (en) Specifically substituted 2-alkyl-6-alkoxyphenyl-3-pyrrolin-2-ones and their use as herbicides
WO2019219585A1 (en) New 3-(4-alkynyl-6-alkoxy-2-chlorophenyl)-3-pyrrolin-2-ones and their use as herbicides
EP4143181A1 (en) 1-pyrazinylpyrazolyl-3-oxyalkyl acids and their derivatives, and their use for control of undesired plant growth
EP3802521A1 (en) Herbicidally active bicyclic benzoylpyrazoles
WO2019233862A1 (en) Herbicidally active substituted phenylpyrimidines
EP3360417A1 (en) Use of sulfonylindol as herbicide

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21716741

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21716741

Country of ref document: EP

Kind code of ref document: A1