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WO2025114275A1 - 3-heterocyclyl-benzamides and use thereof as herbicides - Google Patents

3-heterocyclyl-benzamides and use thereof as herbicides Download PDF

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Publication number
WO2025114275A1
WO2025114275A1 PCT/EP2024/083604 EP2024083604W WO2025114275A1 WO 2025114275 A1 WO2025114275 A1 WO 2025114275A1 EP 2024083604 W EP2024083604 W EP 2024083604W WO 2025114275 A1 WO2025114275 A1 WO 2025114275A1
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WIPO (PCT)
Prior art keywords
alkyl
methyl
hydrogen
chloro
ethyl
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PCT/EP2024/083604
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German (de)
French (fr)
Inventor
Christian Waldraff
Hartmut Ahrens
Harald Jakobi
Birgit BOLLENBACH-WAHL
Elisabeth ASMUS
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Bayer AG
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Bayer AG
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Publication of WO2025114275A1 publication Critical patent/WO2025114275A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/32—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms

Definitions

  • the invention relates to the technical field of herbicides, in particular to herbicides for the selective control of weeds and grass weeds in crops.
  • WO 2012/028579 A1 discloses herbicidally active benzamides that can bear a variety of substituents in the 3-position of the phenyl ring.
  • the benzoylamides known from the above-mentioned document do not always exhibit sufficient herbicidal activity and/or compatibility with crop plants.
  • the object of the present invention is to provide alternative herbicidally active ingredients.
  • R x means (C 1 -C 6 )-alkyl
  • X is halogen or (C 1 -C 6 )-alkyl
  • Y is halogen-(C 1 -C 6 )-alkoxy
  • Z represents Z-1, Z-2, Z-3 or Z-4, where Z-1 to Z-4 have the following meanings
  • R 1 means hydrogen, (C 1 -C 6 )-alkyl or halogen-(C 1 -C 6 )-alkyl
  • R 2 means hydrogen, (C 1 -C 6 )-alkyl or (C 3 -C 6 )-cycloalkyl
  • R 3 means (C 1 -C 6 )-alkyl, halogen-(C 1 -C 6 )-alkyl or (C 3 -C 6 )-cycloalkyl
  • R 4 and R 5 independently represent hydrogen, (C 1 -C 6 )-alkyl, (C 1 -C 6 )-
  • alkyl radicals with more than two carbon atoms can be straight-chain or branched.
  • Alkyl radicals are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl, and 1,3-dimethylbutyl.
  • alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl, and 1-methylbut-2-en-1-yl.
  • Alkynyl means, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, and 1-methyl-but-3-yn-1-yl.
  • the multiple bond can be located in any position of the unsaturated radical.
  • Cycloalkyl means a carbocyclic, saturated ring system with three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.
  • Halogen represents fluorine, chlorine, bromine, or iodine.
  • the compounds of formula (I) or (II) can exist as stereoisomers depending on the nature and linkage of the substituents. If, for example, one or more asymmetrically substituted carbon atoms are present, enantiomers and diastereomers can occur. Stereoisomers can be obtained from the mixtures obtained during production using conventional separation methods, for example, chromatographic separation processes.
  • Stereoisomers can also be selectively prepared using stereoselective reactions using optically active starting materials and/or auxiliaries.
  • the invention also relates to all stereoisomers and mixtures thereof encompassed by formula (I) or (II) but not specifically defined.
  • Preferred compounds of formula (I) are those in which the symbols and indices have the following meanings: R x means (C 1 -C 6 )-alkyl, X is halogen or (C 1 -C 6 )-alkyl, Y is OCF 3 , OCHF 2 or OCF 2 Me Z means Z-1, Z-2, Z-3 or Z-4, where Z-1 to Z-4 have the following meanings: R 1 means hydrogen or (C 1 -C 6 )-alkyl, R 2 means hydrogen, (C 1 -C 6 )-alkyl or (C 3 -C 6 )-cycloalkyl, R 3 means (C 1 -C 6 )-alkyl or halogen-(C 1 -C
  • R x means methyl or ethyl
  • X means chlorine, bromine, methyl or ethyl
  • Y means OCF 3 or OCHF 2
  • Z means Z-1, Z-2, Z-3 or Z-4, where Z-1 to Z-4 have the following meanings
  • R 1 means hydrogen or methyl
  • R 2 means hydrogen, methyl, ethyl or c-propyl
  • R 3 means methyl, ethyl or i-propyl
  • R 4 and R 5 The following combinations are hydrogen and hydrogen, hydrogen and methyl, hydrogen and ethyl, hydrogen and cyclopropyl, cyclopropyl and cyclopropyl, hydrogen and methoxymethyl, or hydrogen and cyanomethyl.
  • the present invention thus further provides compounds of formula (II), where the symbols and indices have the following meanings:
  • L means halogen or R 6 O
  • X means halogen or (C 1 -C 6 )-alkyl
  • Y is halogen-(C 1 -C 6 )-alkoxy
  • Z represents Z-1, Z-2, Z-3 or Z-4, where Z-1 to Z-4 have the following meanings
  • R 1 means hydrogen, (C 1 -C 6 )-alkyl or halogen-(C 1 -C 6 )-alkyl
  • R 2 means hydrogen, (C 1 -C 6 )-alkyl or (C 3 -C 6 )-cycloalkyl
  • R 2 can also be Si((C 1 -C 6 )-Alkyl) 3 mean if L OR 6 means and R 6 for (C 1 -C 6 )-alkyl, R 3 means (C 1 -C 6 )-alkyl, halogen-(
  • Preferred compounds (II) are those in which L is chlorine, methoxy or hydroxy, X is chlorine, bromine, methyl or ethyl, Y is OCF 3 or OCHF 2 , Z means Z-1, Z-2, Z-3 or Z-4, where Z-1 to Z-4 have the following meanings R 1 means hydrogen or methyl, R 2 means hydrogen, methyl, ethyl or c-propyl, or R 2 can also mean Si(Me)3 if L is methoxy, R 3 means methyl, ethyl or i-propyl, R 4 and R 5
  • the following combinations are hydrogen and hydrogen, hydrogen and methyl, hydrogen and ethyl, hydrogen and cyclopropyl, cyclopropyl and cyclopropyl, hydrogen and methoxymethyl, or hydrogen and cyanomethyl.
  • chromatography equipment for example, from ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.
  • the listed equipment results in a modular approach in which the individual work steps are automated, but manual operations must be performed between the work steps.
  • This can be circumvented by the use of partially or fully integrated automation systems in which the respective automation modules are operated, for example, by robots.
  • Such automation systems can be obtained, for example, from Caliper, Hopkinton, MA 01748, USA.
  • the execution of individual or multiple synthesis steps can be supported by the use of polymer-supported reagents/scavenger resins.
  • the subject of thisThe invention also relates to libraries containing at least two compounds of formula (I) and salts thereof.
  • the compounds of the invention exhibit excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous annual weeds. Even difficult-to-control perennial weeds that sprout from rhizomes, rootstocks, or other permanent organs are effectively controlled by the active ingredients.
  • the present invention therefore also provides a method for controlling undesirable plants or for regulating the growth of plants, preferably in plant crops, in which one or more compounds of the invention are applied to the plants (e.g., weeds such as monocotyledonous or dicotyledonous weeds or undesirable crop plants), the seed (e.g., grains, seeds, or vegetative propagation organs such as tubers or shoot parts with buds), or the area on which the plants grow (e.g., the cultivated area).
  • the compounds of the invention can be applied, for example, by pre-sowing (optionally also by incorporation into the soil), pre-emergence, or post-emergence methods.
  • Monocotyledonous harmful plants of the genera 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, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria and Sorghum.
  • the compounds according to the invention are applied to the soil surface before germination, either the emergence of weed seedlings is completely prevented, or the weeds grow to the cotyledon stage, but then cease growth and finally die completely after three to four weeks.
  • the active ingredients are applied post-emergence to the green parts of the plant, growth stops after treatment, and the weeds remain in the same area as they were at the time of application.They remain in the current growth stage or die completely after a certain period of time, thus eliminating weed competition that is harmful to the crops very early and sustainably.
  • the compounds according to the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops, e.g.
  • the present compounds are highly suitable for the selective control of undesirable plant growth in plant crops such as agricultural crops or ornamental plants.
  • the compounds according to the invention depending on their respective chemical structure and the applied rate, exhibit outstanding growth-regulating properties in crops. They regulate the plant's own metabolism and can thus be used to specifically influence plant constituents and facilitate harvesting, for example by inducing desiccation and stunting.
  • they are also suitable for the general control and inhibition of undesirable vegetative growth without killing the plants. Inhibition of vegetative growth plays a major role in many monocotyledonous and dicotyledonous crops, since, for example, lodging can be reduced or completely prevented as a result.
  • the active ingredients can also be used to control weeds in crops of plants modified genetically or by conventional mutagenesis.
  • the transgenic plants are generally characterized by particularly advantageous properties, for example, resistance to certain pesticides, 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 harvested crop in terms of quantity, quality, storability, composition, and specific ingredients.
  • transgenic plants with increased starch content or altered starch quality, or those with a different fatty acid composition of the harvested crop are known.
  • transgenic crops With regard to transgenic crops, the use of the compounds according to the invention is preferred in economically important transgenic crops of crops and ornamental plants, e.g., cereals such as wheat, barley, rye, oats, millet, rice, and maize, or also crops of sugar beet, cotton, soybeans, rapeseed, potatoes, cassava, tomatoes, peas, and other vegetables.
  • the compounds according to the invention can preferably be used as herbicides in crop crops. that are resistant to the phytotoxic effects of herbicides or have been genetically engineered to be resistant.
  • Conventional methods for producing new plants with modified traits compared to existing plants include, for example, classical breeding methods and the creation of mutants.
  • new plants with modified traits can be created using genetic engineering techniques (see, for example, EP-A-0221044, EP-A-0131624).
  • genetic engineering techniques see, for example, EP-A-0221044, EP-A-0131624.
  • the following have been described in several cases: - genetic modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/11376, WO 92/14827, WO 91/19806), - transgenic crop plants which are resistant to certain herbicides of the glufosinate type (cf. e.g.
  • Bt toxins Bacillus thuringiensis toxins
  • EP-A-0193259 Bacillus thuringiensis toxins
  • - Transgenic crops with modified fatty acid composition WO 91/13972.
  • nucleic acid molecules can be introduced into plasmids that allow mutagenesis or sequence modification through recombination of DNA sequences.
  • base substitutions can be performed, partial sequences can be removed, or natural or synthetic sequences can be added.
  • Adapters or linkers can be attached to the DNA fragments to connect them to one another, see, for example, [1].
  • the production of plant cells with reduced activity of a gene product can be achieved, for example, by expressing at least one corresponding antisense RNA, a sense RNA to achieve a cosuppression effect, or the expression of at least one appropriately constructed ribozyme that specifically cleaves transcripts of the aforementioned gene product.
  • DNA molecules can be used that comprise the entire coding sequence of a gene product, including any flanking sequences present, as well as DNA molecules that comprise only parts of the coding sequence, whereby these parts must be long enough to produce an antisense effect in the cells. It is also possible to use DNA sequences that exhibit a high degree of homology to the coding sequences of a gene product, but are not completely identical.
  • nucleic acid molecules When nucleic acid molecules are expressed in plants, the synthesized protein can be localized in any compartment of the plant cell. However, to achieve localization in a specific compartment, the coding region can, for example, be linked to DNA sequences that ensure localization in a specific 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. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). Expression of nucleic acid molecules can also occur in the organelles of plant cells. 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, i.e., both monocotyledonous and dicotyledonous plants.
  • the compounds according to the invention can preferably be used in transgenic crops which are resistant to growth factors, such as dicamba, or to herbicides which inhibit essential plant enzymes, e.g. B.
  • ALS acetolactate synthases
  • EPSP glutamine synthases
  • HPPD hydroxyphenylpyruvate dioxygenases
  • the active compounds according to the invention are used in transgenic crops, in addition to the effects against weeds observed in other crops, effects often occur that are specific to the application in the respective transgenic crop, for example, a modified or specifically expanded spectrum of weeds that can be controlled, modified application rates that can be used for application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and an influence on the growth and yield of the transgenic crops.
  • the invention therefore also relates to the use of the compounds according to the invention as herbicides for controlling weeds in transgenic crops.
  • the compounds according to the invention can be applied in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts, or granules in the usual preparations.
  • the invention therefore also relates to herbicidal and plant growth-regulating compositions containing the compounds according to the invention.
  • the compounds according to the invention can be formulated in various ways, depending on the biological and/or chemical-physical parameters specified. 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), seed dressings, granules for broadcast and soil application, granules (GR) in the form of microgranules, spray granules, emulsifiable granules, and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG
  • Wettable powders are preparations that are evenly dispersible in water.
  • they contain a diluent or inert substance as well as ionic and/or non-ionic surfactants (wetting agents, dispersants), e.g., polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium ligninsulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate, or sodium oleoylmethyltaurine.
  • ionic and/or non-ionic surfactants e.g., polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethyl
  • the herbicidal active ingredients are finely ground in conventional equipment such as hammer mills, fan mills, and air jet mills and mixed simultaneously or subsequently 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 these organic solvents, with the addition of one or more ionic and/or non-ionic surfactants (emulsifiers).
  • emulsifiers examples include: alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters, or polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan fatty acid esters.
  • alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate
  • nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters,
  • Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g., talc, natural clays such as kaolin, bentonite, and pyrophyllite, 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, with the addition of surfactants, such as those listed above for the other formulation types.
  • Emulsions e.g., oil-in-water emulsions (EW)
  • EW oil-in-water emulsions
  • surfactants such as those listed above for the other formulation types.
  • Granules can be produced either by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates using adhesives, e.g., polyvinyl alcohol, sodium polyacrylate, 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, in a mixture with fertilizers. Water-dispersible granules are generally produced using conventional processes such as spray drying, fluidized-bed granulation, disc granulation, blending with high-speed mixers, and extrusion without solid inert material.
  • adhesives e.g., polyvinyl alcohol, sodium polyacrylate, or mineral oils
  • Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules—if desired, in a mixture with fertilizers.
  • 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 is about 10 to 90% by weight, with the remainder (to 100% by weight) consisting of conventional formulation ingredients.
  • the active ingredient concentration can be about 1 to 90% by weight, preferably 5 to 80% by weight.
  • Dust-like formulations contain 1 to 30 wt.% active ingredient, preferably 5 to 20 wt.% active ingredient; sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt.% active ingredient.
  • the active ingredient content depends partly on whether the active compound is liquid or solid and which granulation aids, fillers, etc. are used. In water-dispersible granules, the active ingredient content is, for example, between 1 and 95 wt.%, preferably between 10 and 80 wt.%.
  • the said active ingredient formulations may contain the usual adhesives, wetting agents, dispersants, emulsifiers, penetration agents, preservatives, antifreeze agents, solvents, fillers, carriers, dyes, defoamers, evaporation inhibitors, and agents that influence the pH and viscosity.
  • combinations with other pesticidally active substances such as insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers, and/or growth regulators, can also be produced, e.g., in the form of a ready-to-use formulation or as a tank mix.
  • the commercially available formulations are diluted in the usual way, e.g., with water for wettable powders, emulsifiable concentrates, dispersions, and water-dispersible granules. Dust-like preparations, soil or...Granules for broadcasting and sprayable solutions are not usually diluted with other inert substances prior to application.
  • the required application rate of the compounds of formula (I) varies depending on external conditions such as temperature, humidity, the type of herbicide used, and others. It can vary within wide limits, e.g., between 0.001 and 1.0 kg/ha or more of active ingredient, but is preferably between 0.005 and 750 g/ha.
  • the compounds of formula (I) according to the invention can also be used in admixture with other herbicides as needed.
  • herbicides or plant growth regulators that can be combined with compounds of formula (I) include, for example, the following active ingredients (the compounds are designated either by the "common name” according to the International Organization for Standardization (ISO) or by the chemical name or by the code number) and always include all application forms such as acids, salts, esters and isomers such as stereoisomers and optical isomers.
  • Abscisic acid and related analogues [e.g. (2Z,4E)-5-[6-Ethynyl-1-hydroxy-2,6-dimethyl-4-oxocyclohex-2-en-1-yl]-3-methylpenta-2,4-dienoic acid, methyl-(2Z,4E)-5-[6-ethynyl-1-hydroxy-2,6- dimethyl-4-oxocyclohex-2-en-1-yl]-3-methylpenta-2,4-dienoate, (2Z,4E)-3-ethyl-5-(1-hydroxy-2,6,6-trimethyl-4-oxocyclohex-2-en-1-yl)penta-2,4-dienoic acid, (2E,4E)-5-(1-hydroxy-2,6,6-trimethyl-4- oxocyclohex-2-en-1-yl)-3-(trifluoromethyl)penta-2,4-dienoic acid, methyl (2E,
  • COs differ from LCOs in that they lack the fatty acid side chain characteristic of LCOs.
  • COs sometimes referred to as N-acetylchitooligosaccharides, are also composed of GlcNAc units, but have side chains that distinguish them from chitin molecules [(C 8 H 13 NO 5 ) n , CAS No.1398-61-4] and chitosan molecules [(C 5 H 11 NO 4 ) n , CAS No.
  • chitin-like compounds chlormequat chloride, cloprop, cyclanilide, 3-(cycloprop-1-enyl)propionic acid, 1-[2-(4-cyano-3,5-dicyclopropylphenyl)acetamido]cyclohexanecarboxylic acid, 1-[2-(4-cyano-3-cyclopropylphenyl)acetamido]cyclohexanecarboxylic acid, 1-cyclopropenylmethanol, daminozide, dazomet, dazomet sodium, n-decanol, dikegulac, dikegulac sodium, endothal, endothal-di-potassium, -di-sodium, and mono(N,N-dimethylalkylammonium), ethephon, 1-ethylcyclopropene, flumetralin, flurenol, flurenol-butyl, flurenol-methyl,
  • LCOs differ in the number of GlcNAc units in the backbone structure, in the length and degree of saturation of the fatty acid chain, and in the substitution of the reducing and non-reducing sugar units).
  • Safeners which can be used in combination with the compounds of formula (I) according to the invention and optionally in combination with other active ingredients such as insecticides, acaricides, herbicides, fungicides as listed above are preferably selected from the group consisting of: S1) Compounds of formula (S1), where the symbols and indices have the following meanings: n A is a natural number from 0 to 5, preferably 0 to 3; R A 1 is halogen, (C 1 -C 4 )Alkyl, (C 1 -C 4 )alkoxy, nitro or (C 1 -C 4 )Haloalkyl; W A is an unsubstituted or substituted divalent heterocyclic radical from the group of the saturated or aromatic five-membered ring heterocycles with 1 to 3 hetero ring atoms from the group N and O, wherein at least one
  • R C 1 is (C 1 -C 4 )Alkyl, (C 1 -C 4 )Haloalkyl, ( C 2 -C 4 )Alkenyl, (C 2 -C 4 )Haloalkenyl, (C 3 -C 7 )Cycloalkyl, preferably dichloromethyl;
  • R C 2 , R C 3 are the same or different hydrogen, (C 1 -C 4 )Alkyl, (C 2 -C 4 )Alkenyl, (C 2 -C 4 )Alkynyl, (C 1 -C 4 )Haloalkyl, (C 2 -C 4 )Haloalkenyl, (C 1 -C 4 )Alkylcarbamoyl-(C 1 -C 4 )alkyl, (C 2 - C 4 )Alkenylcarbam
  • XD is CH or N;
  • R D 1 is CO-NR D 5 R D 6 or NHCO-R D 7 ;
  • R D 2 is halogen, (C 1 -C 4 )-haloalkyl, (C 1 -C 4 )-haloalkoxy, nitro, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, (C 1 -C 4 )- alkylsulfonyl, (C 1 -C 4 )-alkoxycarbonyl or (C 1 -C 4 )-alkylcarbonyl;
  • R D 3 is hydrogen, (C 1 -C 4 )Alkyl, (C 2 -C 4 )alkenyl or (C 2 -C 4 )-alkynyl;
  • R D 4 is hal
  • Active ingredients from the class of hydroxyaromatics and aromatic-aliphatic carboxylic acid derivatives (S5) e.g., ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoate- acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicyclic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid, as described in WO-A-2004/084631, WO-A-2005/015994, WO-A-2005/016001.
  • S5 Active ingredients from the class of hydroxyaromatics and aromatic-aliphatic carboxylic acid derivatives (S5), e.g., ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoate- acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicyclic acid, 2-hydroxycinnamic acid,
  • S6 Active ingredients from the class of 1,2-dihydroquinoxalin-2-ones (S6), e.g., 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-thione, 1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one hydrochloride, 1-(2-methylsulfonylaminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, as described in WO-A-2005/112630.
  • S6 1,2-dihydroquinoxalin-2-ones
  • R E 1 , R E 2 are independently halogen, (C 1 -C 4 )Alkyl, (C 1 -C 4 )Alkoxy, (C 1 -C 4 )Haloalkyl, (C 1 - C 4 )Alkylamino, Di-(C 1 -C 4 )Alkylamino, Nitro;
  • a E is COOR E 3 or COSR E 4 R E 3 , R E 4 are independently hydrogen, (C 1 -C 4 )Alkyl, (C 2 -C 6 )Alkenyl, (C 2 -C 4 )Alkynyl, cyanoalkyl, (C 1 -C 4 )Haloalkyl, phenyl, nitrophenyl, benzyl, halobenzyl, pyridinylalkyl and
  • Phenyl optionally substituted phenoxy, R F 2 Hydrogen or (C 1 -C 4 )Alkyl R F 3 Hydrogen, (C 1 -C 8 )Alkyl, (C 2 -C 4 )Alkenyl, (C 2 -C 4 )alkynyl, or aryl, where each of the abovementioned C-containing radicals is unsubstituted or substituted by one or more, preferably up to three identical or different radicals from the group consisting of halogen and alkoxy; or salts thereof, preferably compounds wherein X F CH, n F an integer from 0 to 2 , R F 1 Halogen, (C 1 -C 4 )Alkyl, (C 1 -C 4 )Haloalkyl, (C 1 -C 4 )Alkoxy, (C 1 -C 4 )Haloalkoxy, R F 2 Hydrogen or (C 1 -C 4 )Alkyl, R F
  • Active ingredients from the class of 3-(5-tetrazolylcarbonyl)-2-quinolones e.g. 1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No. 219479-18-2), 1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No. 95855-00-8), as described in WO-A-1999/000020.
  • S11 Active ingredients of the oxyimino compound type (S11), which are known as seed dressings, such as B.
  • “Oxabetrinil” ((Z)-1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile) (S11-1), which is known as a seed dressing safener for millet against metolachlor damage
  • "Fluxofenim” (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethanone-O-(1,3-dioxolan-2-ylmethyl)-oxime) (S11-2), which is known as a seed dressing safener for millet against metolachlor damage
  • “Cyometrinil” or “CGA-43089” ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3), which is known as a seed dressing safener for millet against metolachlor damage.
  • S12 Active ingredients from the class of isothiochromanones (S12), such as methyl [(3-oxo-1H-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
  • S13 One or more compounds from group (S13): "Naphthalic anhydride” (1,8-naphthalenedicarboxylic anhydride) (S13-1), 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-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (S13-3), known as a seed dressing safener for millet against damage from alachlor and metolachlor, "CL 304415” (CAS Reg. No.
  • Particularly preferred safeners are mefenpyr-diethyl, cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl, benoxacor, dichlormid, and metcamifen.
  • the following examples illustrate the invention. A.
  • Step 1 Preparation of 1-bromo-2-chloro-3-methyl-4-(trifluoromethoxy)benzene (4): 20.35 ml (145.2 mmol) of diisopropylamine were initially charged to 250 ml of tetrahydrofuran under argon, and 79.4 ml (127.1 mmol) of n-butyllithium (1.6 M solution in hexane) were added dropwise at -60°C, and the solution was stirred for 1 h.
  • Step 2 Preparation of 2-chloro-3-methyl-4-(trifluoromethoxy)benzonitrile (5): 18.91 g (65.33 mmol) of 1-bromo-2-chloro-3-methyl-4-(trifluoromethoxy)benzene (4) was dissolved in 150 mL of dimethylformamide, and 11.7 g (130.65 mmol) of copper(I) cyanide was added at room temperature. The resulting reaction mixture was heated to reflux for 12 h. It was then poured into 1 L of cold water and ethyl acetate was added. After vigorous stirring for 10 min, the mixture was filtered and the phases were separated. The organic phase was dried and evaporated.
  • Step 3 Preparation of 2-chloro-3-methyl-4-(trifluoromethoxy)benzoic acid (6): 10.92 g (46.35 mmol) of 2-chloro-3-methyl-4-(trifluoromethoxy)benzonitrile (5) were dissolved in a solution of 17.73 g (443 mmol) of sodium hydroxide in 180 ml of water and heated to reflux for 6 h and then left to stand overnight at room temperature. The mixture was then washed with dichloromethane and the aqueous phase was adjusted to pH 1 with 2 M hydrochloric acid. The mixture was then extracted with ethyl acetate and the organic phase was separated, dried and evaporated.
  • Step 4 Preparation of methyl 2-chloro-3-methyl-4-(trifluoromethoxy)benzoate (7): 22.08 g (86.73 mmol) of 2-chloro-3-methyl-4-(trifluoromethoxy)benzoic acid (6) were initially dissolved in 400 ml of dichloromethane and 3 ml of dimethylformamide, and 11.58 ml (13.09 mmol) of oxalyl chloride were slowly added at room temperature. The mixture was then stirred for 1 h at room temperature. After 20 ml (1734.5 mmol) of methanol was added dropwise, the solution was stirred for 3 h at room temperature and then evaporated to dryness.
  • Step 5 Preparation of methyl 3-(bromomethyl)-2-chloro-4-(trifluoromethoxy)benzoate (8): 10.42 g (38.79 mmol) of methyl 2-chloro-3-methyl-4-(trifluoromethoxy)benzoate (7) was dissolved in 100% chlorobenzene, and 13.81 g (77.58 mmol) of N-bromosuccinimide and 0.64 g (3.88 mmol) of AIBN were added. The reaction mixture was stirred at 120°C for 8 h. It was then evaporated, and the residue was taken up in water and extracted with dichloromethane. The organic phase was separated, dried, and evaporated.
  • Step 6 Preparation of methyl 2-chloro-3-formyl-4-(trifluoromethoxy)benzoate (1): 26.20 g (75 mmol) of methyl 3-(bromomethyl)-2-chloro-4-(trifluoromethoxy)benzoate (8) were placed in 300 mL of acetonitrile, and 26.50 g (226 mmol) of N-methylmorpholine N-oxide were added portionwise at 10°C. After the exothermic reaction had subsided, the reaction mixture was stirred at room temperature for 12 h. The mixture was then evaporated, the residue was taken up in water, and extracted several times with ethyl acetate. The organic phases were combined, dried, and evaporated.
  • Step 1 Preparation of methyl 2-chloro-4-(difluoromethoxy)-3-methylbenzoate (10): 10 g (47.35 mmol) of commercially available methyl 2-chloro-4-hydroxy-3-methylbenzoate (9) were added portionwise to a solution of 19.93 g of potassium hydroxide in 75 ml of acetonitrile and 75 ml of water at 0°C.
  • Step 2 Preparation of methyl 3-(bromomethyl)-2-chloro-4-(difluoromethoxy)benzoate (11): 20.65 g (82.39 mmol) of methyl 2-chloro-4-(difluoromethoxy)-3-methylbenzoate (10) was dissolved in 200 g of chlorobenzene, and 29.33 g (164.79 mmol) of N-bromosuccinimide and 1.35 g (8.24 mmol) of AIBN were added.
  • Step 3 Preparation of methyl 2-chloro-4-(difluoromethoxy)-3-formylbenzoate (2): 5.96 g (18 mmol) of methyl 3-(bromomethyl)-2-chloro-4-(difluoromethoxy)benzoate (11) were placed in 200 ml of acetonitrile, and 6.36 g (54 mmol) of N-methylmorpholine N-oxide were added portionwise at 10°C. After the exothermic reaction had subsided, the reaction mixture was stirred at room temperature for 12 h. The mixture was then evaporated, the residue was taken up in water, and the mixture was extracted several times with ethyl acetate. The organic phases were combined, dried, and evaporated.
  • Step 1 Preparation of 2-chloro-N-(1-methyl-1H-tetrazol-5-yl)-3-(1,3-oxazol-2-yl)-4-(trifluoromethoxy)benzamide (1-12): Step 1: Preparation of methyl 2-chloro-3-[(2,2-dimethoxyethyl)carbamoyl]-4-(trifluoromethoxy)benzoate: 4.58 g (15.34 mmol) of 2-chloro-3-(methoxycarbonyl)-6-(trifluoromethoxy)benzoic acid were initially charged in 200 ml of dichloromethane and 3 ml of dimethylformamide, and 2.05 ml (23.00 mmol) of oxalyl chloride were added at room temperature.
  • reaction solution was stirred for 1 h.
  • the mixture was then evaporated, toluene was added, and the mixture was evaporated again.
  • the residue was dissolved in 45 ml of dichloromethane and added dropwise at 0°C to a solution of 2.51 ml (23.00 mmol) of 2-aminoacetaldehyde dimethyl acetal, 6.68 ml (38.35 mmol) of Hünig's base, and a catalytic amount of dimethylaminopyridine in 200 ml of dry dichloromethane.
  • the reaction mixture was then warmed to room temperature and stirred for 3 h.
  • Step 2 Preparation of methyl 2-chloro-3-[(2-oxoethyl)carbamoyl]-4-(trifluoromethoxy)benzoate: 5.61 g (14.54 mmol) of methyl 2-chloro-3-[(2,2-dimethoxyethyl)carbamoyl]-4-(trifluoromethoxy)benzoate were initially charged in 20 ml of dioxane, and 29.09 ml (58.18 mmol) of 2M hydrochloric acid were added at room temperature. The reaction mixture was then stirred at 80°C for 4 h. The mixture was evaporated, the residue was taken up in water, and extracted with ethyl acetate.
  • Step 3 Preparation of methyl 2-chloro-3-(1,3-oxazol-2-yl)-4-(trifluoromethoxy)benzoate (3-12): 1.40 g (4.12 mmol) of methyl 2-chloro-3-[(2-oxoethyl)carbamoyl]-4-(trifluoromethoxy)benzoate was dissolved in 8 ml of acetonitrile and added to a solution of 2.93 g (12.37 mmol) of hexachloroethane in 20 ml of acetonitrile.
  • reaction mixture was then added portionwise at 0°C with 4.31 ml (24.73 mmol) of Hünig's base and 3.24 g (12.37 mmol) of triphenylphosphine.
  • the mixture was then stirred at room temperature for 4 h.
  • the mixture was then evaporated to dryness, and the residue was dissolved in 2M hydrochloric acid and extracted with dichloromethane.
  • the organic phase was separated.Dried and evaporated.
  • the residue was purified by chromatography (HPLC, normal phase, heptane/ethyl acetate 100/0 ⁇ 60/40).
  • Step 4 Preparation of 2-chloro-3-(1,3-oxazol-2-yl)-4-(trifluoromethoxy)benzoic acid (4-12): 698 mg (2.17 mmol) of methyl 2-chloro-3-(1,3-oxazol-2-yl)-4-(trifluoromethoxy)benzoate (3-12) was initially dissolved in 20 ml of methanol, and 2.17 ml (4.34 mmol) of 2M sodium hydroxide solution was added at room temperature.
  • Step 5 Preparation of 2-chloro-N-(1-methyl-1H-tetrazol-5-yl)-3-(1,3-oxazol-2-yl)-4-(trifluoromethoxy)benzamide (1-12): 200 mg (0.65 mmol) of 2-chloro-3-(1,3-oxazol-2-yl)-4-(trifluoromethoxy)benzoic acid (4-12) and 98.6 mg (0.98 mmol) of 5-amino-1-methyl-1H-tetrazole were initially charged in 3 ml of pyridine, and 0.087 ml (0.98 mmol) of oxalyl chloride was added dropwise at room temperature.
  • Step 1 Preparation of 2-chloro-3-(5-methyl-1,2-oxazol-3-yl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethoxy)benzamide
  • Step 1 Preparation of methyl 2-chloro-3-[(hydroxyimino)methyl]-4-(trifluoromethoxy)benzoate: 3.40 g (12.03 mmol) of methyl 2-chloro-4-(difluoromethoxy)-3-formylbenzoate were placed together with 1.03 g (14.44 mmol) of hydroxylamine hydrochloride (97%) in 120 ml of tetrahydrofuran, and 2.52 ml (14.44 mmol) of Hünig's base were added at room temperature.
  • Step 2 Preparation of methyl 2-chloro-3-(5-methyl-1,2-oxazol-3-yl)-4-(trifluoromethoxy)benzoate (3-13): 1.23 g (4.13 mmol) of methyl 2-chloro-3-[(hydroxyimino)methyl]-4-(trifluoromethoxy)benzoate were initially charged in 50 ml of dimethylformamide, and 579.47 mg (4.34 mmol) of N-chlorosuccinimide were added at room temperature. The mixture was then stirred for 4 h. After cooling the reaction solution to 0°C, 41.33 ml (approx.
  • Step 3 Preparation of 2-chloro-3-(5-methyl-1,2-oxazol-3-yl)-4-(trifluoromethoxy)benzoic acid (4-13): 1.18 g (3.52 mmol) of methyl 2-chloro-3-(5-methyl-1,2-oxazol-3-yl)-4-(trifluoromethoxy)benzoate (3-13) were initially charged in 100 ml of methanol, and 3.52 ml (7.03 mmol) of 2M sodium hydroxide solution were added at room temperature. The reaction mixture was stirred at room temperature for 12 h and then evaporated. The residue was taken up with water, and the aqueous phase was adjusted to pH 1 with 2M hydrochloric acid.
  • Step 4 Preparation of 2-chloro-3-(5-methyl-1,2-oxazol-3-yl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethoxy)benzamide (1-13): 200 mg (0.62 mmol) of 2-chloro-3-(5-methyl-1,2-oxazol-3-yl)-4-(trifluoromethoxy)benzoic acid (4-13) and 94.32 mg (0.93 mmol) of 5-amino-1-methyl-1H-tetrazole were initially dissolved in 3 ml of pyridine, and 0.083 ml (0.93 mmol) of oxalyl chloride was added dropwise at room temperature.
  • Step 1 Preparation of methyl 2-chloro-4-(difluoromethoxy)-3-vinylbenzoate: 25.86 g (11.34 mmol) of Nysted reagent was diluted with 80 ml of tetrahydrofuran under argon, and 0.96 ml (0.76 mmol) of boron trifluoride diethyl etherate was added at 0°C.
  • Step 2 Preparation of (R,S)-methyl 2-chloro-4-(difluoromethoxy)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzoate (3-31): 1.70 g (6.47 mmol) of methyl 2-chloro-4-(difluoromethoxy)-3-vinylbenzoate and 7.06 g (32.36 mmol) of di-tert-butyl dicarbonate were placed in 70 ml of acetonitrile, and 1.86 ml (25.89 mmol) of nitroethane were slowly added. The mixture was then stirred at reflux for 3 h.
  • Step 3 Preparation of (R,S)-2-chloro-4-(difluoromethoxy)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzoic acid (4-31): 810 mg (2.53 mmol) of (R,S)-methyl 2-chloro-4-(difluoromethoxy)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzoate (3-31) were initially charged in 50 ml of methanol, and 2.53 ml (5.07 mmol) of 2M sodium hydroxide solution were added at room temperature. The reaction mixture was stirred at room temperature for 12 h and then evaporated.
  • Step 4 Preparation of (R,S)-2-chloro-4-(difluoromethoxy)-N-(1-ethyl-1H-tetrazol-5-yl)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzamide (2-31): 200 mg (0.65 mmol) of (R,S)-2-chloro-4-(difluoromethoxy)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzoic acid (4-31) and 116.87 mg (0.98 mmol) of 5-amino-1-ethyl-1H-tetrazole were initially charged in 3 ml of pyridine, and 0.087 ml (0.98 mmol) of oxalyl chloride was added dropwise at room temperature.
  • reaction solution was stirred at room temperature for 12 h. After addition of 10 ml of aqueous sat. Sodium bicarbonate solution was stirred for a further 10 min and then extracted with dichloromethane. The organic phase was separated, dried, and evaporated. The residue was purified by chromatography (HPLC, C18, gradient: acetonitrile/water (+0.05% trifluoroacetic acid) 10/90 ⁇ 100/0).
  • Table 3 Compounds of the formula (II) according to the invention, wherein L is methoxy and the other substituents have the meanings given below
  • Table 4 Compounds of the formula (II) according to the invention, wherein L is hydroxy and the other substituents have the meanings given below
  • Table 5 Compounds of the formula (II) according to the invention, wherein L is chlorine and the other substituents have the meanings given below
  • NMR data are disclosed below for numerous compounds of the formula (I) and (II) according to the invention listed in the tables above: Example No.
  • a dust is obtained by mixing 10 parts by weight of a compound of formula (I) and/or salts thereof and 90 parts by weight of talc as an inert substance and comminuting the mixture in a hammer mill.
  • a wettable powder which is easily dispersible in water is obtained by mixing 25 parts by weight of a compound of formula (I) and/or salts thereof, 64 parts by weight of kaolin-containing quartz as inert material, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltaurine as wetting and dispersing agent and grinding in a pin mill.
  • a dispersion concentrate which is easily dispersible in water is obtained by mixing 20 parts by weight of a compound of formula (I) and/or its salts with 6 parts by weight of alkylphenol polyglycol ether (®Triton 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 to over 277 °C) and grinding in a ball mill to a fineness of less than 5 microns.
  • alkylphenol polyglycol ether ®Triton X 207
  • isotridecanol polyglycol ether 8 EO
  • paraffinic mineral oil oil
  • grinding range for example, approx. 255 to over 277 °C
  • An emulsifiable concentrate is obtained from 15 parts by weight of a compound of formula (I) and/or its salts, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.
  • Water-dispersible granules are obtained by mixing 75 parts by weight of a compound of formula (I) and/or its salts, 10 parts by weight of calcium ligninsulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl alcohol, and 7 parts by weight of kaolin, grinding the mixture on a pin mill, and granulating the powder in a fluidized bed by spraying water as the granulating liquid.
  • Water-dispersible granules are also obtained by mixing 25 parts by weight of a compound of formula (I) and/or its salts, 5 parts by weight of 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, 2 parts by weight of oleoylmethyltauric acid sodium, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water are homogenized and pre-crushed in a colloid mill, then ground in a bead mill and the resulting suspension is atomized and dried in a spray tower using a single-component nozzle.
  • a compound of formula (I) and/or its salts 5 parts by weight of 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, 2 parts by weight of oleoylmethyltauric acid sodium, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water
  • weeds mean: ABUTH Abutilon theophrasti ALOMY Alopecurus myosuroides AVEFA Avena fatua AMARE Amaranthus retroflexus CYPES Cyperus esculentus DIGSA Digitaria sanguinalis ECHCG Echinochloa crus-galli HORMU Hordeum murinum KCHSC Kochia scoparia LOLMU Lolium multiflorum LOLRI Lolium rigidum MATIN Matricaria inodora PHBPU Pharbitis purpurea POLCO Polygonum convolvulus SETVI Setaria viridis STEME Stellaria media VERPE Veronica persica VIOTR Viola tricolor 1.
  • Seeds of monocotyledonous or dicotyledonous weeds or cultivated plants are placed in sandy loam soil in wood fibre pots and covered with soil.
  • the compounds of the invention formulated as wettable powders (WP) or emulsion concentrates (EC), are then applied to the surface of the covering soil as an aqueous suspension or emulsion at a water application rate equivalent to 600 to 800 l/ha with the addition of 0.2% wetting agent. After treatment, the pots are placed in the greenhouse and maintained under favorable growth conditions for the test plants.
  • WP wettable powders
  • EC emulsion concentrates
  • Table C-1 Pre-emergence activity at 20 g/ha against ZEAMX in %
  • Table C-2 Pre-emergence effect at 80g/ha against ZEAMX in %
  • Table C-3 Pre-emergence effect at 20g/ha against TRZAS in %
  • Table C-4 Pre-emergence effect at 80g/ha against TRZAS in %
  • Table C-5 Pre-emergence effect at 20g/ha against GLXMA in %
  • Table C-6 Pre-emergence effect at 80g/ha against GLXMA in %
  • Table C-7 Pre-emergence effect at 20g/ha against ABUTH in %
  • Table C-8 Pre-emergence effect at 80g/ha against ABUTH in %
  • Table C-9 Pre-emergence effect at 20g/ha against ALOMY in %
  • Table C-10 Pre-emergence effect at 80g/ha against ALOMY in %
  • Table C-11 Pre-emergence effect at 20g/ha against AMARE in %
  • Table C-12 Pre-emergence effect at 80g/ha against AMARE in %
  • Table C-21 Pre-emergence effect at 20g/ha against PHBPU in %
  • Table C-22 Pre-emergence effect at 80g/ha against PHBPU in %
  • Table C-23 Pre-emergence effect at 20g/ha against POLCO in %
  • Table C-24 Pre-emergence effect at 80g/ha against POLCO in %
  • Table C-25 Pre-emergence efficacy at 20g/ha against SETVI in %
  • Table C-26 Pre-emergence efficacy at 80g/ha against SETVI in %
  • Table C-27 Pre-emergence effect at 20g/ha against VERPE in %
  • Table C-28 Pre-emergence effect at 80g/ha against VERPE in %
  • Table C-29 Pre-emergence effect at 20g/ha against VIOTR in %
  • Table C-30 Pre-emergence effect at 80g/ha against VIOTR in %
  • Table C-31 Pre-emergence effect at 20g/ha against KCHSC in %
  • Table C-32 Pre-emergence effect at 80g/ha against KCHSC in % 2.
  • Post-emergence herbicidal activity against weeds Seeds of monocotyledonous or dicotyledonous weeds or cultivated plants are sown in wood fiber pots in sandy loam soil, covered with soil, and grown in a greenhouse under favorable growth conditions. Two to three weeks after sowing, the test plants are treated at the single-leaf stage.
  • the following tables show examples of the postemergence herbicidal activity of the compounds of the invention, with the herbicidal activity expressed as a percentage.
  • Table C-33 Postemergence activity at 20 g/ha against ZEAMX in %
  • Table C-34 Post-emergence effect at 80g/ha against ZEAMX in %
  • Table C-35 Post-emergence effect at 20g/ha against TRZAS in %
  • Table C-36 Post-emergence effect at 80g/ha against TRZAS in %
  • Table C-37 Post-emergence effect at 20g/ha against ABUTH in %
  • Table C-38 Post-emergence effect at 80g/ha against ABUTH in %
  • Table C-39 Post-emergence effect at 20g/ha against ALOMY in % Table C-40: Post-emergence effect at 80g/ha against ALOMY in % Table C-41: Post-emergence effect at 20g/ha against AMARE in % Table C-42: Post-emergence effect at 80g/ha against AMARE in % Table C-43: Post-emergence effect at 20g/ha against DIGSA in % Table C-44: Post-emergence effect at 80g/ha against DIGSA in % Table C-45: Post-emergence effect at 20g/ha against LOLRI in % Table C-46: Post-emergence effect at 80g/ha against LOLRI in %
  • Table C-47 Post-emergence effect at 20g/ha against MATIN in %
  • Table C-48 Post-emergence effect at 80g/ha against MATIN in %
  • Table C-49 Post-emergence effect at 20g/ha against PHBPU in %
  • Table C-50 Post-emergence effect at 80g/ha against PHBPU in %
  • Table C-51 Post-emergence effect at 80g/ha against POLCO in %
  • Table C-52 Post-emergence effect at 20g/ha against SETVI in %
  • Table C-53 Post-emergence effect at 80g/ha against SETVI in %
  • Table C-54 Post-emergence effect at 20g/ha against VERPE in %
  • Table C-55 Post-emergence effect at 80g/ha against VERPE in %
  • Table C-56 Post-emergence effect at 20g/ha against VIOTR in %
  • Table C-57 Post-emergence effect at 80g/ha against VIOTR in %
  • V-1 2-chloro-4-methoxy-3-[(5RS)-3-methyl-4,5-dihydro-1,2-oxazol-5-yl]-N-(1-methyl-1H-tetrazol-5-yl)benzamide
  • V-2 2-Chloro-N-(1-ethyl-1H-tetrazol-5-yl)-4-methoxy-3-[(5RS)-3-methyl-4,5-dihydro-1,2-oxazol-5-yl]benzamide
  • V-3 2-Chloro-4-methoxy-N-(1-methyl-1H-tetrazol-5-yl)-3-(1,2-oxazol-3-yl)benzamide
  • V-4 2-Chloro-N-(1-ethyl-1H-t

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Abstract

The invention relates to 3-heterocyclyl-benzamides of formula (I) as herbicides. In formula (I), X, Y, Z and Rx represent radicals such as alkyl, cycloalkyl, haloalkyl and halogen.

Description

3-Heterocyclyl-benzamide und ihre Verwendung als Herbizide Die Erfindung betrifft das technische Gebiet der Herbizide, insbesondere das der Herbizide zur selektiven Bekämpfung von Unkräutern und Ungräsern in Nutzpflanzenkulturen. WO 2012/028579 A1 offenbart herbizid wirksame Benzamide, die in 3-Position des Phenylrings eine Vielzahl von Substituenten tragen können. Jedoch weisen die aus der oben genannten Schrift bekannten Benzoylamide nicht immer eine ausreichende herbizide Wirkung und/oder Verträglichkeit gegenüber Kulturpflanzen auf. Aufgabe der vorliegenden Erfindung ist es, alternative herbizid wirksame Wirkstoffe bereitzustellen. Diese Aufgabe wird durch die nachfolgend beschriebenen erfindungsgemäßen Benzamide gelöst, die in 3- Position des Phenylrings einen Heterocyclyl-Rest und zusätzlich in 4-Position einen Halogenalkoxy-Rest tragen. Ein Gegenstand der vorliegenden Erfindung sind somit 3-Acyl-benzamide der Formel (I) oder deren Salze

Figure imgf000002_0001
worin die Symbole und Indizes folgende Bedeutungen haben: Rx bedeutet (C1-C6)-Alkyl, X bedeutet Halogen oder (C1-C6)-Alkyl, Y bedeutet Halogen-(C1-C6)-alkoxy, Z bedeutet Z-1, Z-2, Z-3 oder Z-4, wobei Z-1 bis Z-4 die folgenden Bedeutungen haben
Figure imgf000002_0002
R1 bedeutet Wasserstoff, (C1-C6)-Alkyl oder Halogen-(C1-C6)-alkyl, R2 bedeutet Wasserstoff, (C1-C6)-Alkyl oder (C3-C6)-Cycloalkyl, R3 bedeutet (C1-C6)-Alkyl, Halogen-(C1-C6)-alkyl oder (C3-C6)-Cycloalkyl, und R4 und R5 bedeuten unabhängig voneinander Wasserstoff, (C1-C6)-Alkyl, (C1-C6)-Alkyloxy-(C1-C6)- alkyl, Cyano-(C1-C6)-alkyl oder (C3-C6)-Cycloalkyl. In der Formel (I) und allen nachfolgenden Formeln können Alkylreste mit mehr als zwei Kohlenstoffatomen geradkettig oder verzweigt sein. Alkylreste bedeuten z.B. Methyl, Ethyl, n- oder i-Propyl, n-, i-, t- oder 2-Butyl, Pentyle, Hexyle, wie n-Hexyl, i-Hexyl und 1,3-Dimethylbutyl. Analog bedeutet Alkenyl z.B. Allyl, 1-Methylprop-2-en-1-yl, 2-Methyl-prop-2-en-1-yl, But-2-en-1-yl, But-3-en-1-yl, 1-Methyl-but-3-en-1-yl und 1-Methyl-but-2-en-1-yl. Alkinyl bedeutet z.B. Propargyl, But-2-in-1-yl, But-3-in-1-yl, 1-Methyl-but-3-in-1-yl. Die Mehrfachbindung kann sich jeweils in beliebiger Position des ungesättigten Rests befinden. Cycloalkyl bedeutet ein carbocyclisches, gesättigtes Ringsystem mit drei bis sechs C-Atomen wie Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl. Halogen steht für Fluor, Chlor, Brom oder Iod. Die Verbindungen der Formel (I) oder (II) können je nach Art und Verknüpfung der Substituenten als Stereoisomere vorliegen. Sind beispielsweise ein oder mehrere asymmetrisch substituierte Kohlenstoffatome vorhanden, so können Enantiomere und Diastereomere auftreten. Stereoisomere lassen sich aus den bei der Herstellung anfallenden Gemischen nach üblichen Trennmethoden, beispielsweise durch chromatographische Trennverfahren, erhalten. Ebenso können Stereoisomere durch Einsatz stereoselektiver Reaktionen unter Verwendung optisch aktiver Ausgangs- und/oder Hilfsstoffe selektiv hergestellt werden. Die Erfindung betrifft auch alle Stereoisomeren und deren Gemische, die von der Formel (I) oder (II) umfasst, jedoch nicht spezifisch definiert sind. Bevorzugt sind Verbindungen der Formel (I), worin die Symbole und Indices folgende Bedeutungen haben: Rx bedeutet (C1-C6)-Alkyl, X bedeutet Halogen oder (C1-C6)-Alkyl, Y bedeutet OCF3, OCHF2 oder OCF2Me Z bedeutet Z-1, Z-2, Z-3 oder Z-4, wobei Z-1 bis Z-4 die folgenden Bedeutungen haben
Figure imgf000003_0001
R1 bedeutet Wasserstoff oder (C1-C6)-Alkyl, R2 bedeutet Wasserstoff, (C1-C6)-Alkyl oder (C3-C6)-Cycloalkyl, R3 bedeutet (C1-C6)-Alkyl oder Halogen-(C1-C6)-alkyl, und R4 und R5 bedeuten unabhängig voneinander Wasserstoff, (C1-C6)-Alkyl, (C1-C6)-Alkyloxy-(C1-C6)- alkyl, Cyano-(C1-C6)-alkyl oder (C3-C6)-Cycloalkyl. Besonders bevorzugt sind Verbindungen der Formel (I), worin die Symbole und Indices folgende Bedeutungen haben: Rx bedeutet Methyl oder Ethyl, X bedeutet Chlor, Brom, Methyl oder Ethyl, Y bedeutet OCF3 oder OCHF2, Z bedeutet Z-1, Z-2, Z-3 oder Z-4, wobei Z-1 bis Z-4 die folgenden Bedeutungen haben
Figure imgf000004_0001
R1 bedeutet Wasserstoff oder Methyl, R2 bedeutet Wasserstoff, Methyl, Ethyl oder c-Propyl, R3 bedeutet Methyl, Ethyl oder i-Propyl, und R4 und R5 bedeuten folgende Kombinationen Wasserstoff und Wasserstoff, Wasserstoff und Methyl, Wasserstoff und Ethyl, Wasserstoff und Cyclopropyl, Cyclopropyl und Cyclopropyl, Wasserstoff und Methoxymethyl oder Wasserstoff und Cyanomethyl. In allen nachfolgend genannten Formeln haben die Substituenten und Symbole, sofern nicht anders definiert, dieselbe Bedeutung wie unter Formel (I) beschrieben. Verbindungen der Formel (II) sind neu und eignen sich sehr gut als Intermediate zur Herstellung der erfindungsgemäßen Verbindungen der Formel (I). Ein weiterer Gegenstand vorliegender Erfindung sind somit Verbindungen der Formel (II),
Figure imgf000004_0002
worin die Symbole und Indizes folgende Bedeutungen haben: L bedeutet Halogen oder R6O, X bedeutet Halogen oder (C1-C6)-Alkyl, Y bedeutet Halogen-(C1-C6)-alkoxy, Z bedeutet Z-1, Z-2, Z-3 oder Z-4, wobei Z-1 bis Z-4 die folgenden Bedeutungen haben
Figure imgf000005_0001
R1 bedeutet Wasserstoff, (C1-C6)-Alkyl oder Halogen-(C1-C6)-alkyl, R2 bedeutet Wasserstoff, (C1-C6)-Alkyl oder (C3-C6)-Cycloalkyl, oder R2 kann auch Si((C1-C6)-Alkyl)3 bedeuten, wenn L OR6 bedeutet und R6 für (C1-C6)-Alkyl steht, R3 bedeutet (C1-C6)-Alkyl, Halogen-(C1-C6)-alkyl oder (C3-C6)-Cycloalkyl, R4 und R5 bedeuten unabhängig voneinander Wasserstoff, (C1-C6)-Alkyl, (C1-C6)-Alkyloxy-(C1-C6)- alkyl, Cyano-(C1-C6)-alkyl oder (C3-C6)-Cycloalkyl, und R6 bedeutet Wasserstoff oder (C1-C6)-Alkyl. Bevorzugt sind Verbindungen (II), worin L bedeutet Chlor, Methoxy oder Hydroxy, X bedeutet Chlor, Brom, Methyl oder Ethyl, Y bedeutet OCF3 oder OCHF2, Z bedeutet Z-1, Z-2, Z-3 oder Z-4, wobei Z-1 bis Z-4 die folgenden Bedeutungen haben
Figure imgf000005_0002
R1 bedeutet Wasserstoff oder Methyl, R2 bedeutet Wasserstoff, Methyl, Ethyl oder c-Propyl, oder R2 kann auch Si(Me)3 bedeuten, wenn L für Methoxy steht, R3 bedeutet Methyl, Ethyl oder i-Propyl, R4 und R5 bedeuten folgende Kombinationen Wasserstoff und Wasserstoff, Wasserstoff und Methyl, Wasserstoff und Ethyl, Wasserstoff und Cyclopropyl, Cyclopropyl und Cyclopropyl, Wasserstoff und Methoxymethyl oder Wasserstoff und Cyanomethyl. In allen nachfolgend genannten Formeln haben die Substituenten und Symbole, sofern nicht anders definiert, dieselbe Bedeutung wie unter Formel (I) beschrieben. Erfindungsgemäße Verbindungen der allgemeinen Formel (I) können beispielsweise, wie auch in WO2012/028579 beschrieben, durch die Umsetzung der erfindungsgemäßen Verbindungen der allgemeinen Formel (IIb: Verbindungen II, wobei gilt: L= Hydroxy) mit substituierten Aminotetrazolen hergestellt werden:
Figure imgf000006_0001
Die Synthese der Verbindungen der allgemeinen Formel (IIb) kann beispielsweise gemäß folgendem Schema und dem Fachmann bekannten Methoden erfolgen: Heterocyclen in der 3-Position mit Z = Z-1:
Figure imgf000006_0002
Heterocyclen in der 3-Position mit Z = Z-2:
Figure imgf000007_0001
Kollektionen aus Verbindungen der Formel (I) und/oder deren Salzen, die nach den oben genannten Reaktionen synthetisiert werden können, können auch in parallelisierter Weise hergestellt werden, wobei dies in manueller, teilweise automatisierter oder vollständig automatisierter Weise geschehen kann. Dabei ist es beispielsweise möglich, die Reaktionsdurchführung, die Aufarbeitung oder die Reinigung der Produkte bzw. Zwischenstufen zu automatisieren. Insgesamt wird hierunter eine Vorgehensweise verstanden, wie sie beispielsweise durch D. Tiebes in Combinatorial Chemistry – Synthesis, Analysis, Screening (Herausgeber Günther Jung), Verlag Wiley 1999, auf den Seiten 1 bis 34 beschrieben ist. Zur parallelisierten Reaktionsdurchführung und Aufarbeitung können eine Reihe von im Handel erhältlichen Geräten verwendet werden, beispielsweise Calpyso-Reaktionsblöcke (Caylpso reaction blocks) der Firma Barnstead International, Dubuque, Iowa 52004-0797, USA oder Reaktionsstationen (reaction stations) der Firma Radleys, Shirehill, Saffron Walden, Essex, CB 11 3AZ, England oder MultiPROBE Automated Workstations der Firma Perkin Elmar, Waltham, Massachusetts 02451, USA. Für die parallelisierte Aufreinigung von Verbindungen der Formel (I) und deren Salzen beziehungsweise von bei der Herstellung anfallenden Zwischenprodukten stehen unter anderem Chromatographieapparaturen zur Verfügung, beispielsweise der Firma ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA. Die aufgeführten Apparaturen führen zu einer modularen Vorgehensweise, bei der die einzelnen Arbeitsschritte automatisiert sind, zwischen den Arbeitsschritten jedoch manuelle Operationen durchgeführt werden müssen. Dies kann durch den Einsatz von teilweise oder vollständig integrierten Automationssystemen umgangen werden, bei denen die jeweiligen Automationsmodule beispielsweise durch Roboter bedient werden. Derartige Automationssysteme können zum Beispiel von der Firma Caliper, Hopkinton, MA 01748, USA bezogen werden. Die Durchführung einzelner oder mehrerer Syntheseschritte kann durch den Einsatz von Polymer- supported reagents/Scavanger-Harze unterstützt werden. In der Fachliteratur sind eine Reihe von Versuchsprotokollen beschrieben, beispielsweise in ChemFiles, Vol. 4, No. 1, Polymer-Supported Scavengers and Reagents for Solution-Phase Synthesis (Sigma-Aldrich). Neben den hier beschriebenen Methoden kann die Herstellung von Verbindungen der Formel (I) und deren Salzen vollständig oder partiell durch Festphasen unterstützte Methoden erfolgen. Zu diesem Zweck werden einzelne Zwischenstufen oder alle Zwischenstufen der Synthese oder einer für die entsprechende Vorgehensweise angepassten Synthese an ein Syntheseharz gebunden. Festphasen- unterstützte Synthesemethoden sind in der Fachliteratur hinreichend beschrieben, z.B. Barry A. Bunin in “The Combinatorial Index”, Verlag Academic Press, 1998 und Combinatorial Chemistry – Synthesis, Analysis, Screening (Herausgeber Günther Jung), Verlag Wiley, 1999. Die Verwendung von Festphasen- unterstützten Synthesemethoden erlaubt eine Reihe von literaturbekannten Protokollen, die wiederum manuell oder automatisiert ausgeführt werden können. Die Reaktionen können beispielsweise mittels IRORI-Technologie in Mikroreaktoren (microreactors) der Firma Nexus Biosystems, 12140 Community Road, Poway, CA92064, USA durchgeführt werden. Sowohl in fester als auch in flüssiger Phase kann die Durchführung einzelner oder mehrerer Syntheseschritte durch den Einsatz der Mikrowellen-Technologie unterstützt werden. In der Fachliteratur sind eine Reihe von Versuchsprotokollen beschrieben, beispielsweise in Microwaves in Organic and Medicinal Chemistry (Herausgeber C. O. Kappe und a. Stadler), Verlag Wiley, 2005. Die Herstellung gemäß der hier beschriebenen Verfahren liefert Verbindungen der Formel (I) und deren Salze in Form von Substanzkollektionen, die Bibliotheken genannt werden. Gegenstand der vorliegenden Erfindung sind auch Bibliotheken, die mindestens zwei Verbindungen der Formel (I) und deren Salzen enthalten. Die erfindungsgemäßen Verbindungen weisen eine ausgezeichnete herbizide Wirksamkeit gegen ein breites Spektrum wirtschaftlich wichtiger mono- und dikotyler annueller Schadpflanzen auf. Auch schwer bekämpfbare perennierende Schadpflanzen, die aus Rhizomen, Wurzelstöcken oder anderen Dauerorganen austreiben, werden durch die Wirkstoffe gut erfasst. 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 Verbindung(en) auf die Pflanzen (z.B. Schadpflanzen wie mono- oder dikotyle Unkräuter oder unerwünschte Kulturpflanzen), das Saatgut (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), Vorauflauf- oder Nachauflaufverfahren ausgebracht werden. Im Einzelnen seien beispielhaft einige Vertreter der mono- und dikotylen Unkrautflora genannt, die durch die die erfindungsgemäßen Verbindungen kontrolliert werden können, ohne dass durch die Nennung eine Beschränkung auf bestimmte Arten erfolgen soll. 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, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria und Sorghum. Dikotyle Unkräuter der Gattungen: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola und 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 jedoch dann ihr Wachstum ein und sterben schließlich nach Ablauf von drei bis vier Wochen vollkommen ab. Bei Applikation der Wirkstoffe auf die grünen Pflanzenteile im Nachauflaufverfahren tritt nach der Behandlung Wachstumsstop 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. Obgleich die erfindungsgemäßen Verbindungen eine ausgezeichnete herbizide Aktivität gegenüber mono- und dikotylen Unkräutern aufweisen, werden Kulturpflanzen wirtschaftlich bedeutender Kulturen z.B. dikotyler Kulturen der Gattungen Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Miscanthus, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, oder monokotyler Kulturen der Gattungen Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea, insbesondere Zea und Triticum, abhängig von der Struktur der jeweiligen erfindungsgemäßen Verbindung und deren Aufwandmenge nur unwesentlich oder gar nicht geschädigt. Die vorliegenden Verbindungen eignen sich aus diesen Gründen sehr gut zur selektiven Bekämpfung von unerwünschtem Pflanzenwuchs in Pflanzenkulturen wie landwirtschaftlichen Nutzpflanzungen oder Zierpflanzungen. Darüber hinaus weisen die erfindungsgemäßen Verbindungen, abhängig von ihrer jeweiligen chemischen Struktur und der ausgebrachten Aufwandmenge, hervorragende wachstumsregulatorische Eigenschaften bei Kulturpflanzen auf. Sie greifen regulierend in den pflanzeneigenen Stoffwechsel ein und können damit zur gezielten Beeinflussung von Pflanzeninhaltsstoffen und zur Ernteerleichterung wie z.B. durch Auslösen von Desikkation und Wuchsstauchung eingesetzt werden. Des Weiteren eignen sie sich auch zur generellen Steuerung und Hemmung von unerwünschtem vegetativen Wachstum, ohne dabei die Pflanzen abzutöten. Eine Hemmung des vegetativen Wachstums spielt bei vielen mono- und dikotylen Kulturen eine große Rolle, da beispielsweise die Lagerbildung hierdurch verringert oder völlig verhindert werden kann. Aufgrund ihrer herbiziden und pflanzenwachstumsregulatorischen Eigenschaften können die Wirkstoffe auch zur Bekämpfung von Schadpflanzen in Kulturen von gentechnisch oder durch konventionelle Mutagenese veränderten Pflanzen eingesetzt werden. Die transgenen Pflanzen zeichnen sich in der Regel durch besondere vorteilhafte Eigenschaften aus, beispielsweise durch Resistenzen gegenüber bestimmten Pestiziden, 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 Erntegut 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 Ernteguts bekannt. Bevorzugt bezüglich transgener Kulturen ist die Anwendung der erfindungsgemäßen Verbindungen in wirtschaftlich bedeutenden transgenen Kulturen von Nutz- und Zierpflanzen, z.B. von Getreide wie Weizen, Gerste, Roggen, Hafer, Hirse, Reis und Mais oder auch Kulturen von Zuckerrübe, Baumwolle, Soja, Raps, Kartoffel, Maniok, Tomate, Erbse und anderen Gemüsesorten. Vorzugsweise können die erfindungsgemäßen Verbindungen als Herbizide in Nutzpflanzenkulturen eingesetzt werden, welche gegenüber den phytotoxischen Wirkungen der Herbizide resistent sind bzw. gentechnisch resistent gemacht worden sind. 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-A-0221044, EP-A-0131624). Beschrieben wurden beispielsweise in mehreren Fällen - gentechnische Veränderungen von Kulturpflanzen zwecks Modifikation der in den Pflanzen synthetisierten Stärke (z. B. WO 92/11376, WO 92/14827, WO 91/19806), - transgene Kulturpflanzen, welche gegen bestimmte Herbizide vom Typ Glufosinate (vgl. z. B. EP-A-0242236, EP-A-242246) oder Glyphosate (WO 92/00377) oder der Sulfonylharnstoffe (EP- A-0257993, US-A-5013659) resistent sind, - transgene Kulturpflanzen, beispielsweise Baumwolle, mit der Fähigkeit Bacillus thuringiensis- Toxine (Bt-Toxine) zu produzieren, welche die Pflanzen gegen bestimmte Schädlinge resistent machen (EP-A-0142924, EP-A-0193259). - transgene Kulturpflanzen mit modifizierter Fettsäurezusammensetzung (WO 91/13972). - gentechnisch veränderte Kulturpflanzen mit neuen Inhalts- oder Sekundärstoffen z. B. neuen Phytoalexinen, die eine erhöhte Krankheitsresistenz verursachen (EPA 309862, EPA0464461) - gentechnisch veränderte Pflanzen mit reduzierter Photorespiration, die höhere Erträge und höhere Stresstoleranz aufweisen (EPA 0305398). - Transgene Kulturpflanzen, die pharmazeutisch oder diagnostisch wichtige Proteine produzieren („molecular pharming“) - transgene Kulturpflanzen, die sich durch höhere Erträge oder bessere Qualitat 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 Laboratory Manual, 2. Aufl. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY, oder Winnacker "Gene und Klone", VCH Weinheim 2. Auflage 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. 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. Natl. Acad. Sci. 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. 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 in transgenen Kulturen eingesetzt werden, welche gegen Wuchsstoffe, wie z. B. Dicamba oder gegen Herbizide, die essentielle Pflanzenenzyme, z. B. Acetolactatsynthasen (ALS), EPSP Synthasen, Glutaminsynthasen (GS) oder Hydroxyphenylpyruvat Dioxygenasen (HPPD) hemmen, respektive gegen Herbizide aus der Gruppe der Sulfonylharnstoffe, der Glyphosate, Glufosinate oder Benzoylisoxazole und analogen Wirkstoffe, resistent sind. 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 als Herbizide zur Bekämpfung von Schadpflanzen in transgenen Kulturpflanzen. Die erfindungsgemäßen Verbindungen können in Form von Spritzpulvern, 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. 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), ULV-Formulierungen, 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 Drying" 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, McCutcheon'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, "Grenzflächenaktive Äthylenoxidaddukte", Wiss. Verlagsgesell., Stuttgart 1976, Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hanser Verlag München, 4. Aufl.1986. 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, Fettalkoholpolyglykol-ethersulfate, Alkansulfonate, 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. 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 Fettsäurepolyglykolester, Alkylarylpolyglykolether, Fettalkoholpolyglykolether, Propylenoxid-Ethylenoxid-Kondensationsprodukte, Alkylpolyether, Sorbitanester wie z.B. Sorbitanfettsäureester oder Polyoxethylensorbitanester wie z.B. Polyoxyethylensorbitanfettsäureester. Stäubemittel erhält man durch Vermahlen des Wirkstoffes mit fein verteilten festen Stoffen, z.B. Talkum, natürlichen Tonen, wie Kaolin, Bentonit und Pyrophyllit, 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. 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 Inertmaterial hergestellt werden oder durch Aufbringen von Wirkstoffkonzentraten mittels Klebemitteln, z.B. Polyvinylalkohol, polyacrylsaurem 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. Wasserdispergierbare Granulate werden in der Regel nach den üblichen Verfahren wie Sprühtrocknung, Wirbelbett-Granulierung, Teller-Granulierung, Mischung mit Hochgeschwindigkeitsmischern und Extrusion ohne festes Inertmaterial hergestellt. Zur Herstellung von Teller-, Fließbett-, Extruder- und Sprühgranulate siehe z.B. Verfahren in "Spray-Drying 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. 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. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, Seiten 101-103. Die agrochemischen Zubereitungen enthalten in der Regel 0.1 bis 99 Gew.-%, insbesondere 0.1 bis 95 Gew.-%, erfindungsgemäße Verbindungen. In Spritzpulvern beträgt die Wirkstoffkonzentration 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 wasserdispergierbaren 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 jeweils üblichen Haft-, 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 Spritzpulvern, 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). Sie kann innerhalb weiter Grenzen schwanken, z.B. zwischen 0,001 und 1,0 kg/ha oder mehr Aktivsubstanz, vorzugsweise liegt sie jedoch zwischen 0,005 und 750 g/ha. Die erfindungsgemäßen Verbindungen der Formel (I) können auch nach Bedarf in Mischung mit weiteren Herbiziden angewendet werden. Als Kombinationspartner für die Verbindungen der Formel (I) in Mischungsformulierungen oder im Tank-Mix sind beispielsweise bekannte Wirkstoffe, die auf einer Inhibition von beispielsweise Acetolactat-Synthase, Acetyl-CoA-Carboxylase, Cellulose-Synthase, Enolpyruvylshikimat-3-phosphat-Synthase, Glutamin-Synthetase, p-Hydroxyphenylpyruvat-Dioxygenase, Phytoendesaturase, Photosystem I, Photosystem II, Protoporphyrinogen-Oxidase beruhen oder als Pflanzenwuchsregulatoren wirken, einsetzbar, wie sie z.B. aus Weed Research 26 (1986) 441-445 oder "The Pesticide Manual", 14th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2006 und dort zitierter Literatur beschrieben sind. Als bekannte Herbizide oder Pflanzenwachstumsregulatoren, die mit Verbindungen der Formel (I) kombiniert werden können, sind z.B. folgende Wirkstoffe zu nennen (die Verbindungen sind entweder mit dem "common name" nach der International Organization for Standardization (ISO) oder mit dem chemischen Namen oder mit der Codenummer bezeichnet) und umfassen stets sämtliche Anwendungsformen wie Säuren, Salze, Ester und Isomere wie Stereoisomere und optische Isomere. Dabei sind beispielhaft eine und zum Teil auch mehrere Anwendungsformen genannt: Acetochlor, Acifluorfen, Acifluorfen-methyl, Acifluorfen-Natrium, Aclonifen, Alachlor, Allidochlor, Alloxydim, Alloxydim-Natrium, Ametryn, Amicarbazon, Amidochlor, Amidosulfuron, 4-Amino-3-chlor- 6-(4-chlor-2-fluor-3-methylphenyl)-5-fluorpyridin-2-carbonsäure, Aminocyclopyrachlor, Aminocyclo- pyrachlor-Kalium, Aminocyclopyrachlor-methyl, Aminopyralid, Aminopyralid-dimethylammonium, Aminopyralid-tripromine, Amitrol, Ammoniumsulfamate, Anilofos, Asulam, Asulam-Kalium, Asulam- Natrium, Atrazin, Azafenidin, Azimsulfuron, Beflubutamid, (S)-(-)-Beflubutamid, Beflubutamid-M, Benazolin, Benazolin-ethyl, Benazolin-dimethylammonium, Benazolin-Klaium, Benfluralin, Benfuresate, Bensulfuron, Bensulfuron-methyl, Bensulid, Bentazon, Bentazon-Natrium, Benzobicyclon, Benzofenap, Bicyclopyrone, Bifenox, Bilanafos, Bilanafos-Natium, Bipyrazone, Bispyribac, Bispyribac-Natium, Bixlozon, Bromacil, Bromacil-lithium, Bromacil-Natrium, Bromobutid, Bromofenoxim, Bromoxynil, Bromoxynilbutyrat, Bromoxynil-Kalium, Bromoxynil-heptanoat und Bromoxynil-octanoat, Busoxinon, Butachlor, Butafenacil, Butamifos, Butenachlor, Butralin, Butroxydim, Butylat, Cafenstrol, Cambendichlor, Carbetamide, Carfentrazon, Carfentrazon-Ethyl, Chloramben, Chloramben-ammonium, Chloramben-diolamin, Chlroamben-methyl, Chloramben-methylammonium, Chloramben-Natium, Chlorbromuron, Chlorfenac, Chlorfenac-ammonium, Chlorfenac-Natium, Chlorfenprop, Chlorfenprop- methyl, Chlorflurenol, Chlorflurenol-methyl, Chloridazon, Chlorimuron, Chlorimuron-ethyl, Chlorophthalim, Chlorotoluron, Chlorsulfuron, Chlorthal, Chlorthal-dimethyl, Chlorthal-monomethyl, Cinidon, Cinidon-ethyl, Cinmethylin, exo-(+)-Cinmethylin, d.h. (1R,2S,4S)-4-isopropyl-1-methyl-2-[(2- methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptan, exo-(-)-Cinmethylin, d.h. (1R,2S,4S)-4-isopropyl-1- methyl-2-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptan, Cinosulfuron, Clacyfos, Clethodim, Clodinafop, Clodinafop-ethyl, Clodinafop-propargyl, Clomazon, Clomeprop, Clopyralid, Clopyralid- methyl, Clopyralid-olamin, Clopyralid-Kalium, Clopyralid-tripomin, Cloransulam, Cloransulam-methyl, Cumyluron, Cyanamide, Cyanazine, Cycloat, Cyclopyranil, Cyclopyrimorat, Cyclosulfamuron, Cycloxydim, Cyhalofop, Cyhalofop-butyl, Cyprazin, 2,4-D (sowie die Ammonium, Butotyl, Butyl, Cholin, Diethylammonium, Dimethylammonium, Diolamin, Doboxyl, Dodecylammonium, Etexyl, Ethyl, 2- Ethylhexyl, Heptylammonium, Isobutyl, Isooctyl, Isopropyl, Isopropylammonium, Lithium, Meptyl, Methyl, Kalium, Tetradecylammonium, Triethylammonium, Triisopropanolammonium, Tripromin and Trolamin Salze davon), 2,4-DB, 2,4-DB-butyl, 2,4-DB-Dimethylammonium, 2,4-DB-isooctyl, 2,4-DB- Kalium und 2,4-DB-Natrium, Daimuron (Dymron), Dalapon, Dalapon-Calcium, Dalapon-Magnesium, Dalapon-Natium, Dazomet, Dazomet-Natrium, n-Decanol, 7-Deoxy-D-sedoheptulose, Desmedipham, Detosyl-pyrazolat (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- isopropylammonium, Dicamba-methyl, Dicamba-monoethanolamin, Dicamba-olamin, Dicamba-Kalium, Dicamba-Natium, Dicamba-Triethanolamin), Dichlobenil, 2-(2,4-Dichlorbenzyl)-4,4-dimethyl-1,2- oxazolidin-3-on, 2-(2,5-Dichlorbenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, Dichlorprop, Dichlorprop- butotyl, Dichlorprop-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- metilsulfate, Diflufenican, Diflufenzopyr, Diflufenzopyr-Natrium, Dimefuron, Dimepiperate, Dimesulfazet, Dimethachlor, Dimethametryn, Dimethenamid, Dimethenamid-P, Dimetrasulfuron, Dinitramine, Dinoterb, Dinoterb-Acetate, Diphenamid, Diquat, Diquat-Dibromid, Diquat-Dichloride, Dithiopyr, Diuron, DNOC, DNOC-Ammonium, DNOC-Kalium, DNOC-Natrium, Endothal, Endothal- Diammonium, Endothal-Dikalium, Endothal-Dinatrium, Epyrifenacil (S-3100), EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron, Ethametsulfuron-Methyl, Ethiozin, Ethofumesate, Ethoxyfen, Ethoxyfen- Ethyl, Ethoxysulfuron, Etobenzanid, F-5231, d.h. N-[2-Chlor-4-fluor-5-[4-(3-fluorpropyl)-4,5-dihydro-5- oxo-1H-tetrazol-1-yl]-phenyl]-ethansulfonamid, F-7967, i.e. 3-[7-Chlor-5-fluor-2-(trifluormethyl)-1H- benzimidazol-4-yl]-1-methyl-6-(trifluormethyl)pyrimidin-2,4(1H,3H)-dion, Fenoxaprop, 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, Flucarbazone, Flucarbazone-Natrium, Flucetosulfuron, Fluchloralin, Flufenacet, 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, Glufosinat, Glufosinat- Ammonium, Glufosinat-Natrium, L-Glufosinat-Ammonium, L-Glufosinat-Natrium, Glufosinat-P- Natrium, Glufosinat-P-Ammonium, Glyphosat, Glyphosat-Ammonium, Glyphosat-Isopropylammonium, Glyphosat-Diammonium, Glyphosat-Dimethylammonium, Glyphosat-Kalium, Glyphosat-Natrium, Glyphosat-Sesquinatrium und Glyphosat-Trimesium, H-9201, d.h. O-(2,4-Dimethyl-6-nitrophenyl)-O- ethyl-isopropylphosphoramidothioat, Halauxifen, Halauxifen-methyl, Halosafen, Halosulfuron, Halosulfuron-Methyl, Haloxyfop, Haloxyfop-P, Haloxyfop-Ethoxyethyl, Haloxyfop-P-Ethoxyethyl, Haloxyfop-Methyl, Haloxyfop-P-Methyl, Haloxifop-Natrium, Hexazinon, HNPC-A8169, i.e. Prop-2-yn- 1-yl (2S)-2-{3-[(5-tert-butylpyridin-2-yl)oxy]phenoxy}propanoat, HW-02, d.h. 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, Karbutilat, KUH-043, d.h. 3-({[5-(Difluormethyl)-1-methyl- 3-(trifluormethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-5,5-dimethyl-4,5-dihydro-1,2-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, Methabenzthiazuron, Methiopyrsulfuron, Methiozolin, Methyl isothiocyanat, Metobromuron, Metolachlor, S-Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron, Metsulfuron-Methyl, Molinat, Monolinuron, Monosulfuron, Monosulfuron-Methyl, MT-5950, d.h. N-[3-Chlor-4-(1-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-1,3,4-oxadiazol-2-yl)-5- (trifluormethyl)[1,2,4]triazolo-[4,3-a]pyridin-8-carboxamid, Neburon, Nicosulfuron, Nonansäure (Pelargonsäure), Norflurazon, Ölsäure (Fettsäuren), Orbencarb, Orthosulfamuron, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefone, Oxyfluorfen, Paraquat, Paraquat-dichlorid, Paraquat- Dimethylsulfat, Pebulat, Pendimethalin, Penoxsulam, Pentachlorphenol, Pentoxazon, Pethoxamid, Petroleumöl, Phenmedipham, Phenmedipham-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), Pyrazosulfuron, Pyrazosulfuron-Ethyl, Pyrazoxyfen, Pyribambenz, Pyribambenz-Isopropyl, Pyribambenz-Propyl, Pyribenzoxim, Pyributicarb, Pyridafol, Pyridat, 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-Tefuryl, QYM201, i.e.1-{2-Chlor-3-[(3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazol-4-yl)carbonyl]-6- (trifluormethyl)phe-nyl}piperidin-2-on, Rimsulfuron, Saflufenacil, Sethoxydim, Siduron, Simazine, Simetryn, SL-261, Sulcotrione, Sulfentrazone, Sulfometuron, Sulfometuron-Methyl, Sulfosulfuron, , SYP- 249, d.h. 1-Ethoxy-3-methyl-1-oxobut-3-en-2-yl-5-[2-chlor-4-(trifluormethyl)phenoxy]-2-nitrobenzoat, SYP-300, i.e. 1-[7-Fluor-3-oxo-4-(prop-2-in-1-yl)-3,4-dihydro-2H-1,4-benzoxazin-6-yl]-3-propyl-2- thioxoimidazolidin-4,5-dion, 2,3,6-TBA, TCA (Trichloressigsäure) und seine Salze, z.B. TCA-ammonium, TCA-Calcium, TCA-Ethyl, TCA-Magnesium, TCA-Natrium, Tebuthiuron, Tefuryltrione, Tembotrion, Tepraloxydim, Terbacil, Terbucarb, Terbumeton, Terbuthylazine, Terbutryn, 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, Trifloxysulfuron, Trifloxysulfuron-Natrium, Trifludimoxazin, Trifluralin, Triflusulfuron, Triflusulfuron-Methyl, Tritosulfuron, Harnstoffsulfat, Vernolat, XDE-848, ZJ-0862, d.h.3,4-Dichlor-N-{2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl}anilin, 3- (2-Chlor-4-fluor-5-(3-methyl-2,6-dioxo-4-trifluormethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5- methyl-4,5-dihydroisoxazole-5-carbonsäureethylester, Ethyl-[(3-{2-chlor-4-fluor-5-[3-methyl-2,6-dioxo- 4-(trifluormethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenoxy}pyridin-2-yl)oxy]acetat, 3-Chlor-2-[3- (difluormethyl)isoxazolyl-5-yl]phenyl-5-chlorpyrimidin-2-ylether, 2-(3,4-Dimethoxyphenyl)-4-[(2- hydroxy-6-oxocyclohex-1-en-1-yl)carbonyl]-6-methylpyridazine-3(2H)-on, 2-({2-[(2- Methoxyethoxy)methyl]-6-methylpyridin-3-yl}carbonyl)cyclohexan-1,3-dion, (5-Hydroxy-1-methyl-1H- 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)carbonyl]-1H-pyrazol-5-yl propan-1- sulfonat, 4-{2-Chlor-3-[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]-4-(methylsulfonyl)benzoyl}-1-methyl- 1H-pyrazol-5-yl-1,3-dimethyl-1H-pyrazol-4-carboxylat; Cyanomethyl-4-amino-3-chlor-5-fluor-6-(7- fluor-1H-indol-6-yl)pyridin-2-carboxylat, Prop-2-yn-1-yl 4-amino-3-chlor-5-fluor-6-(7-fluor-1H-indol-6- yl)pyridin-2-carboxylat, Methyl-4-amino-3-chlor-5-fluor-6-(7-fluor-1H-indol-6-yl)pyridin-2-carboxylat, 4-Amino-3-chlor-5-fluor-6-(7-fluor-1H-indol-6-yl)pyridin-2-carbonsäure, Benzyl-4-amino-3-chlor-5- fluor-6-(7-fluor-1H-indol-6-yl)pyridin-2-carboxylat, Ethyl-4-amino-3-chlor-5-fluor-6-(7-fluor-1H-indol- 6-yl)pyridin-2-carboxylat, Methyl-4-amino-3-chlor-5-fluor-6-(7-fluor-1-isobutyryl-1H-indol-6-yl)pyridin- 2-carboxylat, Methyl 6-(1-acetyl-7-fluor-1H-indol-6-yl)-4-amino-3-chlor-5-fluorpyridin-2-carboxylat, Methyl-4-amino-3-chlor-6-[1-(2,2-dimethylpropanoyl)-7-fluor-1H-indol-6-yl]-5-fluorpyridin-2- carboxylat, Methyl-4-amino-3-chlor-5-fluor-6-[7-fluor-1-(methoxyacetyl)-1H-indol-6-yl]pyridin-2- carboxylat, Kalium 4-amino-3-chlor-5-fluor-6-(7-fluor-1H-indol-6-yl)pyridin-2-carboxylat, Natrium-4- amino-3-chlor-5-fluor-6-(7-fluor-1H-indol-6-yl)pyridin-2-carboxylat, Butyl-4-amino-3-chlor-5-fluoro-6- (7-fluoro-1H-indol-6-yl)pyridin-2-carboxylat, 4-Hydroxy-1-methyl-3-[4-(trifluoromethyl)pyridin-2- yl]imidazolidin-2-on, 3-(5-tert-butyl-1,2-oxazol-3-yl)-4-hydroxy-1-methylimidazolidin-2-on, 3-[5-Chlor- 4-(trifluormethyl)pyridin-2-yl]-4-hydroxy-1-methylimidazolidin-2-on, 4-Hydroxy-1-methoxy-5-methyl- 3-[4-(trifluormethyl)pyridin-2-yl]imidazolidin-2-on, 6-[(2-Hydroxy-6-oxocyclohex-1-en-1-yl)carbonyl]- 1,5-dimethyl-3-(2-methylphenyl)chinazolin-2,4(1H,3H)-dion, 3-(2,6-Dimethylphenyl)-6-[(2-hydroxy-6- oxocyclohex-1-en-1-yl)carbonyl]-1-methylchinazolin-2,4(1H,3H)-dion, 2-[2-chlor-4-(methylsulfonyl)-3- (morpholin-4-ylmethyl)benzoyl]-3-hydroxycyclohex-2-en-1-on, 1-(2-carboxyethyl)-4-(pyrimidin-2- yl)pyridazin-1-iumsalz (mit passenden Anionen wie z.B Chlorid, Acetat oder Trifluoracetat), 1-(2- Carboxyethyl)-4-(pyridazin-3-yl)pyridazin-1-iumsalz (mit passenden Anionen wie z.B. Chlorid, Acetat oder Trifluoracetat), 4-(Pyrimidin-2-yl)-1-(2-sulfoethyl)pyridazin-1-ium salz iumsalz (mit passenden Anionen wie z.B Chlorid, Acetat oder Trifluoracetat), 4-(Pyridazin-3-yl)-1-(2-sulfoethyl)pyridazin-1- iumsalz (mit passenden Anionen wie z.B Chlorid, Acetat oder Trifluoracetat), 1-(2-Carboxyethyl)-4-(1,3- thiazol-2-yl)pyridazin-1-iumsalz (mit passenden Anionen wie z.B Chlorid, Acetat oder Trifluoracetat), 1- (2-Carboxyethyl)-4-(1,3,4-thiadiazol-2-yl)pyridazin-1-ium salz (mit passenden Anionen wie z.B Chlorid, Acetat oder Trifluoracetat), Methyl (2R)-2-{[(E)-({2-chlor-4-fluor-5-[3-methyl-2,6-dioxo-4- (trifluormethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenyl}methyliden)amino]oxy}propanoat, Methyl (2S)- 2-{[(E)-({2-chlor-4-fluor-5-[3-methyl-2,6-dioxo-4-(trifluormethyl)-3,6-dihydropyrimidin-1(2H)- yl]phenyl}methyliden)amino]oxy}propanoat, Methyl (2R/S)-2-{[(E)-({2-chlor-4-fluor-5-[3-methyl-2,6- dioxo-4-(trifluormethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenyl}methyliden)amino]oxy}propanoat, (E)- 2-(Trifluormethyl)benzaldehyd-O-{2,6-bis[(4,6-dimethoxypyrimidin-2-yl)oxy]benzoyl}oxim, 2-Fluor-N- (5-methyl-1,3,4-oxadiazol-2-yl)-3-[(R)-propylsulfinyl]-4-(trifluormethyl)benzamid, (2R)-2-[(4-Amino- 3,5-dichlor-6-fluor-2-pyridyl)oxy]propancarbonsäure, 2-Ethoxy-2-oxoethyl-1-{2-chlor-4-fluor-5-[3- methyl-2,6-dioxo-4-(trifluormethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenoxy}cyclopropancarboxylat, 2- Methoxy-2-oxoethyl-1-{2-chlor-4-fluor-5-[3-methyl-2,6-dioxo-4-(trifluormethyl)-3,6-dihydropyrimidin- 1(2H)-yl]phenoxy}cyclopropancarboxylat, {[(1-{2-Chlor-4-fluor-5-[3-methyl-2,6-dioxo-4- (trifluormethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenoxy}cyclopropyl)carbonyl]oxy}essigsäure, 2-(2- Brom-4-chlorbenzyl)-4,4-dimethyl-1,2-oxazolidin-3-on, Methyl 3-{2-chlor-4-fluor-5-[3-methyl-2,6- dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenyl}-3a,4,5,6-tetrahydro-6aH- cyclopenta[d][1,2]oxazol-6a-carboxylat, Ethyl 3-{2-chlor-4-fluor-5-[3-methyl-2,6-dioxo-4- (trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenyl}-3a,4,5,6-tetrahydro-6aH- cyclopenta[d][1,2]oxazol-6a-carboxylat. Abscisinsäure und verwandte Analoga [z.B. (2Z,4E)-5-[6-Ethynyl-1-hydroxy-2,6-dimethyl-4- oxocyclohex-2-en-1-yl]-3-methylpenta-2,4-diensäure, methyl-(2Z,4E)-5-[6-ethynyl-1-hydroxy-2,6- dimethyl-4-oxocyclohex-2-en-1-yl]-3-methylpenta-2,4-dienoat, (2Z,4E)-3-ethyl-5-(1-hydroxy-2,6,6- trimethyl-4-oxocyclohex-2-en-1-yl)penta-2,4-diensäure, (2E,4E)-5-(1-hydroxy-2,6,6-trimethyl-4- oxocyclohex-2-en-1-yl)-3-(trifluoromethyl)penta-2,4-diensäure, methyl (2E,4E)-5-(1-hydroxy-2,6,6- trimethyl-4-oxocyclohex-2-en-1-yl)-3-(trifluoromethyl)penta-2,4-dienoat, (2Z,4E)-5-(2-hydroxy-1,3- dimethyl-5-oxobicyclo[4.1.0]hept-3-en-2-yl)-3-methylpenta-2,4-diensäure], Acibenzolar, Acibenzolar-S- methyl, S-Adenosylhomocystein, Allantoin, 2-Aminoethoxyvinylglycin (AVG), Aminooxyessigsäure and verwandte Ester [z.B. (Isopropyliden)-aminooxyessigsäure-2-(methoxy)-2-oxoethylester, (Isopropyliden)- aminooxyessigsäure-2-(hexyloxy)-2-oxoethylester, (Cyclohexyliden)-aminooxyessigsäure-2- (isopropyloxy)-2-oxoethylester], 1-Aminocycloprop-1-ylcarbonsäure N-Methyl-1-aminocyclopropyl-1- carbonsäure, 1-Aminocyclopropyl-1-carbonsäureamid, substituierte 1-Aminocyclopropyl-1- carbonsäurederivate wie sie in DE3335514, EP30287, DE2906507 oder US5123951 beschrieben werden, 1-Aminocyclopropyl-1-hydroxamsäure, 5-Aminolevulinsäure, Ancymidol, 6-Benzylaminopurin, Bikinin, Brassinolid, Brassinolide-ethyl, L-Canalin, Catechin und catechine (z.B. (2S,3R)-2-(3,4- Dihydroxyphenyl)-3,4-dihydro-2H-chromen-3,5,7-triol), Chitooligosaccharide (CO; COs unterscheiden sich von LCOs dadurch, daß ihnen die für LCOs charakteristische Fettsäureseitenkette fehlt. COs, in manchen Fällen als N-Acetylchitooligosaccharide bezeichnet, sind auch aus GlcNAc-Einheiten aufgebaut, aber haben Seitenketten, durch die sies ich von Chitinmolekülen unterscheiden [(C8H13NO5)n, CAS No.1398-61-4] und chitosan Moleküle [(C5H11NO4)n, CAS No. 9012-76-4]), Chitin-artige Verbindungen, Chlormequat chloride, Cloprop, Cyclanilide, 3-(Cycloprop-1-enyl)propionsäure, 1-[2-(4-Cyano-3,5- dicyclopropylphenyl)acetamido]cyclohexancarbonsäure, 1-[2-(4-Cyano-3- cyclopropylphenyl)acetamido]cyclohexancarbonsäure, 1-Cyclopropenylmethanol, Daminozid, Dazomet, Dazomet-Natrium, n-Decanol, Dikegulac, Dikegulac-Natrium, Endothal, Endothal-di-Kalium, -di- Natrium, und mono(N,N-dimethylalkylammonium), Ethephon, 1-Ethylcyclopropen,Flumetralin, Flurenol, Flurenol-butyl, Flurenol-methyl, Flurprimidol, Forchlorfenuron, Gibberellinsäure, Inabenfid, Indol-3- essigsäure (IAA), 4-Indol-3-ylbuttersäure, Isoprothiolan, Probenazole, Jasmonsäure, Jasmonsäureester oder andere Derivate (z.B. Jasmonsäuremethylester, Jasmonsäureethylester), Lipochitooligosaccharide (LCO, in manchen Fällen auch als Symbiotische Nodulationssignale (Nod oder Nod Faktoren) oder als Myc Faktoren bezeichnet, bestehen aus einem Oligosacchariderückgrat aus β-l,4-verknüpften N-Acetyl-D-Glucosaminresten (“GlcNAc”) mit einer N-verknüpften Fettsäureseitenkette, die am nicht reduzierenden Ende ankondensiert ist. Wie aus der Literatur zu entnehmen ist, unterscheiden sich LCOs in der Zahl an GlcNAc-EInheiten in der Rückgratstruktur, in der Länge und dem Sättigungsgrad der Fettsäurekette sowie in der Substitution der reduzierenden und nicht-reduzierenden Zuckereinheiten), Linoleinsäure oder ihre Derivate, Linolensäure oder ihre Derivate, Maleinsäurehydrazid, Mepiquatchlorid, Mepiquatpentaborat, 1-Methylcyclopropen, 3-Methylcyclopropen, Methoxyvinylglycin (MVG), 3’- Methylabscisinsäure, 1-(4-Methylphenyl)-N-(2-oxo-1-propyl-1,2,3,4-tetrahydrochinolin-6- yl)methansulfonamid und verwandte substituierte (Tetrahydrochinolin-6-yl)methansulfonamide, (3E,3aR,8bS)-3-({[(2R)-4-Methyl-5-oxo-2,5-dihydrofuran-2-yl]oxy}methylen)-3,3a,4,8b-tetrahydro-2H- indeno[1,2-b]furan-2-on und verwandte Laktone wie sie in EP2248421 beschrieben sind, 2-(1- Naphthyl)acetamid, 1-Naphthylessigsäure, 2- Naphthyloxyessigsäure, Nitrophenolatmischung, 4-Oxo- 4[(2-phenylethyl)amino]buttersäure, Paclobutrazol, 4-Phenylbuttersäure and ihre Salze (z.B. Natrium-4- phenylbutanoat, Kalium-4-phenylbutanoat), Phenylalanine, N-Phenylphthalamsäure, Prohexadione, Prohexadion-Calcium, , 1-n-Propylcyclopropen, Putrescin, Prohydrojasmon, Rhizobitoxin, Salicylsäure und Salicyclsäuremethylester, Sarcosin, Natriumcycloprop-1-en-1-ylacetat, Natriumcycloprop-2-en-1- ylacetat, Natrium-3-(cycloprop-2-en-1-yl)propanoat, Natrium-3-(cycloprop-1-en-1-yl)propanoat, Sidefungin, Spermidin, Spermine, Strigolactone, Tecnazene, Thidiazuron, Triacontanol, Trinexapac, Trinexapac-ethyl, Tryptophan, Tsitodef, Uniconazol, Uniconazol-P, 2-Fluoro-N-(3-methoxyphenyl)-9H- purin-6-amin. Obwohl die erfindungsgemäßen Verbindungen der Formel (I) in der Regel eine gute Selektivität gegenüber Kulturpflanzen aufweisen, kann es sinnvoll sein, sie mit bekannten Safenern zu kombinieren. 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: S1) Verbindungen der Formel (S1),
Figure imgf000022_0001
wobei die Symbole und Indizes folgende Bedeutungen haben: nA ist eine natürliche Zahl von 0 bis 5, vorzugsweise 0 bis 3; RA 1 ist Halogen, (C1-C4)Alkyl, (C1-C4)Alkoxy, Nitro oder (C1-C4)Haloalkyl;
Figure imgf000022_0002
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 (WA 1) bis (WA 5), mA ist 0 oder 1; RA 2 ist O RA 3, SRA 3 oder NRA 3RA 4 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 (S1) 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 ORA 3, NHRA 4 oder N(CH3)2, insbesondere der Formel ORA 3; RA 3 ist Wasserstoff oder ein unsubstituierter oder substituierter aliphatischer Kohlenwasserstoffrest, vorzugsweise mit insgesamt 1 bis 18 C-Atomen; RA 4 ist Wasserstoff, (C1-C6)Alkyl, (C1-C6)Alkoxy oder substituiertes oder unsubstituiertes Phenyl; RA 5 ist H, (C1-C8)Alkyl, (C1-C8)Haloalkyl, (C1-C4)Alkoxy(C1-C8)Alkyl, Cyano oder COORA 9, worin RA 9 Wasserstoff, (C1-C8)Alkyl, (C1-C8)Haloalkyl, (C1-C4)Alkoxy-(C1-C4)alkyl, (C1-C6)Hydroxyalkyl, (C3- C12)Cycloalkyl oder Tri-(C1-C4)-alkyl-silyl ist; RA 6, RA 7, RA 8 sind gleich oder verschieden Wasserstoff, (C1-C8)Alkyl, (C1-C8)Haloalkyl, (C3- C12)Cycloalkyl oder substituiertes oder unsubstituiertes Phenyl; RA 10 ist H, (C3-C12)Cycloalkyl, substituiertes oder unsubstituiertes Phenyl oder substituiertes oder unsubstituiertes Heteroaryl; vorzugsweise: a) Verbindungen vom Typ der Dichlorphenylpyrazolin-3-carbonsäure (S1a), vorzugsweise Verbindungen wie 1-(2,4-Dichlorphenyl)-5-(ethoxycarbonyl)-5-methyl- 2-pyrazolin-3-carbonsäure, 1-(2,4-Dichlorphenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazolin-3-carbonsäureethylester (S1-1) ("Mefenpyr-diethyl"), und verwandte Verbindungen, wie sie in der WO-A-91/07874 beschrieben sind; b) Derivate der Dichlorphenylpyrazolcarbonsäure (S1b), vorzugsweise Verbindungen wie 1-(2,4-Dichlorphenyl)-5-methyl-pyrazol-3-carbonsäureethylester (S1-2), 1-(2,4-Di- chlorphenyl)-5-isopropyl-pyrazol-3-carbonsäureethylester (S1-3), 1-(2,4-Dichlor- phenyl)-5-(1,1-dimethyl-ethyl)pyrazol-3-carbonsäureethyl-ester (S1-4) und verwandte Verbindungen, wie sie in EP-A-333131 und EP-A-269806 beschrieben sind; c) Derivate der 1,5-Diphenylpyrazol-3-carbonsäure (S1c), vorzugsweise Verbindungen wie 1-(2,4-Dichlorphenyl)-5-phenylpyrazol-3-carbonsäureethylester (S1-5), 1-(2-Chlorphenyl)-5-phenylpyrazol-3-carbonsäuremethylester (S1-6) und verwandte Verbindungen wie sie beispielsweise in der EP-A-268554 beschrieben sind; d) Verbindungen vom Typ der Triazolcarbonsäuren (S1d), vorzugsweise Verbindungen wie Fenchlorazol(-ethylester), d.h. 1-(2,4-Dichlorphenyl)-5-trichlormethyl-(1H)-1,2,4-triazol-3-carbonsäure- ethylester (S1-7), 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- Diphenyl-2-isoxazolin-3-carbonsäure (S1e), vorzugsweise Verbindungen wie 5-(2,4-Dichlorbenzyl)-2-isoxazolin-3-carbonsäureethylester (S1-8) oder 5-Phenyl-2-isoxazolin-3- carbonsäureethylester (S1-9) und verwandte Verbindungen, wie sie in WO-A-91/08202 beschrieben sind, bzw. 5,5-Diphenyl-2-isoxazolin-3-carbonsäure (S1-10) oder 5,5-Diphenyl-2-isoxazolin-3- carbonsäureethylester (S1-11) ("Isoxadifen-ethyl") oder -n-propylester (S1-12) oder der 5-(4-Fluorphenyl)- 5-phenyl-2-isoxazolin-3-carbonsäureethylester (S1-13), wie sie in der Patentanmeldung WO-A-95/07897 beschrieben sind. f) Verbindungen vom Typ der Triazolyloxyessigsäurederivate (S1f), vorzugsweise Verbindungen wie Methyl-{[1,5-bis(4-chlor-2-fluorphenyl)-1H-1,2,4-triazol-3-yl]oxy}acetat (S1-14) oder {[1,5-Bis(4-chlor- 2-fluorphenyl)-1H-1,2,4-triazol-3-yl]oxy}essigsäure (S1-15) oder Methyl-{[5-(4-chlor-2-fluorphenyl)-1- (2,4-difluorphenyl)-1H-1,2,4-triazol-3-yl]oxy}acetat (S1-16) oder {[5-(4-Chlor-2-fluorphenyl)-1-(2,4- difluorphenyl)-1H-1,2,4-triazol-3-yl]oxy}essigsäure (S1-17) oder Methyl-{[1-(4-chlor-2-fluorphenyl)-5- (2,4-difluorphenyl)-1H-1,2,4-triazol-3-yl]oxy}acetat (S1-18) oder {[1-(4-Chlor-2-fluorphenyl)-5-(2,4- difluorphenyl)-1H-1,2,4-triazol-3-yl]oxy}essigsäure (S1-19), wie sie in der Patentanmeldung WO2021105101 beschrieben sind S2) Chinolinderivate der Formel (S2),
Figure imgf000024_0001
wobei die Symbole und Indizes folgende Bedeutungen haben: RB 1 ist Halogen, (C1-C4)Alkyl, (C1-C4)Alkoxy, Nitro oder (C1-C4)Haloalkyl; nB ist eine natürliche Zahl von 0 bis 5, vorzugsweise 0 bis 3; RB 2 ist ORB 3, SRB 3 oder NRB 3RB 4 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 ORB 3, NHRB 4 oder N(CH3)2, insbesondere der Formel ORB 3; RB 3 ist Wasserstoff oder ein unsubstituierter oder substituierter aliphatischer Kohlenwasserstoffrest, vorzugsweise mit insgesamt 1 bis 18 C-Atomen; RB 4 ist Wasserstoff, (C1-C6)Alkyl, (C1-C6)Alkoxy oder substituiertes oder unsubstituiertes Phenyl; TB ist eine (C1 oder C2)-Alkandiylkette, die unsubstituiert oder mit einem oder zwei (C1-C4)Alkylresten oder mit [(C1-C3)-Alkoxy]-carbonyl substituiert ist; vorzugsweise: a) Verbindungen vom Typ der 8-Chinolinoxyessigsäure (S2a), vorzugsweise (5-Chlor-8-chinolinoxy)essigsäure-(1-methylhexyl)ester ("Cloquintocet-mexyl") (S2-1), (5-Chlor-8- chinolinoxy)essigsäure-(1,3-dimethyl-but-1-yl)ester (S2-2), (5-Chlor-8-chinolinoxy)essigsäure-4-allyloxy-butylester (S2-3), (5-Chlor-8-chinolin-oxy)essigsäure-1- allyloxy-prop-2-ylester (S2-4), (5-Chlor-8-chinolinoxy)essigsäure-ethylester (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)-1-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-191736 oder EP-A-0492366 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 Phosphoniumsalze 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-Chlor- 8-chinolinoxy)malonsäurediallylester, (5-Chlor-8-chinolinoxy)malonsäure-methyl-ethylester und verwandte Verbindungen, wie sie in EP-A-0 582198 beschrieben sind. S3) Verbindungen der Formel (S3)
Figure imgf000025_0001
wobei die Symbole und Indizes folgende Bedeutungen haben: RC 1 ist (C1-C4)Alkyl, (C1-C4)Haloalkyl, ( C2-C4)Alkenyl, (C2-C4)Haloalkenyl, (C3-C7)Cycloalkyl, vorzugsweise Dichlormethyl; RC 2, RC 3 sind gleich oder verschieden Wasserstoff, (C1-C4)Alkyl, (C2-C4)Alkenyl, (C2-C4)Alkinyl, (C1-C4)Haloalkyl, (C2-C4)Haloalkenyl, (C1-C4)Alkylcarbamoyl-(C1-C4)alkyl, (C2- C4)Alkenylcarbamoyl-(C1-C4)alkyl, (C1-C4)Alkoxy-(C1-C4)alkyl, Dioxolanyl-(C1-C4)alkyl, Thiazolyl, Furyl, Furylalkyl, Thienyl, Piperidyl, substituiertes oder unsubstituiertes Phenyl, oder RC 2 und RC 3 bilden zusammen einen substituierten oder unsubstituierten heterocyclischen Ring, vorzugsweise einen Oxazolidin-, Thiazolidin-, Piperidin-, Morpholin-, Hexahydropyrimidin- oder Benzoxazinring; vorzugsweise: Wirkstoffe vom Typ der Dichloracetamide, die häufig als Vorauflaufsafener (bodenwirksame Safener) angewendet werden, wie z. B. "Dichlormid" (N,N-Diallyl-2,2-dichloracetamid) (S3-1), "R-29148" (3-Dichloracetyl-2,2,5-trimethyl-1,3- oxazolidin) der Firma Stauffer (S3-2), "R-28725" (3-Dichloracetyl-2,2,-dimethyl-1,3-oxazolidin) der Firma Stauffer (S3-3), "Benoxacor" (4-Dichloracetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazin) (S3-4), "PPG-1292" (N-Allyl-N-[(1,3-dioxolan-2-yl)-methyl]-dichloracetamid) der Firma PPG Industries (S3-5), "DKA-24" (N-Allyl-N-[(allylaminocarbonyl)methyl]-dichloracetamid) der Firma 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), "TI-35" (1-Dichloracetyl-azepan) der Firma TRI-Chemical RT (S3-8), "Diclonon" (Dicyclonon) oder "BAS145138" oder "LAB145138" (S3-9) ((RS)-1-Dichloracetyl-3,3,8a- trimethylperhydropyrrolo[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). S4) N-Acylsulfonamide der Formel (S4) und ihre Salze,
Figure imgf000026_0001
worin die Symbole und Indizes folgende Bedeutungen haben: XD ist CH oder N; RD 1 ist CO-NRD 5RD 6 oder NHCO-RD 7; RD 2 ist Halogen, (C1-C4)-Haloalkyl, (C1-C4)-Haloalkoxy, Nitro, (C1-C4)-Alkyl, (C1-C4)-Alkoxy, (C1-C4)- Alkylsulfonyl, (C1-C4)-Alkoxycarbonyl oder (C1-C4)-Alkylcarbonyl; RD 3 ist Wasserstoff, (C1-C4)Alkyl, (C2-C4)Alkenyl oder (C2-C4)-Alkinyl; RD 4 ist Halogen, Nitro, (C1-C4)-Alkyl, (C1-C4)-Haloalkyl, (C1-C4)-Haloalkoxy, (C3-C6)-Cycloalkyl, Phenyl, (C1-C4)-Alkoxy, Cyano, (C1-C4)-Alkylthio, (C1-C4)-Alkylsulfinyl, (C1-C4)-Alkylsulfonyl, (C1- C4)Alkoxycarbonyl oder (C1-C4)Alkylcarbonyl; RD 5 ist Wasserstoff, (C1-C6)-Alkyl, (C3-C6)-Cycloalkyl, (C2-C6)-Alkenyl, (C2-C6)-Alkinyl, (C5-C6)- 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, (C1-C6)Haloalkoxy, (C1-C2)Alkylsulfinyl, (C1-C2)Alkylsulfonyl, (C3- C6)Cycloalkyl, (C1-C4)Alkoxycarbonyl, (C1-C4)Alkylcarbonyl und Phenyl und im Falle cyclischer Reste auch (C1-C4) Alkyl und (C1-C4)Haloalkyl substituiert sind; RD 6 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 5 und RD 6 gemeinsam mit dem dem sie tragenden Stickstoffatom einen Pyrrolidinyl- oder Piperidinyl- Rest bilden; RD 7 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, (C1-C4)Alkoxy, (C1- C6)Haloalkoxy und (C1-C4)Alkylthio und im Falle cyclischer Reste auch (C1-C4)Alkyl und (C1-C4)Haloalkyl substituiert sind; nD ist 0, 1 oder 2; mD ist 1 oder 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 imgf000027_0001
worin RD 7 (C1-C6)Alkyl, (C3-C6)Cycloalkyl, wobei die 2 letztgenannten Reste durch vD Substituenten aus der Gruppe Halogen, (C1-C4)Alkoxy, (C1-C6)Haloalkoxy und (C1-C4)Alkylthio und im Falle cyclischer Reste auch (C1-C4)Alkyl und (C1-C4)Haloalkyl substituiert sind; RD 4 Halogen, (C1-C4)Alkyl, (C1-C4)Alkoxy, CF3; mD 1 oder 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 imgf000028_0001
z.B. solche worin RD 5 = Cyclopropyl und (RD 4) = 2-OMe ist ("Cyprosulfamide", S4-1), RD 5 = Cyclopropyl und (RD 4) = 5-Cl-2-OMe ist (S4-2), RD 5 = Ethyl und (RD 4) = 2-OMe ist (S4-3), RD 5 = Isopropyl und (RD 4) = 5-Cl-2-OMe ist (S4-4) und RD 5 = Isopropyl und (RD 4) = 2-OMe ist (S4-5). sowie Verbindungen vom Typ der N-Acylsulfamoylphenylharnstoffe der Formel (S4c), die z.B. bekannt sind aus der EP-A-365484,
Figure imgf000028_0002
worin RD 8 und RD 9 unabhängig voneinander Wasserstoff, (C1-C8)Alkyl, (C3-C8)Cycloalkyl, (C3-C6)Alkenyl, (C3- C6)Alkinyl, RD 4 Halogen, (C1-C4)Alkyl, (C1-C4)Alkoxy, CF3 mD 1 oder 2 bedeutet; beispielsweise 1-[4-(N-2-Methoxybenzoylsulfamoyl)phenyl]-3-methylharnstoff, 1-[4-(N-2-Methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylharnstoff, 1-[4-(N-4,5-Dimethylbenzoylsulfamoyl)phenyl]-3-methylharnstoff. S5) Wirkstoffe aus der Klasse der Hydroxyaromaten und der aromatisch-aliphatischen Carbonsäurederivate (S5), z.B.3,4,5-Triacetoxybenzoesäureethylester, 3,5-Di-methoxy-4-hydroxybenzoe- säure, 3,5-Dihydroxybenzoesäure, 4-Hydroxysalicylsäure, 4-Fluorsalicyclsäure, 2-Hydroxyzimtsäure, 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 1,2-Dihydrochinoxalin-2-one (S6), z.B. 1-Methyl-3-(2-thienyl)-1,2-dihydrochinoxalin-2-on, 1-Methyl-3-(2-thienyl)-1,2-dihydrochinoxalin-2- thion, 1-(2-Aminoethyl)-3-(2-thienyl)-1,2-dihydro-chinoxalin-2-on-hydrochlorid, 1-(2- Methylsulfonylaminoethyl)-3-(2-thienyl)-1,2-dihydrochinoxa-lin-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 imgf000029_0002
worin die Symbole und Indizes folgende Bedeutungen haben: RE 1, RE 2 sind unabhängig voneinander Halogen, (C1-C4)Alkyl, (C1-C4)Alkoxy, (C1-C4)Haloalkyl, (C1- C4)Alkylamino, Di-(C1-C4)Alkylamino, Nitro; AE ist COORE 3 oder COSRE 4 RE 3, RE 4 sind unabhängig voneinander Wasserstoff, (C1-C4)Alkyl, (C2-C6)Alkenyl, (C2-C4)Alkinyl, Cyanoalkyl, (C1-C4)Haloalkyl, Phenyl, Nitrophenyl, Benzyl, Halobenzyl, Pyridinylalkyl und Alkylammonium, nE 1 ist 0 oder 1 nE 2, nE 3 sind unabhängig voneinander 0, 1 oder 2, vorzugsweise Diphenylmethoxyessigsäure, Diphenylmethoxyessigsäureethylester, Diphenyl- methoxyessigsäuremethylester (CAS-Reg.Nr.41858-19-9) (S7-1). S8) Verbindungen der Formel (S8),wie sie in der WO-A-98/27049 beschrieben sind
Figure imgf000029_0001
Worin 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 , RF 1 Halogen, (C1-C4)Alkyl, (C1-C4)Haloalkyl, (C1-C4)Alkoxy, (C1-C4)Haloalkoxy, Nitro, (C1- C4)Alkylthio, (C1-C4)-Alkylsulfonyl, (C1-C4)Alkoxycarbonyl, ggf. substituiertes. Phenyl, ggf. substituiertes Phenoxy, RF 2 Wasserstoff oder (C1-C4)Alkyl RF 3 Wasserstoff, (C1-C8)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 1 Halogen, (C1-C4)Alkyl, (C1-C4)Haloalkyl, (C1-C4)Alkoxy, (C1-C4)Haloalkoxy, RF 2 Wasserstoff oder (C1-C4)Alkyl, RF 3 Wasserstoff, (C1-C8)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. S9) Wirkstoffe aus der Klasse der 3-(5-Tetrazolylcarbonyl)-2-chinolone (S9), z.B. 1,2-Dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-chinolon (CAS-Reg.Nr. 219479-18-2), 1,2- Dihydro-4-hydroxy-1-methyl-3-(5-tetrazolyl-carbonyl)-2-chinolon (CAS-Reg.Nr. 95855-00-8), wie sie in der WO-A-1999/000020 beschrieben sind. S10) Verbindungen der Formeln (S10a) oder (S10b) wie sie in der WO-A-2007/023719 und WO-A-2007/023764 beschrieben sind
Figure imgf000031_0001
worin RG 1 Halogen, (C1-C4)Alkyl, Methoxy, Nitro, Cyano, CF3, OCF3 YG, ZG unabhängig voneinander O oder S, nG eine ganze Zahl von 0 bis 4, RG 2 (C1-C16)Alkyl, (C2-C6)Alkenyl, (C3-C6)Cycloalkyl, Aryl; Benzyl, Halogenbenzyl, RG 3 Wasserstoff oder (C1-C6)Alkyl bedeutet. S11) Wirkstoffe vom Typ der Oxyimino-Verbindungen (S11), die als Saatbeizmittel bekannt sind, wie z. B. "Oxabetrinil" ((Z)-1,3-Dioxolan-2-ylmethoxyimino(phenyl)acetonitril) (S11-1), das als Saatbeiz- Safener für Hirse gegen Schäden von Metolachlor bekannt ist, "Fluxofenim" (1-(4-Chlorphenyl)-2,2,2- trifluor-1-ethanon-O-(1,3-dioxolan-2-ylmethyl)-oxim) (S11-2), das als Saatbeiz-Safener für Hirse gegen Schäden von Metolachlor bekannt ist, und "Cyometrinil" oder "CGA-43089" ((Z)-Cyanomethoxy- imino(phenyl)acetonitril) (S11-3), das als Saatbeiz-Safener für Hirse gegen Schäden von Metolachlor bekannt ist. S12) Wirkstoffe aus der Klasse der Isothiochromanone (S12), wie z.B. Methyl-[(3-oxo-1H-2- benzothiopyran-4(3H)-yliden)methoxy]acetat (CAS-Reg.Nr. 205121-04-6) (S12-1) und verwandte Verbindungen aus WO-A-1998/13361. S13) Eine oder mehrere Verbindungen aus Gruppe (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, "Flurazole" (Benzyl-2-chlor-4-trifluormethyl-1,3-thiazol-5- carboxylat) (S13-3), das als Saatbeiz-Safener für Hirse gegen Schäden von Alachlor und Metolachlor bekannt ist, "CL 304415" (CAS-Reg.Nr. 31541-57-8) (4-Carboxy-3,4-dihydro-2H-1-benzopyran-4- essigsäure) (S13-4) der Firma American Cyanamid, das als Safener für Mais gegen Schäden von Imidazolinonen bekannt ist, "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-838" (CAS-Reg.Nr. 133993-74-5) (2-propenyl 1-oxa-4-azaspiro[4.5]decan-4-carbodithioat) (S13-6) der Firma Nitrokemia, "Disulfoton" (O,O-Diethyl S-2-ethylthioethyl phosphordithioat) (S13-7), "Dietholate" (O,O-Diethyl-O- phenylphosphorothioat) (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. "Dimepiperate" oder "MY-93" (S-1-Methyl-1-phenylethyl- 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-harnstoff), das als Safener für Reis gegen Schäden des Herbizids Imazosulfuron bekannt ist, "Cumyluron" = "JC-940" (3-(2-Chlorphenylmethyl)-1- (1-methyl-1-phenyl-ethyl)harnstoff, siehe JP-A-60087254), das als Safener für Reis gegen Schäden einiger Herbizide bekannt ist, "Methoxyphenon" oder "NK 049" (3,3'-Dimethyl-4-methoxy-benzophenon), das als Safener für Reis gegen Schäden einiger Herbizide bekannt ist, "CSB" (1-Brom-4- (chlormethylsulfonyl)benzol) von Kumiai, (CAS-Reg.Nr. 54091-06-4), das als Safener gegen Schäden einiger Herbizide in Reis bekannt ist. S15) Verbindungen der Formel (S15) oder deren Tautomere wie sie in der WO-A-2008/131861 und WO-A-2008/131860 beschrieben sind
Figure imgf000032_0001
worin RH 1 einen (C1-C6)Haloalkylrest bedeutet und RH 2 Wasserstoff oder Halogen bedeutet und RH 3, RH 4 unabhängig voneinander Wasserstoff, (C1-C16)Alkyl, (C2-C16)Alkenyl oder (C2-C16)Alkinyl, wobei jeder der letztgenannten 3 Reste unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, Hydroxy, Cyano, (C1-C4)Alkoxy, (C1-C4)Haloalkoxy, (C1-C4)Alkylthio, (C1-C4)Alkylamino, Di[(C1-C4)alkyl]-amino, [(C1-C4)Alkoxy]-carbonyl, [(C1-C4)Haloalkoxy]-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 carbocyclischen Ring kondensiert ist, oder (C4-C6)Cycloalkenyl, das an einer Seite des Rings mit einem 4 bis 6-gliedrigen gesättigten oder ungesättigten carbocyclischen 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, (C1-C4)Haloalkyl, (C1-C4)Alkoxy, (C1-C4)Haloalkoxy, (C1-C4)Alkylthio, (C1-C4)Alkylamino, Di[(C1-C4)alkyl]-amino, [(C1-C4)Alkoxy]-carbonyl, [(C1-C4)Haloalkoxy]-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 (C1-C4)-Alkoxy, (C2-C4)Alkenyloxy, (C2-C6)Alkinyloxy oder (C2-C4)Haloalkoxy bedeutet und RH 4 Wasserstoff oder (C1-C4)-Alkyl bedeutet oder RH 3 und RH 4 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, (C1-C4)Haloalkyl, (C1- C4)Alkoxy, (C1-C4)Haloalkoxy und (C1-C4)Alkylthio substituiert ist, bedeutet. S16) Wirkstoffe, die vorrangig als Herbizide eingesetzt werden, jedoch auch Safenerwirkung auf Kulturpflanzen aufweisen, z.B. (2,4-Dichlorphenoxy)essigsäure (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). Besonders bevorzugte Safener sind Mefenpyr-diethyl, Cyprosulfamid, Isoxadifen-ethyl, Cloquintocet- mexyl, Benoxacor, Dichlormid und Metcamifen. Die nachstehenden Beispiele erläutern die Erfindung. A. Chemische Beispiele Synthese von Methyl-2-chlor-3-formyl-4-(trifluormethoxy)benzoat (1): Schritt 1: Herstellung von 1-Brom-2-chlor-3-methyl-4-(trifluormethoxy)benzol (4): 20.35 ml (145.2 mmol) Diisopropylamin wurden unter Argon-Schutzgas in 250 ml Tetrahydrofuran vorgelegt und bei -60°C wurden 79.4 ml (127.1 mmol) n-Butyllithium (1.6 M Lösung in Hexan) zugetropft und die Lösung 1h nachgerührt. Dann wurde kurz auf -40°C erwärmt und dann bei -60°C eine Lösung von 25g (90.8 mmol) 1-Brom-2-chlor-4-(trifluormethoxy)benzol (3) in 60 ml Tetrahydrofuran zugetropft. Die Lösung wurde 1h nachgerührt. Dann wurden 11.5 ml (181.5 mmol) Iodmethan zugetropft und nochmals 1h nachgerührt. Die noch kalte Reaktionslösung wurde mit 800 ml Wasser vermischt und mit konzentrierter Salzsäure auf pH 1 gestellt. Nach Extraktion mit Essigsäureethylester wurde die organische Phase getrennt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, Normalphase, Heptan/Essigsäureethylester 100/0→80/20). Man erhielt 25.00 g (95%) 1-Brom-2-chlor-3-methyl-4- (trifluormethoxy)benzol (4).1H-NMR (400 MHz, DMSO-d6): δ = 7.79 (d, 1H); 7.35 (d, 1H); 2.39 (s, 3H). Schritt 2: Herstellung von 2-Chlor-3-methyl-4-(trifluormethoxy)benzonitril (5): 18.91 g (65.33 mmol) 1- Brom-2-chlor-3-methyl-4-(trifluormethoxy)benzol (4) wurden in 150 ml Dimethylformamid gelöst und bei Raumtemperatur mit 11.70 (130.65 mmol) Kupfer(I)cyanid versetzt. Das resultierende Reaktionsgemisch wurde für 12h am Rückfluss erhitzt. Danach wurde auf 1l kalten Wassers gegossen und mit Essigsäureethylester versetzt. Nach 10min starkem Rühren wurde filtriert und die Phasen wurden getrennt. Die organische Phase wurde getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, Normalphase, Heptan/Essigsäureethylester 100/0→60/40). Man erhielt 11.83 g (77%) 2- Chlor-3-methyl-4-(trifluormethoxy)benzonitril (5).1H-NMR (400 MHz, DMSO-d6): δ = 8.01 (d, 1H); 7.60 (br d, 1H); 2.37 (s, 3H). Schritt 3: Herstellung von 2-Chlor-3-methyl-4-(trifluormethoxy)benzoesäure (6): 10.92 g (46.35 mmol) 2- Chlor-3-methyl-4-(trifluormethoxy)benzonitril (5) wurden in einer Lösung von 17.73g (443 mmol) Natriumhydroxid in 180 ml Wasser gelöst und 6h am Rückfluss erhitzt und anschließend über Nacht bei Raumtemperatur stehengelassen. Danach wurde mit Dichlormethan gewaschen und die wässrige Phase wurde mit 2M Salzsäure auf pH 1 gestellt. Dann wurde mit Essigsäureethylester extrahiert und die organische Phase abgetrennt, getrocknet und eingedampft. Man erhielt 11.07 g (94%) 2-Chlor-3-methyl-4- (trifluormethoxy)benzoesäure (6).1H-NMR (400 MHz, DMSO-d6): δ = 13.59 (br s, 1H); 7.72 (d, 1H); 7.45 (br d, 1H); 2.35 (s, 3H). Schritt 4: Herstellung von Methyl-2-chlor-3-methyl-4-(trifluormethoxy)benzoat (7): 22.08 g (86.73 mmol) 2-Chlor-3-methyl-4-(trifluormethoxy)benzoesäure (6) wurden in 400 ml Dichlormethan und 3 ml Dimethylformamid vorgelegt und bei Raumtemperatur mit 11.58 ml (13.09 mmol) Oxalylchlorid langsam versetzt. Danach wurde 1h bei Raumtemperatur nachgerührt. Nach Zutropfen von 20 ml (1734.5 mmol) Methanol wurde 3h bei Raumtemperatur gerührt und die Lösung ins Trockne eingedampft. Der Rückstand wurde in Wasser aufgenommen und mit Dichlormethan extrahiert. Die organische Phase wurde abgetrennt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, Normalphase, Heptan/Essigsäureethylester 100/0→60/40). Man erhielt 21.26 g (91%) Methyl-2-chlor-3-methyl-4- (trifluormethoxy)benzoat (7). 1H-NMR (400 MHz, DMSO-d6): δ = 7.75 (d, 1H); 7.49 (br d, 1H); 3.88 (s, 3H); 2.36 (s, 3H). Schritt 5: Herstellung von Methyl-3-(brommethyl)-2-chlor-4-(trifluormethoxy)benzoat (8): 10.42 (38.79 mmol) Methyl-2-chlor-3-methyl-4-(trifluormethoxy)benzoat (7) wurden in 100 Chlorbenzol gelöst und mit 13.81 g (77.58 mmol) N-Bromsuccinimid und 0.64 g (3.88 mmol) AIBN versetzt. Die Reaktionsmischung wurde 8h bei 120°C gerührt. Danach wurde sie eingedampft und der Rückstand wurde in Wasser aufgenommen und mit Dichlormethan extrahiert. Die organische Phase wurde abgetrennt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, Normalphase, Heptan/Essigsäureethylester 100/0→60/40). Man erhielt 13.25 g (98%) Methyl-3-(brommethyl)-2-chlor- 4-(trifluormethoxy)benzoat (8).1H-NMR (400 MHz, DMSO-d6): δ = 7.92 (d, 1H); 7.57 (br d, 1H); 4.75 (s, 2H); 3.89 (s, 3H). Schritt 6: Herstellung von Methyl-2-chlor-3-formyl-4-(trifluormethoxy)benzoat (1): 26.20 g (75 mmol) Methyl-3-(brommethyl)-2-chlor-4-(trifluormethoxy)benzoat (8) wurden in 300 ml Acetonitril vorgelegt und bei 10°C portionsweise mit 26.50 g (226 mmol) N-Methylmorpholin-N-oxid versetzt. Nach Abklingen der exothermischen Reaktion wurde die Reaktionsmischung bei Raumtemperatur 12h gerührt. Danach wurde die Mischung eingedampft, der Rückstand wurde in Wasser aufgenommen und mehrmals mit Essigsäureethylester extrahiert. Die organischen Phasen wurden vereinigt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, Normalphase, Heptan/Essigsäureethylester 100/0→80/20). Man erhielt 16.39 g (77%) Methyl-2-chlor-3-formyl-4-(trifluormethoxy)benzoat (1). 1H- NMR (400 MHz, DMSO-d6): δ = 10.37 (s, 1H); 8.12 (d, 1H); 7.66 (br d, 1H); 3.91 (s, 3H). Synthese von Methyl-2-chlor-4-(difluormethoxy)-3-formylbenzoat (2): Schritt 1: Herstellung von Methyl-2-chlor-4-(difluormethoxy)-3-methylbenzoat (10): Zu einer Lösung von 19.93 g Kaliumhydroxid in 75 ml Acetonitril und 75 ml Wasser wurden bei 0°C 10 g (47.35 mmol) kommerziell erhältliches Methyl-2-chlor-4-hydroxy-3-methylbenzoat (9) portionsweise gegeben. Danach wurden 17.52 ml (94.71 mmol) Diethyl-[brom(difluor)methyl]phosphonat zugegeben und die Mischung 1h bei 0°C gerührt. Nach Zugabe von Essigsäureethylester wird die organische Phase abgetrennt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, Normalphase, Heptan/Essigsäureethylester 100/0→85/15). Man erhielt 9.80 g (82%) Methyl-2-chlor-4-(difluormethoxy)- 3-methylbenzoat (10). 1H-NMR (400 MHz, DMSO-d6): δ = 7.71 (d, 1H); 7.33 (t, 1H); 7.27 (d, 1H); 3.86 (s, 3H); 2.31 (s, 3H). Schritt 2: Herstellung von Methyl-3-(brommethyl)-2-chlor-4-(difluormethoxy)benzoat (11): 20.65 (82.39 mmol) Methyl-2-chlor-4-(difluormethoxy)-3-methylbenzoat (10) wurden in 200 Chlorbenzol gelöst und mit 29.33 g (164.79 mmol) N-Bromsuccinimid und 1.35 g (8.24 mmol) AIBN versetzt. Die Reaktionsmischung wurde 8h bei 120°C gerührt. Danach wurde sie eingedampft und der Rückstand wurde in Wasser aufgenommen und mit Dichlormethan extrahiert. Die organische Phase wurde abgetrennt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, Normalphase, Heptan/Essigsäureethylester 100/0→60/40). Man erhielt 26.47 g (97%) Methyl-3-(brommethyl)-2-chlor- 4-(difluormethoxy)benzoat (11). 1H-NMR (400 MHz, DMSO-d6): δ = 7.89 (d, 1H); 7.48 (t, 1H); 7.36 (d, 1H); 4.73 (s, 2H); 3.88 (s, 3H). Schritt 3: Herstellung von Methyl-2-chlor-4-(difluormethoxy)-3-formylbenzoat (2): 5.96 g (18 mmol) Methyl-3-(brommethyl)-2-chlor-4-(difluormethoxy)benzoat (11) wurden in 200 ml Acetonitril vorgelegt und bei 10°C portionsweise mit 6.36 g (54 mmol) N-Methylmorpholin-N-oxid versetzt. Nach Abklingen der exothermischen Reaktion wurde die Reaktionsmischung bei Raumtemperatur 12h gerührt. Danach wurde die Mischung eingedampft, der Rückstand wurde in Wasser aufgenommen und mehrmals mit Essigsäureethylester extrahiert. Die organischen Phasen wurden vereinigt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, Normalphase, Heptan/Essigsäureethylester 100/0→60/40). Man erhielt 4.33 g (90%) Methyl-2-chlor-4-(difluormethoxy)-3-formylbenzoat (1). 1H- NMR (400 MHz, DMSO-d6): δ = 10.34 (s, 1H); 8.06 (d, 1H); 7.44 (d, 1H); 7.39 (t, 1H); 3.89 (s, 3H). Beispiele für die Herstellung der erfindungsgemäßen Verbindungen (II) und (I): Herstellung von 2-Chlor-N-(1-methyl-1H-tetrazol-5-yl)-3-(1,3-oxazol-2-yl)-4-(trifluormethoxy)benzamid (1-12): Schritt 1: Herstellung von Methyl-2-chlor-3-[(2,2-dimethoxyethyl)carbamoyl]-4- (trifluormethoxy)benzoat: 4.58 g (15.34 mmol) 2-Chloro-3-(methoxycarbonyl)-6- (trifluoromethoxy)benzoic acid wurden in 200 ml Dichlormethan und 3 ml Dimethylformamid vorgelegt und bei Raumtemperatur mit 2.05 ml (23.00 mmol) Oxalylchlorid versetzt und die Reaktionslösung wurde 1h nachgerührt. Danach wurde eingedampft, mit Toluol versetzt und wieder eingedampft. Der Rückstand wurde in 45 ml Dichlormethan gelöst und bei 0°C zu einer Lösung von 2.51 ml (23.00 mmol) 2- Aminoacetaldehyd-dimethylacetal, 6.68 ml (38.35 mmol) Hünig’s Base und einer katalytischen Menge Dimethylaminopyridin in 200 ml trockenem Dichlormethan zugetropft. Danach wurde die Reaktionsmischung auf Raumtemperatur erwärmt und 3h gerührt. Nach Verdünnung mit Dichlormethan wurde mit Wasser gewaschen, die organische Phase abgetrennt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, Normalphase, Heptan/Essigsäureethylester 100/0→80/20). Man erhielt 5.61 g (95%) Methyl-2-chlor-3-[(2,2-dimethoxyethyl)carbamoyl]-4- (trifluormethoxy)benzoat. 1H-NMR (400 MHz, DMSO-d6): δ = 8.89 (br t, 1H); 7.94 (d, 1H); 7.56 (br d, 1H); 4.45 (t, 1H); 3.89 (s, 3H); 3.34 (m, 2H); 3.30 (s, 6H). Schritt 2: Herstellung von Methyl-2-chlor-3-[(2-oxoethyl)carbamoyl]-4-(trifluormethoxy)benzoat: 5.61 g (14.54 mmol) Methyl-2-chlor-3-[(2,2-dimethoxyethyl)carbamoyl]-4-(trifluormethoxy)benzoat wurden in 20 ml Dioxan vorgelegt und bei Raumtemperatur mit 29.09 ml (58.18 mmol) 2M Salzsäure versetzt. Danach wurde die Reaktionsmischung 4h bei 80°C gerührt. Die Mischung wurde eingedampft, der Rückstand wurde in Wasser aufgenommen und mit Essigsäureethylester extrahiert. Die organische Phase wurde abgetrennt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, Normalphase, Heptan/Essigsäureethylester 100/0→80/20). Man erhielt 4.45 g (90%) Methyl-2-chlor-3-[(2- oxoethyl)carbamoyl]-4-(trifluormethoxy)benzoat. 1H-NMR (400 MHz, DMSO-d6): δ = 9.53 (s, 1H); 9.25 (br t, 1H); 7.97 (d, 1H); 7.59 (br d, 1H); 4.13 (m, 2H); 3.89 (s, 3H). Schritt 3: Herstellung von Methyl-2-chlor-3-(1,3-oxazol-2-yl)-4-(trifluormethoxy)benzoat (3-12): 1.40 g (4.12 mmol) Methyl-2-chlor-3-[(2-oxoethyl)carbamoyl]-4-(trifluormethoxy)benzoat wurden in 8 ml Acetonitril gelöst und zu einer Lösung von 2.93 g (12.37 mmol) Hexachlorethan in 20 ml Acetonitril zugegeben. Die Reaktionsmischung wurde dann bei 0°C portionsweise mit 4.31 ml (24.73 mmol) Hünig’s Base und 3.24 g (12.37 mmol) Triphenylphosphin versetzt. Die Mischung wurde danach bei Raumtemperatur 4h gerührt. Danach wurde ins Trockne eingedampft und der Rückstand wurde in 2M Salzäure aufgenommen und mit Dichlormethan extrahiert. Die organische Phase wurde abgetrennt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, Normalphase, Heptan/Essigsäureethylester 100/0→60/40). Man erhielt 689 mg (49%) Methyl-2-chlor-3-(1,3-oxazol-2- yl)-4-(trifluormethoxy)benzoat (3-12). Schritt 4: Herstellung von 2-Chlor-3-(1,3-oxazol-2-yl)-4- (trifluormethoxy)benzoesäure (4-12): 698 mg (2.17 mmol) Methyl-2-chlor-3-(1,3-oxazol-2-yl)-4- (trifluormethoxy)benzoat (3-12) wurden in 20 ml Methanol vorgelegt und bei Raumtemperatur mit 2.17 ml (4.34 mmol) 2M Natronlauge versetzt. Die Reaktionsmischung wurde 12h bei Raumtemperatur gerührt und danach eingedampft. Der Rückstand wurde mit Wasser aufgenommen, und die wässrige Phase wurde mit 2M Salzsäure auf pH 1 gestellt. Die organische Phase wurde abgetrennt, getrocknet und eingedampft. Man erhielt 655 mg (98%) 2-Chlor-3-(1,3-oxazol-2-yl)-4-(trifluormethoxy)benzoesäure (4-12). Schritt 5: Herstellung von 2-Chlor-N-(1-methyl-1H-tetrazol-5-yl)-3-(1,3-oxazol-2-yl)-4- (trifluormethoxy)benzamid (1-12): 200 mg (0.65 mmol) 2-Chlor-3-(1,3-oxazol-2-yl)-4- (trifluormethoxy)benzoesäure (4-12) und 98.6 mg (0.98 mmol) 5-Amino-1-methyl-1H-tetrazol wurden in 3 ml Pyridin vorgelegt, und bei Raumtemperatur wurden 0.087 ml (0.98 mmol) Oxalylchlorid zugetropft. Die Reaktionslösung wurde 12h bei Raumtemperatur gerührt. Nach Zugabe von 10 ml wässr. ges. Natriumhydrogencarbonat-Lösung wurde nochmals 10 min gerührt und danach wurde mit Dichlormethan extrahiert. Die organische Phase wurde getrennt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, C18, Gradient: Acetonitril/Wasser (+0.05% Trifluoressigsäure) 10/90→100/0). Man erhielt 146 mg (55%) 2-Chlor-N-(1-methyl-1H-tetrazol-5-yl)-3-(1,3-oxazol-2-yl)-4- (trifluormethoxy)benzamid (1-12). Herstellung von 2-Chlor-3-(5-methyl-1,2-oxazol-3-yl)-N-(1-methyl-1H-tetrazol-5-yl)-4- (trifluormethoxy)benzamid (1-13): Schritt 1: Herstellung von Methyl-2-chlor-3-[(hydroxyimino)methyl]-4-(trifluormethoxy)benzoat: 3.40 g (12.03 mmol) Methyl-2-chlor-4-(difluormethoxy)-3-formylbenzoat wurden zusammen mit 1.03 g (14.44 mmol) Hydroxylamin-hydrochlorid (97%) in 120 ml Tetrahydrofuran vorgelegt und bei Raumtemperatur mit 2.52 ml (14.44 mmol) Hünig’s Base versetzt. Die Reaktionslösung wurde 3h gerührt und danach eingedampft. Der Rückstand wurde mit 2N Salzsäure aufgenommen und mit Essigsäureethylester extrahiert. Die organische Phase wurde abgetrennt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, Normalphase, Heptan/Essigsäureethylester 100/0→70/30). Man erhielt 3.70 g (98%) Methyl-2-chlor-3-[(hydroxyimino)methyl]-4-(trifluormethoxy)benzoat.1H-NMR (400 MHz, DMSO-d6): δ = 11.98 (s, 1H); 8.23 (s, 1H); 7.92 (d, 1H); 7.61 (br d, 1H); 3.89 (s, 3H). Schritt 2: Herstellung von Methyl-2-chlor-3-(5-methyl-1,2-oxazol-3-yl)-4-(trifluormethoxy)benzoat (3- 13): 1.23 g (4.13 mmol) Methyl-2-chlor-3-[(hydroxyimino)methyl]-4-(trifluormethoxy)benzoat wurden in 50 ml Dimethylformamid vorgelegt und bei Raumtemperatur mit 579,47 mg (4.34 mmol) N- Chlorsuccinimid versetzt. Danach wurde 4h gerührt. Nach Abkühlen der Reaktionslösung auf 0°C wurden 41.33 ml (ca.41 mmol) einer 5%igen Lösung von Prop-1-in in Tetrahydrofuran und anschließend 1.08 ml (6.20 mmol) Hünig’s Base zugetropft. Nach 1h Rühren bei Raumtemperatur wurde die Mischung eingedampft, der Rückstand wurde in Wasser aufgenommen und mit Dichlormethan extrahiert. Die organische Phase wurde abgetrennt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, Normalphase, Heptan/Essigsäureethylester 100/0→50/50). Man erhielt 1.18 g (81%) Methyl-2-chlor-3-(5-methyl-1,2-oxazol-3-yl)-4-(trifluormethoxy)benzoat (3-13). Schritt 3: Herstellung von 2-Chlor-3-(5-methyl-1,2-oxazol-3-yl)-4-(trifluormethoxy)benzoesäure (4-13): 1.18 g (3.52 mmol) Methyl-2-chlor-3-(5-methyl-1,2-oxazol-3-yl)-4-(trifluormethoxy)benzoat (3-13) wurden in 100 ml Methanol vorgelegt und bei Raumtemperatur mit 3.52 ml (7.03 mmol) 2M Natronlauge versetzt. Die Reaktionsmischung wurde 12h bei Raumtemperatur gerührt und danach eingedampft. Der Rückstand wurde mit Wasser aufgenommen, und die wässrige Phase wurde mit 2M Salzsäure auf pH 1 gestellt. Die organische Phase wurde abgetrennt, getrocknet und eingedampft. Man erhielt 1.18 g (99%) 2- Chlor-3-(5-methyl-1,2-oxazol-3-yl)-4-(trifluormethoxy)benzoesäure (4-13). Schritt 4: Herstellung von 2-Chlor-3-(5-methyl-1,2-oxazol-3-yl)-N-(1-methyl-1H-tetrazol-5-yl)-4- (trifluormethoxy)benzamid (1-13): 200 mg (0.62 mmol) 2-Chlor-3-(5-methyl-1,2-oxazol-3-yl)-4- (trifluormethoxy)benzoesäure (4-13) und 94.32 mg (0.93 mmol) 5-Amino-1-methyl-1H-tetrazol wurden in 3 ml Pyridin vorgelegt, und bei Raumtemperatur wurden 0.083 ml (0.93 mmol) Oxalylchlorid zugetropft. Die Reaktionslösung wurde 12h bei Raumtemperatur gerührt. Nach Zugabe von 10 ml wässr. ges. Natriumhydrogencarbonat-Lösung wurde nochmals 10 min gerührt und danach wurde mit Dichlormethan extrahiert. Die organische Phase wurde getrennt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, C18, Gradient: Acetonitril/Wasser (+0.05% Trifluoressigsäure) 10/90→100/0). Man erhielt 133 mg (50%) 2-Chlor-3-(5-methyl-1,2-oxazol-3-yl)-N-(1-methyl-1H- tetrazol-5-yl)-4-(trifluormethoxy)benzamid (1-13). Herstellung von (R,S)-2-Chlor-4-(difluormethoxy)-N-(1-ethyl-1H-tetrazol-5-yl)-3-(3-methyl-4,5-dihydro- 1,2-oxazol-5-yl)benzamid (2-31): Schritt 1: Herstellung von Methyl-2-chlor-4-(difluormethoxy)-3-vinylbenzoat: 25.86 (11.34 mmol) Nysted-Reagens wurden unter Argon-Schutzgas mit 80 ml Tetrahydrofuran verdünnt und bei 0°C wurden 0.96 ml (0.76 mmol) Bortrifluorid-diethyletherat zugegeben und die Reaktionsmischung wurde 10 min gerührt. Danach wurde eine Lösung von 2.00 g (7.56 mmol) Methyl-2-chlor-4-(difluormethoxy)-3- formylbenzoat in 20 ml Tetrahydrofuran zugetropft. Nach Aufwärmen auf Raumtemperatur wurde 3h gerührt. Die Mischung wurde vorsichtig auf 2M Salzsäure gegossen und mit Dichlormethan extrahiert. Die organische Phase wurde abgetrennt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, Normalphase, Heptan/Essigsäureethylester 100/0→50/50). Man erhielt 1.80 g (91%) Methyl-2-chlor-4-(difluormethoxy)-3-vinylbenzoat. 1H-NMR (400 MHz, DMSO-d6): δ = 7.75 (d, 1H); 7.34 (t, 1H); 7.32 (d, 1H); 6.71 (dd, 1H); 5.79 (m, 2H); 3.86 (s, 3H). Schritt 2: Herstellung von (R,S)-Methyl-2-chlor-4-(difluormethoxy)-3-(3-methyl-4,5-dihydro-1,2-oxazol- 5-yl)benzoat (3-31): 1.70 g (6.47 mmol) Methyl-2-chlor-4-(difluormethoxy)-3-vinylbenzoat und 7.06 g (32.36 mmol) Di-tert-butyldicarbonat wurden in 70 ml Acetonitril vorgelegt und langsam mit 1.86 ml (25.89 mmol) Nitroethan versetzt. Danach wurde 3h bei Rückfluss gerührt. Nach Eindampfen der Mischung wurde in Wasser und Dichlormethan aufgenommen. Die organische Phase wurde abgetrennt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, Normalphase, Heptan/Essigsäureethylester 100/0→40/60). Man erhielt 2.15 g (91%) (R,S)-Methyl-2-chlor-4- (difluormethoxy)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzoat (3-31). Schritt 3: Herstellung von (R,S)-2-Chlor-4-(difluormethoxy)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5- yl)benzoesäure (4-31): 810 mg (2.53 mmol) (R,S)-Methyl-2-chlor-4-(difluormethoxy)-3-(3-methyl-4,5- dihydro-1,2-oxazol-5-yl)benzoat (3-31) wurden in 50 ml Methanol vorgelegt und bei Raumtemperatur mit 2.53 ml (5.07 mmol) 2M Natronlauge versetzt. Die Reaktionsmischung wurde 12h bei Raumtemperatur gerührt und danach eingedampft. Der Rückstand wurde mit Wasser aufgenommen, und die wässrige Phase wurde mit 2M Salzsäure auf pH 1 gestellt. Die organische Phase wurde abgetrennt, getrocknet und eingedampft. Man erhielt 708 mg (87%) (R,S)-2-Chlor-4-(difluormethoxy)-3-(3-methyl-4,5-dihydro-1,2- oxazol-5-yl)benzoesäure (4-31). Schritt 4: Herstellung von (R,S)-2-Chlor-4-(difluormethoxy)-N-(1-ethyl-1H-tetrazol-5-yl)-3-(3-methyl- 4,5-dihydro-1,2-oxazol-5-yl)benzamid (2-31): 200 mg (0.65 mmol) (R,S)-2-Chlor-4-(difluormethoxy)-3- (3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzoesäure (4-31) und 116.87 mg (0.98 mmol) 5-Amino-1-ethyl- 1H-tetrazol wurden in 3 ml Pyridin vorgelegt, und bei Raumtemperatur wurden 0.087 ml (0.98 mmol) Oxalylchlorid zugetropft. Die Reaktionslösung wurde 12h bei Raumtemperatur gerührt. Nach Zugabe von 10 ml wässr. ges. Natriumhydrogencarbonat-Lösung wurde nochmals 10 min gerührt und danach wurde mit Dichlormethan extrahiert. Die organische Phase wurde getrennt, getrocknet und eingedampft. Der Rückstand wurde chromatographisch gereinigt (HPLC, C18, Gradient: Acetonitril/Wasser (+0.05% Trifluoressigsäure) 10/90→100/0). Man erhielt 106 mg (38%) (R,S)-2-Chlor-4-(difluormethoxy)-N-(1- ethyl-1H-tetrazol-5-yl)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzamid (2-31). Die in nachfolgenden Tabellen aufgeführten Beispiele wurden analog oben genannten Methoden hergestellt beziehungsweise sind analog oben genannten Methoden erhältlich. Diese Verbindungen sind ganz besonders bevorzugt. Die verwendeten Abkürzungen bedeuten: Me = Methyl Et = Ethyl c-Pr = cyclo-Propyl Tabelle 1: Erfindungsgemäße Verbindungen der Formel (I), worin Rx für eine Methylgruppe steht und die anderen Substituenten die unten genannten Bedeutungen haben.
Figure imgf000040_0001
Figure imgf000040_0002
3-Heterocyclylbenzamides and Their Use as Herbicides The invention relates to the technical field of herbicides, in particular to herbicides for the selective control of weeds and grass weeds in crops. WO 2012/028579 A1 discloses herbicidally active benzamides that can bear a variety of substituents in the 3-position of the phenyl ring. However, the benzoylamides known from the above-mentioned document do not always exhibit sufficient herbicidal activity and/or compatibility with crop plants. The object of the present invention is to provide alternative herbicidally active ingredients. This object is achieved by the benzamides according to the invention described below, which bear a heterocyclyl radical in the 3-position of the phenyl ring and additionally a haloalkoxy radical in the 4-position. The present invention thus provides 3-acylbenzamides of the formula (I) or salts thereof.
Figure imgf000002_0001
where the symbols and indices have the following meanings: Rxmeans (C1-C6)-alkyl, X is halogen or (C1-C6)-alkyl, Y is halogen-(C1-C6)-alkoxy, Z represents Z-1, Z-2, Z-3 or Z-4, where Z-1 to Z-4 have the following meanings
Figure imgf000002_0002
R1means hydrogen, (C1-C6)-alkyl or halogen-(C1-C6)-alkyl, R2means hydrogen, (C1-C6)-alkyl or (C3-C6)-cycloalkyl, R3means (C1-C6)-alkyl, halogen-(C1-C6)-alkyl or (C3-C6)-cycloalkyl, and R4and R5independently represent hydrogen, (C1-C6)-alkyl, (C1-C6)-alkyloxy-(C1-C6)-alkyl, cyano-(C1-C6)-alkyl or (C3-C6)-Cycloalkyl. In formula (I) and all subsequent formulae, alkyl radicals with more than two carbon atoms can be straight-chain or branched. Alkyl radicals are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl, and 1,3-dimethylbutyl. Analogously, alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl, and 1-methylbut-2-en-1-yl. Alkynyl means, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, and 1-methyl-but-3-yn-1-yl. The multiple bond can be located in any position of the unsaturated radical. Cycloalkyl means a carbocyclic, saturated ring system with three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. Halogen represents fluorine, chlorine, bromine, or iodine. The compounds of formula (I) or (II) can exist as stereoisomers depending on the nature and linkage of the substituents. If, for example, one or more asymmetrically substituted carbon atoms are present, enantiomers and diastereomers can occur. Stereoisomers can be obtained from the mixtures obtained during production using conventional separation methods, for example, chromatographic separation processes. Stereoisomers can also be selectively prepared using stereoselective reactions using optically active starting materials and/or auxiliaries. The invention also relates to all stereoisomers and mixtures thereof encompassed by formula (I) or (II) but not specifically defined. Preferred compounds of formula (I) are those in which the symbols and indices have the following meanings: Rxmeans (C1-C6)-alkyl, X is halogen or (C1-C6)-alkyl, Y is OCF3, OCHF2or OCF2Me Z means Z-1, Z-2, Z-3 or Z-4, where Z-1 to Z-4 have the following meanings:
Figure imgf000003_0001
R1means hydrogen or (C1-C6)-alkyl, R2means hydrogen, (C1-C6)-alkyl or (C3-C6)-cycloalkyl, R3means (C1-C6)-alkyl or halogen-(C1-C6)-alkyl, and R4and R5independently represent hydrogen, (C1-C6)-alkyl, (C1-C6)-alkyloxy-(C1-C6)-alkyl, cyano-(C1-C6)-alkyl or (C3-C6)-cycloalkyl. Particularly preferred compounds of formula (I) are those in which the symbols and indices have the following meanings: Rxmeans methyl or ethyl, X means chlorine, bromine, methyl or ethyl, Y means OCF3or OCHF2, Z means Z-1, Z-2, Z-3 or Z-4, where Z-1 to Z-4 have the following meanings
Figure imgf000004_0001
R1means hydrogen or methyl, R2means hydrogen, methyl, ethyl or c-propyl, R3means methyl, ethyl or i-propyl, and R4and R5The following combinations are hydrogen and hydrogen, hydrogen and methyl, hydrogen and ethyl, hydrogen and cyclopropyl, cyclopropyl and cyclopropyl, hydrogen and methoxymethyl, or hydrogen and cyanomethyl. In all of the following formulas, unless otherwise defined, the substituents and symbols have the same meaning as described under formula (I). Compounds of formula (II) are novel and are very suitable as intermediates for the preparation of the compounds of formula (I) according to the invention. The present invention thus further provides compounds of formula (II),
Figure imgf000004_0002
where the symbols and indices have the following meanings: L means halogen or R6O, X means halogen or (C1-C6)-alkyl, Y is halogen-(C1-C6)-alkoxy, Z represents Z-1, Z-2, Z-3 or Z-4, where Z-1 to Z-4 have the following meanings
Figure imgf000005_0001
R1means hydrogen, (C1-C6)-alkyl or halogen-(C1-C6)-alkyl, R2means hydrogen, (C1-C6)-alkyl or (C3-C6)-cycloalkyl, or R2can also be Si((C1-C6)-Alkyl)3mean if L OR6means and R6for (C1-C6)-alkyl, R3means (C1-C6)-alkyl, halogen-(C1-C6)-alkyl or (C3-C6)-cycloalkyl, R4and R5independently represent hydrogen, (C1-C6)-alkyl, (C1-C6)-alkyloxy-(C1-C6)-alkyl, cyano-(C1-C6)-alkyl or (C3-C6)-cycloalkyl, and R6means hydrogen or (C1-C6)-alkyl. Preferred compounds (II) are those in which L is chlorine, methoxy or hydroxy, X is chlorine, bromine, methyl or ethyl, Y is OCF3or OCHF2, Z means Z-1, Z-2, Z-3 or Z-4, where Z-1 to Z-4 have the following meanings
Figure imgf000005_0002
R1means hydrogen or methyl, R2means hydrogen, methyl, ethyl or c-propyl, or R2can also mean Si(Me)3 if L is methoxy, R3means methyl, ethyl or i-propyl, R4and R5The following combinations are hydrogen and hydrogen, hydrogen and methyl, hydrogen and ethyl, hydrogen and cyclopropyl, cyclopropyl and cyclopropyl, hydrogen and methoxymethyl, or hydrogen and cyanomethyl. In all formulas mentioned below, the substituents and symbols, unless otherwise defined, have the same meaning as described under formula (I). Compounds of the general formula (I) according to the invention can be prepared, for example, as also described in WO2012/028579, by reacting the compounds of the general formula (IIb: compounds II, where L = hydroxy) according to the invention with substituted aminotetrazoles:
Figure imgf000006_0001
The synthesis of compounds of general formula (IIb) can be carried out, for example, according to the following scheme and methods known to those skilled in the art: Heterocycles in the 3-position with Z = Z-1:
Figure imgf000006_0002
Heterocycles in the 3-position with Z = Z-2:
Figure imgf000007_0001
Collections of compounds of formula (I) and/or their salts, which can be synthesized using the above-mentioned reactions, can also be prepared in a parallelized manner, whereby this can be done manually, partially automated, or fully automated. For example, it is possible to automate the reaction procedure, the processing, or the purification of the products or intermediates. Overall, this refers to a procedure such as that described, for example, by D. Tiebes in Combinatorial Chemistry – Synthesis, Analysis, Screening (editor Günther Jung), Wiley Publishers 1999, on pages 1 to 34. A range of commercially available devices can be used for parallelized reaction execution and workup, for example, Calpyso reaction blocks from Barnstead International, Dubuque, Iowa 52004-0797, USA; reaction stations from Radleys, Shirehill, Saffron Walden, Essex, CB 11 3AZ, England; or MultiPROBE Automated Workstations from Perkin Elmar, Waltham, Massachusetts 02451, USA. For the parallel purification of compounds of formula (I) and their salts, or intermediates obtained during their preparation, chromatography equipment is available, for example, from ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA. The listed equipment results in a modular approach in which the individual work steps are automated, but manual operations must be performed between the work steps. This can be circumvented by the use of partially or fully integrated automation systems in which the respective automation modules are operated, for example, by robots. Such automation systems can be obtained, for example, from Caliper, Hopkinton, MA 01748, USA. The execution of individual or multiple synthesis steps can be supported by the use of polymer-supported reagents/scavenger resins. A number of experimental protocols are described in the specialist literature, for example in ChemFiles, Vol. 4, No. 1, Polymer-Supported Scavengers and Reagents for Solution-Phase Synthesis (Sigma-Aldrich). In addition to the methods described here, the preparation of compounds of formula (I) and their salts can be carried out entirely or partially by solid-phase-supported methods. For this purpose, individual intermediates or all intermediates of the synthesis or of a synthesis adapted for the corresponding procedure are bound to a synthesis resin. Solid-phase-assisted synthesis methods are well described in the literature, e.g., Barry A. Bunin in "The Combinatorial Index," Academic Press, 1998, and Combinatorial Chemistry – Synthesis, Analysis, Screening (editor Günther Jung), Wiley, 1999. The use of solid-phase-assisted synthesis methods allows for a range of well-known protocols, which can be performed manually or automatically. For example, the reactions can be carried out using IRORI technology in microreactors from Nexus Biosystems, 12140 Community Road, Poway, CA 92064, USA. Both in the solid and liquid phases, the execution of individual or multiple synthesis steps can be supported by the use of microwave technology. A number of experimental protocols are described in the literature, for example, in Microwaves in Organic and Medicinal Chemistry (editors C. O. Kappe and A. Stadler), Wiley Publishers, 2005. Preparation according to the methods described here yields compounds of formula (I) and their salts in the form of collections of substances called libraries. The subject of thisThe invention also relates to libraries containing at least two compounds of formula (I) and salts thereof. The compounds of the invention exhibit excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous annual weeds. Even difficult-to-control perennial weeds that sprout from rhizomes, rootstocks, or other permanent organs are effectively controlled by the active ingredients. The present invention therefore also provides a method for controlling undesirable plants or for regulating the growth of plants, preferably in plant crops, in which one or more compounds of the invention are applied to the plants (e.g., weeds such as monocotyledonous or dicotyledonous weeds or undesirable crop plants), the seed (e.g., grains, seeds, or vegetative propagation organs such as tubers or shoot parts with buds), or the area on which the plants grow (e.g., the cultivated area). The compounds of the invention can be applied, for example, by pre-sowing (optionally also by incorporation into the soil), pre-emergence, or post-emergence methods. Some representatives of the monocotyledonous and dicotyledonous weed flora that can be controlled by the compounds of the invention are mentioned as examples, without implying a restriction to specific species. Monocotyledonous harmful plants of the genera: 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, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria and Sorghum. Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, and Xanthium. If the compounds according to the invention are applied to the soil surface before germination, either the emergence of weed seedlings is completely prevented, or the weeds grow to the cotyledon stage, but then cease growth and finally die completely after three to four weeks. When the active ingredients are applied post-emergence to the green parts of the plant, growth stops after treatment, and the weeds remain in the same area as they were at the time of application.They remain in the current growth stage or die completely after a certain period of time, thus eliminating weed competition that is harmful to the crops very early and sustainably. Although the compounds according to the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops, e.g. dicotyledonous crops of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Miscanthus, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, or monocotyledonous crops of the genera Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea, in particular Zea and Triticum, are only insignificantly damaged or not damaged at all, depending on the structure of the respective compound according to the invention and the application rate thereof. For these reasons, the present compounds are highly suitable for the selective control of undesirable plant growth in plant crops such as agricultural crops or ornamental plants. Furthermore, the compounds according to the invention, depending on their respective chemical structure and the applied rate, exhibit outstanding growth-regulating properties in crops. They regulate the plant's own metabolism and can thus be used to specifically influence plant constituents and facilitate harvesting, for example by inducing desiccation and stunting. Furthermore, they are also suitable for the general control and inhibition of undesirable vegetative growth without killing the plants. Inhibition of vegetative growth plays a major role in many monocotyledonous and dicotyledonous crops, since, for example, lodging can be reduced or completely prevented as a result. Due to their herbicidal and plant growth-regulating properties, the active ingredients can also be used to control weeds in crops of plants modified genetically or by conventional mutagenesis. The transgenic plants are generally characterized by particularly advantageous properties, for example, resistance to certain pesticides, 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 harvested crop in terms of quantity, quality, storability, composition, and specific ingredients. Thus, transgenic plants with increased starch content or altered starch quality, or those with a different fatty acid composition of the harvested crop, are known. With regard to transgenic crops, the use of the compounds according to the invention is preferred in economically important transgenic crops of crops and ornamental plants, e.g., cereals such as wheat, barley, rye, oats, millet, rice, and maize, or also crops of sugar beet, cotton, soybeans, rapeseed, potatoes, cassava, tomatoes, peas, and other vegetables. The compounds according to the invention can preferably be used as herbicides in crop crops. that are resistant to the phytotoxic effects of herbicides or have been genetically engineered to be resistant. Conventional methods for producing new plants with modified traits compared to existing plants include, for example, classical breeding methods and the creation of mutants. Alternatively, new plants with modified traits can be created using genetic engineering techniques (see, for example, EP-A-0221044, EP-A-0131624). For example, the following have been described in several cases: - genetic modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/11376, WO 92/14827, WO 91/19806), - transgenic crop plants which are resistant to certain herbicides of the glufosinate type (cf. e.g. EP-A-0242236, EP-A-242246) or glyphosate (WO 92/00377) or sulfonylureas (EP-A-0257993, US-A-5013659), - 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-A-0142924, EP-A-0193259). - Transgenic crops with modified fatty acid composition (WO 91/13972). - Genetically modified crops with new ingredients or secondary substances, e.g., new phytoalexins, which cause increased disease resistance (EPA 309862, EPA0464461). - Genetically modified plants with reduced photorespiration that exhibit higher yields and greater stress tolerance (EPA 0305398). - Transgenic crops that produce pharmaceutically or diagnostically important proteins ("molecular pharming") - Transgenic crops characterized by higher yields or better quality - Transgenic crops characterized by a combination of, e.g., 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, B. 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 that allow mutagenesis or sequence modification through recombination of DNA sequences. Using standard procedures, base substitutions can be performed, partial sequences can be removed, or natural or synthetic sequences can be added. Adapters or linkers can be attached to the DNA fragments to connect them to one another, see, for example, [1]. B. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY, or Winnacker "Gene and Clones", VCH Weinheim, 2nd ed. 1996. The production of plant cells with reduced activity of a gene product can be achieved, for example, by expressing at least one corresponding antisense RNA, a sense RNA to achieve a cosuppression effect, or the expression of at least one appropriately constructed ribozyme that specifically cleaves transcripts of the aforementioned gene product. For this purpose, DNA molecules can be used that comprise the entire coding sequence of a gene product, including any flanking sequences present, as well as DNA molecules that comprise only parts of the coding sequence, whereby these parts must be long enough to produce an antisense effect in the cells. It is also possible to use DNA sequences that exhibit a high degree of homology to the coding sequences of a gene product, but are not completely identical. When nucleic acid molecules are expressed in plants, the synthesized protein can be localized in any compartment of the plant cell. However, to achieve localization in a specific compartment, the coding region can, for example, be linked to DNA sequences that ensure localization in a specific 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. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). Expression of nucleic acid molecules can also occur in the organelles of plant cells. 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, i.e., both monocotyledonous and dicotyledonous plants. Thus, transgenic plants can be obtained which exhibit altered properties through the overexpression, suppression, or inhibition of homologous (= natural) genes or gene sequences, or the expression of heterologous (= foreign) genes or gene sequences. The compounds according to the invention can preferably be used in transgenic crops which are resistant to growth factors, such as dicamba, or to herbicides which inhibit essential plant enzymes, e.g. B. inhibit acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD), or are resistant to herbicides from the group of sulfonylureas, glyphosates, glufosinates or benzoyl isoxazoles and analogous active ingredients. When the active compounds according to the invention are used in transgenic crops, in addition to the effects against weeds observed in other crops, effects often occur that are specific to the application in the respective transgenic crop, for example, a modified or specifically expanded spectrum of weeds that can be controlled, modified application rates that can be used for application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and an influence on the growth and yield of the transgenic crops. The invention therefore also relates to the use of the compounds according to the invention as herbicides for controlling weeds in transgenic crops. The compounds according to the invention can be applied in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts, or granules in the usual preparations. The invention therefore also relates to herbicidal and plant growth-regulating compositions containing the compounds according to the invention. The compounds according to the invention can be formulated in various ways, depending on the biological and/or chemical-physical parameters specified. 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), seed dressings, granules for broadcast and soil application, granules (GR) in the form of microgranules, spray granules, emulsifiable granules, and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV 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 ed. 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd ed. 1979, G. Goodwin Ltd. London. The necessary formulation aids 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, McCutcheon'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, "Interfacially active ethylene oxide adducts", Wiss. Publishing company, Stuttgart 1976, Winnacker-Küchler, "Chemical Technology," Volume 7, C. Hanser Verlag Munich, 4th edition, 1986. Wettable powders are preparations that are evenly dispersible in water. In addition to the active ingredient, they contain a diluent or inert substance as well as ionic and/or non-ionic surfactants (wetting agents, dispersants), e.g., polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium ligninsulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate, or sodium oleoylmethyltaurine. To produce the wettable powders, the herbicidal active ingredients are finely ground in conventional equipment such as hammer mills, fan mills, and air jet mills and mixed simultaneously or subsequently 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 these organic solvents, with the addition of one or more ionic and/or non-ionic surfactants (emulsifiers). Examples of emulsifiers that can be used include: alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters, or polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan fatty acid esters. Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g., talc, natural clays such as kaolin, bentonite, and pyrophyllite, 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, with the addition of surfactants, such as those listed above for the other formulation types. Emulsions, e.g., oil-in-water emulsions (EW), can be produced using stirrers, colloid mills, and/or static mixers using aqueous organic solvents and, if appropriate, surfactants, such as those listed above for the other formulation types. Granules can be produced either by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates using adhesives, e.g., polyvinyl alcohol, sodium polyacrylate, 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, in a mixture with fertilizers. Water-dispersible granules are generally produced using conventional processes such as spray drying, fluidized-bed granulation, disc granulation, blending with high-speed mixers, and extrusion without solid inert material. For the production of disc, fluidized-bed, extruder, and spray granules, see, for example, the methods in "Spray-Drying Handbook," 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration," Chemical and Engineering 1967, pp. 147 ff.; and "Perry's Chemical Engineer's Handbook," 5th ed., McGraw-Hill, New York 1973, pp. 8-57. For further details on the formulation of crop protection products, see, for example, G.C. Klingman, "Weed Control as a Science," John Wiley and Sons, Inc., New York, 1961, pages 81-96, and J.D. Freyer, S.A. Evans, "Weed Control Handbook," 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103. 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. In wettable powders, for example, the active ingredient concentration is about 10 to 90% by weight, with the remainder (to 100% by weight) consisting of conventional formulation ingredients. In emulsifiable concentrates, the active ingredient concentration can be about 1 to 90% by weight, preferably 5 to 80% by weight. Dust-like formulations contain 1 to 30 wt.% active ingredient, preferably 5 to 20 wt.% active ingredient; sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt.% active ingredient. In water-dispersible granules, the active ingredient content depends partly on whether the active compound is liquid or solid and which granulation aids, fillers, etc. are used. In water-dispersible granules, the active ingredient content is, for example, between 1 and 95 wt.%, preferably between 10 and 80 wt.%. In addition, the said active ingredient formulations may contain the usual adhesives, wetting agents, dispersants, emulsifiers, penetration agents, preservatives, antifreeze agents, solvents, fillers, carriers, dyes, defoamers, evaporation inhibitors, and agents that influence the pH and viscosity. Based on these formulations, combinations with other pesticidally active substances, such as insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers, and/or growth regulators, can also be produced, e.g., in the form of a ready-to-use formulation or as a tank mix. For application, the commercially available formulations are diluted in the usual way, e.g., with water for wettable powders, emulsifiable concentrates, dispersions, and water-dispersible granules. Dust-like preparations, soil or...Granules for broadcasting and sprayable solutions are not usually diluted with other inert substances prior to application. The required application rate of the compounds of formula (I) varies depending on external conditions such as temperature, humidity, the type of herbicide used, and others. It can vary within wide limits, e.g., between 0.001 and 1.0 kg/ha or more of active ingredient, but is preferably between 0.005 and 750 g/ha. The compounds of formula (I) according to the invention can also be used in admixture with other herbicides as needed. As combination partners for the compounds of formula (I) in mixture formulations or in the tank mix, known active ingredients which are based on the inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate 3-phosphate synthase, glutamine synthetase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, protoporphyrinogen oxidase or which act as plant growth regulators can be used, as described, for example, in Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 14th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2006 and literature cited therein. Known herbicides or plant growth regulators that can be combined with compounds of formula (I) include, for example, the following active ingredients (the compounds are designated either by the "common name" according to the International Organization for Standardization (ISO) or by the chemical name or by the code number) and always include all application forms such as acids, salts, esters and isomers such as stereoisomers and optical isomers. One and sometimes several application forms are mentioned as examples: Acetochlor, Acifluorfen, Acifluorfen-methyl, Acifluorfen-sodium, Aclonifen, Alachlor, Allidochlor, Alloxydim, Alloxydim-sodium, Ametryn, Amicarbazon, Amidochlor, Amidosulfuron, 4-Amino-3-chloro-6-(4-chloro-2-fluoro-3-methylphenyl)-5-fluoropyridine-2-carboxylic acid, Aminocyclopyrachlor, Aminocyclopyrachlor-potassium, Aminocyclopyrachlor-methyl, Aminopyralid, Aminopyralid-dimethylammonium, Aminopyralid-tripromine, Amitrol, Ammonium sulfamate, Anilofos, Asulam, Asulam-potassium, Asulam-sodium, Atrazine, Azafenidine, Azimsulfuron, Beflubutamid, (S)-(-)-Beflubutamide, Beflubutamid-M, Benazoline, Benazoline-ethyl, Benazoline-dimethylammonium, Benazoline-Klaium, Benfluralin, Benfuresate, Bensulfuron, Bensulfuron-methyl, Bensulide, Bentazone, Bentazone sodium, Benzobicyclon, Benzofenap, Bicyclopyrone, Bifenox, Bilanafos, Bilanafos sodium, bipyrazone, bispyribac, bispyribac sodium, bixlozone, bromacil, bromacil lithium, bromacil sodium, bromobutide, bromofenoxime, bromoxynil, bromoxynil butyrate, bromoxynil potassium, bromoxynil heptanoate and bromoxynil octanoate, busoxinone, Butachlor, Butafenacil, Butamifos, Butenachlor, Butralin, Butroxydim, Butylate, Cafenstrol, Cambendichlor, Carbetamide, Carfentrazone, Carfentrazone Ethyl, Chloramben, Chloramben Ammonium, Chlorambendiolamine, Chloramben Methyl, Chloramben Methylammonium, Chloramben Sodium, Chlorbromuron, Chlorfenac, Chlorfenac Ammonium, Chlorfenac Sodium, Chlorfenprop, Chlorfenprop- methyl, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlorophthalim, chlorotoluron, chlorsulfuron, chlorthal, chlorthal-dimethyl, chlorthal-monomethyl, cinidon, cinidon-ethyl, cinmethylin, exo-(+)-cinmethylin, i.e. (1R,2S,4S)-4-isopropyl-1-methyl-2-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptane, exo-(-)-cinmethyline, i.e. (1R,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-olamine, Clopyralid-potassium, Clopyralid-tripomin, Cloransulam, Cloransulam-methyl, Cumyluron, Cyanamide, Cyanazine, Cycloate, Cyclopyranil, Cyclopyrimorate, Cyclosulfamuron, Cycloxydim, Cyhalofop, Cyhalofop-butyl, cyprazine, 2,4-D (as well as ammonium, butotyl, butyl, choline, diethylammonium, dimethylammonium, diolamine, doboxyl, dodecylammonium, etexyl, ethyl, 2-ethylhexyl, heptylammonium, isobutyl, isooctyl, isopropyl, isopropylammonium, lithium, meptyl, Methyl, potassium, tetradecylammonium, triethylammonium, triisopropanolammonium, tripromine and trolamine salts thereof), 2,4-DB, 2,4-DB-butyl, 2,4-DB-dimethylammonium, 2,4-DB-isooctyl, 2,4-DB-potassium and 2,4-DB-sodium, Daimuron (Dymron), Dalapon, Dalapon calcium, Dalapon magnesium, Dalapon sodium, Dazomet, Dazomet sodium, n-decanol, 7-deoxy-D-sedoheptulose, Desmedipham, Detosyl pyrazolate (DTP), Dicamba and its salts (e.g., Dicamba biproamine, Dicamba N,N-bis(3-aminopropyl)methylamine, Dicamba butotyl, Dicamba choline, Dicamba diglycolamine, Dicamba dimethylammonium, Dicamba diethanolamine ammonium, Dicamba diethylammonium, Dicamba isopropylammonium, dicamba-methyl, dicamba-monoethanolamine, dicamba-olamine, dicamba potassium, dicamba sodium, dicamba-triethanolamine), dichlobenil, 2-(2,4-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, 2-(2,5-Dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, dichlorprop, dichlorprop-butotyl, dichlorprop-dimethylammonium, dichlorprop-etexyl, dichlorprop-ethylammonium, dichlorprop-isoctyl, dichlorprop-methyl, dichlorprop-potassium, dichlorprop-sodium, dichlorprop-P, Dichlorprop-P-dimethylammonium, dichlorprop-P-etexyl, dichlorprop-P potassium, dichlorprop sodium, diclofop, Diclofop-methyl, Diclofop-P, Diclofop-P-methyl, Diclosulam, Difenzoquat, Difenzoquat-methylsulfate, Diflufenican, Diflufenzopyr, Diflufenzopyr sodium, Dimefuron, Dimepiperate, Dimesulfazet, Dimethachlor, Dimethametryn, Dimethenamid, Dimethenamid-P, Dimetrasulfuron, Dinitramine, Dinoterb, Dinoterb Acetate, Diphenamide, Diquat, Diquat Dibromide, Diquat Dichloride, Dithiopyr, Diuron, DNOC, DNOC Ammonium, DNOC Potassium, DNOC Sodium, Endothal, Endothal Diammonium, Endothal Dipotassium, Endothal Disodium, Epyrifenacil (S-3100), EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanide, F-5231, i.e. N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5- oxo-1H-tetrazol-1-yl]-phenyl]-ethanesulfonamide, F-7967, i.e. 3-[7-Chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione, Fenoxaprop, Fenoxaprop-P, Fenoxaprop-Ethyl, Fenoxaprop-P-Ethyl, Fenoxasulfone, Fenpyrazone, Fenquinotrione, Fentrazamide, 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, flucarbazone, flucarbazone sodium, flucetosulfuron, Fluchloraline, Flufenacet, Flufenpyr, Flufenpyr-Ethyl, Flumetsulam, Flumiclorac, Flumiclorac-Pentyl, Flumioxazine, Fluometuron, Flurenol, Flurenol-Butyl, -Dimethylammonium and -Methyl, Fluoroglycofen, Fluoroglycofen-Ethyl, Flupropanate, Flupropanate-Sodium, Flupyrsulfuron, Flupyrsulfuron-Methyl, Flupyrsulfuron-Methyl-Sodium, Fluridone, Flurochloridone, Fluroxypyr, Fluroxypyr-Butometyl, Fluroxypyr-Meptyl, Flurtamone, Fluthiacet, Fluthiacet-Methyl, Fomesafen, Fomesafen-Sodium, Foramsulfuron, Foramsulfuron-Sodium, Fosamine, Fosamine-Ammonium, Glufosinate, Glufosinate ammonium, glufosinate sodium, L-glufosinate ammonium, L-glufosinate sodium, glufosinate P-sodium, glufosinate P-ammonium, glyphosate, glyphosate ammonium, glyphosate isopropyl ammonium, glyphosate diammonium, glyphosate dimethyl ammonium, Glyphosate potassium, glyphosate sodium, glyphosate sesquinodium and glyphosate trimesium, H-9201, i.e. O-(2,4-dimethyl-6-nitrophenyl)-O-ethyl-isopropylphosphoramidothioate, Halauxifen, Halauxifen-methyl, Halosafen, Halosulfuron, Halosulfuron-Methyl, Haloxyfop, Haloxyfop-P, Haloxyfop-Ethoxyethyl, Haloxyfop-P-Ethoxyethyl, Haloxyfop-Methyl, Haloxyfop-P-Methyl, Haloxifop Sodium, Hexazinone, HNPC-A8169, i.e. Prop-2-yn-1-yl (2S)-2-{3-[(5-tert-butylpyridin-2-yl)oxy]phenoxy}propanoate, HW-02, i.e. 1-(Dimethoxyphosphoryl)-ethyl-(2,4-dichlorophenoxy)acetate, Hydantocidin, Imazamethabenz, Imazamethabenz-Methyl, Imazamox, Imazamox ammonium, Imazapic, Imazapic ammonium, Imazapyr, Imazapyr isopropyl ammonium, Imazaquin, Imazaquin ammonium, Imazaquin methyl, Imazethapyr, Imazethapyr ammonium, Imazosulfuron, Indanofan, Indaziflam, Iodosulfuron, Iodosulfuron-Methyl, Iodosulfuron Methyl Sodium, Ioxynil, Ioxynil Lithium, -Octanoate, -Potassium and Sodium, Ipfencarbazone, Isoproturon, Isouron, Isoxaben, Isoxaflutole, Carbutilate, KUH-043, i.e. 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-trolamin, Mecoprop-P, Mecoprop-P-Butotyl, -Dimethylammonium, -2-Ethylhexyl and -potassium, mefenacet, mefluidide, mefluidide-diolamine, mefluidide-potassium, mesosulfuron, mesosulfuron-methyl, mesosulfuron-sodium, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, Methiopyrsulfuron, Methiozoline, Methyl isothiocyanate, Metobromuron, Metolachlor, S-Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron, Metsulfuron-Methyl, Molinat, Monolinuron, Monosulfuron, Monosulfuron-Methyl, MT-5950, i.e. N-[3-Chloro-4-(1-methylethyl)-phenyl]-2-methylpentanamide, NGGC-011, Napropamide, NC-310, i.e.4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole, NC-656, i.e. 3-[(Isopropylsulfonyl)methyl]-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)[1,2,4]triazolo-[4,3-a]pyridine-8-carboxamide, Neburone, Nicosulfuron, Nonanoic acid (pelargonic acid), Norflurazone, Oleic acid (fatty acids), Orbencarb, Orthosulfamuron, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefone, Oxyfluorfen, Paraquat, Paraquat dichloride, Paraquat dimethyl sulfate, Pebulat, Pendimethalin, Penoxsulam, Pentachlorophenol, Pentoxazone, Pethoxamide, Petroleum oil, phenmedipham, phenmedipham ethyl, picloram, picloram dimethylammonium, picloram etexyl, picloram isoctyl, picloram methyl, picloram olamine, picloram potassium, picloram triethylammonium, picloram tripromine, picloram trolamine, picolinafen, pinoxaden, piperophos, Pretilachlor, Primisulfuron, Primisulfuron-Methyl, Prodiamine, Profoxydim, Prometon, Prometryn, Propachlor, Propanil, Propaquizafop, Propazine, Propham, Propisochlor, Propoxycarbazone, Propoxycarbazone-Sodium, Propyrisulfuron, Propyzamide, Prosulfocarb, Prosulfuron, Pyraclonil, Pyraflufen, Pyraflufen-Ethyl, Pyrasulfotol, Pyrazolynate (Pyrazolate), Pyrazosulfuron, Pyrazosulfuron-Ethyl, Pyrazoxyfen, Pyribambenz, Pyribambenz-Isopropyl, Pyribambenz-Propyl, Pyribenzoxime, Pyributicarb, Pyridafol, Pyridate, Pyriftalid, Pyriminobac, Pyriminobac-Methyl, Pyrimisulfan, Pyrithiobac, Pyrithiobac-Sodium, Pyroxasulfone, Pyroxsulam, Quinclorac, Quinclorac-Dimethylammonium, Quinclorac-Methyl, Quinmerac, Quinoclamine, Quizalofop, Quizalofop-Ethyl, Quizalofop-P, Quizalofop-P-Ethyl, Quizalofop-P-Tefuryl, QYM201, i.e.1-{2-Chloro-3-[(3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazol-4-yl)carbonyl]-6- (trifluoromethyl)phe-nyl}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-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, SYP-300, i.e. 1-[7-Fluoro-3-oxo-4-(prop-2-yn-1-yl)-3,4-dihydro-2H-1,4-benzoxazin-6-yl]-3-propyl-2-thioxoimidazolidine-4,5-dione, 2,3,6-TBA, TCA (trichloroacetic acid) and its salts, e.g. TCA ammonium, TCA-Calcium, TCA-Ethyl, TCA-Magnesium, TCA-Sodium, Tebuthiuron, Tefuryltrione, Tembotrion, Tepraloxydim, Terbacil, Terbucarb, Terbumetone, Terbuthylazine, Terbutryn, Tetflupyrolimet, Thaxtomin, Thenylchlor, Thiazopyr, Thiencarbazone, Thiencarbazone-Methyl, Thifensulfuron, Thifensulfuron-Methyl, Thiobencarb, Tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamon, tri-allate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-choline, triclopyr-ethyl, triclopyr-triethylammonium, trietazine, trifloxysulfuron, Trifloxysulfuron sodium, trifludimoxazine, trifluralin, triflusulfuron, triflusulfuron-methyl, tritosulfuron, urea sulfate, vernolate, (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, ethyl [(3-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo- 4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenoxy}pyridin-2-yl)oxy]acetate, 3-chloro-2-[3-(difluoromethyl)isoxazolyl-5-yl]phenyl-5-chloropyrimidin-2-yl ether, 2-(3,4-dimethoxyphenyl)-4-[(2- hydroxy-6-oxocyclohex-1-en-1-yl)carbonyl]-6-methylpyridazine-3(2H)-one, 2-({2-[(2-methoxyethoxy)methyl]-6-methylpyridin-3-yl}carbonyl)cyclohexane-1,3-dione, (5-hydroxy-1-methyl-1H- 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)carbonyl]-1H-pyrazol-5-yl propan-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-pyrazol-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)pyridin-2-carboxylate, ethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridin-2-carboxylate, Methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1-isobutyryl-1H-indol-6-yl)pyridine-2-carboxylate, Methyl 6-(1-acetyl-7-fluoro-1H-indol-6-yl)-4-amino-3-chloro-5-fluoropyridine-2-carboxylate, Methyl 4-amino-3-chloro-6-[1-(2,2-dimethylpropanoyl)-7-fluoro-1H-indol-6-yl]-5-fluoropyridine-2-carboxylate, Methyl 4-amino-3-chloro-5-fluoro-6-[7-fluoro-1-(methoxyacetyl)-1H-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-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, butyl-4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)pyridine-2- yl]imidazolidin-2-one, 3-(5-tert-butyl-1,2-oxazol-3-yl)-4-hydroxy-1-methylimidazolidin-2-one, 3-[5-chloro- 4-(trifluoromethyl)pyridin-2-yl]-4-hydroxy-1-methylimidazolidin-2-one, 4-hydroxy-1-methoxy-5-methyl- 3-[4-(trifluoromethyl)pyridin-2-yl]imidazolidin-2-one, 6-[(2-hydroxy-6-oxocyclohex-1-en-1-yl)carbonyl]-1,5-dimethyl-3-(2-methylphenyl)quinazolin-2,4(1H,3H)-dione, 3-(2,6-Dimethylphenyl)-6-[(2-hydroxy-6- oxocyclohex-1-en-1-yl)carbonyl]-1-methylquinazolin-2,4(1H,3H)-dione, 2-[2-chloro-4-(methylsulfonyl)-3-(morpholin-4-ylmethyl)benzoyl]-3-hydroxycyclohex-2-en-1-one, 1-(2-carboxyethyl)-4-(pyrimidin-2-yl)pyridazin-1-ium salt (with suitable anions such as chloride, acetate or trifluoroacetate), 1-(2-carboxyethyl)-4-(pyridazin-3-yl)pyridazin-1-ium salt (with suitable anions such as chloride, acetate or trifluoroacetate), 4-(pyrimidin-2-yl)-1-(2-sulfoethyl)pyridazin-1-ium salt (with suitable anions such as chloride, acetate or trifluoroacetate), 4-(Pyridazin-3-yl)-1-(2-sulfoethyl)pyridazin-1-ium salt (with suitable anions such as chloride, acetate or trifluoroacetate), 1-(2-carboxyethyl)-4-(1,3-thiazol-2-yl)pyridazin-1-ium salt (with suitable anions such as chloride, acetate or trifluoroacetate), 1-(2-carboxyethyl)-4-(1,3,4-thiadiazol-2-yl)pyridazin-1-ium salt (with suitable anions such as chloride, acetate or trifluoroacetate), Methyl (2R)-2-{[(E)-({2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenyl}methylidene)amino]oxy}propanoate, Methyl (2S)- 2-{[(E)-({2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenyl}methylidene)amino]oxy}propanoate, methyl (2R/S)-2-{[(E)-({2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenyl}methylidene)amino]oxy}propanoate, (E)- 2-(Trifluoromethyl)benzaldehyde-O-{2,6-bis[(4,6-dimethoxypyrimidin-2-yl)oxy]benzoyl}oxime, 2-fluoro-N- (5-methyl-1,3,4-oxadiazol-2-yl)-3-[(R)-propylsulfinyl]-4-(trifluoromethyl)benzamide, (2R)-2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanecarboxylic acid, 2-ethoxy-2-oxoethyl-1-{2-chloro-4-fluoro-5-[3- methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenoxy}cyclopropanecarboxylate, 2-methoxy-2-oxoethyl-1-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidine- 1(2H)-yl]phenoxy}cyclopropane carboxylate, {[(1-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenoxy}cyclopropyl)carbonyl]oxy}acetic acid, 2-(2-bromo-4-chlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, methyl 3-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenyl}-3a,4,5,6-tetrahydro-6aH-cyclopenta[d][1,2]oxazole-6a-carboxylate, ethyl 3-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4- (trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenyl}-3a,4,5,6-tetrahydro-6aH-cyclopenta[d][1,2]oxazole-6a-carboxylate. Abscisic acid and related analogues [e.g. (2Z,4E)-5-[6-Ethynyl-1-hydroxy-2,6-dimethyl-4-oxocyclohex-2-en-1-yl]-3-methylpenta-2,4-dienoic acid, methyl-(2Z,4E)-5-[6-ethynyl-1-hydroxy-2,6- dimethyl-4-oxocyclohex-2-en-1-yl]-3-methylpenta-2,4-dienoate, (2Z,4E)-3-ethyl-5-(1-hydroxy-2,6,6-trimethyl-4-oxocyclohex-2-en-1-yl)penta-2,4-dienoic acid, (2E,4E)-5-(1-hydroxy-2,6,6-trimethyl-4- oxocyclohex-2-en-1-yl)-3-(trifluoromethyl)penta-2,4-dienoic acid, methyl (2E,4E)-5-(1-hydroxy-2,6,6-trimethyl-4-oxocyclohex-2-en-1-yl)-3-(trifluoromethyl)penta-2,4-dienoate, (2Z,4E)-5-(2-hydroxy-1,3- dimethyl-5-oxobicyclo[4.1.0]hept-3-en-2-yl)-3-methylpenta-2,4-dienoic acid], acibenzolar, acibenzolar-S-methyl, S-adenosylhomocysteine, allantoin, 2-aminoethoxyvinylglycine (AVG), aminooxyacetic acid and related esters [e.g. (Isopropylidene)-aminooxyacetic acid 2-(methoxy)-2-oxoethyl ester, (Isopropylidene)-aminooxyacetic acid 2-(hexyloxy)-2-oxoethyl ester, (Cyclohexylidene)-aminooxyacetic acid 2-(isopropyloxy)-2-oxoethyl ester], 1-Aminocycloprop-1-ylcarboxylic acid N-Methyl-1-aminocyclopropyl-1-carboxylic acid, 1-Aminocyclopropyl-1-carboxamide, substituted 1-Aminocyclopropyl-1-carboxylic acid derivatives as described in DE3335514, EP30287, DE2906507 or US5123951, 1-Aminocyclopropyl-1-hydroxamic acid, 5-Aminolevulinic acid, Ancymidol, 6-Benzylaminopurine, Bikinin, Brassinolide, Brassinolide-ethyl, L-Canalin, Catechin and catechins (e.g. (2S,3R)-2-(3,4-dihydroxyphenyl)-3,4-dihydro-2H-chromene-3,5,7-triol), chitooligosaccharides (CO; COs differ from LCOs in that they lack the fatty acid side chain characteristic of LCOs. COs, sometimes referred to as N-acetylchitooligosaccharides, are also composed of GlcNAc units, but have side chains that distinguish them from chitin molecules [(C8H13NO5)n, CAS No.1398-61-4] and chitosan molecules [(C5H11NO4)n, CAS No. 9012-76-4]), chitin-like compounds, chlormequat chloride, cloprop, cyclanilide, 3-(cycloprop-1-enyl)propionic acid, 1-[2-(4-cyano-3,5-dicyclopropylphenyl)acetamido]cyclohexanecarboxylic acid, 1-[2-(4-cyano-3-cyclopropylphenyl)acetamido]cyclohexanecarboxylic acid, 1-cyclopropenylmethanol, daminozide, dazomet, dazomet sodium, n-decanol, dikegulac, dikegulac sodium, endothal, endothal-di-potassium, -di-sodium, and mono(N,N-dimethylalkylammonium), ethephon, 1-ethylcyclopropene, flumetralin, flurenol, flurenol-butyl, flurenol-methyl, flurprimidol, forchlorfenuron, gibberellic acid, Inabenfid, indole-3-acetic acid (IAA), 4-indol-3-ylbutyric acid, isoprothiolane, probenazole, jasmonic acid, jasmonic acid esters or other derivatives (e.g., jasmonic acid methyl ester, jasmonic acid ethyl ester), lipochitooligosaccharides (LCO, sometimes also referred to as symbiotic nodulation signals (Nod or Nod factors) or Myc factors, consist of an oligosaccharide backbone of β-l,4-linked N-acetyl-D-glucosamine residues (“GlcNAc”) with an N-linked fatty acid side chain fused to the non-reducing end. As can be seen from the literature, LCOs differ in the number of GlcNAc units in the backbone structure, in the length and degree of saturation of the fatty acid chain, and in the substitution of the reducing and non-reducing sugar units). Linoleic acid or its derivatives, linolenic acid or its derivatives, maleic hydrazide, mepiquat chloride, mepiquat pentaborate, 1-methylcyclopropene, 3-methylcyclopropene, methoxyvinylglycine (MVG), 3'-methylabscisic acid, 1-(4-methylphenyl)-N-(2-oxo-1-propyl-1,2,3,4-tetrahydroquinolin-6-yl)methanesulfonamide and related substituted (tetrahydroquinolin-6-yl)methanesulfonamides, (3E,3aR,8bS)-3-({[(2R)-4-Methyl-5-oxo-2,5-dihydrofuran-2-yl]oxy}methylene)-3,3a,4,8b-tetrahydro-2H-indeno[1,2-b]furan-2-one and related lactones as described in EP2248421, 2-(1-Naphthyl)acetamide, 1-Naphthylacetic acid, 2-Naphthyloxyacetic acid, Nitrophenolate mixture, 4-Oxo-4[(2-phenylethyl)amino]butyric acid, Paclobutrazol, 4-Phenylbutyric acid and its salts (e.g. sodium 4-phenylbutanoate, potassium 4-phenylbutanoate), Phenylalanine, N-Phenylphthalamic acid, Prohexadione, Prohexadione calcium, , 1-n-Propylcyclopropene, putrescine, prohydrojasmone, rhizobitoxin, salicylic acid and methyl salicylate, sarcosine, sodium cycloprop-1-en-1-yl acetate, sodium cycloprop-2-en-1-yl acetate, sodium 3-(cycloprop-2-en-1-yl)propanoate, sodium 3-(cycloprop-1-en-1-yl)propanoate, sidefungin, spermidine, spermine, strigolactone, tecnazene, thidiazuron, triacontanol, trinexapac, trinexapac-ethyl, tryptophan, tsitodef, uniconazole, uniconazole-P, 2-fluoro-N-(3-methoxyphenyl)-9H-purin-6-amine. Although the compounds of formula (I) according to the invention generally exhibit good selectivity towards crop plants, it may be useful to combine them with known safeners. Safeners which can be used in combination with the compounds of formula (I) according to the invention and optionally in combination with other active ingredients such as insecticides, acaricides, herbicides, fungicides as listed above are preferably selected from the group consisting of: S1) Compounds of formula (S1),
Figure imgf000022_0001
where the symbols and indices have the following meanings: nAis a natural number from 0 to 5, preferably 0 to 3; RA 1is halogen, (C1-C4)Alkyl, (C1-C4)alkoxy, nitro or (C1-C4)Haloalkyl;
Figure imgf000022_0002
WAis an unsubstituted or substituted divalent heterocyclic radical from the group of the saturated or aromatic five-membered ring heterocycles with 1 to 3 hetero ring atoms from the group N and O, wherein at least one N atom and at most one O atom is contained in the ring, preferably a radical from the group (WA 1) to (WA 5), mAis 0 or 1; RA 2is O RA 3, SRA 3or NRA 3RA 4or a saturated or unsaturated 3- to 7-membered heterocycle having at least one N atom and up to 3 heteroatoms, preferably from the group O and S, which is linked via the N atom to the carbonyl group in (S1) and is unsubstituted or substituted by radicals from the group (C1-C4)Alkyl, (C1-C4)alkoxy or optionally substituted phenyl, preferably a radical of the formula ORA 3, NHRA 4or N(CH3)2, in particular of the formula ORA 3; RA 3is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably with a total of 1 to 18 C atoms; RA 4is hydrogen, (C1-C6)Alkyl, (C1-C6)alkoxy or substituted or unsubstituted phenyl; RA 5is H, (C1-C8)Alkyl, (C1-C8)Haloalkyl, (C1-C4)Alkoxy(C1-C8)Alkyl, cyano or COORA 9, where RA 9Hydrogen, (C1-C8)Alkyl, (C1-C8)Haloalkyl, (C1-C4)Alkoxy-(C1-C4)alkyl, (C1-C6)Hydroxyalkyl, (C3- C12)cycloalkyl or tri-(C1-C4)-alkyl-silyl; RA 6, RA 7, RA 8are the same or different hydrogen, (C1-C8)Alkyl, (C1-C8)Haloalkyl, (C3- C12)Cycloalkyl or substituted or unsubstituted phenyl; RA 10is H, (C3-C12)Cycloalkyl, substituted or unsubstituted phenyl or substituted or unsubstituted heteroaryl; preferably: a) compounds of the dichlorophenylpyrazolin-3-carboxylic acid type (S1a), preferably compounds such as 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazole-3-carboxylic acid, 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazole-3-carboxylic acid ethyl ester (S1-1) ("Mefenpyr-diethyl"), and related compounds as described in WO-A-91/07874; b) derivatives of dichlorophenylpyrazolecarboxylic acid (S1b), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-methyl-pyrazole-3-carboxylate (S1-2), ethyl 1-(2,4-dichlorophenyl)-5-isopropyl-pyrazole-3-carboxylate (S1-3), ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethyl-ethyl)pyrazole-3-carboxylate (S1-4) and related compounds as described in EP-A-333131 and EP-A-269806; c) derivatives of 1,5-diphenylpyrazole-3-carboxylic acid (S1c), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-5), methyl 1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-6) and related compounds as described, for example, in EP-A-268554; d) Compounds of the triazolecarboxylic acid type (S1d), preferably compounds such as fenchlorazole (ethyl ester), i.e. 1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylic acid ethyl ester (S1-7), and related compounds as described in EP-A-174562 and EP-A-346620; e) compounds of the type 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (S1e), preferably compounds such as ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (S1-8) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (S1-9) and related compounds as described in WO-A-91/08202, or ethyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (S1-10) or ethyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (S1-11) ("Isoxadifen-ethyl") or -n-propyl ester (S1-12) or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (S1-13) as described in patent application WO-A-95/07897. f) Compounds of the triazolyloxyacetic acid derivative type (S1f), preferably compounds such as methyl {[1,5-bis(4-chloro-2-fluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate (S1-14) or {[1,5-bis(4-chloro-2-fluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid (S1-15) or methyl {[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate (S1-16) or {[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid (S1-17) or methyl {[1-(4-chloro-2-fluorophenyl)-5- (2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate (S1-18) or {[1-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid (S1-19), as described in patent application WO2021105101 S2) Quinoline derivatives of the formula (S2),
Figure imgf000024_0001
where the symbols and indices have the following meanings: RB 1is halogen, (C1-C4)Alkyl, (C1-C4)alkoxy, nitro or (C1-C4)Haloalkyl; nBis a natural number from 0 to 5, preferably 0 to 3; RB 2is ORB 3, SRB 3or NRB 3RB 4or a saturated or unsaturated 3- to 7-membered heterocycle having at least one N atom and up to 3 heteroatoms, preferably from the group O and S, which is bonded to the carbonyl group via the N atom in (S2) and is unsubstituted or substituted by residues from the group (C1-C4)Alkyl, (C1-C4)alkoxy or optionally substituted phenyl, preferably a radical of the formula ORB 3, NHRB 4or N(CH3)2, especially the formula ORB 3; RB 3is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably with a total of 1 to 18 C atoms; RB 4is hydrogen, (C1-C6)Alkyl, (C1-C6)alkoxy or substituted or unsubstituted phenyl; TB is a (C1or C2)-alkanediyl chain which is unsubstituted or substituted with one or two (C1-C4)alkyl radicals or with [(C1-C3)-alkoxy]-carbonyl; preferably: a) compounds of the 8-quinolinoxyacetic acid type (S2a), preferably (5-chloro-8-quinolinoxy)acetic acid (1-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-chloro-8-quinolinoxy)acetic acid 1-allyloxy-prop-2-yl ester (S2-4), (5-chloro-8-quinolinoxy)acetate ethyl ester (S2-5), (5-chloro-8-quinolinoxy)acetate methyl ester (S2-6), (5-chloro-8-quinolinoxy)acetate allyl ester (S2-7), (5-chloro-8- quinolinoxy)acetic acid 2-(2-propylidene-iminoxy)-1-ethyl ester (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-191736 or EP-A-0492366, and (5-chloro-8-quinolinoxy)acetic acid (S2-10), their 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 type of (5-chloro-8-quinolinoxy)malonic acid (S2b), preferably compounds such as (5-chloro-8-quinolinoxy)malonic acid diethyl ester, (5-chloro-8-quinolinoxy)malonic acid diallyl ester, (5-chloro-8-quinolinoxy)malonic acid methyl ethyl ester and related compounds as described in EP-A-0 582198. S3) Compounds of formula (S3)
Figure imgf000025_0001
where the symbols and indices have the following meanings: RC 1is (C1-C4)Alkyl, (C1-C4)Haloalkyl, ( C2-C4)Alkenyl, (C2-C4)Haloalkenyl, (C3-C7)Cycloalkyl, preferably dichloromethyl; RC 2, RC 3are the same or different hydrogen, (C1-C4)Alkyl, (C2-C4)Alkenyl, (C2-C4)Alkynyl, (C1-C4)Haloalkyl, (C2-C4)Haloalkenyl, (C1-C4)Alkylcarbamoyl-(C1-C4)alkyl, (C2- C4)Alkenylcarbamoyl-(C1-C4)alkyl, (C1-C4)Alkoxy-(C1-C4)alkyl, dioxolanyl-(C1-C4)alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or RC 2and RC 3together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine, piperidine, morpholine, hexahydropyrimidine or benzoxazine ring; preferably: active ingredients of the dichloroacetamide type, which are frequently used as pre-emergence safeners (soil-active safeners), 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), "Benoxacor" (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4), "PPG-1292" (N-allyl-N-[(1,3-dioxolan-2-yl)-methyl]-dichloroacetamide) from PPG Industries (S3-5), "DKA-24" (N-allyl-N-[(allylaminocarbonyl)methyl]-dichloroacetamide) from Sagro-Chem (S3-6), "AD-67" or "MON 4660" (3-dichloroacetyl-1-oxa-3-aza-spiro[4,5]decane) from Nitrokemia or Monsanto (S3-7), "TI-35" (1-dichloroacetyl-azepane) from TRI-Chemical RT (S3-8), "Diclonon" (dicyclonone) or "BAS145138" or "LAB145138" (S3-9) ((RS)-1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[1,2-a]pyrimidin-6-one) from BASF, "Furilazol" or "MON 13900" ((RS)- 3-Dichloroacetyl-5-(2-furyl)-2,2-dimethyloxazolidine) (S3-10); and its (R)-isomer (S3-11). S4) N-acylsulfonamides of the formula (S4) and their salts,
Figure imgf000026_0001
where the symbols and indices have the following meanings: XD is CH or N; RD 1is CO-NRD 5RD 6or NHCO-RD 7; RD 2is halogen, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy, nitro, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)- alkylsulfonyl, (C1-C4)-alkoxycarbonyl or (C1-C4)-alkylcarbonyl; RD 3is hydrogen, (C1-C4)Alkyl, (C2-C4)alkenyl or (C2-C4)-alkynyl; RD 4is halogen, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy, (C3-C6)-cycloalkyl, phenyl, (C1-C4)-alkoxy, cyano, (C1-C4)-alkylthio, (C1-C4)-alkylsulfinyl, (C1-C4)-alkylsulfonyl, (C1- C4)alkoxycarbonyl or (C1-C4)Alkylcarbonyl; RD 5is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C5-C6)- Cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl containing vDHeteroatoms from the group nitrogen, oxygen and sulfur, with the last seven residues being replaced by vDSubstituents from the group halogen, (C1-C6)Alkoxy, (C1-C6)Haloalkoxy, (C1-C2)Alkylsulfinyl, (C1-C2)Alkylsulfonyl, (C3- C6)Cycloalkyl, (C1-C4)Alkoxycarbonyl, (C1-C4)alkylcarbonyl and phenyl and in the case of cyclic residues also (C1-C4) alkyl and (C1-C4)haloalkyl substituted; RD 6is hydrogen, (C1-C6)Alkyl, (C2-C6)alkenyl or (C2-C6)alkynyl, where the last three radicals are replaced by vDResidues from the group halogen, hydroxy, (C1-C4)Alkyl, (C1-C4)alkoxy and (C1- C4)alkylthio, or RD 5and RD 6together with the nitrogen atom carrying them form a pyrrolidinyl or piperidinyl radical; RD 7is hydrogen, (C1-C4)Alkylamino, Di-(C1-C4)alkylamino, (C1-C6)Alkyl, (C3-C6)Cycloalkyl, where the last two radicals are replaced by vDSubstituents from the group halogen, (C1-C4)Alkoxy, (C1- C6)haloalkoxy and (C1-C4)alkylthio and in the case of cyclic residues also (C1-C4)alkyl and (C1-C4)haloalkyl substituted; nDis 0, 1 or 2; mDis 1 or 2; vDis 0, 1, 2 or 3; of these, preference is given to compounds of the N-acylsulfonamide type, e.g. of the following formula (S4a), which are known, for example, from WO-A-97/45016
Figure imgf000027_0001
where RD 7(C1-C6)Alkyl, (C3-C6)Cycloalkyl, where the last two radicals are replaced by vDSubstituents from the group halogen, (C1-C4)Alkoxy, (C1-C6)haloalkoxy and (C1-C4)alkylthio and in the case of cyclic residues also (C1-C4)alkyl and (C1-C4)haloalkyl substituted; RD 4Halogen, (C1-C4)Alkyl, (C1-C4)Alkoxy, CF3;mD1 or 2; vDis 0, 1, 2 or 3 means; and acylsulfamoylbenzoic acid amides, e.g. of the following formula (S4b), which are known, for example, from WO-A-99/16744,
Figure imgf000028_0001
e.g. those where RD 5= Cyclopropyl and (RD 4) = 2-OMe is ("Cyprosulfamide", S4-1), RD 5= Cyclopropyl and (RD 4) = 5-Cl-2-OMe is (S4-2), RD 5= Ethyl and (RD 4) = 2-OMe is (S4-3), RD 5= Isopropyl and (RD 4) = 5-Cl-2-OMe is (S4-4) and RD 5= Isopropyl and (RD 4) = 2-OMe (S4-5). as well as compounds of the N-acylsulfamoylphenylurea type of the formula (S4c), which are known, for example, from EP-A-365484,
Figure imgf000028_0002
where RD 8and RD 9independently of each other hydrogen, (C1-C8)Alkyl, (C3-C8)Cycloalkyl, (C3-C6)Alkenyl, (C3- C6)Alkynyl, RD 4Halogen, (C1-C4)Alkyl, (C1-C4)Alkoxy, CF3mD means 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. S5) Active ingredients from the class of hydroxyaromatics and aromatic-aliphatic carboxylic acid derivatives (S5), e.g., ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoate- acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicyclic acid, 2-hydroxycinnamic 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 1,2-dihydroquinoxalin-2-ones (S6), e.g., 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-thione, 1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one hydrochloride, 1-(2-methylsulfonylaminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, as described in WO-A-2005/112630. S7) Compounds of formula (S7), as described in WO-A-1998/38856
Figure imgf000029_0002
where the symbols and indices have the following meanings: RE 1, RE 2are independently halogen, (C1-C4)Alkyl, (C1-C4)Alkoxy, (C1-C4)Haloalkyl, (C1- C4)Alkylamino, Di-(C1-C4)Alkylamino, Nitro; AEis COORE 3or COSRE 4RE 3, RE 4are independently hydrogen, (C1-C4)Alkyl, (C2-C6)Alkenyl, (C2-C4)Alkynyl, cyanoalkyl, (C1-C4)Haloalkyl, phenyl, nitrophenyl, benzyl, halobenzyl, pyridinylalkyl and alkylammonium, nE 1is 0 or 1 nE 2, nE 3are independently 0, 1, or 2, preferably diphenylmethoxyacetic acid, ethyl diphenylmethoxyacetate, or methyl diphenylmethoxyacetate (CAS Reg. No. 41858-19-9) (S7-1). S8) Compounds of formula (S8), as described in WO-A-98/27049
Figure imgf000029_0001
Where XFCH or N, nFin case XF=N is an integer from 0 to 4 and in case XF=CH is an integer from 0 to 5 , RF 1Halogen, (C1-C4)Alkyl, (C1-C4)Haloalkyl, (C1-C4)Alkoxy, (C1-C4)Haloalkoxy, Nitro, (C1- C4)Alkylthio, (C1-C4)-alkylsulfonyl, (C1-C4)Alkoxycarbonyl, optionally substituted. Phenyl, optionally substituted phenoxy, RF 2Hydrogen or (C1-C4)Alkyl RF 3Hydrogen, (C1-C8)Alkyl, (C2-C4)Alkenyl, (C2-C4)alkynyl, or aryl, where each of the abovementioned C-containing radicals is unsubstituted or substituted by one or more, preferably up to three identical or different radicals from the group consisting of halogen and alkoxy; or salts thereof, preferably compounds wherein XFCH, nFan integer from 0 to 2 , RF 1Halogen, (C1-C4)Alkyl, (C1-C4)Haloalkyl, (C1-C4)Alkoxy, (C1-C4)Haloalkoxy, RF 2Hydrogen or (C1-C4)Alkyl, RF 3Hydrogen, (C1-C8)Alkyl, (C2-C4)Alkenyl, (C2-C4)Alkynyl, or aryl, where each of the aforementioned C-containing radicals is unsubstituted or substituted by one or more, preferably up to three identical or different radicals from the group consisting of halogen and alkoxy, or salts thereof. S9) Active ingredients from the class of 3-(5-tetrazolylcarbonyl)-2-quinolones (S9), e.g. 1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No. 219479-18-2), 1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No. 95855-00-8), as described in WO-A-1999/000020. S10) Compounds of the formulas (S10a) or (S10b) as described in WO-A-2007/023719 and WO-A-2007/023764
Figure imgf000031_0001
where RG 1Halogen, (C1-C4)Alkyl, Methoxy, Nitro, Cyano, CF3, OCF3YG, ZGindependently of each other O or S, nGan integer from 0 to 4, RG 2(C1-C16)Alkyl, (C2-C6)Alkenyl, (C3-C6)cycloalkyl, aryl; Benzyl, halobenzyl, RG 3Hydrogen or (C1-C6)Alkyl. S11) Active ingredients of the oxyimino compound type (S11), which are known as seed dressings, such as B. "Oxabetrinil" ((Z)-1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile) (S11-1), which is known as a seed dressing safener for millet against metolachlor damage, "Fluxofenim" (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethanone-O-(1,3-dioxolan-2-ylmethyl)-oxime) (S11-2), which is known as a seed dressing safener for millet against metolachlor damage, and "Cyometrinil" or "CGA-43089" ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3), which is known as a seed dressing safener for millet against metolachlor damage. S12) Active ingredients from the class of isothiochromanones (S12), such as methyl [(3-oxo-1H-2-benzothiopyran-4(3H)-ylidene)methoxy]acetate (CAS Reg. No. 205121-04-6) (S12-1) and related compounds from WO-A-1998/13361. S13) One or more compounds from group (S13): "Naphthalic anhydride" (1,8-naphthalenedicarboxylic anhydride) (S13-1), 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-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (S13-3), known as a seed dressing safener for millet against damage from alachlor and metolachlor, "CL 304415" (CAS Reg. No. 31541-57-8) (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4) from American Cyanamid, which is known as a corn safener against damage caused by imidazolinones, "MG 191" (CAS Reg. No. 96420-72-3) (2-Dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia, which is known as a corn safener, "MG-838" (CAS Reg. No. 133993-74-5) (2-propenyl 1-oxa-4-azaspiro[4.5]decane-4-carbodithioate) (S13-6) from Nitrokemia, "Disulfoton" (O,O-Diethyl S-2-ethylthioethyl phosphodithioate) (S13-7), "Dietholate" (O,O-Diethyl-O- phenylphosphorothioate) (S13-8), "Mephenate" (4-chlorophenyl methylcarbamate) (S13-9). S14) Active ingredients that, in addition to herbicidal activity against weeds, also have a safener effect on crops such as rice, such as: B. "Dimepiperate" or "MY-93" (S-1-methyl-1-phenylethyl-piperidine-1-carbothioate), which is known as a safener for rice against damage from the herbicide Molinate, "Daimuron" or "SK 23" (1-(1-methyl-1-phenylethyl)-3-p-tolylurea), which is known as a safener for rice against damage from the herbicide Imazosulfuron, "Cumyluron" = "JC-940" (3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)urea, see JP-A-60087254), which is known as a safener for rice against damage from some herbicides, "Methoxyphenone" or "NK 049" (3,3'-dimethyl-4-methoxybenzophenone), which is known as a safener for rice against damage from some herbicides, "CSB" (1-bromo-4-(chloromethylsulfonyl)benzene) from Kumiai (CAS Reg. No. 54091-06-4), which is known as a safener against the damage of some herbicides in rice. S15) Compounds of formula (S15) or their tautomers as described in WO-A-2008/131861 and WO-A-2008/131860
Figure imgf000032_0001
where RH 1one (C1-C6)haloalkyl radical and RH 2hydrogen or halogen and RH 3, RH 4independently of each other hydrogen, (C1-C16)Alkyl, (C2-C16)alkenyl or (C2-C16)Alkynyl, where each of the last three radicals is unsubstituted or substituted by one or more radicals from the group halogen, hydroxy, cyano, (C1-C4)Alkoxy, (C1-C4)Haloalkoxy, (C1-C4)Alkylthio, (C1-C4)Alkylamino, Di[(C1-C4)alkyl]amino, [(C1-C4)alkoxy]carbonyl, [(C1-C4)Haloalkoxy]carbonyl, (C3-C6)Cycloalkyl which is unsubstituted or substituted, phenyl which is unsubstituted or substituted, and heterocyclyl which is unsubstituted or substituted, or (C3-C6)Cycloalkyl, (C4-C6)Cycloalkenyl, (C3- C6)Cycloalkyl which is fused on one side of the ring with a 4 to 6-membered saturated or unsaturated carbocyclic ring, or (C4-C6)Cycloalkenyl which is fused on one side of the ring with a 4 to 6-membered saturated or unsaturated carbocyclic ring, each of the last-mentioned 4 radicals being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, hydroxy, cyano, (C1-C4)Alkyl, (C1-C4)Haloalkyl, (C1-C4)Alkoxy, (C1-C4)Haloalkoxy, (C1-C4)Alkylthio, (C1-C4)Alkylamino, Di[(C1-C4)alkyl]amino, [(C1-C4)alkoxy]carbonyl, [(C1-C4)Haloalkoxy]carbonyl, (C3-C6)Cycloalkyl which is unsubstituted or substituted, phenyl which is unsubstituted or substituted, and heterocyclyl which is unsubstituted or substituted,means or RH 3(C1-C4)-alkoxy, (C2-C4)Alkenyloxy, (C2-C6)alkynyloxy or (C2-C4)haloalkoxy and RH 4Hydrogen or (C1-C4)-alkyl or RH 3and RH 4together with the directly bonded N-atom, a four- to eight-membered heterocyclic ring which, in addition to the N-atom, may also contain further hetero ring atoms, preferably up to two further hetero ring atoms from the group N, O and S and which may be unsubstituted or substituted by one or more radicals from the group halogen, cyano, nitro, (C1-C4)Alkyl, (C1-C4)Haloalkyl, (C1- C4)Alkoxy, (C1-C4)haloalkoxy and (C1-C4)Alkylthio is substituted. S16) Active ingredients that are primarily used as herbicides, but also have safener effects on crops, e.g. (2,4-dichlorophenoxy)acetic acid (2,4-D), (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 (lactidichloroethyl). Particularly preferred safeners are mefenpyr-diethyl, cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl, benoxacor, dichlormid, and metcamifen. The following examples illustrate the invention. A. Chemical Examples Synthesis of methyl 2-chloro-3-formyl-4-(trifluoromethoxy)benzoate (1): Step 1: Preparation of 1-bromo-2-chloro-3-methyl-4-(trifluoromethoxy)benzene (4): 20.35 ml (145.2 mmol) of diisopropylamine were initially charged to 250 ml of tetrahydrofuran under argon, and 79.4 ml (127.1 mmol) of n-butyllithium (1.6 M solution in hexane) were added dropwise at -60°C, and the solution was stirred for 1 h. The mixture was then briefly warmed to -40°C and then, at -60°C, a solution of 25 g (90.8 mmol) of 1-bromo-2-chloro-4-(trifluoromethoxy)benzene (3) in 60 ml of tetrahydrofuran was added dropwise. The solution was stirred for 1 h. Then, 11.5 ml (181.5 mmol) of iodomethane were added dropwise and stirred for a further 1 h. The still-cold reaction solution was mixed with 800 ml of water and adjusted to pH 1 with concentrated hydrochloric acid. After extraction with ethyl acetate, the organic phase was separated, dried, and evaporated. The residue was purified by chromatography (HPLC, normal phase, heptane/ethyl acetate 100/0→80/20). This gave 25.00 g (95%) of 1-bromo-2-chloro-3-methyl-4-(trifluoromethoxy)benzene (4).1H-NMR (400 MHz, DMSO-d6): δ = 7.79 (d, 1H); 7.35 (d, 1H); 2.39 (s, 3H). Step 2: Preparation of 2-chloro-3-methyl-4-(trifluoromethoxy)benzonitrile (5): 18.91 g (65.33 mmol) of 1-bromo-2-chloro-3-methyl-4-(trifluoromethoxy)benzene (4) was dissolved in 150 mL of dimethylformamide, and 11.7 g (130.65 mmol) of copper(I) cyanide was added at room temperature. The resulting reaction mixture was heated to reflux for 12 h. It was then poured into 1 L of cold water and ethyl acetate was added. After vigorous stirring for 10 min, the mixture was filtered and the phases were separated. The organic phase was dried and evaporated. The residue was purified by chromatography (HPLC, normal phase, heptane/ethyl acetate 100/0→60/40). 11.83 g (77%) of 2-chloro-3-methyl-4-(trifluoromethoxy)benzonitrile (5) were obtained.1H-NMR (400 MHz, DMSO-d6): δ = 8.01 (d, 1H); 7.60 (br d, 1H); 2.37 (s, 3H). Step 3: Preparation of 2-chloro-3-methyl-4-(trifluoromethoxy)benzoic acid (6): 10.92 g (46.35 mmol) of 2-chloro-3-methyl-4-(trifluoromethoxy)benzonitrile (5) were dissolved in a solution of 17.73 g (443 mmol) of sodium hydroxide in 180 ml of water and heated to reflux for 6 h and then left to stand overnight at room temperature. The mixture was then washed with dichloromethane and the aqueous phase was adjusted to pH 1 with 2 M hydrochloric acid. The mixture was then extracted with ethyl acetate and the organic phase was separated, dried and evaporated. 11.07 g (94%) of 2-chloro-3-methyl-4-(trifluoromethoxy)benzoic acid (6) were obtained.1H-NMR (400 MHz, DMSO-d6): δ = 13.59 (br s, 1H); 7.72 (d, 1H); 7.45 (br d, 1H); 2.35 (s, 3H). Step 4: Preparation of methyl 2-chloro-3-methyl-4-(trifluoromethoxy)benzoate (7): 22.08 g (86.73 mmol) of 2-chloro-3-methyl-4-(trifluoromethoxy)benzoic acid (6) were initially dissolved in 400 ml of dichloromethane and 3 ml of dimethylformamide, and 11.58 ml (13.09 mmol) of oxalyl chloride were slowly added at room temperature. The mixture was then stirred for 1 h at room temperature. After 20 ml (1734.5 mmol) of methanol was added dropwise, the solution was stirred for 3 h at room temperature and then evaporated to dryness. The residue was taken up in water and extracted with dichloromethane. The organic phase was separated, dried, and evaporated. The residue was purified by chromatography (HPLC, normal phase, heptane/ethyl acetate 100/0→60/40). This yielded 21.26 g (91%) of methyl 2-chloro-3-methyl-4-(trifluoromethoxy)benzoate (7).1H-NMR (400 MHz, DMSO-d6): δ = 7.75 (d, 1H); 7.49 (br d, 1H); 3.88 (s, 3H); 2.36 (s, 3H). Step 5: Preparation of methyl 3-(bromomethyl)-2-chloro-4-(trifluoromethoxy)benzoate (8): 10.42 g (38.79 mmol) of methyl 2-chloro-3-methyl-4-(trifluoromethoxy)benzoate (7) was dissolved in 100% chlorobenzene, and 13.81 g (77.58 mmol) of N-bromosuccinimide and 0.64 g (3.88 mmol) of AIBN were added. The reaction mixture was stirred at 120°C for 8 h. It was then evaporated, and the residue was taken up in water and extracted with dichloromethane. The organic phase was separated, dried, and evaporated. The residue was purified by chromatography (HPLC, normal phase, heptane/ethyl acetate 100/0→60/40). This yielded 13.25 g (98%) of methyl 3-(bromomethyl)-2-chloro-4-(trifluoromethoxy)benzoate (8).1H-NMR (400 MHz, DMSO-d6): δ = 7.92 (d, 1H); 7.57 (br d, 1H); 4.75 (s, 2H); 3.89 (s, 3H). Step 6: Preparation of methyl 2-chloro-3-formyl-4-(trifluoromethoxy)benzoate (1): 26.20 g (75 mmol) of methyl 3-(bromomethyl)-2-chloro-4-(trifluoromethoxy)benzoate (8) were placed in 300 mL of acetonitrile, and 26.50 g (226 mmol) of N-methylmorpholine N-oxide were added portionwise at 10°C. After the exothermic reaction had subsided, the reaction mixture was stirred at room temperature for 12 h. The mixture was then evaporated, the residue was taken up in water, and extracted several times with ethyl acetate. The organic phases were combined, dried, and evaporated. The residue was purified by chromatography (HPLC, normal phase, heptane/ethyl acetate 100/0→80/20). 16.39 g (77%) of methyl 2-chloro-3-formyl-4-(trifluoromethoxy)benzoate (1) was obtained.1H-NMR (400 MHz, DMSO-d6): δ = 10.37 (s, 1H); 8.12 (d, 1H); 7.66 (br d, 1H); 3.91 (s, 3H). Synthesis of methyl 2-chloro-4-(difluoromethoxy)-3-formylbenzoate (2): Step 1: Preparation of methyl 2-chloro-4-(difluoromethoxy)-3-methylbenzoate (10): 10 g (47.35 mmol) of commercially available methyl 2-chloro-4-hydroxy-3-methylbenzoate (9) were added portionwise to a solution of 19.93 g of potassium hydroxide in 75 ml of acetonitrile and 75 ml of water at 0°C. Then, 17.52 ml (94.71 mmol) of diethyl [bromo(difluoro)methyl]phosphonate were added, and the mixture was stirred at 0°C for 1 h. After addition of ethyl acetate, the organic phase was separated, dried, and evaporated. The residue was purified by chromatography (HPLC, normal phase, heptane/ethyl acetate 100/0→85/15). This yielded 9.80 g (82%) of methyl 2-chloro-4-(difluoromethoxy)-3-methylbenzoate (10).1H-NMR (400 MHz, DMSO-d6): δ = 7.71 (d, 1H); 7.33 (t, 1H); 7.27 (d, 1H); 3.86 (s, 3H); 2.31 (s, 3H). Step 2: Preparation of methyl 3-(bromomethyl)-2-chloro-4-(difluoromethoxy)benzoate (11): 20.65 g (82.39 mmol) of methyl 2-chloro-4-(difluoromethoxy)-3-methylbenzoate (10) was dissolved in 200 g of chlorobenzene, and 29.33 g (164.79 mmol) of N-bromosuccinimide and 1.35 g (8.24 mmol) of AIBN were added. The reaction mixture was stirred at 120°C for 8 h. It was then evaporated, and the residue was taken up in water and extracted with dichloromethane. The organic phase was separated, dried, and evaporated. The residue was purified by chromatography (HPLC, normal phase, heptane/ethyl acetate 100/0→60/40). This yielded 26.47 g (97%) of methyl 3-(bromomethyl)-2-chloro-4-(difluoromethoxy)benzoate (11).1H-NMR (400 MHz, DMSO-d6): δ = 7.89 (d, 1H); 7.48 (t, 1H); 7.36 (d, 1H); 4.73 (s, 2H); 3.88 (s, 3H). Step 3: Preparation of methyl 2-chloro-4-(difluoromethoxy)-3-formylbenzoate (2): 5.96 g (18 mmol) of methyl 3-(bromomethyl)-2-chloro-4-(difluoromethoxy)benzoate (11) were placed in 200 ml of acetonitrile, and 6.36 g (54 mmol) of N-methylmorpholine N-oxide were added portionwise at 10°C. After the exothermic reaction had subsided, the reaction mixture was stirred at room temperature for 12 h. The mixture was then evaporated, the residue was taken up in water, and the mixture was extracted several times with ethyl acetate. The organic phases were combined, dried, and evaporated. The residue was purified by chromatography (HPLC, normal phase, heptane/ethyl acetate).(100/0→60/40). 4.33 g (90%) of methyl 2-chloro-4-(difluoromethoxy)-3-formylbenzoate (1) was obtained.1H-NMR (400 MHz, DMSO-d6): δ = 10.34 (s, 1H); 8.06 (d, 1H); 7.44 (d, 1H); 7.39 (t, 1H); 3.89 (s, 3H). Examples of the preparation of the compounds (II) and (I) according to the invention: Preparation of 2-chloro-N-(1-methyl-1H-tetrazol-5-yl)-3-(1,3-oxazol-2-yl)-4-(trifluoromethoxy)benzamide (1-12): Step 1: Preparation of methyl 2-chloro-3-[(2,2-dimethoxyethyl)carbamoyl]-4-(trifluoromethoxy)benzoate: 4.58 g (15.34 mmol) of 2-chloro-3-(methoxycarbonyl)-6-(trifluoromethoxy)benzoic acid were initially charged in 200 ml of dichloromethane and 3 ml of dimethylformamide, and 2.05 ml (23.00 mmol) of oxalyl chloride were added at room temperature. The reaction solution was stirred for 1 h. The mixture was then evaporated, toluene was added, and the mixture was evaporated again. The residue was dissolved in 45 ml of dichloromethane and added dropwise at 0°C to a solution of 2.51 ml (23.00 mmol) of 2-aminoacetaldehyde dimethyl acetal, 6.68 ml (38.35 mmol) of Hünig's base, and a catalytic amount of dimethylaminopyridine in 200 ml of dry dichloromethane. The reaction mixture was then warmed to room temperature and stirred for 3 h. After dilution with dichloromethane, the residue was washed with water, and the organic phase was separated, dried, and evaporated. The residue was purified by chromatography (HPLC, normal phase, heptane/ethyl acetate 100/0→80/20). This gave 5.61 g (95%) of methyl 2-chloro-3-[(2,2-dimethoxyethyl)carbamoyl]-4-(trifluoromethoxy)benzoate.1H-NMR (400 MHz, DMSO-d6): δ = 8.89 (br t, 1H); 7.94 (d, 1H); 7.56 (br d, 1H); 4.45 (t, 1H); 3.89 (s, 3H); 3.34 (m, 2H); 3.30 (s, 6H). Step 2: Preparation of methyl 2-chloro-3-[(2-oxoethyl)carbamoyl]-4-(trifluoromethoxy)benzoate: 5.61 g (14.54 mmol) of methyl 2-chloro-3-[(2,2-dimethoxyethyl)carbamoyl]-4-(trifluoromethoxy)benzoate were initially charged in 20 ml of dioxane, and 29.09 ml (58.18 mmol) of 2M hydrochloric acid were added at room temperature. The reaction mixture was then stirred at 80°C for 4 h. The mixture was evaporated, the residue was taken up in water, and extracted with ethyl acetate. The organic phase was separated, dried, and evaporated. The residue was purified by chromatography (HPLC, normal phase, heptane/ethyl acetate 100/0→80/20). This yielded 4.45 g (90%) of methyl 2-chloro-3-[(2-oxoethyl)carbamoyl]-4-(trifluoromethoxy)benzoate.1H-NMR (400 MHz, DMSO-d6): δ = 9.53 (s, 1H); 9.25 (br t, 1H); 7.97 (d, 1H); 7.59 (br d, 1H); 4.13 (m, 2H); 3.89 (s, 3H). Step 3: Preparation of methyl 2-chloro-3-(1,3-oxazol-2-yl)-4-(trifluoromethoxy)benzoate (3-12): 1.40 g (4.12 mmol) of methyl 2-chloro-3-[(2-oxoethyl)carbamoyl]-4-(trifluoromethoxy)benzoate was dissolved in 8 ml of acetonitrile and added to a solution of 2.93 g (12.37 mmol) of hexachloroethane in 20 ml of acetonitrile. The reaction mixture was then added portionwise at 0°C with 4.31 ml (24.73 mmol) of Hünig's base and 3.24 g (12.37 mmol) of triphenylphosphine. The mixture was then stirred at room temperature for 4 h. The mixture was then evaporated to dryness, and the residue was dissolved in 2M hydrochloric acid and extracted with dichloromethane. The organic phase was separated.Dried and evaporated. The residue was purified by chromatography (HPLC, normal phase, heptane/ethyl acetate 100/0→60/40). This yielded 689 mg (49%) of methyl 2-chloro-3-(1,3-oxazol-2-yl)-4-(trifluoromethoxy)benzoate (3-12). Step 4: Preparation of 2-chloro-3-(1,3-oxazol-2-yl)-4-(trifluoromethoxy)benzoic acid (4-12): 698 mg (2.17 mmol) of methyl 2-chloro-3-(1,3-oxazol-2-yl)-4-(trifluoromethoxy)benzoate (3-12) was initially dissolved in 20 ml of methanol, and 2.17 ml (4.34 mmol) of 2M sodium hydroxide solution was added at room temperature. The reaction mixture was stirred at room temperature for 12 h and then evaporated. The residue was taken up with water, and the aqueous phase was adjusted to pH 1 with 2M hydrochloric acid. The organic phase was separated, dried, and evaporated. 655 mg (98%) of 2-chloro-3-(1,3-oxazol-2-yl)-4-(trifluoromethoxy)benzoic acid (4-12) was obtained. Step 5: Preparation of 2-chloro-N-(1-methyl-1H-tetrazol-5-yl)-3-(1,3-oxazol-2-yl)-4-(trifluoromethoxy)benzamide (1-12): 200 mg (0.65 mmol) of 2-chloro-3-(1,3-oxazol-2-yl)-4-(trifluoromethoxy)benzoic acid (4-12) and 98.6 mg (0.98 mmol) of 5-amino-1-methyl-1H-tetrazole were initially charged in 3 ml of pyridine, and 0.087 ml (0.98 mmol) of oxalyl chloride was added dropwise at room temperature. The reaction solution was stirred for 12 h at room temperature. After addition of 10 ml of saturated aqueous sodium bicarbonate solution, the mixture was stirred for a further 10 min, and then extracted with dichloromethane. The organic phase was separated, dried, and evaporated. The residue was purified by chromatography (HPLC, C18, gradient: acetonitrile/water (+0.05% trifluoroacetic acid) 10/90→100/0). 146 mg (55%) of 2-chloro-N-(1-methyl-1H-tetrazol-5-yl)-3-(1,3-oxazol-2-yl)-4-(trifluoromethoxy)benzamide (1-12) was obtained. Preparation of 2-chloro-3-(5-methyl-1,2-oxazol-3-yl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethoxy)benzamide (1-13): Step 1: Preparation of methyl 2-chloro-3-[(hydroxyimino)methyl]-4-(trifluoromethoxy)benzoate: 3.40 g (12.03 mmol) of methyl 2-chloro-4-(difluoromethoxy)-3-formylbenzoate were placed together with 1.03 g (14.44 mmol) of hydroxylamine hydrochloride (97%) in 120 ml of tetrahydrofuran, and 2.52 ml (14.44 mmol) of Hünig's base were added at room temperature. The reaction solution was stirred for 3 h and then evaporated. The residue was taken up with 2N hydrochloric acid and extracted with ethyl acetate. The organic phase was separated, dried, and evaporated. The residue was purified by chromatography (HPLC, normal phase, heptane/ethyl acetate 100/0→70/30). This yielded 3.70 g (98%) of methyl 2-chloro-3-[(hydroxyimino)methyl]-4-(trifluoromethoxy)benzoate.1H-NMR (400 MHz, DMSO-d6): δ = 11.98 (s, 1H); 8.23 (s, 1H); 7.92 (d, 1H); 7.61 (br d, 1H); 3.89 (s, 3H). Step 2: Preparation of methyl 2-chloro-3-(5-methyl-1,2-oxazol-3-yl)-4-(trifluoromethoxy)benzoate (3-13): 1.23 g (4.13 mmol) of methyl 2-chloro-3-[(hydroxyimino)methyl]-4-(trifluoromethoxy)benzoate were initially charged in 50 ml of dimethylformamide, and 579.47 mg (4.34 mmol) of N-chlorosuccinimide were added at room temperature. The mixture was then stirred for 4 h. After cooling the reaction solution to 0°C, 41.33 ml (approx. 41 mmol) of a 5% solution of prop-1-yne in tetrahydrofuran and then 1.08 ml Hünig's base (6.20 mmol) was added dropwise. After stirring for 1 h at room temperature, the mixture was evaporated, the residue was taken up in water, and extracted with dichloromethane. The organic phase was separated, dried, and evaporated. The residue was purified by chromatography (HPLC, normal phase, heptane/ethyl acetate 100/0→50/50). This yielded 1.18 g (81%) of methyl 2-chloro-3-(5-methyl-1,2-oxazol-3-yl)-4-(trifluoromethoxy)benzoate (3-13). Step 3: Preparation of 2-chloro-3-(5-methyl-1,2-oxazol-3-yl)-4-(trifluoromethoxy)benzoic acid (4-13): 1.18 g (3.52 mmol) of methyl 2-chloro-3-(5-methyl-1,2-oxazol-3-yl)-4-(trifluoromethoxy)benzoate (3-13) were initially charged in 100 ml of methanol, and 3.52 ml (7.03 mmol) of 2M sodium hydroxide solution were added at room temperature. The reaction mixture was stirred at room temperature for 12 h and then evaporated. The residue was taken up with water, and the aqueous phase was adjusted to pH 1 with 2M hydrochloric acid. The organic phase was separated, dried, and evaporated. This yielded 1.18 g (99%) of 2-chloro-3-(5-methyl-1,2-oxazol-3-yl)-4-(trifluoromethoxy)benzoic acid (4-13). Step 4: Preparation of 2-chloro-3-(5-methyl-1,2-oxazol-3-yl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethoxy)benzamide (1-13): 200 mg (0.62 mmol) of 2-chloro-3-(5-methyl-1,2-oxazol-3-yl)-4-(trifluoromethoxy)benzoic acid (4-13) and 94.32 mg (0.93 mmol) of 5-amino-1-methyl-1H-tetrazole were initially dissolved in 3 ml of pyridine, and 0.083 ml (0.93 mmol) of oxalyl chloride was added dropwise at room temperature. The reaction solution was stirred at room temperature for 12 h. After adding 10 ml of saturated aqueous sodium bicarbonate solution, the mixture was stirred for a further 10 min and then extracted with dichloromethane. The organic phase was separated, dried, and evaporated. The residue was purified by chromatography (HPLC, C18, gradient: acetonitrile/water (+0.05% trifluoroacetic acid) 10/90→100/0). This gave 133 mg (50%) of 2-chloro-3-(5-methyl-1,2-oxazol-3-yl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethoxy)benzamide (1-13). Preparation of (R,S)-2-chloro-4-(difluoromethoxy)-N-(1-ethyl-1H-tetrazol-5-yl)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzamide (2-31): Step 1: Preparation of methyl 2-chloro-4-(difluoromethoxy)-3-vinylbenzoate: 25.86 g (11.34 mmol) of Nysted reagent was diluted with 80 ml of tetrahydrofuran under argon, and 0.96 ml (0.76 mmol) of boron trifluoride diethyl etherate was added at 0°C. The reaction mixture was stirred for 10 min. A solution of 2.00 g (7.56 mmol) of methyl 2-chloro-4-(difluoromethoxy)-3-formylbenzoate in 20 ml of tetrahydrofuran was then added dropwise. After warming to room temperature, the mixture was stirred for 3 h. The mixture was carefully poured into 2M hydrochloric acid and extracted with dichloromethane. The organic phase was separated, dried, and evaporated. The residue was purified by chromatography (HPLC, normal phase, heptane/ethyl acetate 100/0→50/50). This yielded 1.80 g (91%) of methyl 2-chloro-4-(difluoromethoxy)-3-vinylbenzoate.1H-NMR (400 MHz, DMSO-d6): δ = 7.75 (d, 1H); 7.34 (t, 1H); 7.32 (d, 1H); 6.71 (dd, 1H); 5.79 (m, 2H); 3.86 (s, 3H). Step 2: Preparation of (R,S)-methyl 2-chloro-4-(difluoromethoxy)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzoate (3-31): 1.70 g (6.47 mmol) of methyl 2-chloro-4-(difluoromethoxy)-3-vinylbenzoate and 7.06 g (32.36 mmol) of di-tert-butyl dicarbonate were placed in 70 ml of acetonitrile, and 1.86 ml (25.89 mmol) of nitroethane were slowly added. The mixture was then stirred at reflux for 3 h. After evaporation, the residue was taken up in water and dichloromethane. The organic phase was separated, dried, and evaporated. The residue was purified by chromatography (HPLC, normal phase, heptane/ethyl acetate 100/0→40/60). 2.15 g (91%) of (R,S)-methyl 2-chloro-4-(difluoromethoxy)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzoate (3-31) were obtained. Step 3: Preparation of (R,S)-2-chloro-4-(difluoromethoxy)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzoic acid (4-31): 810 mg (2.53 mmol) of (R,S)-methyl 2-chloro-4-(difluoromethoxy)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzoate (3-31) were initially charged in 50 ml of methanol, and 2.53 ml (5.07 mmol) of 2M sodium hydroxide solution were added at room temperature. The reaction mixture was stirred at room temperature for 12 h and then evaporated. The residue was taken up with water, and the aqueous phase was adjusted to pH 1 with 2M hydrochloric acid. The organic phase was separated, dried, and evaporated. This yielded 708 mg (87%) of (R,S)-2-chloro-4-(difluoromethoxy)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzoic acid (4-31). Step 4: Preparation of (R,S)-2-chloro-4-(difluoromethoxy)-N-(1-ethyl-1H-tetrazol-5-yl)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzamide (2-31): 200 mg (0.65 mmol) of (R,S)-2-chloro-4-(difluoromethoxy)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzoic acid (4-31) and 116.87 mg (0.98 mmol) of 5-amino-1-ethyl-1H-tetrazole were initially charged in 3 ml of pyridine, and 0.087 ml (0.98 mmol) of oxalyl chloride was added dropwise at room temperature. The reaction solution was stirred at room temperature for 12 h. After addition of 10 ml of aqueous sat. Sodium bicarbonate solution was stirred for a further 10 min and then extracted with dichloromethane. The organic phase was separated, dried, and evaporated. The residue was purified by chromatography (HPLC, C18, gradient: acetonitrile/water (+0.05% trifluoroacetic acid) 10/90→100/0). This gave 106 mg (38%) of (R,S)-2-chloro-4-(difluoromethoxy)-N-(1-ethyl-1H-tetrazol-5-yl)-3-(3-methyl-4,5-dihydro-1,2-oxazol-5-yl)benzamide (2-31). The examples listed in the following tables were prepared analogously to the methods mentioned above or are obtainable analogously to the methods mentioned above. These compounds are particularly preferred. The abbreviations used mean: Me = Methyl Et = Ethyl c-Pr = cyclopropyl Table 1: Compounds of the formula (I) according to the invention, wherein Rxrepresents a methyl group and the other substituents have the meanings given below.
Figure imgf000040_0001
Figure imgf000040_0002

Figure imgf000041_0001
Tabelle 2: Erfindungsgemäße Verbindungen der Formel (I), worin Rx für eine Ethylgruppe steht und die anderen Substituenten die unten genannten Bedeutungen haben.
Figure imgf000042_0001
Figure imgf000042_0002
Figure imgf000041_0001
Table 2: Compounds of the formula (I) according to the invention, wherein R x represents an ethyl group and the other substituents have the meanings given below.
Figure imgf000042_0001
Figure imgf000042_0002

Figure imgf000043_0001
Tabelle 3: Erfindungsgemäße Verbindungen der Formel (II), worin L für Methoxy steht und die anderen Substituenten die unten genannten Bedeutungen haben,
Figure imgf000044_0001
Figure imgf000044_0002
Figure imgf000045_0001
Tabelle 4: Erfindungsgemäße Verbindungen der Formel (II), worin L für Hydroxy steht und die anderen Substituenten die unten genannten Bedeutungen haben,
Figure imgf000046_0001
Figure imgf000046_0002
Figure imgf000047_0001
Tabelle 5: Erfindungsgemäße Verbindungen der Formel (II), worin L für Chlor steht und die anderen Substituenten die unten genannten Bedeutungen haben
Figure imgf000048_0001
Figure imgf000048_0002
Figure imgf000049_0001
Zu zahlreichen in obigen Tabellen genannten erfindungsgemäßen Verbindungen der Formel (I) und (II) werden zur weiteren Charakterisierung nachfolgend NMR-Daten offenbart: Beispiel-Nr. 1-11: 1H-NMR (400 MHz, DMSO-d6): δ = 11.87 (br s, 1H); 7.88 (d, 1H); 7.61 (d, 1H); 6.05 (dd, 1H); 4.01 (s, 3H); 3.49 (dd, 1H); 3.12 (dd, 1H); 1.98 (s, 3H); Beispiel-Nr. 1-12: 1H-NMR (400 MHz, DMSO-d6): δ = 11.98 (br s, 1H); 8.46 (s, 1H); 8.14 (d, 1H); 7.82 (d, 1H); 7.57 (s, 1H); 4.01 (s, 3H); Beispiel-Nr. 1-13: 1H-NMR (400 MHz, DMSO-d6): δ = 11.97 (br s, 1H); 9.22 (s, 1H); 8.09 (d, 1H); 7.79 (d, 1H); 6.91 (s, 1H); 4.01 (s, 3H); Beispiel-Nr. 1-14: 1H-NMR (400 MHz, DMSO-d6): δ = 11.95 (br s, 1H); 8.06 (d, 1H); 7.76 (d, 1H); 6.53 (s, 1H); 4.01 (s, 3H); 2.54 (s, 3H); Beispiel-Nr. 1-15: 1H-NMR (400 MHz, DMSO-d6): δ = 11.95 (br s, 1H); 8.06 (d, 1H); 7.76 (d, 1H); 6.49 (s, 1H); 4.01 (s, 3H); 2.27 (m, 1H); 1.14 (m, 2H); 0.98 (m, 2H); Beispiel-Nr. 1-31: 1H-NMR (400 MHz, DMSO-d6): δ = 11.81 (br s, 1H); 7.81 (d, 1H); 7.38 (d, 1H); 7.32 (t, 1H); 6.07 (dd, 1H); 4.00 (s, 3H); 3.40 (dd, 1H); 3.14 (dd, 1H); 1.97 (s, 3H); Beispiel-Nr. 1-32: 1H-NMR (400 MHz, DMSO-d6): δ = 11.92 (br s, 1H); 8.40 (s, 1H); 8.07 (d, 1H); 7.58 (d, 1H); 7.52 (s, 1H); 7.41 (t, 1H); 4.00 (s, 3H); Beispiel-Nr. 1-33: 1H-NMR (400 MHz, DMSO-d6): δ = 11.90 (br s, 1H); 9.17 (s, 1H); 8.01 (d, 1H); 7.54 (d, 1H); 7.35 (t, 1H); 6.82 (s, 1H); 4.00 (s, 3H); Beispiel-Nr. 1-34: 1H-NMR (400 MHz, DMSO-d6): δ = 11.88 (br s, 1H); 7.98 (d, 1H); 7.52 (d, 1H); 7.35 (t, 1H); 6.45 (s, 1H); 4.00 (s, 3H); 2.52 (s, 3H); Beispiel-Nr. 1-35: 1H-NMR (400 MHz, DMSO-d6): δ = 11.88 (br s, 1H); 7.98 (d, 1H); 7.52 (d, 1H); 7.34 (t, 1H); 6.41 (s, 1H); 4.00 (s, 3H); 2.25 (m, 1H); 1.13 (m, 2H); 0.98 (m, 2H); Beispiel-Nr. 1-48: 1H-NMR (400 MHz, DMSO-d6): δ = 11.95 (br s, 1H); 8.02 (d, 1H); 7.74 (d, 2H); 4.97 (m, 1H); 4.01 (s, 3H); 3.43 (dd, 1H); 2.88 (dd, 1H); 1.33 (d, 3H); Beispiel-Nr. 1-49: 1H-NMR (400 MHz, DMSO-d6): δ = 11.94 (br s, 1H); 8.02 (d, 1H); 7.73 (d, 1H); 4.81 (m, 1H); 4.01 (s, 3H); 3.39 (dd, 1H); 2.94 (dd, 1H); 1.66 (m, 2H); 0.95 (t, 3H); Beispiel-Nr.1-50: 1H-NMR (400 MHz, DMSO-d6): δ = 11.93 (br s, 1H); 8.02 (d, 1H); 7.73 (br d, 1H); 5.01 (m, 1H); 4.01 (s, 3H); 3.49 (m, 2H); 3.38 (dd, 1H); 3.33 (s, 3H); 3.09 (dd, 1H); Beispiel-Nr.1-51: 1H-NMR (400 MHz, DMSO-d6): δ = 11.93 (br s, 1H); 8.04 (d, 1H); 7.73 (br d, 1H); 5.18 (m, 1H); 4.01 (s, 3H); 3.54 (dd, 1H); 3.15 (dd, 1H); 3.07 (dd, 1H); 2.95 (dd, 1H); Beispiel-Nr.1-52: 1H-NMR (400 MHz, DMSO-d6): δ = 11.93 (br s, 1H); 8.01 (d, 1H); 7.72 (br d, 1H); 4.01 (s, 3H); 3.06 (s, 2H); 1.25 (m, 2H); 5.00 (m, 6H); 0.35 (m, 2H); Beispiel-Nr. 1-62: 1H-NMR (400 MHz, DMSO-d6): δ = 11.86 (br s, 1H); 7.94 (d, 1H); 7.49 (d, 1H); 7.41 (t, 1H); 4.77 (m, 1H); 4.00 (s, 3H); 3.34 (dd, 1H); 2.91 (dd, 1H); 1.67 (m, 2H); 0.95 (s, 3H); Beispiel-Nr. 1-63: 1H-NMR (400 MHz, DMSO-d6): δ = 11.86 (br s, 1H); 7.94 (d, 1H); 7.49 (d, 1H); 7.41 (t, 1H); 4.98 (m, 1H); 4.00 (s, 3H); 3.48 (m, 2H); 3.34 (m, 1H); 3.33 (s, 3H); 3.03 (dd, 1H); Beispiel-Nr. 1-64: 1H-NMR (400 MHz, DMSO-d6): δ = 11.87 (br s, 1H); 7.96 (d, 1H); 7.50 (d, 1H); 7.40 (t, 1H); 5.15 (m, 1H); 4.00 (s, 3H); 3.51 (dd, 1H); 3.09 (dd, 1H); 3.02 (dd, 1H); 2.92 (dd, 1H); Beispiel-Nr. 1-65: 1H-NMR (400 MHz, DMSO-d6): δ = 11.87 (br s, 1H); 7.93 (d, 1H); 7.48 (d, 1H); 7.43 (t, 1H); 4.00 (s, 3H); 3.00 (s, 2H); 1.25 (m, 2H); 0.50 (m, 6H); 0.37 (m, 2H); Beispiel-Nr.1-67: 1H-NMR (400 MHz, DMSO-d6): δ = 11.94 (br s, 1H); 8.02 (d, 1H); 7.74 (br d, 1H); 4.43 (m, 1H); 4.01 (s, 3H); 4.44 (dd, 1H); 3.05 (dd, 1H); 1.12 (m, 1H); 0.55 (m, 2H); 0.38 (m, 2H); Beispiel-Nr. 1-68: 1H-NMR (400 MHz, DMSO-d6): δ = 11.88 (br s, 1H); 7.95 (d, 1H); 7.49 (d, 1H); 7.42 (t, 1H); 4.39 (m, 1H); 4.00 (s, 3H); 3.39 (dd, 1H); 3.02 (dd, 1H); 1.13 (m, 1H); 0.55 (m, 2H); 0.38 (m, 2H); Beispiel-Nr. 2-11: 1H-NMR (400 MHz, DMSO-d6): δ = 11.78 (br s, 1H); 7.87 (d, 1H); 7.61 (d, 1H); 6.05 (dd, 1H); 4.37 (q, 2H); 3.49 (dd, 1H); 3.13 (dd, 1H); 1.98 (s, 3H); 1.47 (t, 3H); Beispiel-Nr. 2-12: 1H-NMR (400 MHz, DMSO-d6): δ = 11.88 (br s, 1H); 8.46 (s, 1H); 8.14 (d, 1H); 7.82 (d, 1H); 7.57 (s, 1H); 4.37 (q, 2H); 1.47 (t, 3H); Beispiel-Nr. 2-13: 1H-NMR (400 MHz, DMSO-d6): δ = 11.87 (br s, 1H); 9.22 (s, 1H); 8.08 (d, 1H); 7.79 (d, 1H); 6.92 (s, 1H); 4.37 (q, 2H); 1.47 (t, 3H); Beispiel-Nr. 2-14: 1H-NMR (400 MHz, DMSO-d6): δ = 11.85 (br s, 1H); 8.06 (d, 1H); 7.77 (d, 1H); 6.53 (s, 1H); 4.37 (q, 2H); 2.54 (s, 3H); 1.46 (t, 3H); Beispiel-Nr. 2-15: 1H-NMR (400 MHz, DMSO-d6): δ = 11.85 (br s, 1H); 8.05 (d, 1H); 7.76 (d, 1H); 6.49 (s, 1H); 4.37 (q, 2H); 2.27 (m, 1H); 1.47 (t, 3H); 1.15 (m, 2H); 0.98 (m, 2H); Beispiel-Nr. 2-31: 1H-NMR (400 MHz, DMSO-d6): δ = 11.71 (br s, 1H); 7.80 (d, 1H); 7.38 (d, 1H); 7.32 (t, 1H); 6.07 (dd, 1H); 4.36 (q, 2H); 3.43 (dd, 1H);3.14 (dd, 1H); 1.97 (s, 3H); 1.47 (t, 3H); Beispiel-Nr. 2-32: 1H-NMR (400 MHz, DMSO-d6): δ = 11.81 (br s, 1H); 8.41 (s, 1H); 8.06 (d, 1H); 7.57 (d, 1H); 7.52 (s, 1H); 7.41 (t, 1H); 4.36 (q, 2H); 1.46 (t, 3H); Beispiel-Nr. 2-33: 1H-NMR (400 MHz, DMSO-d6): δ = 11.80 (br s, 1H); 9.17 (s, 1H); 8.00 (d, 1H); 7.54 (d, 1H); 7.35 (t, 1H); 6.83 (s, 1H); 4.36 (q, 2H); 1.46 (t, 3H); Beispiel-Nr. 2-34: 1H-NMR (400 MHz, DMSO-d6): δ = 11.78 (br s, 1H); 7.98 (d, 1H); 7.52 (d, 1H); 7.35 (t, 1H); 6.45 (s, 1H); 4.36 (q, 2H); 2.52 (s, 3H); 1.47 (t, 3H); Beispiel-Nr. 2-35: 1H-NMR (400 MHz, DMSO-d6): δ = 11.78 (br s, 1H); 7.97 (d, 1H); 7.52 (d, 1H); 7.34 (t, 1H); 6.41 (s, 1H); 4.36 (q, 2H); 2.25 (m, 1H); 1.46 (t, 3H); 1.14 (m, 2H); 0.97 (m, 2H); Beispiel-Nr. 2-48: 1H-NMR (400 MHz, DMSO-d6): δ = 11.85 (br s, 1H); 8.02 (d, 1H); 7.73 (d, 1H); 4.98 (m, 1H); 4.37 (q, 2H); 3.43 (dd, 1H); 2.89 (dd, 1H); 1.47 (t, 3H); 1.33 (d, 3H); Beispiel-Nr. 2-49: 1H-NMR (400 MHz, DMSO-d6): δ = 11.85 (br s, 1H); 8.01 (d, 1H); 7.73 (d, 1H); 4.80 (m, 1H); 4.37 (q, 2H); 3.36 (m, 1H); 2.94 (dd, 1H); 1.66 (m, 2H); 1.47 (t, 3H); 0.95 (t, 3H); Beispiel-Nr.2-50: 1H-NMR (400 MHz, DMSO-d6): δ = 11.83 (br s, 1H); 8.02 (d, 1H); 7.73 (br d, 1H); 5.01 (m, 1H); 4.37 (q, 2H); 3.50 (m, 2H); 3.38 (dd, 1H); 3.33 (s, 3H); 3.08 (dd, 1H); 1.47 (t, 3H); Beispiel-Nr.2-51: 1H-NMR (400 MHz, DMSO-d6): δ = 11.83 (br s, 1H); 8.03 (d, 1H); 7.74 (br d, 1H); 5.18 (m, 1H); 4.37 (q, 2H); 3.54 (dd, 1H); 3.15 (dd, 1H); 3.07 (dd, 1H); 2.95 (dd, 1H); 1.47 (t, 3H); Beispiel-Nr.2-52: 1H-NMR (400 MHz, DMSO-d6): δ = 11.84 (br s, 1H); 8.00 (d, 1H); 7.72 (br d, 1H); 4.36 (q, 2H); 3.06 (s, 2H); 1.47 (t, 3H); 1.26 (m, 2H); Beispiel-Nr. 2-62: 1H-NMR (400 MHz, DMSO-d6): δ = 11.76 (br s, 1H); 7.93 (d, 1H); 7.49 (d, 1H); 7.42 (t, 1H); 4.77 (m, 1H); 4.36 (q, 2H); 3.34 (dd, 1H); 2.92 (dd, 1H); 1.66 (m, 1H); 1.47 (t, 3H); 0.95 (t, 3H); Beispiel-Nr. 2-63: 1H-NMR (400 MHz, DMSO-d6): δ = 11.76 (br s, 1H); 7.94 (d, 1H); 7.49 (d, 1H); 7.41 (t, 1H); 4.98 (m, 1H); 4.36 (q, 2H); 3.48 (m, 2H); 3.33 (s, 3H); 3.33 (dd, 1H); 3.03 (dd, 1H); 1.47 (t, 3H); Beispiel-Nr. 2-64: 1H-NMR (400 MHz, DMSO-d6): δ = 11.77 (br s, 1H); 7.95 (d, 1H); 7.50 (d, 1H); 7.40 (t, 1H); 5.15 (m, 1H); 4.36 (q, 1H); 3.51 (dd, 1H); 3.09 (dd, 1H); 3.02 (dd, 1H); 2.92 (dd, 1H); 1.47 (t, 3H); Beispiel-Nr. 2-65: 1H-NMR (400 MHz, DMSO-d6): δ = 11.77 (br s, 1H); 7.93 (d, 1H); 7.48 (d, 1H); 7.43 (t, 1H); 4.35 (q, 2H); 3.00 (s, 2H); 1.47 (t, 3H); 1.24 (m, 2H); 0.50 (m, 6H); 0.38 (m, 2H); Beispiel-Nr.2-67: 1H-NMR (400 MHz, DMSO-d6): δ = 11.84 (br s, 1H); 8.02 (d, 1H); 7.74 (br d, 1H); 4.43 (m, 1H); 4.37 (q, 2H); 4.44 (dd, 1H); 3.06 (dd, 1H); 1.47 (t, 3H); 1.12 (m, 1H); 0.55 (m, 2H); 0.39 (m, 2H); Beispiel-Nr. 2-68: 1H-NMR (400 MHz, DMSO-d6): δ = 11.78 (br s, 1H); 7.94 (d, 1H); 7.49 (d, 1H); 7.42 (t, 1H); 4.38 (m, 3H); 3.39 (dd, 1H); 3.02 (dd, 1H); 1.47 (t, 3H); 1.13 (m, 1H); 0.55 (m, 2H); 0.39 (m, 2H); Beispiel-Nr. 3-11: 1H-NMR (400 MHz, DMSO-d6): δ = 7.86 (d, 1H); 7.55 (br d, 1H); 6.05 (dd, 1H); 3.88 (s, 3H); 3.45 (m, 1H); 3.11 (m, 1H); 1.97 (s, 3H); Beispiel-Nr.3-12: 1H-NMR (400 MHz, DMSO-d6): δ = 8.44 (s, 1H); 8.16 (d, 1H); 7.76 (br d, 1H); 7.55 (s, 1H); 3.91 (s, 3H); Beispiel-Nr.3-14: 1H-NMR (400 MHz, DMSO-d6): δ = 8.07 (d, 1H); 7.70 (br d, 1H); 6.51 (s, 1H); 3.91 (s, 3H); 2.52 (s, 3H); Beispiel-Nr.3-15: 1H-NMR (400 MHz, DMSO-d6): δ = 8.07 (d, 1H); 7.70 (br d, 1H); 6.47 (s, 1H); 3.90 (s, 3H); 2.26 (m, 1H); 1.14 (m, 2H); 0.96 (m, 2H); Beispiel-Nr. 3-31: 1H-NMR (400 MHz, DMSO-d6): δ = 7.82 (d, 1H); 7.32 (d, 1H); 7.30 (t, 1H); 6.08 (dd, 1H); 3.86 (s, 3H); 3.39 (m, 1H); 3.12 (m, 1H); 1.95 (s, 3H); Beispiel-Nr. 3-32: 1H-NMR (400 MHz, DMSO-d6): δ = 8.38 (s, 1H); 8.12 (d, 1H); 7.52 (d, 1H); 7.51 (s, 1H); 7.41 (t, 1H); 3.89 (s, 3H); Beispiel-Nr. 3-34: 1H-NMR (400 MHz, DMSO-d6): δ = 8.02 (d, 1H); 7.47 (d, 1H); 7.34 (t, 1H); 6.43 (s, 1H); 3.88 (s, 3H); 2.52 (s, 3H); Beispiel-Nr. 3-35: 1H-NMR (400 MHz, DMSO-d6): δ = 8.02 (d, 1H); 7.46 (d, 1H); 7.33 (t, 1H); 6.40 (s, 1H); 3.88 (s, 3H); 2.24 (m, 1H); 1.13 (m, 2H); 0.97 (m, 2H); Beispiel-Nr.3-41: 1H-NMR (400 MHz, DMSO-d6): δ = 8.07 (d, 1H); 7.71 (br d, 1H); 7.01 (s, 1H); 3.90 (s, 3H); 0.37 (s, 9H); Beispiel-Nr. 3-42: 1H-NMR (400 MHz, DMSO-d6): δ = 8,02 (d, 1H); 7.47 (d, 1H); 7.33 (t, 1H); 6.93 (s, 1H); 3.88 (s, 3H); 0.37 (s, 9H); Beispiel-Nr. 3-50: 1H-NMR (400 MHz, DMSO-d6): δ = 8.04 (br d, 1H); 7.67 (d, 1H); 4.95 (m, 1H); 3.89 (s, 3H); 3.39 (dd, 1H); 2.85 (dd, 1H); 1.32 (d, 3H); Beispiel-Nr. 3-51: 1H-NMR (400 MHz, DMSO-d6): δ = 8.04 (d, 1H); 7.67 (br d, 1H); 4.78 (m, 1H); 3.90 (s, 3H); 3.36 (dd, 1H); 2.92 (dd, 1H); 1.65 (m, 2H); 0.94 (t, 3H); Beispiel-Nr. 3-52: 1H-NMR (400 MHz, DMSO-d6): δ = 7.92 (d, 1H); 7.32 (br d, 1H); 5.01 (m, 1H); 3.96 (s, 3H); 3.63 (dd, 1H); 3.56 (dd, 1H); 3.45 (s, 3H); 3.34 (dd, 1H); 1.13 (dd, 1H); Beispiel-Nr. 3-53: 1H-NMR (400 MHz, DMSO-d6): δ = 8.06 (d, 1H); 7.67 (br d, 1H); 5.15 (m, 1H); 3.90 (s, 3H); 3.51 (m, 1H); 3.12 (m, 1H); 2.99 (m, 2H); Beispiel-Nr.3-54: 1H-NMR (400 MHz, DMSO-d6): δ = 8.03 (d, 1H); 7.66 (br d, 1H); 3.89 (s, 3H); 3.03 (s, 2H); 1.24 (m, 2H); 0.49 (m, 6H); 0.35 (m, 2H); Beispiel-Nr. 3-60: 1H-NMR (400 MHz, DMSO-d6): δ = 7.98 (d, 1H); 7.08 (d, 1H); 6.59 (t, 1H); 5.09 (m, 1H); 3.91 (s, 3H); 3.50 (dd, 1H); 3.15 (dd, 1H); 2.56 (s, 3H); Beispiel-Nr. 3-64: 1H-NMR (400 MHz, DMSO-d6): δ = 7.99 (d, 1H); 7.41 (d, 1H); 7.40 (t, 1H); 4.33 (m, 1H); 3.88 (s, 3H); 3.31 (dd, 1H); 2.89 (dd, 1H); 1.64 (m, 2H); 0.94 (t, 3H); Beispiel-Nr. 3-65: 1H-NMR (400 MHz, DMSO-d6): δ = 7.99 (d, 1H); 7.43 (d, 1H); 7.39 (t, 1H); 4.95 (m, 1H); 3.88 (s, 3H); 3.47 (m, 2H); 3.32 (s, 3H); 3.30 (m, 1H); 3.00 (m, 1H); Beispiel-Nr. 3-66: 1H-NMR (400 MHz, DMSO-d6): δ = 8.01 (d, 1H); 7.45 (d, 1H); 7.39 (t, 1H); 5.14 (m, 1H); 3.88 (s, 3H); 3.48 (m, 1H); 3.06 (m, 1H); 3.95 (m, 2H); Beispiel-Nr. 3-67: 1H-NMR (400 MHz, DMSO-d6): δ = 7.98 (d, 1H); 7.42 (d, 1H); 7.41 (t, 1H); 3.87 (s, 3H); 2.97 (s, 2H); 1.22 (m, 2H); 0.51 (m, 2H); 0.48 (m, 4H); 0.37 (m, 2H); Beispiel-Nr. 3-69: 1H-NMR (400 MHz, DMSO-d6): δ = 8.04 (d, 1H); 7.67 (br d, 1H); 4.40 (m, 1H); 3.90 (s, 3H); 4.41 (dd, 1H); 3.02 (dd, 1H); 1.10 (m, 1H); 0.53 (m, 1H); 0.38 (m, 2H); Beispiel-Nr. 3-70: 1H-NMR (400 MHz, DMSO-d6): δ = 7.99 (d, 1H); 7.43 (d, 1H); 7.40 (t, 1H); 4.37 (m, 1H); 3.88 (s, 3H); 3.36 (dd, 1H); 2.99 (dd, 1H); 1.11 (m, 1H); 0.53 (m, 2H); 0.37 (m, 2H); Beispiel-Nr. 3-71: 1H-NMR (400 MHz, DMSO-d6): δ = 7.91 (d, 1H); 7.54 (br d, 1H); 4.05 (dd, 1H); 3.78 (s, 3H); 3.33 (dd, 1H); 2.92 (t, 1H); -0.12 (s, 9H); Beispiel-Nr.4-11: 1H-NMR (400 MHz, DMSO-d6): δ = 13.70 (br s, 1H); 7.82 (d, 1H); 7.55 (br d, 1H); 6.05 (dd, 1H); 3.46 (m, 3H); 3.10 (m, 1H); 1.97 (s, 3H); Beispiel-Nr. 4-12: 1H-NMR (400 MHz, DMSO-d6): δ = 13.90 (br s, 1H); 8.43 (s, 1H); 8.13 (d, 1H); 7.71 (br d, 1H); 7.54 (s, 1H); Beispiel-Nr. 4-13: 1H-NMR (400 MHz, DMSO-d6): δ = 13.80 (br s, 1H); 9.18 (s, 1H); 8.06 (d, 1H); 7.67 (br d, 1H); 6.89 (s, 1H); Beispiel-Nr.4-14: 1H-NMR (400 MHz, DMSO-d6): δ = 13.80 (br s, 1H); 8.04 (d, 1H); 7.66 (br d, 1H); 6.50 (s, 1H); 2.52 (s, 3H); Beispiel-Nr.4-15: 1H-NMR (400 MHz, DMSO-d6): δ = 13.70 (br s, 1H); 8.03 (d, 1H); 7.65 (br d, 1H); 6.47 (s, 1H); 2.25 (m, 1H); 1.12 (m, 2H); 0.96 (m, 1H); Beispiel-Nr. 4-31: 1H-NMR (400 MHz, DMSO-d6): δ = 13.40 (br s, 1H); 7.79 (d, 1H); 7.28 (d, 1H); 7.28 (t, 1H); 6.08 (dd, 1H); 3.38 (m, 1H); 3.12 (m, 1H); 1.95 (s, 3H); Beispiel-Nr. 4-32: 1H-NMR (400 MHz, DMSO-d6): δ = 13.65 (br s, 1H); 8.37 (s, 1H); 8.09 (d, 1H); 7.48 (s, 1H); 7.47 (d, 1H); 7.38 (t, 1H); Beispiel-Nr. 4-33: 1H-NMR (400 MHz, DMSO-d6): δ = 13.60 (br s, 1H); 9.13 (s, 1H); 8.02 (d, 1H); 7.44 (d, 1H); 7.31 (t, 1H); 6.80 (s, 1H); Beispiel-Nr. 4-34: 1H-NMR (400 MHz, DMSO-d6): δ = 13.50 (br s, 1H); 7.99 (d, 1H); 7.43 (d, 1H); 7.31 (t, 1H); 6.42 (s, 1H); 2.52 (s, 3H); Beispiel-Nr. 4-35: 1H-NMR (400 MHz, DMSO-d6): δ = 13.50 (br s, 1H); 7.99 (d, 1H); 7.42 (d, 1H); 7.30 (t, 1H); 6.39 (s, 1H); 2.23 (m, 1H); 1.12 (m, 2H); 0.96 (m, 2H); Beispiel-Nr.4-48: 1H-NMR (400 MHz, DMSO-d6): δ = 13.90 (br s, 1H); 8.00 (d, 1H); 7.62 (br d, 1H); 4.95 (m, 1H); 3.39 (dd, 1H); 2.85 (dd, 1H); 1.32 (d, 3H); Beispiel-Nr.4-49: 1H-NMR (400 MHz, DMSO-d6): δ = 13.87 (br s, 1H); 8.00 (d, 1H); 7.62 (br d, 1H); 4.78 (m, 1H); 3.36 (dd, 1H); 2.92 (dd, 1H); 1.65 (m, 2H); 0.94 (t, 3H); Beispiel-Nr.4-50: 1H-NMR (400 MHz, DMSO-d6): δ = 13.81 (br s, 1H); 8.00 (d, 1H); 7.62 (br d, 1H); 4.98 (m, 1H); 3.48 (m, 2H); 3.35 (dd, 1H); 3.32 (s, 3H); 3.05 (dd, 1H); Beispiel-Nr.4-51: 1H-NMR (400 MHz, DMSO-d6): δ = 13.88 (br s, 1H); 8.02 (d, 1H); 7.63 (br d, 1H); 5.15 (m, 1H); 3.51 (dd, 1H); 3.12 (dd, 1H); 3.05 (dd, 1H); 2.93 (dd, 1H); Beispiel-Nr.4-52: 1H-NMR (400 MHz, DMSO-d6): δ = 13.85 (br s, 1H); 7.99 (d, 1H); 7.61 (br d, 1H); 3.03 (br s, 2H); 1.24 (m, 2H); 0.49 (m, 6H); 0.36 (m, 2H); Beispiel-Nr. 4-63: 1H-NMR (400 MHz, DMSO-d6): δ = 8.11 (d, 1H); 7.24 (d, 1H); 6.60 (t, 1H); 5.02 (m, 1H); 3.65 (dd, 1H); 3.58 (dd, 1H); 3.46 (s, 3H); 3.35 (dd, 1H); 3.14 (dd, 1H); Beispiel-Nr. 4-64: 1H-NMR (400 MHz, DMSO-d6): δ = 7.99 (d, 1H); 7.41 (d, 1H); 7.37 (t, 1H); 5.13 (m, 1H); 3.47 (m, 1H); 3.06 (m, 1H); 2.95 (m, 2H); Beispiel-Nr. 4-65: 1H-NMR (400 MHz, DMSO-d6): δ = 13.62 (br s, 1H); 7.95 (d, 1H); 7.39 (t, 1H); 7.38 (d, 1H); 2.97 (br s, 2H); 1.23 (m, 2H); 0.49 (m, 6H); 0.37 (m, 2H) Beispiel-Nr.4-67: 1H-NMR (400 MHz, DMSO-d6): δ = 13.85 (br s, 1H); 8.00 (d, 1H); 7.62 (br d, 1H); 4.40 (m, 1H); 3.41 (dd, 1H); 3.02 (dd, 1H); 1.10 (m, 1H); 0.52 (m, 2H); 0.38 (m, 2H); Beispiel-Nr. 4-68: 1H-NMR (400 MHz, DMSO-d6): δ = 13.63 (br s, 1H); 7.96 (d, 1H); 7.40 (d, 1H); 7.38 (t, 1H); 4.36 (m, 1H); 3.35 (dd, 1H); 2.99 (dd, 1H); 1.11 (m, 1H); 0.53 (m, 2H); 0.38 (m, 2H). B. 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 (®Triton X 207), 3 Gew.-Teilen Isotridecanolpolyglykolether (8 EO) und 71 Gew.-Teilen paraffinischem Mineralöl (Siedebereich z.B. ca. 255 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 75 Gew.-Teile einer Verbindung der Formel (I) und/oder deren Salze, 10 Gew.-Teile ligninsulfonsaures Calcium, 5 Gew.-Teile Natriumlaurylsulfat, 3 Gew.-Teile Polyvinylalkohol und 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 25 Gew.-Teile einer Verbindung der Formel (I) und/oder deren Salze, 5 Gew.-Teile 2,2'-dinaphthylmethan-6,6'-disulfonsaures Natrium 2 Gew.-Teile oleoylmethyltaurinsaures Natrium, 1 Gew.-Teil Polyvinylalkohol, 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. C. Biologische Beispiele Die für die Schadpflanzen verwendeten Abkürzungen bedeuten: ABUTH Abutilon theophrasti ALOMY Alopecurus myosuroides AVEFA Avena fatua AMARE Amaranthus retroflexus CYPES Cyperus esculentus DIGSA Digitaria sanguinalis ECHCG Echinochloa crus-galli HORMU Hordeum murinum KCHSC Kochia scoparia LOLMU Lolium multiflorum LOLRI Lolium rigidum MATIN Matricaria inodora PHBPU Pharbitis purpurea POLCO Polygonum convolvulus SETVI Setaria viridis STEME Stellaria media VERPE Veronica persica VIOTR Viola tricolor 1. Herbizide Wirkung gegen Schadpflanzen im Vorauflauf 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 800 l/ha unter Zusatz von 0,2% Netzmittel auf die Oberfläche der Abdeckerde appliziert. Nach der Behandlung werden die Töpfe im Gewächshaus aufgestellt und unter guten Wachstumsbedingungen für die Testpflanzen gehalten. Die visuelle Bonitur der Schäden an den 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). Dabei zeigten zahlreiche erfindungsgemäße Verbindungen eine sehr gute Wirkung gegen eine Vielzahl bedeutender Schadpflanzen. Die nachfolgenden Tabellen zeigen beispielhaft die herbizide Wirkung der erfindungsgemäßen Verbindungen im Nachauflauf, wobei die herbizide Wirkung in Prozent angegeben ist. Tabelle C-1: Vorauflaufwirkung bei 20g/ha gegen ZEAMX in %
Figure imgf000058_0001
Tabelle C-2: Vorauflaufwirkung bei 80g/ha gegen ZEAMX in %
Figure imgf000058_0002
Tabelle C-3: Vorauflaufwirkung bei 20g/ha gegen TRZAS in %
Figure imgf000058_0003
Figure imgf000059_0001
Tabelle C-4: Vorauflaufwirkung bei 80g/ha gegen TRZAS in %
Figure imgf000059_0002
Tabelle C-5: Vorauflaufwirkung bei 20g/ha gegen GLXMA in %
Figure imgf000059_0003
Tabelle C-6: Vorauflaufwirkung bei 80g/ha gegen GLXMA in %
Figure imgf000060_0001
Tabelle C-7: Vorauflaufwirkung bei 20g/ha gegen ABUTH in %
Figure imgf000060_0002
Tabelle C-8: Vorauflaufwirkung bei 80g/ha gegen ABUTH in %
Figure imgf000060_0003
Figure imgf000061_0001
Tabelle C-9: Vorauflaufwirkung bei 20g/ha gegen ALOMY in %
Figure imgf000061_0002
Tabelle C-10: Vorauflaufwirkung bei 80g/ha gegen ALOMY in %
Figure imgf000061_0003
Tabelle C-11: Vorauflaufwirkung bei 20g/ha gegen AMARE in %
Figure imgf000062_0002
Tabelle C-12: Vorauflaufwirkung bei 80g/ha gegen AMARE in %
Figure imgf000062_0001
Figure imgf000063_0001
Tabelle C-13: Vorauflaufwirkung bei 20g/ha gegen DIGSA in %
Figure imgf000063_0002
Tabelle C-14: Vorauflaufwirkung bei 80g/ha gegen DIGSA in %
Figure imgf000063_0003
Figure imgf000064_0001
Tabelle C-15: Vorauflaufwirkung bei 20g/ha gegen ECHCG in %
Figure imgf000064_0002
Tabelle C-16: Vorauflaufwirkung bei 80g/ha gegen ECHCG in %
Figure imgf000064_0003
Tabelle C-17: Vorauflaufwirkung bei 20g/ha gegen LOLRI in %
Figure imgf000065_0002
Tabelle C-18: Vorauflaufwirkung bei 80g/ha gegen LOLRI in %
Figure imgf000065_0001
Tabelle C-19: Vorauflaufwirkung bei 20g/ha gegen MATIN in %
Figure imgf000066_0002
Tabelle C-20: Vorauflaufwirkung bei 80g/ha gegen MATIN in %
Figure imgf000066_0001
Figure imgf000043_0001
Table 3: Compounds of the formula (II) according to the invention, wherein L is methoxy and the other substituents have the meanings given below,
Figure imgf000044_0001
Figure imgf000044_0002
Figure imgf000045_0001
Table 4: Compounds of the formula (II) according to the invention, wherein L is hydroxy and the other substituents have the meanings given below,
Figure imgf000046_0001
Figure imgf000046_0002
Figure imgf000047_0001
Table 5: Compounds of the formula (II) according to the invention, wherein L is chlorine and the other substituents have the meanings given below
Figure imgf000048_0001
Figure imgf000048_0002
Figure imgf000049_0001
For the purpose of further characterization, NMR data are disclosed below for numerous compounds of the formula (I) and (II) according to the invention listed in the tables above: Example No. 1-11: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.87 (br s, 1H); 7.88 (d, 1H); 7.61 (d, 1H); 6.05 (dd, 1H); 4.01 (s, 3H); 3.49 (dd, 1H); 3.12 (dd, 1H); 1.98 (s, 3H); Example No. 1-12: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.98 (br s, 1H); 8.46 (s, 1H); 8.14 (d, 1H); 7.82 (d, 1H); 7.57 (s, 1H); 4.01 (s, 3H); Example no. 1-13: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.97 (br s, 1H); 9.22 (s, 1H); 8.09 (d, 1H); 7.79 (d, 1H); 6.91 (s, 1H); 4.01 (s, 3H); Example no. 1-14: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.95 (br s, 1H); 8.06 (d, 1H); 7.76 (d, 1H); 6.53 (s, 1H); 4.01 (s, 3H); 2.54 (s, 3H); Example no. 1-15: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.95 (br s, 1H); 8.06 (d, 1H); 7.76 (d, 1H); 6.49 (s, 1H); 4.01 (s, 3H); 2.27 (m, 1H); 1.14 (m, 2H); 0.98 (m, 2H); Example no. 1-31: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.81 (br s, 1H); 7.81 (d, 1H); 7.38 (d, 1H); 7.32 (t, 1H); 6.07 (dd, 1H); 4.00 (s, 3H); 3.40 (dd, 1H); 3.14 (dd, 1H); 1.97 (s, 3H); Example no. 1-32: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.92 (br s, 1H); 8.40 (s, 1H); 8.07 (d, 1H); 7.58 (d, 1H); 7.52 (s, 1H); 7.41 (t, 1H); 4.00 (s, 3H); Example no. 1-33: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.90 (br s, 1H); 9.17 (s, 1H); 8.01 (d, 1H); 7.54 (d, 1H); 7.35 (t, 1H); 6.82 (s, 1H); 4.00 (s, 3H); Example no. 1-34: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.88 (br s, 1H); 7.98 (d, 1H); 7.52 (d, 1H); 7.35 (t, 1H); 6.45 (s, 1H); 4.00 (s, 3H); 2.52 (s, 3H); Example no. 1-35: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.88 (br s, 1H); 7.98 (d, 1H); 7.52 (d, 1H); 7.34 (t, 1H); 6.41 (s, 1H); 4.00 (s, 3H); 2.25 (m, 1H); 1.13 (m, 2H); 0.98 (m, 2H); Example no. 1-48: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.95 (br s, 1H); 8.02 (d, 1H); 7.74 (d, 2H); 4.97 (m, 1H); 4.01 (s, 3H); 3.43 (dd, 1H); 2.88 (dd, 1H); 1.33 (d, 3H); Example no. 1-49: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.94 (br s, 1H); 8.02 (d, 1H); 7.73 (d, 1H); 4.81 (m, 1H); 4.01 (s, 3H); 3.39 (dd, 1H); 2.94 (dd, 1H); 1.66 (m, 2H); 0.95 (t, 3H); Example No. 1-50: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.93 (br s, 1H); 8.02 (d, 1H); 7.73 (br d, 1H); 5.01 (m, 1H); 4.01 (s, 3H); 3.49 (m, 2H); 3.38 (dd, 1H); 3.33 (s, 3H); 3.09 (dd, 1H); Example No. 1-51: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.93 (br s, 1H); 8.04 (d, 1H); 7.73 (br d, 1H); 5.18 (m, 1H); 4.01 (s, 3H); 3.54 (dd, 1H); 3.15 (dd, 1H); 3.07 (dd, 1H); 2.95 (dd, 1H); Example No. 1-52: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.93 (br s, 1H); 8.01 (d, 1H); 7.72 (br d, 1H); 4.01 (s, 3H); 3.06 (s, 2H); 1.25 (m, 2H); 5.00 (m, 6H); 0.35 (m, 2H); Example no. 1-62: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.86 (br s, 1H); 7.94 (d, 1H); 7.49 (d, 1H); 7.41 (t, 1H); 4.77 (m, 1H); 4.00 (s, 3H); 3.34 (dd, 1H); 2.91 (dd, 1H); 1.67 (m, 2H); 0.95 (s, 3H); Example no. 1-63: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.86 (br s, 1H); 7.94 (d, 1H); 7.49 (d, 1H); 7.41 (t, 1H); 4.98 (m, 1H); 4.00 (s, 3H); 3.48 (m, 2H); 3.34 (m, 1H); 3.33 (s, 3H); 3.03 (dd, 1H); Example no. 1-64: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.87 (br s, 1H); 7.96 (d, 1H); 7.50 (d, 1H); 7.40 (t, 1H); 5.15 (m, 1H); 4.00 (s, 3H); 3.51 (dd, 1H); 3.09 (dd, 1H); 3.02 (dd, 1H); 2.92 (dd, 1H); Example no. 1-65: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.87 (br s, 1H); 7.93 (d, 1H); 7.48 (d, 1H); 7.43 (t, 1H); 4.00 (s, 3H); 3.00 (s, 2H); 1.25 (m, 2H); 0.50 (m, 6H); 0.37 (m, 2H); Example No. 1-67: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.94 (br s, 1H); 8.02 (d, 1H); 7.74 (br d, 1H); 4.43 (m, 1H); 4.01 (s, 3H); 4.44 (dd, 1H); 3.05 (dd, 1H); 1.12 (m, 1H); 0.55 (m, 2H); 0.38 (m, 2H); Example no. 1-68: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.88 (br s, 1H); 7.95 (d, 1H); 7.49 (d, 1H); 7.42 (t, 1H); 4.39 (m, 1H); 4.00 (s, 3H); 3.39 (dd, 1H); 3.02 (dd, 1H); 1.13 (m, 1H); 0.55 (m, 2H); 0.38 (m, 2H); Example no. 2-11: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.78 (br s, 1H); 7.87 (d, 1H); 7.61 (d, 1H); 6.05 (dd, 1H); 4.37 (q, 2H); 3.49 (dd, 1H); 3.13 (dd, 1H); 1.98 (s, 3H); 1.47 (t, 3H); Example no. 2-12: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.88 (br s, 1H); 8.46 (s, 1H); 8.14 (d, 1H); 7.82 (d, 1H); 7.57 (s, 1H); 4.37 (q, 2H); 1.47 (t, 3H); Example no. 2-13: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.87 (br s, 1H); 9.22 (s, 1H); 8.08 (d, 1H); 7.79 (d, 1H); 6.92 (s, 1H); 4.37 (q, 2H); 1.47 (t, 3H); Example no. 2-14: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.85 (br s, 1H); 8.06 (d, 1H); 7.77 (d, 1H); 6.53 (s, 1H); 4.37 (q, 2H); 2.54 (s, 3H); 1.46 (t, 3H); Example no. 2-15: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.85 (br s, 1H); 8.05 (d, 1H); 7.76 (d, 1H); 6.49 (s, 1H); 4.37 (q, 2H); 2.27 (m, 1H); 1.47 (t, 3H); 1.15 (m, 2H); 0.98 (m, 2H); Example no. 2-31: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.71 (br s, 1H); 7.80 (d, 1H); 7.38 (d, 1H); 7.32 (t, 1H); 6.07 (dd, 1H); 4.36 (q, 2H); 3.43 (dd, 1H);3.14 (dd, 1H); 1.97 (s, 3H); 1.47 (t, 3H); Example no. 2-32: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.81 (br s, 1H); 8.41 (s, 1H); 8.06 (d, 1H); 7.57 (d, 1H); 7.52 (s, 1H); 7.41 (t, 1H); 4.36 (q, 2H); 1.46 (t, 3H); Example no. 2-33: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.80 (br s, 1H); 9.17 (s, 1H); 8.00 (d, 1H); 7.54 (d, 1H); 7.35 (t, 1H); 6.83 (s, 1H); 4.36 (q, 2H); 1.46 (t, 3H); Example no. 2-34: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.78 (br s, 1H); 7.98 (d, 1H); 7.52 (d, 1H); 7.35 (t, 1H); 6.45 (s, 1H); 4.36 (q, 2H); 2.52 (s, 3H); 1.47 (t, 3H); Example no. 2-35: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.78 (br s, 1H); 7.97 (d, 1H); 7.52 (d, 1H); 7.34 (t, 1H); 6.41 (s, 1H); 4.36 (q, 2H); 2.25 (m, 1H); 1.46 (t, 3H); 1.14 (m, 2H); 0.97 (m, 2H); Example no. 2-48: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.85 (br s, 1H); 8.02 (d, 1H); 7.73 (d, 1H); 4.98 (m, 1H); 4.37 (q, 2H); 3.43 (dd, 1H); 2.89 (dd, 1H); 1.47 (t, 3H); 1.33 (d, 3H); Example no. 2-49: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.85 (br s, 1H); 8.01 (d, 1H); 7.73 (d, 1H); 4.80 (m, 1H); 4.37 (q, 2H); 3.36 (m, 1H); 2.94 (dd, 1H); 1.66 (m, 2H); 1.47 (t, 3H); 0.95 (t, 3H); Example No.2-50: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.83 (br s, 1H); 8.02 (d, 1H); 7.73 (br d, 1H); 5.01 (m, 1H); 4.37 (q, 2H); 3.50 (m, 2H); 3.38 (dd, 1H); 3.33 (s, 3H); 3.08 (dd, 1H); 1.47 (t, 3H); Example No. 2-51: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.83 (br s, 1H); 8.03 (d, 1H); 7.74 (br d, 1H); 5.18 (m, 1H); 4.37 (q, 2H); 3.54 (dd, 1H); 3.15 (dd, 1H); 3.07 (dd, 1H); 2.95 (dd, 1H); 1.47 (t, 3H); Example No. 2-52: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.84 (br s, 1H); 8.00 (d, 1H); 7.72 (br d, 1H); 4.36 (q, 2H); 3.06 (s, 2H); 1.47 (t, 3H); 1.26 (m, 2H); Example no. 2-62: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.76 (br s, 1H); 7.93 (d, 1H); 7.49 (d, 1H); 7.42 (t, 1H); 4.77 (m, 1H); 4.36 (q, 2H); 3.34 (dd, 1H); 2.92 (dd, 1H); 1.66 (m, 1H); 1.47 (t, 3H); 0.95 (t, 3H); Example no. 2-63: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.76 (br s, 1H); 7.94 (d, 1H); 7.49 (d, 1H); 7.41 (t, 1H); 4.98 (m, 1H); 4.36 (q, 2H); 3.48 (m, 2H); 3.33 (s, 3H); 3.33 (dd, 1H); 3.03 (dd, 1H); 1.47 (t, 3H); Example no. 2-64: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.77 (br s, 1H); 7.95 (d, 1H); 7.50 (d, 1H); 7.40 (t, 1H); 5.15 (m, 1H); 4.36 (q, 1H); 3.51 (dd, 1H); 3.09 (dd, 1H); 3.02 (dd, 1H); 2.92 (dd, 1H); 1.47 (t, 3H); Example no. 2-65: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.77 (br s, 1H); 7.93 (d, 1H); 7.48 (d, 1H); 7.43 (t, 1H); 4.35 (q, 2H); 3.00 (s, 2H); 1.47 (t, 3H); 1.24 (m, 2H); 0.50 (m, 6H); 0.38 (m, 2H); Example No. 2-67: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.84 (br s, 1H); 8.02 (d, 1H); 7.74 (br d, 1H); 4.43 (m, 1H); 4.37 (q, 2H); 4.44 (dd, 1H); 3.06 (dd, 1H); 1.47 (t, 3H); 1.12 (m, 1H); 0.55 (m, 2H); 0.39 (m, 2H); Example no. 2-68: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 11.78 (br s, 1H); 7.94 (d, 1H); 7.49 (d, 1H); 7.42 (t, 1H); 4.38 (m, 3H); 3.39 (dd, 1H); 3.02 (dd, 1H); 1.47 (t, 3H); 1.13 (m, 1H); 0.55 (m, 2H); 0.39 (m, 2H); Example no. 3-11: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 7.86 (d, 1H); 7.55 (br d, 1H); 6.05 (dd, 1H); 3.88 (s, 3H); 3.45 (m, 1H); 3.11 (m, 1H); 1.97 (s, 3H); Example No.3-12: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 8.44 (s, 1H); 8.16 (d, 1H); 7.76 (br d, 1H); 7.55 (s, 1H); 3.91 (s, 3H); Example No.3-14: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 8.07 (d, 1H); 7.70 (br d, 1H); 6.51 (s, 1H); 3.91 (s, 3H); 2.52 (s, 3H); Example No.3-15: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 8.07 (d, 1H); 7.70 (br d, 1H); 6.47 (s, 1H); 3.90 (s, 3H); 2.26 (m, 1H); 1.14 (m, 2H); 0.96 (m, 2H); Example no. 3-31: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 7.82 (d, 1H); 7.32 (d, 1H); 7.30 (t, 1H); 6.08 (dd, 1H); 3.86 (s, 3H); 3.39 (m, 1H); 3.12 (m, 1H); 1.95 (s, 3H); Example No. 3-32: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 8.38 (s, 1H); 8.12 (d, 1H); 7.52 (d, 1H); 7.51 (s, 1H); 7.41 (t, 1H); 3.89 (s, 3H); Example No. 3-34: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 8.02 (d, 1H); 7.47 (d, 1H); 7.34 (t, 1H); 6.43 (s, 1H); 3.88 (s, 3H); 2.52 (s, 3H); Example No. 3-35: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 8.02 (d, 1H); 7.46 (d, 1H); 7.33 (t, 1H); 6.40 (s, 1H); 3.88 (s, 3H); 2.24 (m, 1H); 1.13 (m, 2H); 0.97 (m, 2H); Example No.3-41: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 8.07 (d, 1H); 7.71 (br d, 1H); 7.01 (s, 1H); 3.90 (s, 3H); 0.37 (s, 9H); Example no. 3-42: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 8.02 (d, 1H); 7.47 (d, 1H); 7.33 (t, 1H); 6.93 (s, 1H); 3.88 (s, 3H); 0.37 (s, 9H); Example no. 3-50: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 8.04 (br d, 1H); 7.67 (d, 1H); 4.95 (m, 1H); 3.89 (s, 3H); 3.39 (dd, 1H); 2.85 (dd, 1H); 1.32 (d, 3H); Example no. 3-51: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 8.04 (d, 1H); 7.67 (br d, 1H); 4.78 (m, 1H); 3.90 (s, 3H); 3.36 (dd, 1H); 2.92 (dd, 1H); 1.65 (m, 2H); 0.94 (t, 3H); Example no. 3-52: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 7.92 (d, 1H); 7.32 (br d, 1H); 5.01 (m, 1H); 3.96 (s, 3H); 3.63 (dd, 1H); 3.56 (dd, 1H); 3.45 (s, 3H); 3.34 (dd, 1H); 1.13 (dd, 1H); Example no. 3-53: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 8.06 (d, 1H); 7.67 (br d, 1H); 5.15 (m, 1H); 3.90 (s, 3H); 3.51 (m, 1H); 3.12 (m, 1H); 2.99 (m, 2H); Example No.3-54: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 8.03 (d, 1H); 7.66 (br d, 1H); 3.89 (s, 3H); 3.03 (s, 2H); 1.24 (m, 2H); 0.49 (m, 6H); 0.35 (m, 2H); Example no. 3-60: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 7.98 (d, 1H); 7.08 (d, 1H); 6.59 (t, 1H); 5.09 (m, 1H); 3.91 (s, 3H); 3.50 (dd, 1H); 3.15 (dd, 1H); 2.56 (s, 3H); Example no. 3-64: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 7.99 (d, 1H); 7.41 (d, 1H); 7.40 (t, 1H); 4.33 (m, 1H); 3.88 (s, 3H); 3.31 (dd, 1H); 2.89 (dd, 1H); 1.64 (m, 2H); 0.94 (t, 3H); Example no. 3-65: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 7.99 (d, 1H); 7.43 (d, 1H); 7.39 (t, 1H); 4.95 (m, 1H); 3.88 (s, 3H); 3.47 (m, 2H); 3.32 (s, 3H); 3.30 (m, 1H); 3.00 (m, 1H); Example no. 3-66: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 8.01 (d, 1H); 7.45 (d, 1H); 7.39 (t, 1H); 5.14 (m, 1H); 3.88 (s, 3H); 3.48 (m, 1H); 3.06 (m, 1H); 3.95 (m, 2H); Example no. 3-67: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 7.98 (d, 1H); 7.42 (d, 1H); 7.41 (t, 1H); 3.87 (s, 3H); 2.97 (s, 2H); 1.22 (m, 2H); 0.51 (m, 2H); 0.48 (m, 4H); 0.37 (m, 2H); Example no. 3-69: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 8.04 (d, 1H); 7.67 (br d, 1H); 4.40 (m, 1H); 3.90 (s, 3H); 4.41 (dd, 1H); 3.02 (dd, 1H); 1.10 (m, 1H); 0.53 (m, 1H); 0.38 (m, 2H); Example no. 3-70: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 7.99 (d, 1H); 7.43 (d, 1H); 7.40 (t, 1H); 4.37 (m, 1H); 3.88 (s, 3H); 3.36 (dd, 1H); 2.99 (dd, 1H); 1.11 (m, 1H); 0.53 (m, 2H); 0.37 (m, 2H); Example no. 3-71: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 7.91 (d, 1H); 7.54 (br d, 1H); 4.05 (dd, 1H); 3.78 (s, 3H); 3.33 (dd, 1H); 2.92 (t, 1H); -0.12 (s, 9H); Example No. 4-11: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.70 (br s, 1H); 7.82 (d, 1H); 7.55 (br d, 1H); 6.05 (dd, 1H); 3.46 (m, 3H); 3.10 (m, 1H); 1.97 (s, 3H); Example no. 4-12: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.90 (br s, 1H); 8.43 (s, 1H); 8.13 (d, 1H); 7.71 (br d, 1H); 7.54 (s, 1H); Example no. 4-13: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.80 (br s, 1H); 9.18 (s, 1H); 8.06 (d, 1H); 7.67 (br d, 1H); 6.89 (s, 1H); Example No. 4-14: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.80 (br s, 1H); 8.04 (d, 1H); 7.66 (br d, 1H); 6.50 (s, 1H); 2.52 (s, 3H); Example No. 4-15: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.70 (br s, 1H); 8.03 (d, 1H); 7.65 (br d, 1H); 6.47 (s, 1H); 2.25 (m, 1H); 1.12 (m, 2H); 0.96 (m, 1H); Example no. 4-31: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.40 (br s, 1H); 7.79 (d, 1H); 7.28 (d, 1H); 7.28 (t, 1H); 6.08 (dd, 1H); 3.38 (m, 1H); 3.12 (m, 1H); 1.95 (s, 3H); Example no. 4-32: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.65 (br s, 1H); 8.37 (s, 1H); 8.09 (d, 1H); 7.48 (s, 1H); 7.47 (d, 1H); 7.38 (t, 1H); Example no. 4-33: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.60 (br s, 1H); 9.13 (s, 1H); 8.02 (d, 1H); 7.44 (d, 1H); 7.31 (t, 1H); 6.80 (s, 1H); Example no. 4-34: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.50 (br s, 1H); 7.99 (d, 1H); 7.43 (d, 1H); 7.31 (t, 1H); 6.42 (s, 1H); 2.52 (s, 3H); Example no. 4-35: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.50 (br s, 1H); 7.99 (d, 1H); 7.42 (d, 1H); 7.30 (t, 1H); 6.39 (s, 1H); 2.23 (m, 1H); 1.12 (m, 2H); 0.96 (m, 2H); Example No. 4-48: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.90 (br s, 1H); 8.00 (d, 1H); 7.62 (br d, 1H); 4.95 (m, 1H); 3.39 (dd, 1H); 2.85 (dd, 1H); 1.32 (d, 3H); Example No. 4-49: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.87 (br s, 1H); 8.00 (d, 1H); 7.62 (br d, 1H); 4.78 (m, 1H); 3.36 (dd, 1H); 2.92 (dd, 1H); 1.65 (m, 2H); 0.94 (t, 3H); Example No. 4-50: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.81 (br s, 1H); 8.00 (d, 1H); 7.62 (br d, 1H); 4.98 (m, 1H); 3.48 (m, 2H); 3.35 (dd, 1H); 3.32 (s, 3H); 3.05 (dd, 1H); Example No. 4-51: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.88 (br s, 1H); 8.02 (d, 1H); 7.63 (br d, 1H); 5.15 (m, 1H); 3.51 (dd, 1H); 3.12 (dd, 1H); 3.05 (dd, 1H); 2.93 (dd, 1H); Example No. 4-52: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.85 (br s, 1H); 7.99 (d, 1H); 7.61 (br d, 1H); 3.03 (br s, 2H); 1.24 (m, 2H); 0.49 (m, 6H); 0.36 (m, 2H); Example no. 4-63: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 8.11 (d, 1H); 7.24 (d, 1H); 6.60 (t, 1H); 5.02 (m, 1H); 3.65 (dd, 1H); 3.58 (dd, 1H); 3.46 (s, 3H); 3.35 (dd, 1H); 3.14 (dd, 1H); Example no. 4-64: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 7.99 (d, 1H); 7.41 (d, 1H); 7.37 (t, 1H); 5.13 (m, 1H); 3.47 (m, 1H); 3.06 (m, 1H); 2.95 (m, 2H); Example no. 4-65: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.62 (br s, 1H); 7.95 (d, 1H); 7.39 (t, 1H); 7.38 (d, 1H); 2.97 (br s, 2H); 1.23 (m, 2H); 0.49 (m, 6H); 0.37 (m, 2H) Example No. 4-67: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.85 (br s, 1H); 8.00 (d, 1H); 7.62 (br d, 1H); 4.40 (m, 1H); 3.41 (dd, 1H); 3.02 (dd, 1H); 1.10 (m, 1H); 0.52 (m, 2H); 0.38 (m, 2H); Example no. 4-68: 1 H-NMR (400 MHz, DMSO-d 6 ): δ = 13.63 (br s, 1H); 7.96 (d, 1H); 7.40 (d, 1H); 7.38 (t, 1H); 4.36 (m, 1H); 3.35 (dd, 1H); 2.99 (dd, 1H); 1.11 (m, 1H); 0.53 (m, 2H); 0.38 (m, 2H). B. Formulation examples a) A dust is obtained by mixing 10 parts by weight of a compound of formula (I) and/or salts thereof and 90 parts by weight of talc as an inert substance and comminuting the mixture in a hammer mill. b) A wettable powder which is easily dispersible in water is obtained by mixing 25 parts by weight of a compound of formula (I) and/or salts thereof, 64 parts by weight of kaolin-containing quartz as inert material, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltaurine as wetting and dispersing agent and grinding in a pin mill. c) A dispersion concentrate which is easily dispersible in water is obtained by mixing 20 parts by weight of a compound of formula (I) and/or its salts with 6 parts by weight of alkylphenol polyglycol ether (®Triton 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 to over 277 °C) and grinding in a 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 its salts, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier. e) Water-dispersible granules are obtained by mixing 75 parts by weight of a compound of formula (I) and/or its salts, 10 parts by weight of calcium ligninsulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl alcohol, and 7 parts by weight of kaolin, grinding the mixture on a pin mill, and granulating the powder in a fluidized bed by spraying water as the granulating liquid. f) Water-dispersible granules are also obtained by mixing 25 parts by weight of a compound of formula (I) and/or its salts, 5 parts by weight of 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, 2 parts by weight of oleoylmethyltauric acid sodium, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water are homogenized and pre-crushed in a colloid mill, then ground in a bead mill and the resulting suspension is atomized and dried in a spray tower using a single-component nozzle. C. Biological examples The abbreviations used for the weeds mean: ABUTH Abutilon theophrasti ALOMY Alopecurus myosuroides AVEFA Avena fatua AMARE Amaranthus retroflexus CYPES Cyperus esculentus DIGSA Digitaria sanguinalis ECHCG Echinochloa crus-galli HORMU Hordeum murinum KCHSC Kochia scoparia LOLMU Lolium multiflorum LOLRI Lolium rigidum MATIN Matricaria inodora PHBPU Pharbitis purpurea POLCO Polygonum convolvulus SETVI Setaria viridis STEME Stellaria media VERPE Veronica persica VIOTR Viola tricolor 1. Herbicidal action against weeds in pre-emergence Seeds of monocotyledonous or dicotyledonous weeds or cultivated plants are placed in sandy loam soil in wood fibre pots and covered with soil. The compounds of the invention, formulated as wettable powders (WP) or emulsion concentrates (EC), are then applied to the surface of the covering soil as an aqueous suspension or emulsion at a water application rate equivalent to 600 to 800 l/ha with the addition of 0.2% wetting agent. After treatment, the pots are placed in the greenhouse and maintained under favorable growth conditions for the test plants. Visual assessment of damage to the test plants is carried out after a trial period of 3 weeks in comparison to untreated controls (herbicidal activity in percent (%): 100% activity = plants died, 0% activity = same as control plants). Numerous compounds of the invention demonstrated very good activity against a variety of important weeds. The following tables show examples of the post-emergence herbicidal activity of the compounds of the invention, with the herbicidal activity expressed as a percentage. Table C-1: Pre-emergence activity at 20 g/ha against ZEAMX in %
Figure imgf000058_0001
Table C-2: Pre-emergence effect at 80g/ha against ZEAMX in %
Figure imgf000058_0002
Table C-3: Pre-emergence effect at 20g/ha against TRZAS in %
Figure imgf000058_0003
Figure imgf000059_0001
Table C-4: Pre-emergence effect at 80g/ha against TRZAS in %
Figure imgf000059_0002
Table C-5: Pre-emergence effect at 20g/ha against GLXMA in %
Figure imgf000059_0003
Table C-6: Pre-emergence effect at 80g/ha against GLXMA in %
Figure imgf000060_0001
Table C-7: Pre-emergence effect at 20g/ha against ABUTH in %
Figure imgf000060_0002
Table C-8: Pre-emergence effect at 80g/ha against ABUTH in %
Figure imgf000060_0003
Figure imgf000061_0001
Table C-9: Pre-emergence effect at 20g/ha against ALOMY in %
Figure imgf000061_0002
Table C-10: Pre-emergence effect at 80g/ha against ALOMY in %
Figure imgf000061_0003
Table C-11: Pre-emergence effect at 20g/ha against AMARE in %
Figure imgf000062_0002
Table C-12: Pre-emergence effect at 80g/ha against AMARE in %
Figure imgf000062_0001
Figure imgf000063_0001
Table C-13: Pre-emergence effect at 20g/ha against DIGSA in %
Figure imgf000063_0002
Table C-14: Pre-emergence effect at 80g/ha against DIGSA in %
Figure imgf000063_0003
Figure imgf000064_0001
Table C-15: Pre-emergence efficacy at 20g/ha against ECHCG in %
Figure imgf000064_0002
Table C-16: Pre-emergence efficacy at 80g/ha against ECHCG in %
Figure imgf000064_0003
Table C-17: Pre-emergence efficacy at 20g/ha against LOLRI in %
Figure imgf000065_0002
Table C-18: Pre-emergence efficacy at 80g/ha against LOLRI in %
Figure imgf000065_0001
Table C-19: Pre-emergence effect at 20g/ha against MATIN in %
Figure imgf000066_0002
Table C-20: Pre-emergence effect at 80g/ha against MATIN in %
Figure imgf000066_0001

Figure imgf000067_0001
Tabelle C-21: Vorauflaufwirkung bei 20g/ha gegen PHBPU in %
Figure imgf000067_0002
Tabelle C-22: Vorauflaufwirkung bei 80g/ha gegen PHBPU in %
Figure imgf000067_0003
Figure imgf000068_0001
Tabelle C-23: Vorauflaufwirkung bei 20g/ha gegen POLCO in %
Figure imgf000068_0002
Tabelle C-24: Vorauflaufwirkung bei 80g/ha gegen POLCO in %
Figure imgf000068_0003
Tabelle C-25: Vorauflaufwirkung bei 20g/ha gegen SETVI in %
Figure imgf000068_0004
Figure imgf000069_0001
Tabelle C-26: Vorauflaufwirkung bei 80g/ha gegen SETVI in %
Figure imgf000069_0002
Tabelle C-27: Vorauflaufwirkung bei 20g/ha gegen VERPE in %
Figure imgf000069_0003
Tabelle C-28: Vorauflaufwirkung bei 80g/ha gegen VERPE in %
Figure imgf000070_0001
Tabelle C-29: Vorauflaufwirkung bei 20g/ha gegen VIOTR in %
Figure imgf000070_0002
Tabelle C-30: Vorauflaufwirkung bei 80g/ha gegen VIOTR in %
Figure imgf000070_0003
Figure imgf000067_0001
Table C-21: Pre-emergence effect at 20g/ha against PHBPU in %
Figure imgf000067_0002
Table C-22: Pre-emergence effect at 80g/ha against PHBPU in %
Figure imgf000067_0003
Figure imgf000068_0001
Table C-23: Pre-emergence effect at 20g/ha against POLCO in %
Figure imgf000068_0002
Table C-24: Pre-emergence effect at 80g/ha against POLCO in %
Figure imgf000068_0003
Table C-25: Pre-emergence efficacy at 20g/ha against SETVI in %
Figure imgf000068_0004
Figure imgf000069_0001
Table C-26: Pre-emergence efficacy at 80g/ha against SETVI in %
Figure imgf000069_0002
Table C-27: Pre-emergence effect at 20g/ha against VERPE in %
Figure imgf000069_0003
Table C-28: Pre-emergence effect at 80g/ha against VERPE in %
Figure imgf000070_0001
Table C-29: Pre-emergence effect at 20g/ha against VIOTR in %
Figure imgf000070_0002
Table C-30: Pre-emergence effect at 80g/ha against VIOTR in %
Figure imgf000070_0003

Figure imgf000071_0001
Tabelle C-31: Vorauflaufwirkung bei 20g/ha gegen KCHSC in %
Figure imgf000071_0002
Figure imgf000072_0002
Tabelle C-32: Vorauflaufwirkung bei 80g/ha gegen KCHSC in %
Figure imgf000072_0001
2. Herbizide Wirkung gegen Schadpflanzen im Nachauflauf 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 Wochen 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 l/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). Dabei zeigten zahlreiche erfindungsgemäße Verbindungen eine sehr gute Wirkung gegen eine Vielzahl bedeutender Schadpflanzen. Die nachfolgenden Tabellen zeigen beispielhaft die herbizide Wirkung der erfindungsgemäßen Verbindungen im Nachauflauf, wobei die herbizide Wirkung in Prozent angegeben ist. Tabelle C-33: Nachauflaufwirkung bei 20g/ha gegen ZEAMX in %
Figure imgf000073_0001
Tabelle C-34: Nachauflaufwirkung bei 80g/ha gegen ZEAMX in %
Figure imgf000073_0002
Tabelle C-35: Nachauflaufwirkung bei 20g/ha gegen TRZAS in %
Figure imgf000073_0003
Tabelle C-36: Nachauflaufwirkung bei 80g/ha gegen TRZAS in %
Figure imgf000073_0004
Figure imgf000074_0001
Tabelle C-37: Nachauflaufwirkung bei 20g/ha gegen ABUTH in %
Figure imgf000074_0002
Tabelle C-38: Nachauflaufwirkung bei 80g/ha gegen ABUTH in %
Figure imgf000074_0003
Figure imgf000071_0001
Table C-31: Pre-emergence effect at 20g/ha against KCHSC in %
Figure imgf000071_0002
Figure imgf000072_0002
Table C-32: Pre-emergence effect at 80g/ha against KCHSC in %
Figure imgf000072_0001
2. Post-emergence herbicidal activity against weeds. Seeds of monocotyledonous or dicotyledonous weeds or cultivated plants are sown in wood fiber pots in sandy loam soil, covered with soil, and grown in a greenhouse under favorable growth conditions. Two to three weeks after sowing, the test plants are treated at the single-leaf stage. The compounds of the invention, formulated as wettable powders (WP) or emulsion concentrates (EC), are then sprayed onto the green plant parts as an aqueous suspension or emulsion at a water application rate of the equivalent of 600 to 800 l/ha with the addition of 0.2% wetting agent. After approximately three weeks of the test plants in the greenhouse under optimal growth conditions, the effectiveness of the preparations is visually assessed in comparison to untreated controls (herbicidal activity in percent (%): 100% activity = plants are dead, 0% activity = same as control plants). Numerous compounds of the invention showed very Good activity against a variety of important weeds. The following tables show examples of the postemergence herbicidal activity of the compounds of the invention, with the herbicidal activity expressed as a percentage. Table C-33: Postemergence activity at 20 g/ha against ZEAMX in %
Figure imgf000073_0001
Table C-34: Post-emergence effect at 80g/ha against ZEAMX in %
Figure imgf000073_0002
Table C-35: Post-emergence effect at 20g/ha against TRZAS in %
Figure imgf000073_0003
Table C-36: Post-emergence effect at 80g/ha against TRZAS in %
Figure imgf000073_0004
Figure imgf000074_0001
Table C-37: Post-emergence effect at 20g/ha against ABUTH in %
Figure imgf000074_0002
Table C-38: Post-emergence effect at 80g/ha against ABUTH in %
Figure imgf000074_0003

Figure imgf000075_0001
Tabelle C-39: Nachauflaufwirkung bei 20g/ha gegen ALOMY in %
Figure imgf000075_0002
Tabelle C-40: Nachauflaufwirkung bei 80g/ha gegen ALOMY in %
Figure imgf000075_0003
Figure imgf000076_0001
Tabelle C-41: Nachauflaufwirkung bei 20g/ha gegen AMARE in %
Figure imgf000076_0002
Tabelle C-42: Nachauflaufwirkung bei 80g/ha gegen AMARE in %
Figure imgf000076_0003
Figure imgf000077_0001
Tabelle C-43: Nachauflaufwirkung bei 20g/ha gegen DIGSA in %
Figure imgf000077_0002
Tabelle C-44: Nachauflaufwirkung bei 80g/ha gegen DIGSA in %
Figure imgf000077_0003
Figure imgf000078_0001
Tabelle C-45: Nachauflaufwirkung bei 20g/ha gegen LOLRI in %
Figure imgf000078_0002
Tabelle C-46: Nachauflaufwirkung bei 80g/ha gegen LOLRI in %
Figure imgf000078_0003
Figure imgf000075_0001
Table C-39: Post-emergence effect at 20g/ha against ALOMY in %
Figure imgf000075_0002
Table C-40: Post-emergence effect at 80g/ha against ALOMY in %
Figure imgf000075_0003
Figure imgf000076_0001
Table C-41: Post-emergence effect at 20g/ha against AMARE in %
Figure imgf000076_0002
Table C-42: Post-emergence effect at 80g/ha against AMARE in %
Figure imgf000076_0003
Figure imgf000077_0001
Table C-43: Post-emergence effect at 20g/ha against DIGSA in %
Figure imgf000077_0002
Table C-44: Post-emergence effect at 80g/ha against DIGSA in %
Figure imgf000077_0003
Figure imgf000078_0001
Table C-45: Post-emergence effect at 20g/ha against LOLRI in %
Figure imgf000078_0002
Table C-46: Post-emergence effect at 80g/ha against LOLRI in %
Figure imgf000078_0003

Figure imgf000079_0001
Tabelle C-47: Nachauflaufwirkung bei 20g/ha gegen MATIN in %
Figure imgf000079_0002
Figure imgf000080_0001
Tabelle C-48: Nachauflaufwirkung bei 80g/ha gegen MATIN in %
Figure imgf000080_0002
Tabelle C-49: Nachauflaufwirkung bei 20g/ha gegen PHBPU in %
Figure imgf000081_0001
Tabelle C-50: Nachauflaufwirkung bei 80g/ha gegen PHBPU in %
Figure imgf000081_0002
Tabelle C-51: Nachauflaufwirkung bei 80g/ha gegen POLCO in %
Figure imgf000082_0001
Tabelle C-52: Nachauflaufwirkung bei 20g/ha gegen SETVI in %
Figure imgf000082_0002
Tabelle C-53: Nachauflaufwirkung bei 80g/ha gegen SETVI in %
Figure imgf000082_0003
Figure imgf000083_0001
Tabelle C-54: Nachauflaufwirkung bei 20g/ha gegen VERPE in %
Figure imgf000083_0002
Tabelle C-55: Nachauflaufwirkung bei 80g/ha gegen VERPE in %
Figure imgf000083_0003
Figure imgf000084_0001
Tabelle C-56: Nachauflaufwirkung bei 20g/ha gegen VIOTR in %
Figure imgf000084_0002
Tabelle C-57: Nachauflaufwirkung bei 80g/ha gegen VIOTR in %
Figure imgf000084_0003
Figure imgf000079_0001
Table C-47: Post-emergence effect at 20g/ha against MATIN in %
Figure imgf000079_0002
Figure imgf000080_0001
Table C-48: Post-emergence effect at 80g/ha against MATIN in %
Figure imgf000080_0002
Table C-49: Post-emergence effect at 20g/ha against PHBPU in %
Figure imgf000081_0001
Table C-50: Post-emergence effect at 80g/ha against PHBPU in %
Figure imgf000081_0002
Table C-51: Post-emergence effect at 80g/ha against POLCO in %
Figure imgf000082_0001
Table C-52: Post-emergence effect at 20g/ha against SETVI in %
Figure imgf000082_0002
Table C-53: Post-emergence effect at 80g/ha against SETVI in %
Figure imgf000082_0003
Figure imgf000083_0001
Table C-54: Post-emergence effect at 20g/ha against VERPE in %
Figure imgf000083_0002
Table C-55: Post-emergence effect at 80g/ha against VERPE in %
Figure imgf000083_0003
Figure imgf000084_0001
Table C-56: Post-emergence effect at 20g/ha against VIOTR in %
Figure imgf000084_0002
Table C-57: Post-emergence effect at 80g/ha against VIOTR in %
Figure imgf000084_0003

Figure imgf000085_0001
Tabelle C-58: Nachauflaufwirkung bei 20g/ha gegen KCHSC in %
Figure imgf000085_0002
Figure imgf000086_0002
Tabelle C-59: Nachauflaufwirkung bei 80g/ha gegen KCHSC in %
Figure imgf000086_0001
Vergleichsversuche In den folgenden Versuchen wurde die herbizide Wirkung zahlreicher erfindungsgemäßer und die der strukturell nächsten aus WO2012/028579 bekannten Verbindungen unter den oben genannten Bedingungen im Vorauflauf und Nachauflauf verglichen. Die in den Tabellen genannten Beispiel-Nr. beziehen sich auf die erfindungsgemäßen Verbindungen der vorliegenden Anmeldung; die jeweiligen Vergleichsverbindungen werden im oben genannten Dokument offenbart, aber nicht spezifisch genannt (Verbindungen V-1 bis V-8) und sind mit ihrem IUPAC-Namen im Folgenden bezeichnet: V-1: 2-Chlor-4-methoxy-3-[(5RS)-3-methyl-4,5-dihydro-1,2-oxazol-5-yl]-N-(1-methyl-1H-tetrazol-5- yl)benzamid V-2: 2-Chlor-N-(1-ethyl-1H-tetrazol-5-yl)-4-methoxy-3-[(5RS)-3-methyl-4,5-dihydro-1,2-oxazol-5- yl]benzamid V-3: 2-Chlor-4-methoxy-N-(1-methyl-1H-tetrazol-5-yl)-3-(1,2-oxazol-3-yl)benzamid V-4: 2-Chlor-N-(1-ethyl-1H-tetrazol-5-yl)-4-methoxy-3-(1,2-oxazol-3-yl)benzamid V-5: 2-Chlor-4-methoxy-3-(5-methyl-1,2-oxazol-3-yl)-N-(1-methyl-1H-tetrazol-5-yl)benzamid V-6: 2-Chlor-N-(1-ethyl-1H-tetrazol-5-yl)-4-methoxy-3-(5-methyl-1,2-oxazol-3-yl)benzamid V-7: 2-Chlor-3-(5-cyclopropyl-1,2-oxazol-3-yl)-4-methoxy-N-(1-methyl-1H-tetrazol-5-yl)benzamid V-8: 2-Chlor-3-(5-cyclopropyl-1,2-oxazol-3-yl)-N-(1-ethyl-1H-tetrazol-5-yl)-4-methoxybenzamid Herbizide Wirkung im Vorauflauf: efg = erfindungsgemäß, Verbindung der vorliegenden Anmeldung
Figure imgf000087_0001
Figure imgf000087_0002
Figure imgf000087_0003
Figure imgf000087_0004
Figure imgf000088_0001
Figure imgf000088_0002
Figure imgf000088_0003
Figure imgf000088_0004
Figure imgf000088_0005
Figure imgf000088_0006
Figure imgf000089_0001
Figure imgf000089_0002
Figure imgf000089_0003
Figure imgf000089_0004
Figure imgf000089_0005
Figure imgf000089_0006
Figure imgf000090_0001
Figure imgf000090_0002
Figure imgf000090_0003
Figure imgf000090_0004
Figure imgf000090_0005
Figure imgf000090_0006
Figure imgf000091_0001
Herbizide Wirkung im Nachauflauf: efg = erfindungsgemäß, Verbindung der vorliegenden Anmeldung
Figure imgf000091_0002
Figure imgf000091_0003
Figure imgf000091_0004
Figure imgf000091_0005
Figure imgf000092_0001
Figure imgf000092_0002
Figure imgf000085_0001
Table C-58: Post-emergence effect at 20g/ha against KCHSC in %
Figure imgf000085_0002
Figure imgf000086_0002
Table C-59: Post-emergence effect at 80g/ha against KCHSC in %
Figure imgf000086_0001
Comparative Experiments In the following experiments, the herbicidal activity of numerous compounds according to the invention and those structurally closest to them, known from WO2012/028579, was compared under the above-mentioned pre-emergence and post-emergence conditions. The example numbers listed in the tables refer to the compounds according to the invention of the present application; the respective comparison compounds are disclosed in the above-mentioned document but not specifically named (compounds V-1 to V-8) and are designated below by their IUPAC name: V-1: 2-chloro-4-methoxy-3-[(5RS)-3-methyl-4,5-dihydro-1,2-oxazol-5-yl]-N-(1-methyl-1H-tetrazol-5-yl)benzamide V-2: 2-Chloro-N-(1-ethyl-1H-tetrazol-5-yl)-4-methoxy-3-[(5RS)-3-methyl-4,5-dihydro-1,2-oxazol-5-yl]benzamide V-3: 2-Chloro-4-methoxy-N-(1-methyl-1H-tetrazol-5-yl)-3-(1,2-oxazol-3-yl)benzamide V-4: 2-Chloro-N-(1-ethyl-1H-tetrazol-5-yl)-4-methoxy-3-(1,2-oxazol-3-yl)benzamide V-5: 2-Chloro-4-methoxy-3-(5-methyl-1,2-oxazol-3-yl)-N-(1-methyl-1H-tetrazol-5-yl)benzamide V-6: 2-Chloro-N-(1-ethyl-1H-tetrazol-5-yl)-4-methoxy-3-(5-methyl-1,2-oxazol-3-yl)benzamide V-7: 2-Chloro-3-(5-cyclopropyl-1,2-oxazol-3-yl)-4-methoxy-N-(1-methyl-1H-tetrazol-5-yl)benzamide V-8: 2-Chloro-3-(5-cyclopropyl-1,2-oxazol-3-yl)-N-(1-ethyl-1H-tetrazol-5-yl)-4-methoxybenzamide Herbicidal action in pre-emergence: efg = inventive compound of the present application
Figure imgf000087_0001
Figure imgf000087_0002
Figure imgf000087_0003
Figure imgf000087_0004
Figure imgf000088_0001
Figure imgf000088_0002
Figure imgf000088_0003
Figure imgf000088_0004
Figure imgf000088_0005
Figure imgf000088_0006
Figure imgf000089_0001
Figure imgf000089_0002
Figure imgf000089_0003
Figure imgf000089_0004
Figure imgf000089_0005
Figure imgf000089_0006
Figure imgf000090_0001
Figure imgf000090_0002
Figure imgf000090_0003
Figure imgf000090_0004
Figure imgf000090_0005
Figure imgf000090_0006
Figure imgf000091_0001
Post-emergence herbicidal activity: efg = compound of the present application
Figure imgf000091_0002
Figure imgf000091_0003
Figure imgf000091_0004
Figure imgf000091_0005
Figure imgf000092_0001
Figure imgf000092_0002

Claims

Patentansprüche: 1. 3-Heterocyclyl-benzamide der Formel (I) oder deren Salze
Figure imgf000093_0001
worin die Symbole und Indizes folgende Bedeutungen haben: Rx bedeutet (C1-C6)-Alkyl, X bedeutet Halogen oder (C1-C6)-Alkyl, Y bedeutet Halogen-(C1-C6)-alkoxy, Z bedeutet Z-1, Z-2, Z-3 oder Z-4, wobei Z-1 bis Z-4 die folgenden Bedeutungen haben
Figure imgf000093_0002
R1 bedeutet Wasserstoff, (C1-C6)-Alkyl oder Halogen-(C1-C6)-alkyl, R2 bedeutet Wasserstoff, (C1-C6)-Alkyl oder (C3-C6)-Cycloalkyl, R3 bedeutet (C1-C6)-Alkyl, Halogen-(C1-C6)-alkyl oder (C3-C6)-Cycloalkyl, und R4 und R5 bedeuten unabhängig voneinander Wasserstoff, (C1-C6)-Alkyl, (C1-C6)-Alkyloxy-(C1- C6)-alkyl, Cyano-(C1-C6)-alkyl oder (C3-C6)-Cycloalkyl. Claims: 1. 3-Heterocyclyl-benzamides of formula (I) or their salts
Figure imgf000093_0001
wherein the symbols and indices have the following meanings: R x means (C 1 -C 6 )-alkyl, X means halogen or (C 1 -C 6 )-alkyl, Y means halogen-(C 1 -C 6 )-alkoxy, Z means Z-1, Z-2, Z-3 or Z-4, where Z-1 to Z-4 have the following meanings
Figure imgf000093_0002
R 1 is hydrogen, (C 1 -C 6 )-alkyl or halo-(C 1 -C 6 )-alkyl, R 2 is hydrogen, (C 1 -C 6 )-alkyl or (C 3 -C 6 )-cycloalkyl, R 3 is (C 1 -C 6 )-alkyl, halo-(C 1 -C 6 )-alkyl or (C 3 -C 6 )-cycloalkyl, and R 4 and R 5 are independently hydrogen, (C 1 -C 6 )-alkyl, (C 1 -C 6 )-alkyloxy-(C 1 -C 6 )-alkyl, cyano-(C 1 -C 6 )-alkyl or (C 3 -C 6 )-cycloalkyl. 2. 3-Heterocyclyl-benzamide gemäß Anspruch 1, wobei die Symbole folgende Bedeutungen haben: Rx bedeutet (C1-C6)-Alkyl, X bedeutet Halogen oder (C1-C6)-Alkyl, Y bedeutet OCF3, OCHF2 oder OCF2Me Z bedeutet Z-1, Z-2, Z-3 oder Z-4, wobei Z-1 bis Z-4 die folgenden Bedeutungen haben
Figure imgf000094_0001
R1 bedeutet Wasserstoff oder (C1-C6)-Alkyl, R2 bedeutet Wasserstoff, (C1-C6)-Alkyl oder (C3-C6)-Cycloalkyl, R3 bedeutet (C1-C6)-Alkyl oder Halogen-(C1-C6)-alkyl, und R4 und R5 bedeuten unabhängig voneinander Wasserstoff, (C1-C6)-Alkyl, (C1-C6)-Alkyloxy-(C1- C6)-alkyl, Cyano-(C1-C6)-alkyl oder (C3-C6)-Cycloalkyl. 3. 2. 3-Heterocyclyl-benzamides according to claim 1, wherein the symbols have the following meanings: R x is (C 1 -C 6 )-alkyl, X is halogen or (C 1 -C 6 )-alkyl, Y is OCF 3 , OCHF 2 or OCF 2 Me Z is Z-1, Z-2, Z-3 or Z-4, where Z-1 to Z-4 have the following meanings
Figure imgf000094_0001
R 1 is hydrogen or (C 1 -C 6 )-alkyl, R 2 is hydrogen, (C 1 -C 6 )-alkyl or (C 3 -C 6 )-cycloalkyl, R 3 is (C 1 -C 6 )-alkyl or halo-(C 1 -C 6 )-alkyl, and R 4 and R 5 are independently hydrogen, (C 1 -C 6 )-alkyl, (C 1 -C 6 )-alkyloxy-(C 1 -C 6 )-alkyl, cyano-(C 1 -C 6 )-alkyl or (C 3 -C 6 )-cycloalkyl. 3. 3-Heterocyclyl-benzamide gemäß Anspruch 1 oder, wobei die Symbole folgende Bedeutungen haben: Rx bedeutet Methyl oder Ethyl, X bedeutet Chlor, Brom, Methyl oder Ethyl, Y bedeutet OCF3 oder OCHF2, Z bedeutet Z-1, Z-2, Z-3 oder Z-4, wobei Z-1 bis Z-4 die folgenden Bedeutungen haben (
Figure imgf000094_0002
R1 bedeutet Wasserstoff oder Methyl, R2 bedeutet Wasserstoff, Methyl, Ethyl oder c-Propyl, R3 bedeutet Methyl, Ethyl oder i-Propyl, und R4 und R5 bedeuten folgende Kombinationen Wasserstoff und Wasserstoff, Wasserstoff und Methyl, Wasserstoff und Ethyl, Wasserstoff und Cyclopropyl, Cyclopropyl und Cyclopropyl, Wasserstoff und Methoxymethyl oder Wasserstoff und Cyanomethyl. 3-Heterocyclyl-benzamides according to claim 1 or, where the symbols have the following meanings: R x is methyl or ethyl, X is chlorine, bromine, methyl or ethyl, Y is OCF 3 or OCHF 2 , Z is Z-1, Z-2, Z-3 or Z-4, where Z-1 to Z-4 have the following meanings (
Figure imgf000094_0002
R 1 represents hydrogen or methyl, R 2 represents hydrogen, methyl, ethyl or c-propyl, R 3 represents methyl, ethyl or i-propyl, and R 4 and R 5 represent the following combinations: hydrogen and hydrogen, hydrogen and methyl, hydrogen and ethyl, hydrogen and cyclopropyl, cyclopropyl and cyclopropyl, hydrogen and methoxymethyl or hydrogen and cyanomethyl. 4. Herbizide Mittel enthaltend mindestens ein 3-Heterocyclyl-benzamid gemäß einem der Ansprüche 1 bis 3 in Mischung mit Formulierungshilfsmitteln. 4. Herbicidal compositions comprising at least one 3-heterocyclylbenzamide according to one of claims 1 to 3 in a mixture with formulation auxiliaries. 5. Herbizide Mittel gemäß Anspruch 4 enthaltend mindestens einen weiteren pestizid wirksamen Stoff aus der Gruppe Insektizide, Akarizide, Herbizide, Fungizide, Safener und Wachstumsregulatoren. 5. Herbicidal compositions according to claim 4 containing at least one further pesticidally active substance from the group consisting of insecticides, acaricides, herbicides, fungicides, safeners and growth regulators. 6. Verfahren zur Bekämpfung unerwünschter Pflanzen, dadurch gekennzeichnet, daß man eine wirksame Menge mindestens eines 3-Heterocyclyl-benzamids gemäß einem der Ansprüche 1 bis 3 oder von herbiziden Mitteln nach Anspruch 4 oder 5 auf die Pflanzen oder auf den Ort des unerwünschten Pflanzenwachstums appliziert. 6. A method for controlling undesirable plants, characterized in that an effective amount of at least one 3-heterocyclylbenzamide according to one of claims 1 to 3 or of herbicidal compositions according to claim 4 or 5 is applied to the plants or to the site of undesirable plant growth. 7. Verwendung von 3-Heterocyclyl-benzamiden der Formel (I) gemäß einem der Ansprüche 1 bis 3 oder von herbiziden Mitteln nach Anspruch 4 oder 5 zur Bekämpfung unerwünschter Pflanzen. 7. Use of 3-heterocyclyl-benzamides of the formula (I) according to any one of claims 1 to 3 or of herbicidal compositions according to claim 4 or 5 for controlling undesirable plants. 8. Verwendung nach Anspruch 7, dadurch gekennzeichnet, daß die 3-Heterocyclyl-benzamide der Formel (I) zur Bekämpfung unerwünschter Pflanzen in Kulturen von Nutzpflanzen eingesetzt werden. 8. Use according to claim 7, characterized in that the 3-heterocyclyl-benzamides of the formula (I) are used to combat undesirable plants in crops of useful plants. 9. Verwendung nach Anspruch 8, dadurch gekennzeichnet, daß die Nutzpflanzen transgene Nutzpflanzen sind. 9. Use according to claim 8, characterized in that the crop plants are transgenic crop plants. 10. Verbindungen der Formel (II),
Figure imgf000095_0001
worin die Symbole und Indizes folgende Bedeutungen haben: L bedeutet Halogen oder R6O, X bedeutet Halogen oder (C1-C6)-Alkyl, Y bedeutet Halogen-(C1-C6)-alkoxy, Z bedeutet Z-1, Z-2, Z-3 oder Z-4, wobei Z-1 bis Z-4 die folgenden Bedeutungen haben
Figure imgf000095_0002
R1 bedeutet Wasserstoff, (C1-C6)-Alkyl oder Halogen-(C1-C6)-alkyl, R2 bedeutet Wasserstoff, (C1-C6)-Alkyl oder (C3-C6)-Cycloalkyl, oder R2 kann auch Si((C1-C6)-Alkyl)3 bedeuten, wenn L OR6 bedeutet und R6 für (C1-C6)-Alkyl steht, R3 bedeutet (C1-C6)-Alkyl, Halogen-(C1-C6)-alkyl oder (C3-C6)-Cycloalkyl, R4 und R5 bedeuten unabhängig voneinander Wasserstoff, (C1-C6)-Alkyl, (C1-C6)-Alkyloxy-(C1- C6)-alkyl, Cyano-(C1-C6)-alkyl oder (C3-C6)-Cycloalkyl, und R6 bedeutet Wasserstoff oder (C1-C6)-Alkyl. 10. Compounds of formula (II),
Figure imgf000095_0001
wherein the symbols and indices have the following meanings: L is halogen or R 6 O, X is halogen or (C 1 -C 6 )-alkyl, Y is halogen-(C 1 -C 6 )-alkoxy, Z is Z-1, Z-2, Z-3 or Z-4, where Z-1 to Z-4 have the following meanings
Figure imgf000095_0002
R 1 is hydrogen, (C 1 -C 6 )-alkyl or halo-(C 1 -C 6 )-alkyl, R 2 is hydrogen, (C 1 -C 6 )-alkyl or (C 3 -C 6 )-cycloalkyl, or R 2 can also be Si((C 1 -C 6 )-alkyl) 3 if L is OR 6 and R 6 is (C 1 -C 6 )-alkyl, R 3 is (C 1 -C 6 )-alkyl, halogen-(C 1 -C 6 )-alkyl or (C 3 -C 6 )-cycloalkyl, R 4 and R 5 are each independently hydrogen, (C 1 -C 6 )-alkyl, (C 1 -C 6 )-alkyloxy-(C 1 -C 6 )-alkyl, cyano-(C 1 -C 6 )-alkyl or (C 3 -C 6 )-cycloalkyl, and R 6 is hydrogen or (C 1 -C 6 )-alkyl. 11. Verbindungen der Formel (II) nach Anspruch 10, worin L bedeutet Chlor, Methoxy oder Hydroxy, X bedeutet Chlor, Brom, Methyl oder Ethyl, Y bedeutet OCF3 oder OCHF2, Z bedeutet Z-1, Z-2, Z-3 oder Z-4, wobei Z-1 bis Z-4 die folgenden Bedeutungen haben
Figure imgf000096_0001
R1 bedeutet Wasserstoff oder Methyl, R2 bedeutet Wasserstoff, Methyl, Ethyl oder c-Propyl, oder R2 kann auch Si(Me)3 bedeuten, wenn L für Methoxy steht, R3 bedeutet Methyl, Ethyl oder i-Propyl, und R4 und R5 bedeuten folgende Kombinationen Wasserstoff und Wasserstoff, Wasserstoff und Methyl, Wasserstoff und Ethyl, Wasserstoff und Cyclopropyl, Cyclopropyl und Cyclopropyl, Wasserstoff und Methoxymethyl oder Wasserstoff und Cyanomethyl. 11. Compounds of formula (II) according to claim 10, wherein L is chlorine, methoxy or hydroxy, X is chlorine, bromine, methyl or ethyl, Y is OCF 3 or OCHF 2 , Z is Z-1, Z-2, Z-3 or Z-4, where Z-1 to Z-4 have the following meanings
Figure imgf000096_0001
R 1 is hydrogen or methyl, R 2 is hydrogen, methyl, ethyl or c-propyl, or R 2 can also be Si(Me) 3 when L is methoxy, R 3 is methyl, ethyl or i-propyl, and R 4 and R 5 are the following combinations: hydrogen and hydrogen, hydrogen and methyl, hydrogen and ethyl, hydrogen and cyclopropyl, cyclopropyl and cyclopropyl, hydrogen and methoxymethyl or hydrogen and cyanomethyl.
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Citations (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2906507A1 (en) 1979-02-20 1980-08-28 Bayer Ag Plant growth regulating compsn. - contg. alpha amino cyclo:alkanoic acid derivs., e.g. for dwarfing cereals
EP0030287A1 (en) 1979-11-29 1981-06-17 Bayer Ag 1-Aminocyclopropanecarboxylic acid derivatives, methods for their production, their use as plant-growth regulators and compositions containing such derivatives
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 PLASMIDES FOR TRANSFORMING PLANT CELLS.
DE3335514A1 (en) 1983-09-30 1985-04-18 Bayer Ag, 5090 Leverkusen 1-METHYLAMINO-CYCLOPROPAN-1-CARBONIC ACID DERIVATIVES
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
EP0333131A1 (en) 1988-03-17 1989-09-20 Hoechst Aktiengesellschaft Plant protective agent based on pyrazolecarboxylic acid derivatives
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
EP0365484A1 (en) 1988-10-20 1990-04-25 Ciba-Geigy Ag Sulfamoyl phenyl ureas
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
WO1991007874A1 (en) 1989-11-30 1991-06-13 Hoechst Aktiengesellschaft Pyrazolines for the protection of crops against herbicides
WO1991008202A1 (en) 1989-11-25 1991-06-13 Hoechst Aktiengesellschaft Isoxazolines, method of preparation thereof, and their use as plant-protection agents
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
WO1992000377A1 (en) 1990-06-25 1992-01-09 Monsanto Company Glyphosate tolerant plants
US5123951A (en) 1986-03-31 1992-06-23 Rhone-Poulenc Nederland B.V. Synergistic plant growth regulator compositions
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
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
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
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
WO2002034048A1 (en) 2000-10-23 2002-05-02 Syngenta Participations Ag Agrochemical compositions with quinoline safeners
WO2004084631A1 (en) 2003-03-26 2004-10-07 Bayer Cropscience Gmbh Use of aromatic hydroxy compounds as safeners
WO2005015994A1 (en) 2003-08-05 2005-02-24 Bayer Cropscience Gmbh Use of aromatic compounds as safeners
WO2005016001A1 (en) 2003-08-05 2005-02-24 Bayer Cropscience Gmbh Safener based on aromatic-aliphatic carboxylic 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
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
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
EP2248421A1 (en) 2009-05-07 2010-11-10 GMI - Gregor-Mendel-Institut für Molekulare Pflanzenbiologie GmbH Accumulation of biomass in plants
WO2012028579A1 (en) 2010-09-01 2012-03-08 Bayer Cropscience Ag N-(tetrazol-5-yl)- and n-(triazol-5-yl)arylcarboxamides and use thereof as herbicides
WO2021105101A1 (en) 2019-11-26 2021-06-03 Bayer Aktiengesellschaft [(1,5-diphenyl-1h-1,2,4-triazol-3-yl)oxy]acetic acid derivatives and salts thereof, crop protection compositions comprising them, methods for producing them and use thereof as safeners
WO2021209383A1 (en) * 2020-04-17 2021-10-21 Syngenta Crop Protection Ag Herbicidal compounds
WO2022233727A1 (en) * 2021-05-07 2022-11-10 Syngenta Crop Protection Ag Herbicidal compounds

Patent Citations (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2906507A1 (en) 1979-02-20 1980-08-28 Bayer Ag Plant growth regulating compsn. - contg. alpha amino cyclo:alkanoic acid derivs., e.g. for dwarfing cereals
EP0030287A1 (en) 1979-11-29 1981-06-17 Bayer Ag 1-Aminocyclopropanecarboxylic acid derivatives, methods for their production, their use as plant-growth regulators and compositions containing such derivatives
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 PLASMIDES FOR TRANSFORMING PLANT CELLS.
EP0142924A2 (en) 1983-09-26 1985-05-29 Mycogen Plant Science, Inc. Insect resistant plants
DE3335514A1 (en) 1983-09-30 1985-04-18 Bayer Ag, 5090 Leverkusen 1-METHYLAMINO-CYCLOPROPAN-1-CARBONIC ACID DERIVATIVES
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
US5123951A (en) 1986-03-31 1992-06-23 Rhone-Poulenc Nederland B.V. Synergistic plant growth regulator compositions
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
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
EP0333131A1 (en) 1988-03-17 1989-09-20 Hoechst Aktiengesellschaft Plant protective agent based on pyrazolecarboxylic acid derivatives
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
EP0365484A1 (en) 1988-10-20 1990-04-25 Ciba-Geigy Ag Sulfamoyl phenyl ureas
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
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
WO1992000377A1 (en) 1990-06-25 1992-01-09 Monsanto Company Glyphosate tolerant plants
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
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
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
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
WO2002034048A1 (en) 2000-10-23 2002-05-02 Syngenta Participations Ag Agrochemical compositions with quinoline safeners
WO2004084631A1 (en) 2003-03-26 2004-10-07 Bayer Cropscience Gmbh Use of aromatic hydroxy compounds as safeners
WO2005015994A1 (en) 2003-08-05 2005-02-24 Bayer Cropscience Gmbh Use of aromatic compounds as safeners
WO2005016001A1 (en) 2003-08-05 2005-02-24 Bayer Cropscience Gmbh Safener based on aromatic-aliphatic carboxylic 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
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
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
EP2248421A1 (en) 2009-05-07 2010-11-10 GMI - Gregor-Mendel-Institut für Molekulare Pflanzenbiologie GmbH Accumulation of biomass in plants
WO2012028579A1 (en) 2010-09-01 2012-03-08 Bayer Cropscience Ag N-(tetrazol-5-yl)- and n-(triazol-5-yl)arylcarboxamides and use thereof as herbicides
WO2021105101A1 (en) 2019-11-26 2021-06-03 Bayer Aktiengesellschaft [(1,5-diphenyl-1h-1,2,4-triazol-3-yl)oxy]acetic acid derivatives and salts thereof, crop protection compositions comprising them, methods for producing them and use thereof as safeners
WO2021209383A1 (en) * 2020-04-17 2021-10-21 Syngenta Crop Protection Ag Herbicidal compounds
WO2022233727A1 (en) * 2021-05-07 2022-11-10 Syngenta Crop Protection Ag Herbicidal compounds

Non-Patent Citations (22)

* Cited by examiner, † Cited by third party
Title
"Microwaves in Organic and Medicinal Chemistry", 2005, VERLAG WILEY
"Springer Lab Manual", 1995, SPRINGER VERLAG, article "Gene Transfer to Plants"
"The Pesticide Manual", 2006, THE BRITISH CROP PROTECTION COUNCIL AND THE ROYAL SOC. OF CHEMISTRY
B. SAMBROOK ET AL.: "Molecular Cloning, A Laboratory Manual", vol. 2, 1989, COLD SPRING HARBOR LABORATORY PRESS
BARRY A. BUNIN: "The Combinatorial Index", 1998, VERLAG ACADEMIC PRESS
BRAUN ET AL., EMBO J., vol. 11, 1992, pages 3219 - 3227
C. MARSDEN: "Handbook of Insecticide Dust Diluents and Carriers", 1963, J. WILEY & SONS
CHRISTOU, TRENDS IN PLANT SCIENCE, vol. 1, 1996, pages 423 - 431
D. TIEBES: "Combinatorial Chemistry - Synthesis, Analysis, Screening", 1999, VERLAG WILEY, pages: 1 - 34
G.C. KLINGMAN: "Weed Control as a Science", 1961, JOHN WILEY AND SONS, INC., pages: 81 - 96
J.D. FREYERS.A. EVANS: "Weed Control Handbook", 1968, BLACKWELL SCIENTIFIC PUBLICATIONS, pages: 101 - 103
J.E. BROWNING: "Agglomeration", CHEMICAL AND ENGINEERING, 1967, pages 147
K. MARTENS: "Spray Drying'' Handbook", 1979, G. GOODWIN LTD.
no. 133993-74-5
SCHÖNFELDT: "Grenzflächenaktive Äthylenoxidaddukte", 1976, WISS. VERLAGSGESELL.
SISLEYWOOD: "Encyclopedia of Surface Active Agents", 1964, CHEM. PUBL. CO. INC.
SONNEWALD ET AL., PLANT J., vol. 1, 1991, pages 95 - 106
WADE VAN VALKENBURG: "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, pages: 2
WINNACKER-KÜCHLER: "Chemische Technologie", vol. 7, 4 August 1986, C. HANSER VERLAG
WOLTER ET AL., PROC. NATL. ACAD. SCI. USA, vol. 85, 1988, pages 846 - 850

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