3-acylbenzamides and their use as herbicides

Abstract

This invention relates to the use of 3-acylbenzamide of formula (I) as a herbicide. In formula (I), X, Y, Z, and R... x Examples include alkyl, cycloalkyl, haloalkyl, and halogen.

Description

[0001] This invention relates to the field of herbicide technology, and particularly to the field of herbicide technology for selectively controlling broadleaf weeds and grass weeds in plant crops.

[0002] WO2012 / 028579A1 discloses herbicidal active benzamides that can have various substituents at the 3-position of the benzene ring. WO2017 / 005567A1, EP3118199A1, and WO2017 / 055146A1 also describe herbicidal active phenylamides that can have various substituents at the 3-position of the benzene ring. Furthermore, these publications disclose single phenylamides with an acetyl or cyclopropyl carbonyl group at the 3-position of the benzene ring in Example numbers 1-364 to 1-367 and 1-426 to 1-429, respectively. Finally, WO2019 / 25540 describes a specific 3-acylbenzamide. However, the benzamides known from the above publications do not always possess sufficient herbicidal efficacy and / or compatibility with crop plants.

[0003] One object of the present invention is to provide an alternative herbicidal active ingredient. This object is achieved by the benzamide of the present invention as described below, wherein the benzamide has an acyl group at the 3-position of the benzene ring and a haloalkoxy group at the 4-position.

[0004] Therefore, the present invention provides 3-acylbenzamide of formula (I) or a salt thereof:

[0005]

[0006] The symbols and exponents are defined as follows:

[0007] R x It is (C1-C6)-alkyl.

[0008] X is a halogen, (C1-C6)-alkyl, or (C3-C6)-cycloalkyl.

[0009] Y is a halo-(C1-C6)-alkoxy group.

[0010] Z is (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, halo-(C1-C6)-alkyl, (C1-C6)-alkyl-O-(C1-C6)-alkyl, or (C3-C6)-cycloalkyl-(C1-C6)-alkyl, wherein (C3-C6)-cycloalkyl is represented by R. 1 Group substitution,

[0011] R 1 It is a halogen, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, or (C1-C6)-alkyl-O, and

[0012] m can be 0, 1, 2, or 3.

[0013] In formula (I) and all formulas below, the alkyl group having more than the above carbon atoms can be straight-chain or branched. Alkyl groups are, for example, methyl, ethyl, n-propyl or isopropyl, n-butyl, isobutyl, tert-butyl or 2-butyl, pentyl, hexyl (such as n-hexyl, isohexyl and 1,3-dimethylbutyl). Similarly, alkenyl groups are, 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 groups are, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. Multiple bonds can be located at any position in each unsaturated group. Cycloalkyl groups are carbon-cyclic saturated ring systems with 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

[0014] Halogens are represented by fluorine, chlorine, bromine, or iodine.

[0015] Depending on the nature of the substituents and their connection, compounds of formula (I) or (II) can exist as stereoisomers. For example, if one or more asymmetrically substituted carbon atoms are present, enantiomers and diastereomers may be produced. Stereoisomers can be obtained from the mixtures obtained during the preparation process by conventional separation methods, such as chromatography. Stereoisomers can also be selectively prepared by stereoselective reactions using optically active starting materials and / or auxiliaries. This invention also relates to all stereoisomers and mixtures thereof covered by but not specifically defined by formula (I) or (II).

[0016] The preferred formula (I) is used for compounds, where the symbols and indices are defined as follows:

[0017] R x It is (C1-C6)-alkyl.

[0018] X is a halogen, (C1-C6)-alkyl, or (C3-C6)-cycloalkyl.

[0019] Y is OCF3, OCHF2, OCH2CHF2, or OCF2Me.

[0020] Z is (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, halo-(C1-C6)-alkyl, (C1-C6)-alkyl-O-(C1-C6)-alkyl, or (C3-C6)-cycloalkyl-(C1-C6)-alkyl, wherein (C3-C6)-cycloalkyl is represented by R. 1 Group substitution,

[0021] R 1 It is a halogen, (C1-C6)-alkyl, or halo-(C1-C6)-alkyl, and

[0022] m can be 0, 1, or 2.

[0023] The compounds of particularly preferred formula (I) are defined as follows:

[0024] R x For Me, Et,

[0025] X is chlorine, bromine, methyl, ethyl, or cyclopropyl.

[0026] Y is OCF3, OCHF2, or OCH2CHF2, and

[0027] Z can be methyl, ethyl, n-propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl, vinyl, allyl, ethynyl, prop-1-yn-1-yl, methoxymethyl, chloromethyl, cyclopropylmethyl, 1-methylcyclopropyl, or difluoromethyl.

[0028] In all the formulas specified below, unless the definitions differ, the substituents and symbols have the same definitions as those described in formula (I).

[0029] The compound of formula (II) is novel and highly suitable as an intermediate for preparing the compound of formula (I) of the present invention. Therefore, the present invention also provides a compound of formula (II).

[0030]

[0031] The symbols and exponents are defined as follows:

[0032] L is halogen or R is... 2 O,

[0033] X is a halogen, (C1-C6)-alkyl, or (C3-C6)-cycloalkyl.

[0034] Y is a halo-(C1-C6)-alkoxy group.

[0035] Z is (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, halo-(C1-C6)-alkyl, (C1-C6)-alkyl-O-(C1-C6)-alkyl, or (C3-C6)-cycloalkyl-(C1-C6)-alkyl, wherein (C3-C6)-cycloalkyl is represented by R. 1 Group substitution,

[0036] R 1It is a halogen, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, or (C1-C6)-alkyl-O, and

[0037] R 2 It is hydrogen or (C1-C6)-alkyl.

[0038] The preferred compound is of formula (II), wherein

[0039] L represents chlorine, methoxy, or hydroxyl.

[0040] X is chlorine, bromine, methyl, ethyl, or cyclopropyl.

[0041] Y is OCF3, OCHF2, or OCH2CHF2, and

[0042] Z can be methyl, ethyl, n-propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl, vinyl, allyl, ethynyl, prop-1-yn-1-yl, methoxymethyl, chloromethyl, cyclopropylmethyl, 1-methylcyclopropyl, or difluoromethyl.

[0043] In all the formulas specified below, unless the definitions differ, the substituents and symbols have the same definitions as those described in formula (I).

[0044] The compounds of the present invention of general formula (I) can also be prepared, for example, by reacting the compounds of the present invention of general formula (II-b: compound II, wherein: L = hydroxyl) with a substituted aminotetrazole, as described in WO2012 / 028579.

[0045]

[0046] Compounds of general formula (IIb) can be synthesized, for example, according to the following schemes and methods known to those skilled in the art:

[0047]

[0048] The compounds of formula (I) and / or their salts synthesized by the above reaction can also be prepared in parallel, and this method can be carried out manually, partially automatically, or fully automatically. For example, the execution of the reaction, the post-processing or purification of the products and / or intermediates can be automated. Generally, this is understood to refer to, for example, the process described by D. Tiebes in Combinatorial Chemistry – Synthesis, Analysis, Screening (ed. Günther Jung), Wiley, 1999, pp. 1–34.

[0049] For parallel execution of the reaction and post-processing, a range of commercially available equipment can be used, such as the Calypso reaction block from Barnstead International, Dubuque, Iowa 52004-0797, USA; reaction stations from Radleys, Shirehill, Saffron Walden, Essex, CB11 3AZ, England; or multi-probe automated workstations from Perkin Elmer, Waltham, Massachusetts 02451, USA. For parallel purification of the compound of formula (I) and its salts or intermediates generated during the preparation process, available equipment includes, for example, chromatography equipment from ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.

[0050] The equipment detailed above produces a modular procedure in which individual work steps are automated, but manual intervention is required between work steps. This can be circumvented by using partially or fully integrated automation systems in which the individual automation modules are operated, for example, by robots. Such automation systems are available, for example, from Caliper, Hopkinton, MA 01748, USA.

[0051] The execution of single or multiple synthetic steps can be supported by the use of polymer-supported reagent / scavenger resins. A range of experimental protocols are described in professional literature, such as ChemFiles, Volume 4, Issue 1, Polymer-Supported Scavengers and Reagents for Solution-Phase Synthesis (Sigma-Aldrich).

[0052] In addition to the methods described herein, compounds of formula (I) and their salts can be prepared entirely or partially by solid-phase loading. For this purpose, a single or all intermediates in the synthesis or in a synthesis suitable for the corresponding procedure are combined with a synthetic resin. Solid-phase loading synthesis methods are well described in the technical literature, such as Barry A. Bunin, “The Combinatorial Index,” Academic Press, 1998, and Combinatorial Chemistry – Synthesis, Analysis, Screening (edited by Günther Jung), Wiley, 1999. The use of solid-phase loading synthesis methods allows for the use of a variety of schemes known in the literature, which can be performed manually or automatically. These reactions can be performed, for example, in microreactors using the IRORI technology of Nexus Biosystems, 12140 Community Road, Poway, CA 92064, USA.

[0053] Whether in the solid or liquid phase, microwave technology can be used to support the implementation of single or multiple synthetic steps. Various experimental protocols are described in professional literature, such as *Microwaves in Organic and Medicinal Chemistry* (editors: CO Kappe and A. Stadler), Wiley, 2005.

[0054] The collection of substances of formula (I) and their salts prepared by the methods described herein is called a library. This invention also provides a library comprising at least two compounds of formula (I) and their salts.

[0055] The compounds of this invention exhibit excellent herbicidal efficacy against a broad spectrum of economically important monocot and dicot annual pests. The active ingredient is also highly effective against perennial weeds, which produce new shoots from rhizomes, rootstocks, or other perennial organs and are difficult to control.

[0056] Therefore, the present invention also provides a method for controlling unwanted plants or regulating plant growth, preferably in plant crops, wherein one or more compounds of the present invention are applied to the plant (e.g., harmful plants, such as monocot or dicot weeds, or unwanted crop plants), seeds (e.g., cereals, seeds, or vegetative propagules, such as tubers or budding shoots), or the area where the plant grows (e.g., a cultivated area). The compounds of the present invention can be applied, for example, before sowing (or, if appropriate, by adding to the soil), before emergence, or after emergence. Representative specific examples of monocot and dicot weed flora that can be controlled by the compounds of the present invention are as follows, although these enumerations are not intended to impose limitations on any particular species.

[0057] Monocotyledonous harmful plant genera: *Aegilops*, *Agropyron*, *Agrostis*, *Alopecurus*, *Apera*, *Avena*, *Brachiaria*, *Bromus*, *Cenchrus*, *Commelina*, *Cynodon*, *Cyperus*, *Dactyloctenium*, *Digitaria*, *Echinochloa*, *Eleocharis*, *Eleusine*, *Eragrostis*. Genuses include Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochooria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, and Sorghum.

[0058] Dicotyledonous weeds: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Thistle irsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Linderni a) Genus: Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Pig bristles The genera *Salsola*, *Senecio*, *Sesbania*, *Sida*, *Sinapis*, *Solanum*, *Sonchus*, *Sphenoclea*, *Stellaria*, *Taraxacum*, *Thlaspi*, *Trifolium*, *Urtica*, *Veronica*, *Viola*, and *Xanthium*.

[0059] When the compounds of this invention are applied to the soil surface before germination, they will either completely prevent the emergence of weed seedlings or cause the weeds to stop growing after reaching the cotyledon stage and eventually die completely after three to four weeks.

[0060] If the active ingredient is applied to the green parts of the plant after emergence, growth stops after treatment, and harmful plants remain at the growth stage at the time of application or die completely after a certain period of time. As a result, competition from harmful weeds is eliminated early and continuously.

[0061] Although the compounds of the present invention exhibit outstanding herbicidal activity against both monocot and dicot weeds, the economically important crops, even if damaged (if any), are affected by the specific compounds according to the present invention at the appropriate application rates. Examples of such damage include dicotyledonous genera such as: *Arachis*, *Beta*, *Brassica*, *Cucumis*, *Cucurbita*, *Helianthus*, *Daucus*, *Glycine*, *Gossypium*, *Ipomoea*, *Lactuca*, *Linum*, and *Lycopersi*. The compounds of this invention are suitable for selectively controlling unwanted plant growth in plant crops, including those of the genera *Con*, *Miscanthus*, *Nicotiana*, *Phaseolus*, *Pisum*, *Solanum*, *Vicia*, or monocotyledonous genera such as *Allium*, *Ananas*, *Asparagus*, *Avena*, *Hordeum*, *Oryza*, *Panicum*, *Saccharum*, *Secale*, *Sorghum*, *Triticale*, *Triticum*, and *Zea*, particularly *Zea* and *Wheat*. For these reasons, the compounds of this invention are well-suited for selectively controlling unwanted plant growth in plant crops, such as agriculturally useful or ornamental plants.

[0062] Furthermore, depending on their specific chemical structures and the amount applied, the compounds of this invention exhibit outstanding growth-regulating properties in crops. They act on regulatory systems within the plant's own metabolism, and thus can be used to controllably influence plant composition and promote harvest, for example, by inducing drying and growth inhibition. In addition, they are suitable for routine control and suppression of unwanted vegetative growth without killing the plant. Suppression of vegetative growth plays an important role in many monocot and dicot crops because, for example, it can reduce or completely prevent lodging.

[0063] Due to its weed-controlling and plant growth-regulating properties, this active ingredient can also be used to control harmful plants in crops from genetically modified plants or plants modified through conventional mutagenesis. Genetically modified plants typically possess specific advantageous traits, such as resistance to certain pesticides (especially certain herbicides), or resistance to plant diseases or plant disease pathogens (e.g., certain insects or microorganisms, such as fungi, bacteria, or viruses). Other specific characteristics relate to, for example, yield, quality, storability, composition, and specific components of the harvest. For instance, known genetically modified plants have increased starch content or altered starch quality, or different fatty acid compositions in the harvested material.

[0064] For genetically modified crops, the compounds of the present invention are preferably used in genetically modified crops of economically important useful plants and ornamental plants, such as cereals, such as wheat, barley, rye, oats, millet / sorghum, rice and corn, or crops of sugar beets, cotton, soybeans, rapeseed, potatoes, cassava, tomatoes, peas and other vegetables.

[0065] Preferably, the compounds of the present invention can be used as herbicides in crops of useful plants that are resistant to the phytotoxic effects of herbicides or have been genetically engineered to be resistant.

[0066] Conventional methods for producing novel plants with improved characteristics compared to existing plants include, for example, traditional cultivation methods and the generation of mutants. Alternatively, novel plants with improved characteristics can be produced using recombination methods (see, for example, EP-A-0221044 and EP-A-0131624). Numerous examples have been described, for instance:

[0067] - Genetic modifications to crop plants to alter the synthesis of starch in plants (e.g., WO92 / 11376, WO92 / 14827, WO 91 / 19806).

[0068] -Transgenic crop plants resistant to specific glufosinate-ammonium herbicides (see, for example, EP-A-0242236, EP-A-242246), glyphosate (WO92 / 00377), or sulfonylureas (EP-A-0257993, US-A-5013659).

[0069] - Genetically modified crops (such as cotton) capable of producing Bacillus thuringiensis toxin (Bt toxin) (EP-A-0142924, EP-A-0193259) make the plant resistant to certain pests.

[0070] - Genetically modified crops with altered fatty acid composition (WO91 / 13972).

[0071] - Genetically modified crops containing novel components or secondary metabolites, such as novel phytoalexins, can enhance disease resistance (EPA309862, EPA0464461).

[0072] - Transgenic plants with reduced photorespiration have higher yields and greater stress resistance (EPA0305398).

[0073] - Genetically modified crop plants that produce pharmaceutically or diagnostically important proteins (“molecular farms”).

[0074] - Genetically modified crop plants characterized by higher yields or better quality

[0075] - Transgenic crop plants characterized by combinations of novel properties, such as those described above (“gene stacking”).

[0076] Many molecular biological techniques that can be used to produce new transgenic plants with improved characteristics are known in principle; see, for example, I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg, or Christou, “Trends in Plant Science” 1 (1996) 423-431.

[0077] For this type of genetic manipulation, nucleic acid molecules capable of mutagenesis or sequence modification through DNA sequence recombination can be introduced into plasmids. Standard methods can be used to perform operations such as base substitution, deletion of partial sequences, or addition of natural or synthetic sequences. To achieve inter-fragmentation of DNA segments, adaptors or linkers can be added to both ends of the segments; see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., ColdSpring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker “Gene und Klone” [Genes and Clones], VCH Weinheim, 2nd edition, 1996.

[0078] For example, plant cells that produce reduced gene product activity can be achieved by expressing at least one corresponding antisense RNA, a sense RNA for achieving a co-repressive effect, or by expressing at least one appropriately constructed ribozyme that specifically cleaves the transcript of the aforementioned gene product. For this purpose, a DNA molecule comprising the complete coding sequence of the gene product (including any flanking sequences that may be present) can be used, or a DNA molecule comprising only a portion of the coding sequence can be used, in which case these portions must be of sufficient length to have an antisense effect in the cell. Alternatively, a DNA sequence that is highly homologous to but not identical to the coding sequence of the gene product can be used.

[0079] When nucleic acid molecules are expressed in plants, the synthesized proteins can be localized to any desired compartment of the plant cell. However, to achieve localization in a specific compartment, the coding region can be linked to a DNA sequence that ensures localization in that specific compartment. Such sequences are well known to those 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). Nucleic acid molecules can also be expressed in organelles of plant cells.

[0080] Transgenic plant cells can be regenerated into complete plants using known technologies. In principle, transgenic plants can be any desired plant species, that is, not only monocots but also dicots.

[0081] Transgenic plants obtained in this way have altered characteristics due to overexpression, suppression or repression of homologous (=natural) genes or gene sequences or expression of heterologous (=exogenous) genes or gene sequences.

[0082] The compounds of the present invention are preferably used in transgenic crops that are resistant to growth regulators (e.g., dicamba), or to herbicides that inhibit essential plant enzymes (e.g., acetolactate synthase (ALS), EPSP synthase, glutamine synthase (GS), or hydroxyphenylpyruvate dioxygenase (HPPD)), or to herbicides that are resistant to sulfonylureas, glyphosate, glufosinate, or benzoylisoxazole and similar active ingredients.

[0083] When the active ingredients of this invention are applied to genetically modified crops, they not only produce the effects on harmful plants observed in other crops, but also often produce specific effects in specific applications of genetically modified crops, such as changes or broadening of the spectrum of weed control, changes in the amount applied, preferably good binding with herbicides resistant to genetically modified crops, and effects on the growth and yield of genetically modified crop plants.

[0084] Therefore, the present invention also provides the use of the compounds of the present invention as herbicides for controlling harmful plants in genetically modified crops.

[0085] The compounds of the present invention can be applied in conventional formulations as wettable powders, emulsifiable concentrates, sprayable solutions, dusting products, or granules. Therefore, the present invention also provides herbicidal and plant growth regulating compositions comprising the compounds of the present invention.

[0086] The compounds of this invention can be formulated in a variety of ways according to desired biological and / or physicochemical parameters. Possible formulations 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-based or water-based dispersants, oil-miscible solutions, microcapsule suspensions (CS), dusting products (DP), dressings, granules for broadcasting or soil application, granules in microparticle form (GR), spray granules, absorbent and adsorbent granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules, and waxes.

[0087] The types of formulations are known in principle and described in, for example: Winnacker-Küchler, “Chemische Technologie” [Chemical Engineering], volume 7, C. Hanser Verlag Munich, 4th Ed. 1986; Wade van Valkenburg, “Pesticide Formulations”, Marcel Dekker, NY, 1973; K. Martens, “Spray Drying” Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.

[0088] Essential formulation adjuvants such as inert materials, surfactants, solvents, and other additives are also known and documented in, for example, Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2nd ed., Darland Books; Caldwell NJ, Hv Olphen, “Introduction to Clay Colloid Chemistry”, 2nd ed., J. Wiley & Sons, NY; C. Marsden, “Solvents Guide”, 2nd ed., Interscience, NY 1963; McCutcheon's “Detergents and Emulsifiers Annual”, MC Publ. Corp.; Ridgewood NJ, Sisley and Wood, “Encyclopedia of Surface Active Agents”, Chem. Publ. Co. Inc., NY 1964; Schönfeldt, “Grenzflächenaktive Äthylenoxidaddukte” [Interface-active Ethylene Oxide] Adducts], Wiss. Verlagsgesell., Stuttgart 1976, Winnacker-Küchler, “ChemischeTechnologie”, Volume 7, C. Hanser Verlag Munich, 4th ed. 1986.

[0089] Wettable powders are formulations that are uniformly dispersed in water and, in addition to the active ingredient, diluent, or inert substance, contain ionic and / or nonionic surfactants (wetting agents, dispersants), such as polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyethoxylated fatty amines, fatty alcohol polyethylene glycol ether sulfates, alkyl sulfonates, alkylbenzene sulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate, or sodium oleoylmethyl taurate. To prepare wettable powders, the herbicidal active ingredient is finely ground, for example, in conventional equipment such as a hammer mill, air mill, or air jet mill, and mixed simultaneously or subsequently with formulation adjuvants.

[0090] Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent (such as butanol, cyclohexanone, dimethylformamide, xylene, or a relatively high-boiling aromatic compound or hydrocarbon, or a mixture of organic solvents) and adding one or more ionic and / or nonionic surfactants (emulsifiers). Examples of emulsifiers that can be used are: calcium alkyl aryl sulfonates, such as calcium dodecylbenzene sulfonate; or nonionic emulsifiers, such as fatty acid polyethylene glycol esters, alkyl aryl polyethylene glycol ethers, fatty alcohol polyethylene glycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, and sorbitol esters (such as sorbitol fatty acid esters or polyoxyethylene sorbitol esters, such as polyoxyethylene sorbitol fatty acid esters).

[0091] Powdered products are obtained by grinding the active ingredients together with finely dispersed solids such as talc, natural clays (such as kaolin, bentonite, and pyrophyllite), or diatomaceous earth.

[0092] The suspension concentrate can be water-based or oil-based. It can be prepared, for example, by wet milling using a commercially available bead mill, and optionally by adding surfactants, such as those listed above for other types of formulations.

[0093] Emulsions, such as oil-in-water emulsions (EW), can be prepared using, for example, agitators, colloid mills, and / or static mixers, as well as aqueous organic solvents and optional surfactants listed above for other types of formulations.

[0094] Granules can be prepared by spraying the active ingredient onto an absorbent granular inert material or by applying a concentrated active ingredient onto the surface of a carrier material (e.g., sand, kaolinite, or granular inert material) using an adhesive (e.g., polyvinyl alcohol, sodium polyacrylate, or mineral oil). Suitable active ingredients can also be granulated using methods conventional for preparing fertilizer granules—if necessary as a mixture with fertilizer.

[0095] Water-dispersible granules are typically prepared by conventional methods such as spray drying, fluidized bed granulation, disc granulation, mixing with a high-speed mixer, and extrusion without the use of solid inert materials.

[0096] For the production of disc pellets, fluidized bed pellets, extruded pellets, and spray pellets, see, for example, the methods in “Spray-Drying Handbook” 3rd ed. 1979, G. Goodwin Ltd., London; JE Browning, “Agglomeration”, Chemical and Engineering 1967, pages 147 ff.; and “Perry’s Chemical Engineer’s Handbook”, 5th ed., McGraw-Hill, New York 1973, pp. 8-57.

[0097] For further details on crop protection product reagents, see, for example, GC Klingman, “Weed Control as a Science”, John Wiley and Sons, Inc., New York, 1961, pages 81-96, and JD Greyer, SA Evans, “Weed Control Handbook”, 5th ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

[0098] Agricultural chemical formulations typically contain 0.1% to 99%, particularly 0.1% to 95% by weight of the compounds of this invention.

[0099] In wettable powders, the concentration of the active ingredient is, for example, about 10% to 90% by weight; the balance, made up to 100% by weight, consists of conventional formulation components. In emulsifiable concentrates, the concentration of the active ingredient can be about 1% to 90% by weight, preferably 5% to 80%. Powdered formulations contain 1% to 30% by weight of the active ingredient, preferably typically 5% to 20% by weight; sprayable solutions contain 0.05% to 80% by weight, preferably 2% to 50% by weight of the active ingredient. In the case of water-dispersible granules, the content of the active ingredient depends in part on whether the active ingredient is in liquid or solid form, and on the granulation aids and fillers used. In water-dispersible granules, the content of the active ingredient is, for example, between 1% and 95% by weight, preferably between 10% and 80% by weight.

[0100] In addition, the active ingredient formulations mentioned may optionally include corresponding conventional adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and reagents that affect pH and viscosity.

[0101] Based on these formulations, compositions can also be prepared with other pesticide active substances, such as insecticides, acaricides, herbicides, fungicides, and other safeners, fertilizers, and / or growth regulators, for example, in the form of finished formulations or as tank mixes.

[0102] For application, commercially available formulations are diluted in a conventional manner, if appropriate, such as with water in the case of wettable powders, emulsifiable concentrates, dispersants, and water-dispersible granules. Powder formulations, granules for soil application or broadcasting, and sprayable solutions generally do not require further dilution with other inert substances before application.

[0103] The required application rate of the compound of formula (I) varies depending on external conditions, including, in particular, temperature, humidity and the type of herbicide used. It can vary in a wide range, for example, between 0.001 and 1.0 kg / ha or more of active substance, but preferably between 0.005 and 750 g / ha.

[0104] The compounds of formula (I) of the present invention can also be used in combination with other herbicides as needed. Combinations of the compounds of formula (I) that can be used in mixtures or tank mixes are, for example, known active ingredients based on inhibition of, for example, acetyllactone synthase, acetyl-CoA carboxylase, cellulase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, or protoporphyrinogen oxidase, or as plant growth regulators, as known 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 the references cited therein.

[0105] Examples of known herbicides or plant growth regulators that can be combined with compounds of formula (I) include the following active ingredients (these compounds are referred to by their common names or chemical names or numbers according to the International Organization for Standardization (ISO),) and always include all forms of use, such as acids, salts, esters, and isomers, such as stereoisomers and optical isomers. This list includes, for example, one application form, and in some cases, more than one application form:

[0106] Acetochlor, acifluorfen, acifluorfen-methyl, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicabazon, 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, amitrole, ammonium aminosulfonate sulfamate, ailofos, asulam, asulam-potassium, asulam-sodium, atrazin, azafenidin, azimsulfuron, beflubutamid, (S)-(-)-beflubutamid, beflubutamid-M, benzolin, benzolin- ethyl, benzolin-dimethylammonium, benzolin-potassium, benzfluralin, benzuresate, benzsulfuron-methyl, benzsulfuron-phosphate, benzsulfuron-sodium, benzsulfuron-sodium, benzylbicyclon, benzofenap.Bicyclopyrone, bifenox, bilanafos, bilanafos-sodium, bipyrazone, bispyribac, bispyribac-sodium, bixlozone, bromacil, bromacil-lithium, bromacil-sodium, bromobutide, bromofenoxim, bromoxynil, bromoxynil Butyrate, bromoxynil-potassium, bromoxynil-heptanoate, bromoxynil-octanoate, busoxinone, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrol, cambendichlor, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chloramben-ammoniur m), chloramben-diolamine, 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, dimethyl chlorthalate, monomethyl chlorthalate, cinidon, cinidon-ethyl, cinmethylin, exo-(+)-cinmethylin, i.e. (1R,2S,4S)-4-isopropyl-1-methyl-2-[(2-methyl) [2.2.1]heptane (benzyl)oxy]-7-oxabicyclo[2.2.1]heptane), exo-(-)-cycloheptanyl ether (exo-(-)-cinmethylin), 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, clonazepam, clomazone, chlorpyrifos omeprop, clopyralid, clopyralid-methyl, clopyralid-olamine, clopyralid-potassium, clopyralid-tripomine, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cycloa te), cyclopyranil, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D (and its ammonium salts), butoxyethyl ester, butyl ester, choline, diethylammonium salt, dimethylammonium salt, diethanolamine salt, propylene glycol butyl ether ester, dodecyl ammonium salt, ethylhexyl ester, ethyl ester, 2-ethylhexyl ester, heptyl ammonium salt, isobutyl ester, isooctyl ester, isopropyl, isopropyl ammonium salt, lithium salt, methyl heptyl ester, methyl ester, potassium salt, tetradecyl ammonium saltTriethylammonium salt, triisopropanolammonium salt, tripromine and triethanolamine salt), 2,4-DB, 2,4-DB-butyl ester, 2,4-DB-dimethylammonium salt, 2,4-DB-isooctyl ester, 2,4-DB-potassium salt and 2,4-DB-sodium salt, daimuron (dymron), dalapon, dalapon-calcium, dalapon-magnesium, dalapon-sodium, dazomet, dazomet-sodium, n-decanol, 7-deoxy-D-sedoheptulose, desmedipham, destosyl 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-diethanolaminemmonium, 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-dimethylammonium2,4-D ethylhexyl propionate (dichlorprop-etexyl), 2,4-ethylammonium propionate (dichlorprop-ethylammonium), 2,4-isoctyl propionate (dichlorprop-isoctyl), 2,4-methyl propionate (dichlorprop-methyl), 2,4-potassium propionate (dichlorprop-potassium), 2,4-sodium propionate (dichlorprop-sodium), purified 2,4-propionic acid (dichlorprop-P), purified 2,4-dimethylammonium propionate (dichlorprop-P) Dimethylammonium, dichlorprop-P-etexyl, dichlorprop-P-potassium, dichlorprop-sodium, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, difenzoquat, difenzoquat methylsulfonate (difenzoquat-metilsulfate), diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron, dimepiperate, dimesulfazet, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimetrasulfuron, diflubenzuron itramine, dinoterb, dinoterb-acetate, diphenamid, diquat, diquat-dibromide, diquat-dichloride, dithiopyr, diuron, DNOC, DNOC ammonium, DNOC potassium, DNOC sodium, endothalEndothal-diammonium, endothal-dipotassium, endothal-disodium, epyrifenacil (S-3100), EPTC, esprocarb, etalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethyozin, ethofumesate, ethoxy fen), ethoxyfen-ethyl, ethoxysulfuron, etobenzanid, F-5231 (N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazole-1-yl]phenyl]ethanesulfonamide), F-7967 (3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)pyrimidin-2,4(1H,3H)-dione), fenoxaprop, fenoxaprop-P, fenoxaprop ethyl ester (fenoxaprop-ethyl), fenoxaprop-P-ethyl, fenoxasulfone, fenpyrazone, fenquinotrione, fentrazamid, flamprop, flamprop-isoproyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, pyrimisulfuron ( The following herbicides are listed: flazasulfuron, florasulam, florpyrauxifen, florpyrauxifen-benzyl, fluazifop, fluazifop-butyl, fluazifop-methyl, fluazifop-P, fluazifop-P-butyl, flucarbazone, and flucarbazone-sodium.Flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazin, fluometuron, flurenol, fluorenol-butyl, fluorenol-dimethylammonium salt and fluorenol-methyl ester -methyl), fluoroglycofen, fluoroglycofen-ethyl, flupropanat, flupropanat-sodium, flupyrsulfuron, flupyrsulfuron-methyl, flupyrsulfuron-methyl-sodium, fluridon, flurochloridon, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, flurtamon, fluthiacet, fluroxypyr methyl ester thiacet-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-isopropylammonium, glyphosate-diammonium, glyphosate-dimethylammonium, glyphosate-potassium, glyphosate-sodium, glyphosate-sesquisodium, and glyphosate-trimethylsulfonate sium), H-9201, namely O-(2,4-dimethyl-6-nitrophenyl)-O-ethyl isopropyl thiophosphoramide ester, halauxifen, halauxifen-methyl, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop- P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, haloxifop-sodium, hexazinon, HNPC-A8169 (prop-2-yn-1-yl(2S)-2-{3-[(5-tert-butylpyridin-2-yl)oxy]phenoxy}propionate), HW-02 (1-(dimethoxyphosphoryl)ethyl(2,4-dichlorophenoxy)acetate), hydantocidin, imidacloprid, imazamethabenz, methyl imidacloprid. Thabenz-methyl), imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, isopropylammonium, imazaquin, imazaquin-ammonium, imazaquin-methyl, and imazethapyr.Imazethapyr-ammonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron-methyl, iodosulfuron-methyl-sodium, ioxynil, lithium ioxynil, octanoate, potassium ioxynil, and sodium ioxynil (-lithium, -octanoate, -potassium and...) -sodium), triazolecarbazone, isoproturon, isouron, isoxaben, isoxaflutole, karbutilate, KUH-043, namely 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, lactoferrin, lenacil, linuron, MCPA, MCPA-butoxyethyl ester, M MCPA-butyl ester, MCPA-dimethylammonium salt, MCPA-diethanolamine salt, MCPA-2-ethylhexyl ester, MCPA-ethyl ester, MCPA-isobutyl ester, MCPA-isooctyl ester, MCPA-isopropyl ester, MCPA-isopropylammonium salt, MCPA-methyl ester, MCPA-ethanolamine salt, MCPA-potassium salt, MCPA-sodium salt, and MCPA-triethanolamine salt (MCPA-butotyl, -butyl, -dimethylammonium, -diolamine, -2-ethylhexyl, -ethyl, -isobutyl, -isoctyl, -isopropyl, -isopropylammonium, -methyl, -olamine, -potassium, -sodium) MCPB, MCPB-methyl ester, MCPB-ethyl ester and MCPB-sodium salt, 2-methyl-4-chloropropionic acid (mecoprop), 2-methyl-4-chloropropionic acid butoxyethyl ester (mecoprop-butotyl), 2-methyl-4-chloropropionic acid dimethylammonium salt (mecoprop-dimethylammonium)2-Methyl-4-chloropropionic acid diethanolamine (mecoprop-diolamine), 2-Methyl-4-chloropropionic acid ethylhexyl (mecoprop-etexyl), 2-Methyl-4-chloropropionic acid ethadyl, 2-Methyl-4-chloropropionic acid isooctyl (mecoprop-isoctyl), 2-Methyl-4-chloropropionic acid methyl (mecoprop-methyl), 2-Methyl-4-chloropropionic acid potassium (mecoprop-potassium), 2-Methyl-4-chloropropionic acid sodium (m (ecoprop-sodium), and 2-methyl-4-chloropropionic acid triethanolamine salt (mecoprop-trolamine), purified 2-methyl-4-chloropropionic acid (mecoprop-P), purified 2-methyl-4-chloropropionic acid butoxyethyl ester, purified 2-methyl-4-chloropropionic acid dimethylammonium salt, purified 2-methyl-4-chloropropionic acid-2-ethylhexyl ester, and purified 2-methyl-4-chloropropionic acid potassium salt (mecoprop-P-butotyl, -dimethylammonium, -2-ethylhexyl) and -potassium), mefenacet, mefluidid, mefluidid-diolamine, mefluidid-potassium, mesosulfuron, mesosulfuron-methyl, mesosulfuron-sodium, mesosulfuron, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methiopyrsulfuron, methiozolin, methyl isothiocyanate isothiocyanate, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, and monosulfuron.Monosulfuron-methyl, MT-5950 (N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide), NGGC-011, napropamide, NC-310 (4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole), NC-656 (3-[(isopropylsulfonyl)methyl]-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide), neburon, nicosulfuron, nonanoic acid (pelargonic acid), norflurazon, oleic acid (fatty acid) acids), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, paraquat-dichloride, paraquat-dimethylsulfate, pebulate, pendimethalin, penoxsulam, pentachlorophenol, penoxazone, pethoxamid, petroleum oil), phenmedipham, phenmedipham-ethyl, picloram, picloram-dimethylammonium, picloram-etexyl, picloram-isoctyl, picloram-methyl, picloram-olamine, picloram-potassium, picloram-triethylammonium, picloram-triprominepicloram-trolamine, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, p-methazine ropazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamid, prosulfocarb, prosulfuron, pyraclonil, pyraflufen-ethyl, pyrasulfotol, pyrazolynat (pyrazolat), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxim, pyributicarb, pyridafol, pyridat, pyriftalid, pyrazosulfuron (p) yriminobac), pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfon, pyroxsulam, quinclorac, quinclorac-dimethylammonium, quinclorac-methyl, quinmeracQuinoclamin, 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)phenyl}piperidin-2-one), rimsulfuron, saflufenacil, sethoxy Dim, siduron, simazine, simetryn, SL-261, sulcotrione, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, SYP-249 (1-ethoxy-3-methyl-1-oxobut-3-en-2-yl5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzene ester), SYP-300 (1-[7-fluoro-3-oxo-4-(prop-2-yne)]... -1-yl)-3,4-dihydro-2H-1,4-benzoxazine-6-yl]-3-propyl-2-thioimidazolidine-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, tembotrione, tepraloxydim, and other similar products. Terbacil, terbucarb, terbumeton, terbuthylazine, terbutryn, tetflupyrolimet, thaxtomin, thenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methylThiobencarb, tiafenacil, tolpyralat, toramezone, tralkoxydim, triafamon, triallate, triasulfuron, triaziflam, tribenuron-methyl, tribenuron-methyl, trilopyr, trilopyr-butotyl, trilopyr-choline oline, triclopyr-ethyl, triclopyr-triethylammonium, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazin, trifluralin, triflusulfuron-methyl, triflusulfuron-methyl, tritosulfuron, urea sulfate sulfate), Vernolate, XDE-848, ZJ-0862, namely 3,4-dichloro-N-{2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl}aniline, 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, [(3-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenoxy}pyridine [Pyridin-2-yl)oxy]ethyl acetate, 3-chloro-2-[3-(difluoromethyl)isoxazolyl-5-yl]phenyl-5-chloropyrimidin-2-yl ester, 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-dioxo-2,3-dihydro-1-benzothiophene-5-yl) methyl ketone,1-Methyl-4-[(3,3,4-trimethyl-1,1-dioxo-2,3-dihydro-1-benzothiophene-5-yl)carbonyl]-1H-pyrazol-5-ylpropane-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)pyridine-2-carboxylate, prop-2-yn-1-yl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2- Carboxylic acid esters, methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid, benzyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, ethyl 4-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-1-isobutyryl-1H-indol-6-yl)pyridine-2-carboxylate, 6-(1-acetyl-7-fluoro-1H-indol-6-yl)-4- Methyl 4-amino-3-chloro-5-fluoropyridine-2-carboxylate, 4-amino-3-chloro-6-[1-(2,2-dimethylpropionyl)-7-fluoro-1H-indol-6-yl]-5-fluoropyridine-2-carboxylate, 4-amino-3-chloro-5-fluoro-6-[7-fluoro-1-(methoxyacetyl)-1H-indol-6-yl]pyridine-2-carboxylate, potassium salt of 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, sodium salt of 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate, 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)pyridin-2-yl]imidazolidin-2-one, 3-(5-tert-butyl-1,2-oxazol-3-yl)-4-hydroxy-1-methylimidazolidin-2-one, 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-oxocyclohexyl-1-en-1-yl)carbonyl]-1-methylquinazolin-2,4(1H,3H)-dione, 2-[2-chloro-4-(methanesulfonyl)-3-(morpholin-4-ylmethyl)benzoyl]-3-hydroxycyclohexyl-2-en-1-one, 1-(2-carboxyethyl)-4-(pyrimidin-2-yl)pyridazin-1-onium salt (with a suitable anion, such as chloride, acetate or trifluoroacetate), 1-(2-carboxyethyl)-4-(pyridazin-3-yl)pyridazin-1-onium salt (with a suitable anion, such as chloride, acetate or trifluoroacetate), 4-(pyrimidin-2-yl)-1-(2-sulfoethyl)pyridazin-1- Ononium salts (with suitable anions, such as chloride, acetate, or trifluoroacetate), 4-(pyridazin-3-yl)-1-(2-sulfoethyl)pyridazin-1-onium salts (with suitable anions, such as chloride, acetate, or trifluoroacetate), 1-(2-carboxyethyl)-4-(1,3-thiazol-2-yl)pyridazin-1-onium salts (with suitable anions, such as chloride, acetate, or trifluoroacetate), 1-(2-carboxyethyl)-4-(1,3,4-thiadiazol-2-yl)pyridazin-1-onium salts (with suitable anions, such as chloride, acetate, or trifluoroacetate), (2R)-2-{[(E)-({2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl) Methyl propionate of (2S)-2-{[(E)-({2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenyl}methylene)amino]oxy}, methyl propionate of (2R / S)-2-{[(E)-({2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenyl}methylene)amino]oxy}, methyl propionate of (E)-2-(trifluoromethyl)benzaldehyde O-{2,6-bis[(4,6-dimethoxypyrimidin-2-yl)oxy]benzaldehyde Formicyl}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-pyridinyl)oxy]propanecarboxylic acid, 1-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenoxy}cyclopropanecarboxylic acid 2-ethoxy-2-oxoethyl ester, 1-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenoxy}cyclopropanecarboxylic acid 2-methoxy-2-oxoethyl ester,{[(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 ... =3a,4,5,6-tetrahydro-6aH-cyclopentane[d][1,2]oxazol-6a-carboxylic acid ester, 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-cyclopentane[d][1,2]oxazol-6a-carboxylic acid ethyl ester.

[0107] Abscisic acid and related analogues [e.g., (2Z,4E)-5-[6-ethynyl-1-hydroxy-2,6-dimethyl-4-oxocyclohexyl-2-en-1-yl]-3-methylpent-2,4-dienoic acid, methyl(2Z,4E)-5-[6-ethynyl-1-hydroxy-2,6-dimethyl-4-oxocyclohexyl-2-en-1-yl]-3-methylpent-2,4-dienoic acid, (2Z,4E)-3-ethyl-5-(1-hydroxy-2,6,6-trimethyl-4-oxocyclohexyl-2-en-1-yl)pent-2,4-dienoic acid, (2E,4E)-5-(1-hydroxy-2,6,6-trimethyl-4-oxocyclohexyl-2-en-1-yl)-3-(tri... Fluoromethyl)pentane-2,4-dienoic acid, methyl(2E,4E)-5-(1-hydroxy-2,6,6-trimethyl-4-oxocyclohexyl-2-en-1-yl)-3-(trifluoromethyl)pentane-2,4-dienoic acid ester, (2Z,4E)-5-(2-hydroxy-1,3-dimethyl-5-oxobicyclo[4.1.0]hept-3-en-2-yl)-3-methylpentane-2,4-dienoic acid, acibenzolar, activated ester (acibenzolar-S-methyl), S-adenosylhomocysteine, allantoin, 2-amino Ethoxyvinylglycine (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-aminocyclopropyl-1-ylcarboxylic acid, N-methyl-1-aminocyclopropyl-1-carboxylic acid, 1-aminocyclopropyl-1-carboxamide, substituted 1-aminocyclopropyl-1-carboxylic acid derivatives described in DE3335514, EP30287, DE2906507 or US5123951, 1-aminocyclopropyl-1-isohydroxyoxime acid, 5-aminoacetyl Propionic acid, ancymidol, 6-benzylaminopurine, bikinin, brassinolide, brassinolide-ethyl, L-canaline, catechol, and catechins (e.g., (2S,3R)-2-(3,4-dihydroxyphenyl)-3,4-dihydro-2H-benzopyran-3,5,7-triol), chitooligosaccharides (CO; COs differ from LCOs in that they lack the fatty acid side chains characteristic of LCOs).COs are sometimes referred to as N-acetyl chitosan oligosaccharides, which are also constructed from GlcNAc units, but have distinct properties from chitin molecules [(C8H]. 13 NO5) n [CAS No. 1398-61-4] and chitosan molecules [(C5H] 11 NO4) nSide chains of [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, daminozid, dazomet, dazomet-sodium, n-decanol, dikegulac, dikegulac-sodium, endothal, dipotassium endothal, disodium endothal, and endothal-dipotassium, -disodium, 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-indole-3-ylbutyric acid, isoprothiolane, probenazole, jasmonic acid, jasmonic esters or other derivatives (e.g., jasmonic acid methyl ester, jasmonic acid ethyl ester) ester), lipochitooligosaccharides (LCO, also known in some cases as symbiotic nodulation signal (NOD or NOD factor) or Myc factor, consists of an oligosaccharide backbone composed of β-1,4-bonded N-acetyl-D-glucosamine residues ("GlcNAc") and an N-bonded fatty acid side chain attached to a non-reducing end.From the literature, it can be inferred that LCO differs in the number of GlcNAc units in its skeletal structure, the length and saturation of fatty acid chains, and the substitution of reducing and non-reducing sugar units. Other related compounds include linoleic acid or its derivatives, linolenic acid or its derivatives, maleic hydrazide, mepiquat chloride, and mepiquat pentaborate. pentaborate), 1-methylcyclopropene, 3-methylcyclopropene, methoxyvinylglycine (MVG), 3'-methylabscisic acid, 1-(4-methylphenyl)-N-(2-oxo-1-propyl-1,2,3,4-tetrahydroquinoline-6-yl)methanesulfonamide and related substituted (tetrahydroquinoline-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 described in EP2248421, 2-(1-naphthalene) Acetamide, 1-naphthylacetic acid, 2-naphthyloxyacetic acid, nitrophenoxy mixture, 4-oxo-4-[(2-phenylethyl)amino]butyric acid, paclobutrazol, 4-phenylbutyric acid and its salts (e.g., sodium 4-phenylbutyrate, potassium 4-phenylbutyrate), phenylalanine, N-phenylphthalic acid, prohexadione, prohexadione-calcium, 1-n-propylcyclopropene, putrescine, prohydrojasmone, rhizobitoxin, salicylic acid (acid) and methyl salicylate, sarcosine, sodium cyclopropion-1-en-1-ylacetate, sodium cyclopropion-2-en-1-ylacetate, sodium 3-(cyclopropion-2-en-1-yl)propionate, sodium 3-(cyclopropion-1-en-1-yl)propionate, sidefungin, spermidine, spermine, strigolactone, tetrachloronitrobenzene, thidiazuron, triacontanol, trinexapac, trinexapac-ethyl, tryptophan, tsitodef, uniconazole, uniconazole-P, 2-fluoro-N-(3-methoxyphenyl)-9H-purine-6-amine.

[0108] Although the compounds of the present invention of formula (I) generally have good selectivity for crops, it may be useful to combine them with known safeners.

[0109] Safes that can be used in combination with the compounds of the present invention of formula (I) and optionally in combination with other active ingredients (e.g., the above-mentioned insecticides, acaricides, herbicides, and fungicides) are preferably selected from:

[0110] Compounds of formula (S1)

[0111]

[0112] The symbols and exponents are defined as follows:

[0113] n A It is a natural number from 0 to 5, preferably from 0 to 3;

[0114] R A 1 It is a halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, nitro, or (C1-C4)-haloalkyl;

[0115]

[0116] W A It is an unsubstituted or substituted divalent heterocyclic group selected from partially unsaturated or aromatic five-membered heterocycles, having 1 to 3 cyclic heteroatoms from N and O groups, wherein at least one nitrogen atom and at most one oxygen atom are present in the ring, preferably selected from (W A 1 ) to (W A 5 ) group,

[0117] m A It can be 0 or 1;

[0118] R A 2 OR A 3 SR A 3 or NR A 3 R A 4 Or a saturated or unsaturated 3- to 7-membered heterocycle having at least one nitrogen atom and at most three heteroatoms (preferably selected from O and S), which is linked to a carbonyl group in (S1) via a nitrogen atom, and is unsubstituted or substituted with a group selected from: (C1-C4)-alkyl, (C1-C4)-alkoxy, or optionally substituted phenyl groups, preferably of the formula OR A3 NHR A 4 Or N(CH3)2, especially the formula OR A 3 Substitution of groups;

[0119] R A 3 It is a hydrogen or unsubstituted or substituted aliphatic hydrocarbon group, preferably having a total of 1 to 18 carbon atoms;

[0120] R A 4 It is hydrogen, (C1-C6)-alkyl, (C1-C6)-alkoxy, or substituted or unsubstituted phenyl;

[0121] R A 5 It is H, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C1-C4)-alkoxy-(C1-C8)-alkyl, cyano, or COOR. A 9 Among them, R A 9 It is hydrogen, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C6)-hydroxyalkyl, (C3-C 12 )-cycloalkyl or tri-(C1-C4)-alkylsilyl;

[0122] R A 6 R A 7 R A 8 They may be the same or different, and each is hydrogen, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C3-C8)-alkyl, or (C1-C8)-alkyl-halogenated. 12 )-cycloalkyl or substituted or unsubstituted phenyl;

[0123] R A 10 For H, (C3-C 12 )-cycloalkyl, substituted or unsubstituted phenyl or substituted or unsubstituted heteroaryl;

[0124] Preferred options are:

[0125] a) Dichlorophenylpyrazoline-3-carboxylic acid compounds (S1) aPreferred compounds include, for example, 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid, ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid (S1-1) (“mefenpyr-diethyl”), and related compounds described in WO-A-91 / 07874;

[0126] b) Dichlorophenylpyrazole carboxylic acid derivatives (S1) b Preferred compounds include, for example, the following: ethyl 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S1-2), ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (S1-3), ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (S1-4) and related compounds described in EP-A-333131 and EP-A-269806;

[0127] c) 1,5-Diphenylpyrazole-3-carboxylic acid derivatives (S1) c Preferably, the following compounds are preferred: ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-5), methyl 1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-6), and related compounds described in, for example, EP-A-268554;

[0128] d) Triazole carboxylic acid compounds (S1) d Preferred compounds include, for example, fenchlorazole (-ethyl ester), namely 1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylic acid ethyl ester (S1-7) and related compounds described in EP-A-174562 and EP-A-346620;

[0129] e) 5-Benzyl or 5-phenyl-2-isooxazoline-3-carboxylic acid or 5,5-diphenyl-2-isooxazoline-3-carboxylic acid compounds (S1) ePreferably, the following compounds are preferred: ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (S1-8) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (S1-9) and the related compounds 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 5,5-diphenyl-2-isoxazoline-3-carboxylate (S1-12) or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (S1-13), as described in patent application WO-A-95 / 07897;

[0130] f) Triazolyloxyacetic acid derivatives (S1f), preferably, for example, the following compounds: {[1,5-bis(4-chloro-2-fluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid methyl ester (S1-14) or {[1,5-bis(4-chloro-2-fluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid (S1-15) or {[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid methyl ester (S1-16) or {[5 {[1-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid (S1-17) or {[1-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid methyl ester (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;

[0131] Quinoline derivatives of formula (S2),

[0132]

[0133] The symbols and exponents are defined as follows:

[0134] R B 1 It is a halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, nitro, or (C1-C4)-haloalkyl;

[0135] n B It is a natural number from 0 to 5, preferably from 0 to 3;

[0136] RB 2 OR B 3 SR B 3 or NR B 3 R B 4 Or a saturated or unsaturated 3- to 7-membered heterocycle having at least one nitrogen atom and at most three heteroatoms (preferably selected from O and S), which is linked to the carbonyl group in (S2) via the nitrogen atom, and is unsubstituted or substituted with a group selected from: (C1-C4)-alkyl, (C1-C4)-alkoxy, or optionally substituted phenyl groups, preferably of the formula OR B 3 NHR B 4 Or N(CH3)2, especially the formula OR B 3 Substitution of groups;

[0137] R B 3 It is a hydrogen or unsubstituted or substituted aliphatic hydrocarbon group, preferably having a total of 1 to 18 carbon atoms;

[0138] R B 4 It is hydrogen, (C1-C6)-alkyl, (C1-C6)-alkoxy, or substituted or unsubstituted phenyl;

[0139] T B It is an unsubstituted (C1 or C2)-alkyl dimethyl chain or substituted with one or two (C1-C4)-alkyl groups or [(C1-C3)-alkoxy]carbonyl groups;

[0140] Preferred options are:

[0141] a) 8-quinolinoxyacetic acid compounds (S2a), preferably 1-methylhexyl(5-chloro-8-quinolinoxy)acetate ("cloquintocet-mexyl") (S2-1), 1,3-dimethylbut-1-ester (5-chloro-8-quinolinoxy)acetate (S2-2), 4-allyloxybutyl (5-chloro-8-quinolinoxy)acetate (S2-3), 1-allyloxypropyl-2-ester (5-chloro-8-quinolinoxy)acetate (S2-4), ethyl acetate (5-chloro-8-quinolinoxy)acetate (S2-5), methyl acetate (5-chloro-8-quinolinoxy)acetate (S2-6), (5- (5-Chloro-8-quinolinoxy)acetic acid allyl ester (S2-7), (5-chloro-8-quinolinoxy)acetic acid 2-(2-propyleneiminooxy)-1-ethyl ester (S2-8), (5-chloro-8-quinolinoxy)acetic acid 2-oxopropyl-1-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), hydrates and salts thereof, such as lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphine salts, as described in WO-A-2002 / 34048;

[0142] b)(5-chloro-8-quinolinoxy)malonic acid compounds (S2) b Preferably, the following compounds are preferred: diethyl (5-chloro-8-quinolinoxy)malonate, diallyl (5-chloro-8-quinolinoxy)malonate, methyl ethyl (5-chloro-8-quinolinoxy)malonate, and related compounds as described in EP-A-0 582 198;

[0143] Compounds of formula (S3)

[0144]

[0145] The symbols and exponents are defined as follows:

[0146] R C 1 It is (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C2-C4)-alkenyl, (C2-C4)-haloalkenyl, (C3-C7)-cycloalkyl, preferably dichloromethyl;

[0147] R C 2 R C 3For the same or different, and each being 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, dioxolane-(C1-C4)-alkyl, thiazolyl, furanyl, furanylalkyl, thiophene, piperidinyl, substituted or unsubstituted phenyl, or R C 2 With R C 3 Together they form substituted or unsubstituted heterocycles, preferably oxazolidine, thiazolidinidine, piperidine, morpholine, hexahydropyrimidine, or benzoxazine rings; preferably: dichloroacetamide active ingredients, which are commonly used as pre-emergence safeners (soil application safeners); for example, "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) from PPG Industries' "PPG-1292" (N-allyl-N-[(1,3-dioxolane-2-yl)methyl]dichloroacetamide) (S3-5), Sagro-Chem's "DKA-24" (N-allyl-N-[(allylaminocarbonyl)methyl]dichloroacetamide) (S3-6), Nitrokemia or Monsanto's "AD-67" or "MON 4660" (3-dichloroacetyl-1-oxa-3-azaspiro[4,5]decane) (S3-7), TRI-Chemical RT's "TI-35" (1-dichloroacetylazacycloheptane) (S3-8), BASF's "diclonon" (dicyclonone) or "BAS145138" or "LAB145138" (S3-9) ((RS)-1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[1,2-a]pyrimidin-6-one), "furilazole" or "MON 13900" ((RS)-3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyloxazolidine) (S3-10); and its (R) isomer (S3-11).

[0148] N-acylsulfonamides of formula (S4) and their salts,

[0149]

[0150] The symbols and exponents are defined as follows:

[0151] X D For CH or N;

[0152] R D 1 CO-NR D 5 R D 6 or NHCO-R D 7 ;

[0153] R D 2 It is a halogen, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy, nitro, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkylsulfonyl, (C1-C4)-alkoxycarbonyl or (C1-C4)-alkylcarbonyl;

[0154] R D 3 It is hydrogen, (C1-C4)-alkyl, (C2-C4)-alkenyl, or (C2-C4)-alkynyl;

[0155] R D 4 It can be 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;

[0156] R D 5 It is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C5-C6)-cycloalkenyl, phenyl, or contains a group selected from nitrogen, oxygen, and sulfur. D 3- to 6-membered heterocyclic groups with heteroatoms, wherein the latter 7 groups are selected from the following v DSubstituent substitutions: halogen, (C1-C6)-alkoxy, (C1-C6)-haloalkoxy, (C1-C2)-alkylsulfinyl, (C1-C2)-alkylsulfonyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxycarbonyl, (C1-C4)-alkylcarbonyl, and in the case of cyclic groups, (C1-C4)-alkyl and (C1-C4)-haloalkyl;

[0157] R D 6 It is hydrogen, (C1-C6)-alkyl, (C2-C6)-alkenyl, or (C2-C6)-ynyl, wherein the latter three groups are selected from the following v D Group substitutions: halogen, hydroxyl, (C1-C4)-alkyl, (C1-C4)-alkoxy, and (C1-C4)-alkylthio, or

[0158] R D 5 and R D 6 Together with the nitrogen atoms that carry them, they form pyrrolidinyl or piperidinyl groups;

[0159] R D 7 It is hydrogen, (C1-C4)-alkylamino, di-(C1-C4)-alkylamino, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, wherein the latter two groups are selected from the following v D Substituent substitutions: halogen, (C1-C4)-alkoxy, (C1-C6)-haloalkoxy and (C1-C4)-alkylthio, and in the case of cyclic groups, (C1-C4)-alkyl and (C1-C4)-haloalkyl;

[0160] n D It can be 0, 1, or 2;

[0161] m D It can be 1 or 2;

[0162] v D It can be 0, 1, 2, or 3;

[0163] Preferably, N-acylsulfonamide compounds are used, such as those of the following formula (S4) a (See, for example, WO-A-97 / 45016)

[0164]

[0165] in

[0166] R D 7It is (C1-C6)-alkyl, (C3-C6)-cycloalkyl, wherein the latter two groups are selected from the following v D Substituent substitutions: halogen, (C1-C4)-alkoxy, (C1-C6)-haloalkoxy and (C1-C4)-alkylthio, and in the case of cyclic groups, (C1-C4)-alkyl and (C1-C4)-haloalkyl;

[0167] R D 4 It is a halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, or CF3;

[0168] m D It can be 1 or 2;

[0169] v D It can be 0, 1, 2, or 3;

[0170] It also includes acylaminosulfonylbenzamides, such as those with the following formula (S4) b (See, for example, WO-A-99 / 16744,)

[0171]

[0172] For example, among them

[0173] R D 5 = Cyclopropyl and (R D 4 ) = 2-OMe ("cyprosulfamide", S4-1)

[0174] R D 5 = Cyclopropyl and (R D 4 ) = 5-Cl-2-OMe (S4-2),

[0175] R D 5 = Ethyl and (R) D 4 ) = 2-OMe (S4-3),

[0176] R D 5 = Isopropyl and (R D 4 ) = 5-Cl-2-OMe (S4-4), and

[0177] R D 5 = Isopropyl and (RD 4 ) = 2-OMe (S4-5),

[0178] It also includes N-acylaminosulfonylphenylureas, such as the following formula (S4) c (See, for example, EP-A-365484,)

[0179]

[0180] in

[0181] R D 8 and R D 9 Independently hydrogen, (C1-C8)-alkyl, (C3-C8)-cycloalkyl, (C3-C6)-alkenyl, (C3-C6)-ynyl,

[0182] R D 4 It is a halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, or CF3;

[0183] m D It can be 1 or 2;

[0184] For example

[0185] 1-[4-(N-2-methoxybenzoylaminosulfonyl)phenyl]-3-methylurea,

[0186] 1-[4-(N-2-methoxybenzoylaminosulfonyl)phenyl]-3,3-dimethylurea

[0187] 1-[4-(N-4,5-dimethylbenzoylaminosulfonyl)phenyl]-3-methylurea.

[0188] S5) Active ingredients of hydroxy aromatic compounds and aromatic-aliphatic carboxylic acid derivatives (S5), such as ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicylic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid, as described in WO-A-2004 / 084631, WO-A-2005 / 015994, and WO-A-2005 / 016001.

[0189] S6) 1,2-dihydroquinoxaloline-2-ones (S6) are active ingredients, such as...

[0190] 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.

[0191] Compounds of formula (S7), such as those described in WO-A-1998 / 38856,

[0192]

[0193] The symbols and exponents are defined as follows:

[0194] R E 1 R E 2 Independently, it is a halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkyl, (C1-C4)-alkylamino, di-(C1-C4)-alkylamino, or nitro.

[0195] A E For COOR E 3 or COSR E 4 ,

[0196] R E 3 R E 4 Each of these can be independently hydrogen, (C1-C4)-alkyl, (C2-C6)-alkenyl, (C2-C4)-alkynyl, cyanoalkyl, (C1-C4)-haloalkyl, phenyl, nitrophenyl, benzyl, halobenzyl, pyridylalkyl, and alkylammonium.

[0197] n E 1 It can be 0 or 1.

[0198] n E 2 n E 3 Independently 0, 1, or 2,

[0199] Preferred ingredients are diphenylmethoxyacetic acid, ethyl diphenylmethoxyacetate, and methyl diphenylmethoxyacetate (CASreg. no. 41858-19-9) (S7-1).

[0200] Compounds of formula (S8), such as those described in WO-A-98 / 27049,

[0201]

[0202] in

[0203] X F For CH or N,

[0204] n F In X F = N is an integer from 0 to 4, and

[0205] In X F = CH is an integer from 0 to 5.

[0206] R F 1 Halogen, (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

[0207] R F 2 It is hydrogen or (C1-C4)-alkyl.

[0208] R F 3 It is hydrogen, (C1-C8)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl or aryl, wherein each of the above carbon-containing groups is unsubstituted or substituted by one or more (preferably up to three) identical or different groups selected from halogens and alkoxy groups, or salts thereof.

[0209] Preferably, the compound wherein

[0210] X F For CH,

[0211] n F Integers between 0 and 2

[0212] R F 1 It is a halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, or (C1-C4)-haloalkoxy.

[0213] R F 2 It is hydrogen or (C1-C4)-alkyl.

[0214] RF 3 It is hydrogen, (C1-C8)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, or aryl, wherein each of the above carbon-containing groups is unsubstituted or substituted by one or more (preferably up to three) identical or different groups selected from: halogens and alkoxy groups.

[0215] Or its salt.

[0216] S9) 3-(5-tetrazolyl)-2-quinolone (S9) active ingredients, such as

[0217] 1,2-Dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No. 219479-18-2) and 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.

[0218] S10) formula (S10) a ) or (S10 b ) compounds

[0219] As recorded in WO-A-2007 / 023719 and WO-A-2007 / 023764

[0220]

[0221] in

[0222] R G 1 Halogen, (C1-C4)-alkyl, methoxy, nitro, cyano, CF3, OCF3,

[0223] Y G Z G Independently O or S,

[0224] n G Integers from 0 to 4

[0225] R G 2 For (C1-C 16 (C2-C6)-alkyl, (C3-C6)-alkenyl, (C3-C6)-cycloalkyl, aryl; benzyl, halobenzyl,

[0226] R G 3 It is hydrogen or (C1-C6)-alkyl.

[0227] S11) is an active ingredient of the oxyimino compound class (S11), which is known as seed-dressing composition. Compositions such as “oxabetrinil” ((Z)-1,3-dioxolane-2-yl-methoxyimino(phenyl)acetonitrile) (S11-1), used as a seed coating safener for millet / sorghum to resist metolachlor damage; “fluxofenim” (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethylone O-(1,3-dioxolane-2-ylmethyl)oxime) (S11-2), used as a seed coating safener for millet to resist metolachlor damage; and “cyometrinil” or “CGA-43089” ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3), used as a seed coating safener for millet / sorghum to resist metolachlor damage.

[0228] S12) Active components of isothiocyanates (S12), such as methyl acetate [(3-oxo-1H-2-benzothiopyran-4(3H)-ylidene)methoxy]acetate (CAS reg. no. 205121-04-6) (S12-1) and related compounds in WO-A-1998 / 13361.

[0229] One or more compounds in the S13 group: "1,8-naphthalenedicarboxylic anhydride" (S13-1), used as a seed coating safener for corn resistant to thiocarbamate herbicides; "fenclorim" (4,6-dichloro-2-phenylpyrimidine) (S13-2), used as a safener for rice resistant to metolachlor; "flurazole" (2-chloro-4-trifluoromethyl-1,3-thiazolyl-5-carboxylic acid benzyl ester) (S13-3), used as a seed coating safener for millet resistant to metolachlor and isopropylmetolachlor damage; "CL 304415" (CAS reg. no. 31541-57-8) from American Cyanamid (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid). (S13-4), a safer agent for corn against imidazolinone damage, is "MG 191" (CAS reg. no. 96420-72-3) from Nitrokemia (2-dichloromethyl-2-methyl-1,3-dioxolane). (S13-5), a safer agent for corn, is "MG-838" (CAS reg. no. 133993-74-5) from Nitrokemia (1-oxa-4-azaspiro[4.5]decane-4-dithiocarboxylic acid 2-propenyl ester). (S13-6), "disulfoton" (O,O-diethyl-2-ethylthioethyl dithiophosphate). (S13-7), "dietholate" (O,O-diethyl-O-phenylthiophosphate). (S13-8), "mephenate" (4-chlorophenyl methylcarbamate). (S13-9).

[0230] S14) In addition to herbicidal effects on harmful plants, active ingredients that also act as safeners for crops such as rice include: dimepiperate or MY-93 (S-1-methyl-1-phenylethylpiperidine-1-thiocarbamate), which act as a safener for rice against the herbicide quizalofop-p-ethyl; daimuron or SK 23 (1-(1-methyl-1-phenylethyl)-3-p-tolylureuron), which act as a safener for rice against the herbicide azoxystrobin; and cumyluron. "JC-940" (3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)urea, see JP-A-60087254), is used as a safener for rice to resist damage from some herbicides; "methoxyphenone" or "NK049" (3,3'-dimethyl-4-methoxybenzophenone), is used as a safener for rice to resist damage from some herbicides; "CSB" (1-bromo-4-(chloromethylsulfonyl)benzene) (CAS reg. no. 54091-06-4), produced in Kumiai, is used as a safener for rice to resist damage from some herbicides.

[0231] Compounds of formula (S15) or their tautomers

[0232] As described in WO-A-2008 / 131861 and WO-A-2008 / 131860,

[0233]

[0234] in

[0235] R H 1 (C1-C6)-haloalkyl groups, and

[0236] R H 2 It is hydrogen or halogen, and

[0237] R H 3 R H 4 Independently hydrogen, (C1-C 16 )-alkyl, (C2-C 16 )-Alkenyl or (C2-C 16)-Alkyne, wherein the last three groups are each unsubstituted or substituted by one or more groups selected from: halogen, hydroxyl, 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, unsubstituted or substituted (C3-C6)-cycloalkyl, unsubstituted or substituted phenyl, and unsubstituted or substituted heterocyclic groups, or (C3-C6)-cycloalkyl, (C4-C6)-cycloalkenyl, (C3-C6)-cycloalkane fused to one side of a ring with a 4- to 6-membered saturated or unsaturated carbon ring. The group, or (C4-C6)-cycloalkenyl group attached to one side of a ring to a 4- or 6-membered saturated or unsaturated carbon ring, wherein the latter 4 groups are each unsubstituted or substituted by one or more groups selected from: halogen, hydroxyl, 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, unsubstituted or substituted (C3-C6)-cycloalkyl, unsubstituted or substituted phenyl, and unsubstituted or substituted heterocyclic groups,

[0238] or

[0239] R H 3 It is (C1-C4)-alkoxy, (C2-C4)-alkenyloxy, (C2-C6)-alkynyloxy, or (C2-C4)-haloalkoxy, and

[0240] R H 4 It is hydrogen or (C1-C4)-alkyl, or

[0241] R H 3 and R H 4 Together with the nitrogen atom directly attached to it, they form 4 to 8-membered heterocycles.

[0242] In addition to nitrogen atoms, it may contain other cyclic heteroatoms, preferably up to two other cyclic heteroatoms selected from N, O and S, and these heteroatoms are unsubstituted or substituted by one or more groups selected from the following: halogen, cyano, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy and (C1-C4)-alkylthio.

[0243] S16) Active ingredients that are mainly used as herbicides but also act as safeners for crops, such as (2,4-dichlorophenoxy)acetic acid (2,4-D), (4-chlorophenoxy)acetic acid, (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (2-methyl-4-chloropropionic acid), 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 (MCPA), and 1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoic acid.

[0244] The particularly preferred safeners are pyrazole ethyl ester, cyclopropanesulfonamide, bis(oxazolyl) ethyl ester, methylhexyl ester, acetamiprid, allyl acetamiprid and metcamifen.

[0245] The following examples illustrate the present invention.

[0246] A. Chemical Examples

[0247] Synthesis of methyl 2-chloro-4-(difluoromethoxy)-3-carboxybenzoate (2):

[0248] Step 1: Preparation of methyl 2-chloro-4-(difluoromethoxy)-3-methylbenzoate (10)

[0249] 10 g (47.35 mmol) of commercially available methyl 2-chloro-4-hydroxy-3-methylbenzoate (9) was added fractionally to a solution of 19.93 g potassium hydroxide in 75 ml acetonitrile and 75 ml water at 0 °C. Then, 17.52 ml (94.71 mmol) of diethyl bromo(difluoro)methyl]phosphonate was added, and the mixture was stirred at 0 °C for 1 h. After the addition of ethyl acetate, the organic phase was separated, dried, and concentrated. The residue was purified by chromatography (HPLC, normal phase, heptane / ethyl acetate 100 / 0→85 / 15). 9.80 g (82%) of methyl 2-chloro-4-(difluoromethoxy)-3-methylbenzoate (10) was obtained.

[0250] 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).

[0251] Step 2: Preparation of methyl 3-(bromomethyl)-2-chloro-4-(difluoromethoxy)benzoate (11):

[0252] 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 concentrated, and the residue was dissolved in water and extracted with dichloromethane. The organic phase was separated, dried, and concentrated. The residue was purified by chromatography (HPLC, normal phase, heptane / ethyl acetate 100 / 0→60 / 40). 26.47 g (97%) of methyl 3-(bromomethyl)-2-chloro-4-(difluoromethoxy)benzoate (11) was given.

[0253] 1 H-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).

[0254] Step 3: Preparation of methyl 2-chloro-4-(difluoromethoxy)-3-carboxybenzoate (2):

[0255] 6.36 g (54 mmol) of N-methylmorpholine N-oxide was added in portions to an initial feed of 5.96 g (18 mmol) of methyl 3-(bromomethyl)-2-chloro-4-(difluoromethoxy)benzoate (11) in 200 ml of acetonitrile at 10 °C. After the exothermic reaction subsided, the reaction mixture was stirred at room temperature for 12 h. The mixture was then concentrated, and the residue was dissolved in water and repeatedly extracted with ethyl acetate. The organic phases were combined, dried, and concentrated. 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-carboxybenzoate (1) was given. 1 H-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).

[0256] Preparation examples of compounds (II) and (I) of the present invention:

[0257] Preparation of 2-chloro-3-(cyclopropylcarbonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethoxy)benzamide (1-25):

[0258] Step 1: Preparation of methyl (R,S)-2-chloro-3-[cyclopropyl(hydroxy)methyl]-4-(trifluoromethoxy)benzoate:

[0259] 1.00 g (3.53 mmol) of methyl 2-chloro-3-formyl-4-(trifluoromethoxy)benzoate (1) was initially fed into 30 mL of dry tetrahydrofuran under argon protection. Then, 8.49 mL (4.24 mmol) of a 0.5 M solution of cyclopropylmagnesium bromide in tetrahydrofuran was added dropwise at -60 °C, and the reaction mixture was stirred at -60 °C for 1 h, followed by stirring at room temperature for 1 h. The mixture was then poured into 2 M hydrochloric acid and extracted with dichloromethane. The organic phase was separated, dried, and concentrated. The residue was purified by chromatography (HPLC, normal phase, heptane / ethyl acetate 100 / 0→60 / 40). 1.01 g (84%) of (R,S)-2-chloro-3-[cyclopropyl(hydroxy)methyl]-4-(trifluoromethoxy)benzoate was obtained.

[0260] 1 H-NMR (400 MHz, DMSO-d6): δ = 7.74 (d, 1H); 7.46 (br d, 1H); 5.58 (d,1H); 4.47 (m, 1H); 3.87 (s, 3H); 1.48 (m, 1H); 0.60 (m, 1H); 0.48 (m, 1H); 0.37 (m, 1H); 0.18 (m, 1H).

[0261] Step 2: Preparation of methyl 2-chloro-3-(cyclopropylcarbonyl)-4-(trifluoromethoxy)benzoate (3-25):

[0262] A mixture of 2.5 M chromium oxide (VI) (1.5 mL, 3.73 mmol) in water and sulfuric acid in a 3:1 ratio was slowly added dropwise to an initial feed of 1.01 g (3.11 mmol) (R,S)-2-chloro-3-[cyclopropyl(hydroxy)methyl]-4-(trifluoromethoxy)benzoate in 50 mL of acetone. The reaction mixture was then stirred at room temperature for 12 h. After adding isopropanol to destroy excess oxidant, the reaction mixture was concentrated. The residue was dissolved in water and extracted with ethyl acetate; the organic phase was separated, dried, and concentrated. The residue was purified by chromatography (HPLC, normal phase, heptane / ethyl acetate 100 / 0→60 / 40). 0.95 g (90%) methyl 2-chloro-3-(cyclopropylcarbonyl)-4-(trifluoromethoxy)benzoate (3-25) was given.

[0263] Step 3: Preparation of 2-chloro-3-(cyclopropylcarbonyl)-4-(trifluoromethoxy)benzoic acid (4-25):

[0264] To an initial feed of 946 mg (2.93 mmol) methyl 2-chloro-3-(cyclopropylcarbonyl)-4-(trifluoromethoxy)benzoate (3-25) in 50 mL of methanol, 2.2 mL (4.39 mmol) of 2M sodium hydroxide solution was added. The reaction mixture was stirred at room temperature for 12 h and then concentrated. The residue was dissolved in water, and the aqueous phase was adjusted to pH 1 with 2 M hydrochloric acid. The organic phase was separated, dried, and concentrated to give 805 mg (85%) 2-chloro-3-(cyclopropylcarbonyl)-4-(trifluoromethoxy)benzoic acid (4-25).

[0265] Step 4: Preparation of 2-chloro-3-(cyclopropylcarbonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethoxy)benzamide (1-25):

[0266] 0.09 ml (0.97 mmol) of oxaloyl chloride was added dropwise to an initial feed of 200 mg (0.64 mmol) 2-chloro-3-(cyclopropylcarbonyl)-4-(trifluoromethoxy)benzoic acid (4-25) and 98.3 mg (0.97 mmol) 5-amino-1-methyl-1H-tetrazole in 3 ml of pyridine solution. The reaction mixture was stirred at room temperature for 12 h. After adding 10 ml of water, the reaction mixture was stirred for another 10 min and then extracted with dichloromethane. The organic phase was separated, dried, and concentrated. The residue was purified by chromatography (HPLC, C18, gradient: acetonitrile / water (+0.05% trifluoroacetic acid) 10 / 90→100 / 0). 156 mg (59%) of 2-chloro-3-(cyclopropylcarbonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethoxy)benzamide (1-25) was obtained.

[0267] The examples listed in the table below were prepared using methods similar to those described above, or can be obtained using similar methods. These compounds are highly preferred.

[0268] The meanings of the abbreviations used are as follows:

[0269] Me = methyl Et = ethyl Pr = propyl Bu = butyl i-Pr = isopropyl

[0270] c-Pr = cyclopropyl i-Bu = isobutyl s-Bu = sec-butyl

[0271] Table 1: Compounds of the present invention of formula (I), wherein R xIt is a methyl group, and other substituents have the following definitions.

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281] Table 2: Compounds of the present invention of formula (I), wherein R x It is an ethyl group, and other substituents have the following definitions.

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289] Table 3: Compounds of the present invention of formula (II), wherein L is methoxy and the other substituents have the following definitions.

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296] Table 4: Compounds of the present invention of formula (II), wherein L is a hydroxyl group and the other substituents have the following definitions.

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303] Table 5: Compounds of the present invention of formula (II), wherein L is chlorine and the other substituents have the following definitions.

[0304]

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311] The following table discloses NMR data for many of the compounds of the present invention, represented by formulas (I) and (II) mentioned above, for further characterization:

[0312]

[0313]

[0314]

[0315]

[0316]

[0317]

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325] B. Formulation Examples

[0326] a) The powdered product is obtained by mixing 10 parts by weight of a compound of formula (I) and / or its salt with 90 parts by weight of talc as an inert substance, and grinding the mixture in a hammer mill.

[0327] b) A water-dispersible wettable powder is obtained by mixing 25 parts by weight of a compound of formula (I) and / or its salt, 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium lignin sulfonate and 1 part by weight of sodium oleoylmethyl taurate as a wetting agent and dispersant, and grinding the mixture in a pin mill.

[0328] c) A water-dispersible concentrate is obtained by mixing 20 parts by weight of a compound of formula (I) and / or its salt with 6 parts by weight of alkylphenol polyethylene glycol ether (®Triton X 207), 3 parts by weight of isotridecyl polyethylene glycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to above 277 °C), and grinding the mixture in a friction ball mill to a fineness of less than 5 microns.

[0329] d) The emulsifiable concentrate is obtained by mixing 15 parts by weight of a compound of formula (I) and / or its salt, 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of oxyethylated nonylphenol as an emulsifier.

[0330] e) Water-dispersible granules are produced by mixing the following substances:

[0331] 75 parts by weight of a compound of formula (I) and / or its salt,

[0332] 10 parts by weight of calcium lignosulfonate,

[0333] 5 parts by weight of sodium lauryl sulfate,

[0334] 3 parts by weight of polyvinyl alcohol, and

[0335] 7 parts by weight of kaolin,

[0336] The mixture is ground in a disc mill and then granulated in a fluidized bed by spraying water as a granulation liquid.

[0337] f) Water-dispersible granules can also be produced by homogenizing and pre-grinding the following substances on a colloid mill:

[0338] 25 parts by weight of a compound of formula (I) and / or its salt,

[0339] 5 parts by weight of sodium 2,2'-dinaphthylmethane-6,6'-disulfonate

[0340] 2 parts by weight of sodium oleoylmethyl taurate,

[0341] 1 part by weight of polyvinyl alcohol,

[0342] 17 parts by weight of calcium carbonate, and

[0343] 50 parts by weight of water,

[0344] The mixture was then ground in a ball mill, and the resulting suspension was atomized and dried in a spray tower using a single-phase nozzle.

[0345] C. Biological Examples

[0346] The abbreviations used in this article have the following meanings:

[0347]

[0348] 1. Herbicidal effect against harmful plants before emergence

[0349] Seeds of monocotyledonous and dicotyledonous weeds and crops were sown in sandy loam soil in wood-fiber pots and covered with soil. The compounds of the present invention, formulated as wettable powders (WP) or emulsion concentrates (EC), were then applied to the surface of the 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 were placed in a greenhouse and maintained under favorable growing conditions for the test plants. After a 3-week trial period, the damage to the test plants was visually rated compared to the untreated control group (percentage herbicidal effect (%): 100% effect = plant dead, 0% effect = similar to control plants). Many of the compounds of the present invention have shown good efficacy against a variety of important harmful plants. The following table illustrates the post-emergence herbicidal effects of the compounds of the present invention in an illustrative manner, with herbicidal effects expressed as a percentage.

[0350] Table C-1: Pre-emergence effect of 20 g / ha on ZEAMX, expressed as a percentage.

[0351]

[0352] Table C-2: Pre-emergence effect of 80 g / ha on ZEAMX, expressed as a percentage.

[0353]

[0354] Table C-3: Pre-emergence effect of 20 g / ha on TRZAS, expressed as a percentage.

[0355]

[0356] Table C-4: Pre-emergence effect of 80 g / ha on TRZAS, expressed as a percentage.

[0357]

[0358] Table C-5: Pre-emergence effect of 20 g / ha on GLXMA, expressed as a percentage.

[0359]

[0360] Table C-6: Pre-emergence effect of 20 g / ha on ABUTH, expressed as a percentage.

[0361]

[0362] Table C-7: Pre-emergence effect of 80 g / ha on ABUTH, expressed as a percentage.

[0363]

[0364] Table C-8: Pre-emergence effect of 20 g / ha on ALOMY, expressed as a percentage.

[0365]

[0366] Table C-9: Pre-emergence effect of 80 g / ha on ALOMY, expressed as a percentage.

[0367]

[0368] Table C-10: Pre-emergence effect of 20 g / ha on AMARE, expressed as a percentage.

[0369]

[0370] Table C-11: Pre-emergence effect of 80 g / ha on AMARE, expressed as a percentage.

[0371]

[0372] Table C-12: Pre-emergence effect of 20 g / ha on DIGSA, expressed as a percentage.

[0373]

[0374] Table C-13: Pre-emergence effect of 80 g / ha on DIGSA, expressed as a percentage.

[0375]

[0376] Table C-14: Pre-emergence effect of 20 g / ha on ECHCG, expressed as a percentage.

[0377]

[0378] Table C-15: Pre-emergence effect of 80 g / ha on ECHCG, expressed as a percentage.

[0379]

[0380] Table C-16: Pre-emergence effect of 20 g / ha on LOLRI, expressed as a percentage.

[0381]

[0382] Table C-17: Pre-emergence effect of 80 g / ha on LOLRI, expressed as a percentage.

[0383]

[0384] Table C-18: Pre-emergence effect of 20 g / ha on MATIN, expressed as a percentage.

[0385]

[0386] Table C-19: Pre-emergence effect of 80 g / ha on MATIN, expressed as a percentage.

[0387]

[0388] Table C-20: Pre-emergence effect of 80 g / ha on PHBPU, expressed as a percentage.

[0389]

[0390] Table C-21: Pre-emergence effect of 20 g / ha on POLCO, expressed as a percentage.

[0391]

[0392] Table C-22: Pre-emergence effect of 80 g / ha on POLCO, expressed as a percentage.

[0393]

[0394] Table C-23: Pre-emergence effect of 20 g / ha on SETVI, expressed as a percentage.

[0395]

[0396] Table C-24: Pre-emergence effect of 80 g / ha on SETVI, expressed as a percentage.

[0397]

[0398] Table C-25: Effect of 20 g / ha on VERPE before emergence, expressed as a percentage.

[0399]

[0400] Table C-26: Effect of 80 g / ha on VERPE before emergence, expressed as a percentage.

[0401]

[0402] Table C-27: Pre-emergence effect of 20 g / ha on VIOTR, expressed as a percentage.

[0403]

[0404] Table C-28: Pre-emergence effect of 80 g / ha on VIOTR, expressed as a percentage.

[0405]

[0406] Table C-29: Pre-emergence effect of 20 g / ha on KCHSC, expressed as a percentage.

[0407]

[0408] Table C-30: Pre-emergence effect of 80 g / ha on KCHSC, expressed as a percentage.

[0409]

[0410] 2. Herbicidal effect on harmful plants after emergence

[0411] Seeds of monocotyledonous and dicotyledonous weeds and crops were sown in sandy loam in wood-fiber pots, covered with soil, and cultivated in a greenhouse under favorable growing conditions. Two to three weeks after sowing, at the single-leaf stage, the test plants were treated. The compounds of the invention, formulated as wettable powder (WP) or emulsion concentrate (EC), were sprayed onto the green parts of the plants 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 approximately three weeks of optimal growing conditions in a greenhouse, the effect of the formulations was visually evaluated compared to the untreated control group (percentage herbicidal effect (%): 100% effect = plant dead, 0% effect = similar to control plants). Many of the compounds of the invention have shown good efficacy against a variety of important harmful plants. The table below illustrates the post-emergence herbicidal effects of the compounds of the invention in an illustrative manner, with herbicidal effects expressed as a percentage.

[0412] Table C-31: Post-emergence effect of 20 g / ha on ZEAMX, expressed as a percentage.

[0413]

[0414] Table C-32: Post-emergence effect of 20 g / ha on TRZAS, expressed as a percentage.

[0415]

[0416] Table C-33: Post-emergence effect of 80 g / ha on TRZAS, expressed as a percentage.

[0417]

[0418] Table C-34: Post-emergence effect of 20 g / ha on ABUTH, expressed as a percentage.

[0419]

[0420] Table C-35: Post-emergence effect of 80 g / ha on ABUTH, expressed as a percentage.

[0421]

[0422] Table C-36: Effect of 20 g / ha on ALOMY seedlings after emergence, expressed as a percentage.

[0423]

[0424] Table C-37: Post-emergence effect of 80 g / ha on ALOMY, expressed as a percentage.

[0425]

[0426] Table C-38: Post-emergence effect of 20 g / ha on AMARE, expressed as a percentage.

[0427]

[0428] Table C-39: Post-emergence effect of 80 g / ha on AMARE, expressed as a percentage.

[0429]

[0430] Table C-40: Effect of 20 g / ha on DIGSA after emergence, expressed as a percentage.

[0431]

[0432] Table C-41: Post-emergence effect of 80 g / ha on DIGSA, expressed as a percentage.

[0433]

[0434] Table C-42: Post-emergence effect of 20 g / ha on LOLRI, expressed as a percentage.

[0435]

[0436] Table C-43: Post-emergence effect of 80 g / ha on LOLRI, expressed as a percentage.

[0437]

[0438] Table C-44: Post-emergence effect of 20 g / ha on MATIN, expressed as a percentage.

[0439]

[0440] Table C-45: Post-emergence effect of 80 g / ha on MATIN, expressed as a percentage.

[0441]

[0442] Table C-46: Effect of 20 g / ha on PHBPU after emergence, expressed as a percentage.

[0443]

[0444] Table C-47: Effect of 80 g / ha on PHBPU after emergence, expressed as a percentage.

[0445]

[0446] Table C-48: Post-emergence effect of 80 g / ha on POLCO, expressed as a percentage.

[0447]

[0448] Table C-49: Post-emergence effect of 20 g / ha on SETVI, expressed as a percentage.

[0449]

[0450] Table C-50: Post-emergence effect of 80 g / ha on SETVI, expressed as a percentage.

[0451]

[0452] Table C-51: Effect of 20 g / ha on VERPE seedling emergence, expressed as a percentage.

[0453]

[0454] Table C-52: Effect of 80 g / ha on VERPE after emergence, expressed as a percentage.

[0455]

[0456] Table C-53: Post-emergence effect of 20 g / ha on VIOTR, expressed as a percentage.

[0457]

[0458] Table C-54: Post-emergence effect of 80 g / ha on VIOTR, expressed as a percentage.

[0459]

[0460] Table C-55: Post-emergence effect of 20 g / ha on KCHSC, expressed as a percentage.

[0461]

[0462] Table C-56: Post-emergence effect of 80 g / ha on KCHSC, expressed as a percentage.

[0463]

[0464] 3. Comparative Experiment

[0465] In subsequent experiments, the herbicidal activity of numerous compounds of the present invention and the compounds with the closest known structures in WO2012 / 28579 and WO2019 / 25540 was compared under the specific conditions described above, using pre-emergence and post-emergence methods. The example numbers given in the table relate to compounds of the present invention; various comparative compounds are disclosed in the documents cited above, but not specifically mentioned (compounds V-1 to V-6), and are identified by their IUPAC names as shown below:

[0466] V-1: 3-Acetyl-2-chloro-4-methoxy-N-(1-methyl-1H-tetrazole-5-yl)benzamide

[0467] V-2: 2-Chloro-4-methoxy-N-(1-methyl-1H-tetrazol-5-yl)-3-propionylbenzamide

[0468] V-3: 2-Chloro-3-(cyclopropylcarbonyl)-4-methoxy-N-(1-methyl-1H-tetrazole-5-yl)benzamide

[0469] V-4: 3-Acetyl-2-chloro-N-(1-ethyl-1H-tetrazol-5-yl)-4-methoxybenzamide

[0470] V-5: 2-Chloro-N-(1-Ethyl-1H-tetrazol-5-yl)-4-methoxy-3-propionylbenzamide

[0471] V-6: 2-Chloro-3-(cyclopropylcarbonyl)-N-(1-ethyl-1H-tetrazol-5-yl)-4-methoxybenzamide

[0472] Herbicide pre-emergence effects:

[0473] inv. = according to the invention

[0474]

[0475]

[0476]

[0477]

[0478]

[0479]

[0480]

[0481]

[0482]

[0483]

[0484]

[0485]

[0486]

[0487]

[0488]

[0489]

[0490]

[0491]

[0492]

[0493]

[0494]

[0495]

[0496] Post-emergence effects of herbicides:

[0497] inv. = According to the present invention, the compound of this application

[0498]

[0499]

[0500]

[0501]

[0502]

[0503]

[0504]

[0505]

[0506]

[0507]

[0508]

Claims

1. 3-Acylbenzamide of formula (I) or a salt thereof The symbols and exponents are defined as follows: R x It is (C1-C6)-alkyl. X is a halogen, (C1-C6)-alkyl, or (C3-C6)-cycloalkyl. Y is a halo-(C1-C6)-alkoxy group. Z is (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, halo-(C1-C6)-alkyl, (C1-C6)-alkyl-O-(C1-C6)-alkyl, or (C3-C6)-cycloalkyl-(C1-C6)-alkyl, wherein (C3-C6)-cycloalkyl is represented by R. 1 Group substitution, R 1 It is a halogen, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, or (C1-C6)-alkyl-O, and m can be 0, 1, 2, or 3.

2. The 3-acylbenzamide according to claim 1, wherein the symbols are defined as follows: R x It is (C1-C6)-alkyl. X is a halogen, (C1-C6)-alkyl, or (C3-C6)-cycloalkyl. Y is OCF3, OCHF2, OCH2CHF2, or OCF2Me. Z is (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, halo-(C1-C6)-alkyl, (C1-C6)-alkyl-O-(C1-C6)-alkyl, or (C3-C6)-cycloalkyl-(C1-C6)-alkyl, wherein (C3-C6)-cycloalkyl is represented by R. 1 Group substitution, R 1 It is a halogen, (C1-C6)-alkyl, or halo-(C1-C6)-alkyl, and m can be 0, 1, or 2.

3. The 3-acylbenzamide according to claim 1, wherein the symbols are defined as follows: R x For Me, Et, X is chlorine, bromine, methyl, ethyl, or cyclopropyl. Y is OCF3, OCHF2, or OCH2CHF2, and Z can be methyl, ethyl, n-propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl, vinyl, allyl, ethynyl, prop-1-yn-1-yl, methoxymethyl, chloromethyl, cyclopropylmethyl, 1-methylcyclopropyl, or difluoromethyl.

4. A herbicidal composition comprising at least one 3-acylbenzamide of any one of claims 1 to 3, mixed with a formulation adjuvant.

5. The herbicidal composition according to claim 4, comprising at least one other pesticide active substance selected from: insecticides, acaricides, herbicides, fungicides, safeners, and growth regulators.

6. A method for controlling unwanted plants, characterized in that, Apply an effective amount of at least one 3-acylbenzamide according to any one of claims 1 to 3 or the herbicidal composition according to claim 4 or 5 to the growing area of ​​plants or unwanted vegetation.

7. Use of the 3-acylbenzamide of formula (I) according to any one of claims 1 to 3 or the herbicidal composition according to claim 4 or 5 for the control of unwanted plants.

8. The use according to claim 7, wherein the 3-acylbenzamide of formula (I) is used to control unwanted plants in crops containing beneficial plants.

9. The use according to claim 8, characterized in that, The useful plants mentioned are genetically modified useful plants.

10. Compounds of formula (II) The symbols and exponents are defined as follows: L is halogen or R is... 2 O, X is a halogen, (C1-C6)-alkyl, or (C3-C6)-cycloalkyl. Y is a halo-(C1-C6)-alkoxy group. Z is (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, halo-(C1-C6)-alkyl, (C1-C6)-alkyl-O-(C1-C6)-alkyl, or (C3-C6)-cycloalkyl-(C1-C6)-alkyl, wherein (C3-C6)-cycloalkyl is represented by R. 1 Group substitution, R 1 It is a halogen, (C1-C6)-alkyl, halo-(C1-C6)-alkyl, or (C1-C6)-alkyl-O, and R 2 It is hydrogen or (C1-C6)-alkyl.

11. The compound of formula (II) according to claim 10, wherein L represents chlorine, methoxy, or hydroxyl. X is chlorine, bromine, methyl, ethyl, or cyclopropyl. Y is OCF3, OCHF2, or OCH2CHF2, and Z can be methyl, ethyl, n-propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl, vinyl, allyl, ethynyl, prop-1-yn-1-yl, methoxymethyl, chloromethyl, cyclopropylmethyl, 1-methylcyclopropyl, or difluoromethyl.

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