BR112020002715A2 - crystal forms of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one - Google Patents

Abstract

CRYSTAL FORMS OF 2 - [(2,4-DICLOROFENIL) METHIL] -4,4-DIMETHYL-ISOXAZOLIDIN-3-ONA. The present invention relates to crystal forms of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one, a method for preparing these crystal forms, their use in agrochemical formulations and also particular compositions, mixtures or agrochemical formulations comprising these crystal forms.

Description

CRYSTAL FORMS OF 2 - [(2,4-DICLOROFENIL) METHIL] -4,4-DIMETHIL- ISOXAZOLIDIN-3-ONA

[001] The present invention relates to crystal forms of 2- [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one, a method for preparing these crystal forms, their use in agrochemical formulations and also particular compositions, mixtures or agrochemical formulations comprising these crystal forms.

[002] 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one of formula (I) and its herbicidal activity is known in United States patent 4,405,357.

(I)

[003] It is also known that 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one of formula (I) and its salts can be used in combination with other active ingredients and / or with protector described in WO 2012/148689 (A1).

[004] 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one has the empirical formula C12H13Cl2NO2. The CAS number is 81777-95-9.

[005] The compound of formula (I) can be prepared by the methods described in United States patent 4,405,357. The crystal form of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one that is present after preparation without any crystallization / recrystallization steps was characterized for the first time and is referred to here as crystal form A or modification A.

[006] The following 2Θ (2 theta) values (table 1) are measured for the crystal A form of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one using of Cu Kα radiation at 25 ° C (X-ray powder diffractometry): Values 2Θ (2 theta) in ° 10.5 11.8 12.4 14.2 15.9 16.8 17.3 18.5 , 1 19.8 20.3 20.7 21.1 21.8 22.9 23.2 23.6 24.3 24.9 25.9 26.3 26.7 27.7 28.0 28.4 28.6 29.0 29.3 29.5 30.5 30.7 31.6 32.1

33.0 33.3 33.6 33.8 34.2 34.3 34.9 35.9 36.4 36.7 37.0 37.3 37.7 38.2 38.7 39.3 10, 5 11.8 12.4 14.2 Table 1:

[007] The crystal form A is characterized by the fact that the X-ray powder diffractogram using Cu Kα radiation at 25 ° C has at least 3, preferably at least 4, more preferably at least 6, particularly and preferably all the most intense 2Θ (2 theta) signals specified in table 2. 2Θ (2 theta) values in ° 10.5 14.2 18.5 19.8

21.8 23.2 24.3 24.9 Table 2:

[008] All X-ray powder diffractometry data presented in this text refer to the following measurement parameters: Scanning axis gonio Scanning mode transmission Start position [° 2 theta] 2.0066 End position [° 2 theta] 37.9906 Material Cu anode Wavelength K-alpha1 [Å] 1.54060 Wavelength K-alpha2 [Å] 1.54443 Wavelength K-beta [Å] 1.39225 Ratio of K-A2 / K-A1 0, 50000 Generator 40 mA, 40 kV Incident beam monochromator focusing on ray mirror

X Rotation Yes Values 2Θ (2 theta) ± 0.2 °

[009] Modification A of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one is particularly and preferably characterized by the fact that the X-ray powder diffractogram using radiation from Cu Kα at 25 ° C corresponds essentially to the spectrum shown in Figure 1.

[010] The crystal form A is further characterized by Raman spectra. All Raman spectroscopy data presented in this text refers to the following measurement parameters, in which the position of the maximum wave number range is in each case established in cm-1: Bruker Raman RFS 100 / S instrument Number of scans 64

Resolution 2 - 4 cm-1 Laser power 50 mW Laser wavelength 1064 nm

[011] The following bands are measured with Raman spectroscopy for crystal form A of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one (table 3, figure 2): Maximum range [cm-1] 3077 3059 2989 2978 2970 2961 2934 2905 2875 2865 2842 2762 2719 2683 1694 1588 1567 1468 1460 1441 1385 1352 1293 1262 1225 1210

Maximum range [cm-1] 1179 1145 1121 1106 1051 1025 1010 976 964 952 894 857 827 756 719 706 661 604 555 Table 3:

[012] The crystal form A is preferably characterized by the fact that the Raman spectrum has at least the following bands (table 4): Maximum range [cm-1] 3059 2989 2970 2934 1694 1588 719

Maximum range [cm-1] 706 Table 4:

[013] The compound of the formula (I), 2 - [(2,4-dichlorophenyl) methyl] - 4,4-dimethyl-isoxazolidin-3-one, crystallizes in three modifications. The above (hereinafter referred to as modification A / crystal form A) has a melting point of 82 ° C, modification B has a melting point of 72 ° C and modification C has a melting point of 44 ° C . The compound of formula (I) can appear in amorphous form at room temperature; however, it has a great tendency to recrystallize. Modification A appears to be the most thermodynamically stable form.

[014] In another aspect, the present invention relates to a herbicide composition, characterized by the fact that the composition comprises the compound of formula (I), and one or more substances selected from groups (i) and / or (ii) : (i) one or more agrochemically active substances, preferably selected from the group consisting of herbicides, insecticides, acaricides, nematicides, fungicides, protectors, fertilizers and / or growth regulators, (ii) one or more usual formulation aids in protection of the plantation.

[015] Composition comprising modification A of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one in a total amount of at least 5% by weight, based on the amount total of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethylisoxazolidin-3-one present in the composition.

[016] A composition comprising modification A of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one in a total amount of at least 50% by weight, with based on the total amount of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethylisoxazolidin-3-one present in the composition.

[017] Most preferred is a composition comprising modification A of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethylisoxazolidin-3-one in a total amount of at least 80% by weight, based on the total amount of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one present in the composition.

[018] Most preferred is a composition comprising modification A of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethylisoxazolidin-3-one in a total amount of at least 95% by weight, based on the total amount of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one present in the composition.

[019] The compound of the formula (I) and / or its salts can be formulated in several ways, according to the necessary 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, solutions sprayable, suspension concentrates (SC), oil or water based dispersions, oil miscible solutions, capsule suspensions (CS), powder products (DP), seed coating products, granules for sowing and application in the soil, granules (GR) in the form of microgranules, sprayable granules, coated granules and adsorption granules, water dispersible granules (WG), water soluble granules (SG), ULV formulations, microcapsules and waxes.

[020] These types of individual formulation are known in principle and are described, for example, in: Winnacker-Küchler, "Chemische Technologie", Volume 7, C. Hanser Verlag Munich, 4th. ed. 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, Manual "Spray Drying", 3rd ed. 1979, G. Goodwin Ltd. London.

[021] Aids of the necessary formulation, such as inert materials, surfactants, solvents and other additives are also known and described, for example, in: Watkins,

"Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, “Introduction to Clay Colloid Chemistry”; 2nd Ed., J. Wiley & Sons, N.Y .; C. Marsden, “Solvents Guide”; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J .; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Grenzflächenaktive Äthylenoxidaddukte" [Active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie", volume 7, C. Hanser Verlag Munich, 4th. ed. 1986.

[022] Wettable powders are preparations that can be dispersed evenly in water and, as well as the active compound, not considering a diluent or inert substance, also comprise ionic and / or non-ionic surfactants (wetting agents, dispersants), for example example, polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyethoxylated fatty amines, polyglycol ether fatty alcohol sulfates, alkanesulphonates, alkylbenzenesulphonates, sodium lignosulphonate, sodium 2,2'-dinaftilmethane-sodium 6,3'-disulfonate, dibutylna sodium. To prepare wettable powders, the active herbicidal compounds are finely ground in standard devices, such as hammer mills, blower mills and air jet mills, and mixed simultaneously or subsequently with the formulation assistants.

[023] Emulsifiable concentrates are produced by dissolving the active compound in an organic solvent, for example, butanol, cyclohexanone, dimethylformamide, xylene or relatively high boiling aromatics or hydrocarbons or mixtures of organic solvents, with the addition of one or more surfactants than ionic and / or non-ionic type (emulsifiers). The emulsifiers used can, for example, be: alkylaryl sulfonic salts of calcium, such as calcium dodecylbenzenesulfonate or non-ionic emulsifiers, such as polyglycol esters fatty acids, alkyl aryl polyglycol ethers, fatty acids,

polyglycol ethers, condensation products of propylene oxide-ethylene oxide, alkyl polyethers, sorbitan esters, such as sorbitan fatty acid esters or polyoxyethylene sorbitan esters, such as polyoxyethylene fatty acid esters sorbitan.

[024] Dust removal products are obtained by grinding the active compound with finely distributed solid substances, for example talc, natural clays such as kaolin, bentonite and pyrophyllite or diatomaceous earth.

[025] Suspension concentrates can be water or oil based. They can be produced, for example, by wet grinding by means of commercial ball mills with optional addition of surfactants, as already listed above, for example, for the other types of formulation.

[026] Emulsions, e.g. oil-in-water (EW) emulsions can be prepared, for example, by means of agitators, colloid mills and / or static mixers using aqueous organic solvents and, if appropriate, surfactants, as already, for example, listed above in connection with o other types of formulation.

[027] The granules can be produced by spraying the active compound on granulated inert material by adsorption or by applying active concentrates using adhesives, for example, polyvinyl alcohol, sodium polyacrylate or mineral oils, on the surface of carrier substances, such as sand, kaolinite or granulated inert material. Suitable active compounds can also be granulated in the usual way for the production of fertilizer granules - if desired as a mixture with fertilizers.

[028] Water-dispersible granules are generally produced by the usual processes, such as spray drying, fluid bed granulation, container granulation, mixing with high-speed mixers and extrusion without solid inert material.

[029] For the production of container granules, fluidized bed granules, extruder granules and spray granules, see, for example, the processes in "Spray-Drying Handbook" 3a. ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff .; Perry's Chemical Engineer's Handbook, 5th. Ed., McGraw-Hill, New York 1973, p. 8-57.

[030] For further details regarding the formulation of crop protection agents, see, for example, GC Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and JD Freyer, SA Evans, "Weed Control Handbook", 5th. ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

[031] Agrochemical formulations generally comprise from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of the active compound of the formula (I) and / or its salts.

[032] In wettable powders, the concentration of the active compound is, for example, approximately 10 to 90% by weight; the rest at 100% by weight consists of the constituents of the usual formulation. In the case of emulsifiable concentrates, the concentration of the active compound can be approximately 1 to 90, preferably 5 to 80% by weight. Powder type formulations contain from 1 to 30% by weight of active compound, preferably from 5 to 20% by weight of active compound; sprayable solutions contain approximately 0.05 to 80% by weight, preferably 2 to 50% by weight of active compound. In the case of water-dispersible granules, the content of the active compound depends partly on whether the active compound is present in liquid or solid form and in which assistants, fillers etc. are used. granulation. In water-dispersible granules, the content of the active compound is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

[033] In addition, the aforementioned active compound formulations optionally comprise the respective adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze and solvents, fillers, carriers and dyes, foam deformers, evaporation inhibitors and usual agents that influence pH and viscosity. Examples of formulation aids are described, inter alia, in "Chemistry and Technology of Agrochemical Formulations", ed. D. A. Knowles, Kluwer Academic Publishers (1998).

[034] The compound of formula (I) and / or its salts can be used as such or in the form of preparations (formulations) combined with other active compounds with pesticides, for example, insecticides, acaricides, nematicides, herbicides, fungicides, protectors , fertilizers and / or growth regulators, for example, in the form of a finished formulation or as tank mixtures. Combination formulations can be prepared based on the formulations mentioned above, while taking into account the physical properties and stability of the active compounds to be combined.

[035] The weight ratios of herbicide (mixture) to the protector generally depend on the rate of application of the herbicide and the effectiveness of the protector in question and can vary within wide limits, for example with the range of 200: 1 to 1: 200, preferably 100: 1 to 1: 100, in particular 20: 1 to 1:20. Similar to the compound of formula (I), the protectors can be formulated with other herbicides / pesticides and be supplied and used as a finished formulation or tank mixture with the herbicides.

[036] For the application, the herbicide or herbicide / protector formulations present in the commercial form are, if appropriate, diluted in the usual way, for example in the case of wetted powders, emulsifiable concentrates, dispersions and dispersible granules in water with Water. Preparations in the form of powders, granules for application to the soil or granules for diffusion and spraying solutions are generally no longer diluted with other inert substances before application.

[037] The rate of application of the compounds of formula (I) or their salts can vary within wide limits. For application as a herbicide for the control of harmful plants, for example, a range of 0.001 to 10.0 kg / ha of active substance is generally suitable, preferably composed of formula (I) and / or salts thereof are applied in the variation of 0.005 to 5 kg / ha, in particular ranging from 0.01 to 1 kg / ha. This applies to the pre-emergence and post-emergence application.

[038] When used as a plant growth regulator, for example, as a stem stabilizer for crop plants such as those mentioned above, preferably cereal plants such as wheat, barley, rye, triticale, millet, rice or corn, the rate application of the compound of formula (I) and / or its salts is, for example, in the range of 0.001 to 2 kg / ha or more of active substance, preferably in the range of 0.005 to 1 kg / ha, in particular in the range of 10 to 500 g / ha of active substance. This refers to the application by the pre-emergency method and the post-emergency method, with post-emergency treatment being generally preferred.

[039] The application as a stalk stabilizer occurs at various stages of plant growth. It is preferable, for example, to apply after the tillering phase at the beginning of longitudinal growth.

[040] As an alternative, application as a plant growth regulator is also possible when treating the seed, which includes various techniques for dressing and coating the seed. Here, the application rate depends on specific techniques and can be determined in preliminary tests.

[041] The components that can be used in combination with the active compounds according to the invention in mixed or tank mix formulations are, for example, known active compounds, as described in, for example, Weed Research 26, 441- 445 (1986), or "The Pesticide Manual”, 16th edition, The British Crop Protection Council and Royal Soc. De Chemistry, 2006, and in the cited literature, which for example act as acetolactate synthase inhibitors, acetyl- CoA-carboxylase, cellulose synthase, enolpyruvylshikimat-3-phosphate synthase, glutamine synthase, p-hydroxyphenylpyruvate-dioxigenase, phytendesaturase, photosystem I, photosystem II and / or protoporphyrinogen-oxidase.

[042] Examples of active compounds that can be mentioned as herbicides or plant growth regulators known in the literature and that can be combined with the compounds according to the invention are as follows (the compounds are described by "common name" according to with the International Organization for Standardization (ISO) or by chemical name or by a usual code number) and always comprise all applicable forms, such as acids, salts, esters or modifications, as isomers, as stereoisomers and optical isomers. As an example, at least one form and / or applicable modifications can be mentioned. Examples of herbicides are:

[043] Acetochlor, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, alidochlor, aloxidim, aloxidim-sodium, ametrin, amicarbazone, amidochlor, amidosulfuron, 4-amino-3-chloro-6- (4-chloro-2-fluoro- 3-methylphenyl) -5-fluoropyridine-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyraclor-potassium, aminocyclopyrachlor-methyl, aminopiralid, amitrole, ammonium sulfamate, anilophos, asulam, atrazine, azafenidin, benzurine, benzurine , benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazone, benzobicyclon, benzofenap, bicyclopiron, bifenox, bilanafos, bilanafosodium, bispiribac, bispiribac-sodium, bromacil, bromobutide, bromophenoxy, bromoxynil-butyl, bromoxynil-butane, bromoxynil-butyl and -octanoate, busoxinone, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxidim, butylate, cafenstrol, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chlorbromuron, chlorfenac, chlorfenac-chlor, chlorflenol , chloridazon, chlorimuron, chlorimuron-ethyl, chlorophthalim, chlorotoluron, chlortal-dimethyl, clorsulfuron, cinidon, cinidon-ethyl, cinmetilin, cinosulfuron, clacifos, cletodim, clodinafop, clodinafop-clansulam, clodina, clammin, clammin , cumiluron, cyanamide, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cyclooxide, cihalofop, cihalofop-butyl, cyprazine, 2,4-D, 2,4-D-butotyl, - butyl, -dimethylammonium, -diolamin, -ethyl, - 2-ethylhexyl,

-isobutyl, -isooctyl, -isopropylammonium, -potassium, - triisopropanolammonium and -trolamine, 2,4-DB, 2,4-DB-butyl, -dimethylammonium, -isooctyl, -potassium and -sodium, daimuron (dimron), dalapon , dazomet, n-decanol, demedipham, detosylpyrazolate (DTP), dicamba, dichlobenyl, 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-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, difenzoquat, diflufenican, diflufenzopir-, diflufenzopir-, diflufenzopir- sodium, dimefuron, dimepiperate, dimetachlor, dimetametrin, dimetenamid, dimetenamid-P, dimetrasulfuron, dinitramine, dinoterb, diphenamid, diquat, diquat-dibromid, dithiopir, diuron, DNOC, endotal, EPTC, esprocarb, etametsulfon, etametsin, etametsin etiozin, etofumesate, ethoxyfen, ethoxyphenyl, ethoxysulfuron, etobenzanid, F-9600, F-5231, that is, N- {2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -5-oxo -4,5-dihydro-1H-tetrazol-1-yl] phenyl} ethanesulfonamide, F-7967, i.e. 3- [7-chloro-5-fluoro-2- (trifluoromethyl) -1H-benzimidazol-4-yl] -1-methyl- 6- (trifluoromethyl) pyrimidine-2,4 (1H, 3H) -dione, phenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, phenoxasulfone, phenquinotrione, fentrazamide, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-butyl P-butyl, flucarbazone, flucarbazone-sodium, flucetosulfuron, flucloralin, flufenacet, flufenpir, flufenpir-ethyl, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazin, fluometuron, flurenol, flurenol-butyl-fluorin-butyl-fluorin-butyl-fluoride ethyl, flupropanate, flupirsulfuron, flupirsulfuron-methyl-sodium, fluridone, flurochloridone, fluroxypyr, fluroxypyr-meptil, flurtamone, flutiacet, flutiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, phosphine-glufosinate, glufosinate, glufosinate sodium, glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate, glyphosate-ammonium, -isopropylammonium, -diammonium, -dimethyl ammonium, -potassium, -sodium and -trimesium, H-9201, that is, O- (2,4-dimethyl-6-nitrophenyl) O-ethyl isopropylphosphoramidothioate, halauxifene, halauxifene-

methyl, halosafen, halosulfuron, halosulfuron-methyl, haloxifop, haloxifop-P, haloxifop-etoxyethyl, haloxifop-P-etoxyethyl, haloxifop-methyl, haloxifop-P-methyl, hexazinone, HW-02, that is, 1- (dimetoxyphosphyl) ethyl- (2,4-dichlorophenoxy) acetate, imazametabenz, imazametabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazetapan, imazetapir, imazetapir, , indaziflam, iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxynyl-octanoate, -potassium and -sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutol, carbutilate, KUH-043, that is, 3 - ({[5- difluoromethyl) -1-methyl-3- (trifluoromethyl) -1H-pyrazol-4-yl] methyl} sulfonyl) -5,5-dimethyl-4,5-dihydro-1,2-oxazole, quetospiradox, lactofen, lenacil, linuron, MCPA, MCPA-butotyl, - dimethylammonium, -2-ethylhexyl, -isopropylammonium, -potassium and -sodium, MCPB, MCPB-methyl, -ethyl, 1 and -sodium, mecoprop, mecoprop-sodium and - butotyl, mecoprop-P, mecoprop-P-butotyl , - dimethylammonium, -2-ethylhexyl and -potassium, mefenacet, mefluidide, mesosulfuron, mesosulfuron-methyl, mesotrione, metabenztiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, metenztiazuron, metenztiazuron, metiosulfone , S-metolachlor, metosulam, methoxyuron, metribuzin, metsulfuron, metsulfuron-methyl, molinat, monolinuron, monosulfuron, monosulfuron-ester, MT-5950, that is, N- (3-chloro-4-isopropylphenyl) -2-methylpentanide , NGGC-011, napropamide, NC-310, that is, [5- (benzyloxy) -1- methyl-1H-pyrazol-4-yl] (2,4-dichlorophenyl) methanone, neburon, nicosulfuron, nonanoic acid (acid pelargonic), norflurazon, oleic acid (fatty acids), orbencarb, ortosulfamuron, orizalin, oxadiargil, oxadiazon, oxasulfuron, oxaziclomefon, oxifluorfen, paraquat, paraquat dichloride, pebulate, pendimetalam, pentaxamide, pentoxide, pentoxide, pentoxidone , picolinafen, pinoxaden, piperophos, pretilachlor, primisulfide n, primisulfuron-methyl, prodiamine, profoxidim, prometon, prometrin, propachlor, propanyl, propaquizafop, propazine, profam, propisochlor,

propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propizamide, prosulfocarb, prosulfuron, piraclonil, piraflufen, piraflufen-ethyl, pirasulfotol, pyrazolinate (pyrazolate), pirazosulfuron, pirazosulfuron-ethyl, pyrazoxybenzyl, pyrazoxyphenyl, pyrazoxyphenyl, pyrazoxyphenyl, pyrazoxyphenyl, pyrazoxybenzyl, pyrazoxybenzyl, pyrazoxyphenyl, pyrazoxybenipyribyrene , pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, piritiobac, piritiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P, quizalofop-P, quizalofop-P, quizalofop-P -tefuril, rimsulfuron, saflufenacil, setoxidim, siduron, simazine, simetrin, SL-261, sulcotrion, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, SYN-523, SYP-249, that is, 1-ethoxy-3-methyl-3 1-oxobut-3-en-2-yl 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoate, SYP-300, ie 1- [7-fluoro-3-oxo-4- (prop-2-in-1-yl) -3,4-dihydro-2H-1,4-benzoxazin-6-yl] -3-propyl-2-thioxoimidazolidine-4,5-dione, 2,3 , 6-TBA, TCA (tric acid loroacetic), TCA-sodium, tebutiuron, tefuriltrione, tembotrione, tepraloxidim, terbacil, terbucarb, terbumeton, terbutilazin, terbutrin, tenilchlor, thiazopyr, tiencarbazone, tiencarbazone-methyl, thiamensulfuron, tifensulfuron, tifensulfuron, tifensulfuron, tifensulfuron, tifensulfuron, tifensulfuron, tifensulfuron , triafamone, tri-alate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, triclopyr, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazin, trifluralin, triflusulfuron, methoxy-triflusulfon, triflusulfuron, triflusulfuron, -0862, that is, 3,4-dichloro-N- {2- [(4,6-dimethoxypyrimidin-2-yl) oxy] benzyl} aniline and the following compounds:

O O O O O O N N N N Y N Y

OH O O O O CF3 O O

s THE THE

F CF3 N Cl

N O O N

CO2Et

[044] Here are some examples for plant growth regulators:

[045] Acibenzolar, acibenzolar-S-methyl, 5-aminolevulinic acid, ancimidol, 6-benzylaminopurine, Brassinolid, catechin, chlormequat chloride, cloprop, cyclanilide, 3- (cycloprop-1-enyl) propionic acid, daminozide, dazomet, n -decanol, diquegulac, diquegulac-sodium, endotal, endotal-dipotassium, -disodium, and - mono (N, N-dimethylalkylammonium), etefon, flumetralin, flurenol, flurenol-butyl, flurprimidol, forclorfenuron, indium-gibberelic acid 3-acetic acid (IAA), 4-indole-3-ylbutyric acid, isoprothiolane, probenazole, jasmonic acid, maleic hydrazide, mepiquat chloride, 1-methylcyclopropene, methyl jasmonate, 2- (1-naphthyl) acetamide, 1-naphthylacetic acid , 2-naphthyloxyacetic acid, mixture of nitrophenolate, paclobutrazol, N- (2-phenylethyl) -beta-alanine, N-phenylphthalamic acid, prohexadione, prohexadione-calcium, prohydrojasmone, salicylic acid, strigolactone, technazene, tidiazuron, triac trinexapac, trinexapac-ethyl, tsitodef, uniconazole, uniconazole-P. Protectors are preferably selected from the group consisting of:

[046] S1) compounds of the formula (S1)

O (RA1) nA (S1) 2

WA RA where symbols and indices have the following meanings:

[047] nA is a natural number from 0 to 5, preferably from 0 to 3;

[048] RA1 is halogen, (C1-C4) -alkyl, (C1-C4) -alkoxy, nitro or (C1-C4) -haloalkyl;

[049] WA is a divalent substituted or unsubstituted heterocyclic radical of the group consisting of five partially unsaturated or aromatic heterocycles with a ring with 1 to 3 heteroatoms of the group consisting of N and O, in which at least one atom of nitrogen and at most one oxygen atom is present in the ring, preferably a radical of the group consisting of (WA1) to (WA4), NNN - (CH2) mA

N N N

N RA5 RA8 O N RA6 RA7 RA6 (WA1) (WA2) (WA3) (WA4)

[050] mA is 0 or 1;

[051] RA2 is ORA3, SRA3 or NRA3RA4 or a saturated or unsaturated 3- to 7-membered heterocycle having at least one nitrogen atom and up to 3 heteroatoms, preferably from the group consisting of O and S, which is linked via the atom of nitrogen to the carbonyl group in (S1) and which is unsubstituted or substituted by the radicals of the group consisting of (C1-C4) -alkyl, (C1-C4) -alkoxy and optionally substituted phenyl, preferably a radical of the formula ORA3 , NHRA4 or N (CH3) 2, especially of the formula ORA3;

[052] RA3 is a hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having a total of 1 to 18 C atoms;

[053] RA4 is hydrogen, (C1-C6) -alkyl, (C1-C6) -alkoxy or substituted or unsubstituted phenyl;

[054] RA5 is H, (C1-C8) -alkyl, (C1-C8) -haloalkyl, (C1-C4) -alkoxy- (C1-C8) -alkyl, cyan or COORA9, where RA9 is hydrogen, ( C1-C8) - alkyl, (C1-C8) -haloalkyl, (C1-C4) -alkoxy- (C1-C4) -alkyl, (C1-C6) - hydroxyalkyl, (C3-C12) -cycloalkyl or tri- ( C1-C4) -alkylsilyl;

[055] RA6, RA7, RA8 are identical or different and are hydrogen, (C1-C8) -alkyl, (C1-C8) -haloalkyl, (C3-C12) -cycloalkyl or substituted or unsubstituted phenyl; preferably: a) dichlorophenylpyrazoline-3-carboxylic acid (S1a) type compounds, preferably compounds such as 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-carboxylate (S1) ("mefenpir-) diethyl"), and related compounds as described in WO-A-91/07874; b) dichlorophenylpyrazolcarboxylic acid derivatives (S1b), preferably compounds, such as ethyl 1- (2,4-dichlorophenyl) - 5-methylpyrazol-3-carboxylate (S1-2), ethyl 1- (2,4-dichlorophenyl) -5 -isopropylpyrazol-3-carboxylate (S1-3), ethyl 1- (2,4-dichlorophenyl) -5- (1,1-dimethylethyl) pyrazol-3-carboxylate (S1-4) and related compounds, as described in EP -A-333 131 and EP-A-269 806; c) 1,5-diphenylpyrazol-3-carboxylic acid (S1c) derivatives, preferably compounds such as ethyl 1- (2,4-dichlorophenyl) 5-phenylpyrazol-3-carboxylate (S1), methyl 1- (2-chlorophenyl) 5-phenylpyrazole-3-carboxylate (S1-6) and related compounds as described, for example, in EP-A-268554; d) compounds of the type of triazole carboxylic acids (S1d), preferably compounds such as phenclorazole (-ethyl), that is, ethyl 1- (2,4-dichlorophenyl) -5-trichloromethyl- (1H) -1,2,4- triazole-3-carboxylate (S1-7) and related compounds, as described in EP-A-174 562 and EP-A-346 620; e) compounds of the type of 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (S1e), preferably compounds, such as ethyl 5- (2,4-dichlorobenzyl) -2-isoxazoline-3-carboxylate (S1-8) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (S1-9) and related compounds, as described in WO-A- 91/08202 or 5,5-diphenyl-2-isoxazolinocarboxylic acid (S1- 10) or ethyl 5,5-diphenyl-2-isoxazolinocarboxylate (S1-11) ("isoxadifen-ethyl") or n-propyl 5.5- diphenyl-2-isoxazolinocarboxylate (S1-12) or ethyl 5- (4-fluorophenyl) -5-phenyl-2-isoxazolin-3-carboxylate (S1-13), as described in patent application WO-A-95/07897 .

[056] S2) Quinoline derivatives of the formula (S2)

(RB1) nB N (S2)

THE

The 2

TB RB where symbols and indices have the following meanings:

[057] RB1 is halogen, (C1-C4) -alkyl, (C1-C4) -alkoxy, nitro or (C1-C4) -haloalkyl;

[058] nB is a natural number from 0 to 5, preferably from 0 to 3;

[059] RB2 is ORB3, SRB3 or NRB3RB4 or a 3- to 7-membered saturated or unsaturated heterocycle having at least one nitrogen atom and up to 3 hetero atoms, preferably from the group consisting of O and S, which is linked via nitrogen atom to the carbonyl group (S2) and which is unsubstituted or substituted by radicals of the group consisting of (C1-C4) -alkyl, (C1-C4) -alkoxy or optionally substituted phenyl, preferably a radical of the formula ORB3, NHRB4 or N (CH3) 2, in particular the formula ORB3;

[060] RB3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably a total of 1 to 18 carbon atoms;

[061] RB4 is hydrogen, (C1-C6) -alkyl, (C1-C6) -alkoxy or substituted or unsubstituted phenyl;

[062] TB is a (C1 or C2) -alkodiyl chain that is unsubstituted or substituted by one or two (C1-C4) -alkyl radicals or by [(C1-C3) -alkoxy] carbonyl; preferably: a) compounds of the type 8-quinolinoxyacetic acid (S2a), preferably 1-methyl hexyl (5-chloro-8-quinolinoxy) acetate (common name "cloquintocet-mexil" (S2-1), 1,3-dimethyl -but-1-yl (5-chloro-8-quinolinoxy) acetate (S2-2), 4-allyloxybutyl (5-chloro-8-quinolinoxy) acetate (S2-3), 1-allyloxyprop-2-yl (5 -chloro-8-quinolinoxy) acetate (S2-4), ethyl (5-chloro-8-quinolinoxy) acetate (S2-5), methyl (5-chloro-8-quinolinoxy) acetate (S2-6), ally ( 5- chloro-8-quinolinoxy) acetate (S2-7), 2- (2-propylideneiminoxy) -1- ethyl (5-chloro-8-quinolinoxy) acetate (S2-8), 2-oxo-prop-1- useful (5-chloro-8-quinolinoxy) acetate (S2-9) and related compounds,

as described in EP-A-86 750, EP-A-94 349 and EP-A-191 736 or EP-A-0 492 366, and also (5-chloro-8-quinolinoxy) acetic acid (S2-10 ), its hydrates and salts, for example, its lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, as described in WO-A-2002/34048; b) compounds of the type (5-chloro-8-quinolinoxy) malonic acid (S2b), preferably compounds such as 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.

[063] S3) Compounds of the formula (S3)

O 2 1 RC

RC N (S3) 3

RC where symbols and indexes have the following meanings:

[064] RC1 is (C1-C4) -alkyl, (C1-C4) -haloalkyl, (C2-C4) -alkenyl, (C2-C4) -haloalkenyl, (C3-C7) -cycloalkyl, preferably dichloromethyl;

[065] RC2, RC3 are identical or different and are 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) -alkoxi- (C1-C4) - alkyl, dioxolanyl- (C1-C4) -alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl or RC2 and RC 3 together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine ring, piperidine, morpholine, hexahydropyrimidine or benzoxazine; preferably:

[066] Active compounds of the dichloroacetamide type that are often used as pre-emergence protectors (soil-acting protectors), such as "diclormid" (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) of

Stauffer (S3-3), "benoxacor" (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4), "PPG-1292" (N-allyl -N - [(1,3-dioxolan-2-yl) methyl] dichloroacetamide) from PPG Industries (S3-5), "DKA-24" (N-allyl-N - [(allyaminocarbonyl) methyl] dichloroacetamide) from Sagro -Chem (S3-6), "AD-67" or "MON 4660" (3-dichloroacetyl-1-oxa-3-azospiro [4.5] dean) from Nitrokemia or Monsanto (S3-7), "TI-35" (1-dichloroacetylazepan) from TRI-Chemical RT (S3-8), "diclonon" (dicyclonon) or "BAS145138" or "LAB145138" (S3-9) (3-dichloroacetyl-2,5,5-trimethyl-1, BASF 3-diazabicycle [4.3.0] nonane, "furilazole" or "MON 13900" ((RS) -1-dichloroacetyl-3,3,8a trimethylperhydropyrrolo [1,2-a] pyrimidin-6-one) (S3-10) and also its (R) isomer (S3-11).

[067] S4) N-acylsulfonamides of the formula (S4) and their salts (RD4) mD RD1

AD (S4)

XD (RD2) nD where the symbols and indices have the following meanings:

[068] AD is SO2-NRD3-CO or CO-NRD3-SO2;

[069] XD is CH or N;

[070] RD1 is CO-NRD5RD6 or NHCO-RD7;

[071] RD2 is halogen, (C1-C4) -haloalkyl, (C1-C4) -haloalkoxy, nitro, (C1-C4) -alkyl, (C1-C4) -alkoxy, (C1-C4) -alkylsulfonyl, ( C1- C4) -alkoxycarbonyl or (C1-C4) -alkylcarbonyl;

[072] RD3 is hydrogen, (C1-C4) -alkyl, (C2-C4) -alkenyl or (C2-C4) -alkynyl;

[073] RD4 is 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;

[074] RD5 is hydrogen, (C1-C6) -alkyl, (C3-C6) -cycloalkyl, (C2-C6) -alkenyl, (C2-C6) -alkynyl, (C5-C6) -cycloalkenyl, phenyl or heterocyclyl with 3 to 6 members that contain vD heteroatoms of the group consisting of nitrogen, oxygen and sulfur, where the radicals mentioned last are replaced by vD substituents of the group consisting of halogen, (C1-C6) - alkoxy, (C1- C6) -haloalkoxy, (C1-C2) -alkylsulfinyl, (C1-C2) - alkylsulfonyl, (C3-C6) -cycloalkyl, (C1-C4) -alkoxycarbonyl, (C1- C4) -alkylcarbonyl and phenyl and, in the case cyclic radicals, also (C1-C4) -alkyl and (C1-C4) -haloalkyl;

[075] RD6 is hydrogen, (C1-C6) -alkyl, (C2-C6) -alkenyl or (C2-C6) -alkynyl, where the three radicals cited last are replaced by the vD radicals of the group consisting of halogen, hydroxy, (C1-C4) -alkyl, (C1-C4) -alkoxy and (C1-C4) -alkylthio or

[076] RD5 and RD6 together with the nitrogen atom carrying them form a pyrrolidinyl or piperidinyl radical;

[077] RD7 is hydrogen, (C1-C4) -alkylamino, di- (C1-C4) - alkylamino, (C1-C6) -alkyl, (C3-C6) -cycloalkyl, where the 2 radicals quoted last are replaced by the vD substituents of the group consisting of halogen, (C1-C4) -alkoxy, halo- (C1- C6) -alkoxy and (C1-C4) -alkylthio, and in the case of cyclic radicals, also (C1-C4) - alkyl and (C1-C4) -haloalkyl;

[078] nD is 0, 1 or 2;

[079] mD is 1 or 2;

[080] vD is 0, 1, 2 or 3; among these, preference is given to compounds of the type N-acylsulfonamides, for example of the formula (S4a) below, which are known, for example, in WO-A- 97/45016 OOO 4 (RD) mD NSN (S4a) 7

RD H O H where

[081] RD7 is (C1-C6) -alkyl, (C3-C6) -cycloalkyl, where the 2 radicals cited last are replaced by vD substituents of the group consisting of halogen, (C1-C4) -alkoxy, halo- (C1-C6) - alkoxy and (C1-C4) -alkylthio and, in the case of cyclic radicals, also (C1-C4) -alkyl and (C1-C4) -haloalkyl;

[082] RD4 is halogen, (C1-C4) -alkyl, (C1-C4) -alkoxy, CF3;

[083] mD is 1 or 2;

[084] vD is 0, 1, 2 or 3; and also acylsulfamoylbenzamides, for example, of the formula (S4b) below, which are known, for example, in WO-A-99/16744, 5

RD O O 4 N (RD) mD H S N (S4b)

O O H for example, those in which

[085] RD5 = cyclopropyl and (RD4) = 2-OMe ("cyprosulfamide", S4-1),

[086] RD5 = cyclopropyl and (RD4) = 5-Cl-2-OMe (S4-2),

[087] RD5 = ethyl and (RD4) = 2-OMe (S4-3),

[088] RD5 = isopropyl and (RD4) = 5-Cl-2-OMe (S4-4) and

[089] RD5 = isopropyl and (RD4) = 2-OMe (S4-5) and also compounds of the type N-acylsulfamoylphenylureas, of the formula (S4c), which are known, for example, in EP-A-365484, 8 RD OOO 4 (RD) mD NNSN (S4c) 9

RD H O H where

[090] RD8 and RD9 independently of each other are hydrogen, (C1- C8) -alkyl, (C3-C8) -cycloalkyl, (C3-C6) -alkenyl, (C3-C6) - alkynyl,

[091] RD4 is halogen, (C1-C4) -alkyl, (C1-C4) -alkoxy, CF3,

[092] mD is 1 or 2; for example, 1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3-methylurea, 1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3,3-dimethylurea, 1- [4- (N -4,5-dimethylbenzoylsulfamoyl) phenyl] -3-methylurea, and also N-phenylsulfonyltereftalamides of the formula (S4d), which are known, for example, in CN 101838227, 5

RD O O 4 N (RD) mD H N S (S4d)

H O eg, as compounds in which

[093] RD4 is halogen, (C1-C4) -alkyl, (C1-C4) -alkoxy, CF3;

[094] mD is 1 or 2;

[095] RD5 is hydrogen, (C1-C6) -alkyl, (C3-C6) -cycloalkyl, (C2-C6) -alkenyl, (C2-C6) -alkynyl, (C5-C6) -cycloalkenyl.

[096] S5) Active compounds of the hydroxy aromatics class and derivatives of aromatic aliphatic carboxylic acid (S5), for example, ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-di acid -hydroxybenzoic acid, 4-hydroxy salicylic acid, 4-fluoro salicylic acid, 2-cinnamic hydroxy acid, 2,4-dichloro cinnamic acid, as described in WO-A-2004/084631, WO-A-2005/015994, WO- A-2005/016001.

[097] S6) Active compounds of the 1,2-dihydroquinoxalin-2-one (S6) class, for example, 1-methyl-3- (2-thienyl) -1,2-dihydroquinoxalin-2- one, 1-methyl-3- (2-thienyl) -1,2-dihydroquinoxaline-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.

[098] S7) Compounds of the formula (S7), as described in WO-A- 1998/38856,

AE H2C (O) nE1 C (S7) (RE1) nE2 H (RE2) nE3 where the symbols and indices have the following meanings:

[099] RE1, RE2 independently of one another are halogen, (C1- C4) -alkyl, (C1-C4) -alkoxy, (C1-C4) -haloalkyl, (C1-C4) - alkylamino, di- (C1- C4) -alkylamino, nitro;

[100] AE is COORE3 or COSRE4

[101] RE3, RE4 independently of one another are hydrogen, (C1- C4) -alkyl, (C2-C6) -alkenyl, (C2-C4) -alkynyl, cyanoalkyl, (C1- C4) -haloalkyl, phenyl, nitrophenyl , benzyl, halobenzyl, pyridinylalkyl or alkylammonium,

[102] nE1 is 0 or 1;

[103] nE2, nE3 independently of each other are 0, 1 or 2, preferably: diphenylmethoxy acetic acid, ethyl diphenylmethoxyacetate, methyl diphenylmethoxyacetate (CAS Reg. No .: 41858-19-9) (S7-1).

[104] S8) Compounds of the formula (S8), as described in WO-A-98/27049, RF2

O O (S8) (RF1) nF

F XF RF3 where

[105] XF is CH or N,

[106] nF is, if XF = N, an integer from 0 to 4 and is, if XF = CH, an integer from 0 to 5,

[107] RF1 is 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,

[108] RF2 is hydrogen or (C1-C4) -alkyl,

[109] RF3 is hydrogen, (C1-C8) -alkyl, (C2-C4) -alkenyl, (C2-C4) - alkynyl or aryl, where each of the carbon-containing radicals mentioned above is unsubstituted or replaced by one or more, preferably by up to three, identical or different radicals from the group consisting of halogen and alkoxy; or their salts, preferably compounds in which

[110] XF is CH,

[111] nF is an integer from 0 to 2,

[112] RF1 is halogen, (C1-C4) -alkyl, (C1-C4) -haloalkyl, (C1-C4) - alkoxy, (C1-C4) -haloalkoxy,

[113] RF2 is hydrogen or (C1-C4) -alkyl,

[114] RF3 is hydrogen, (C1-C8) -alkyl, (C2-C4) -alkenyl, (C2-C4) - alkynyl or aryl, where each of the carbon-containing radicals mentioned above is unsubstituted or replaced by one or more, preferably by up to three, identical or different radicals from the group consisting of halogen and alkoxy; or its salts,

[115] S9) Active compounds of the class of 3- (5-tetrazolylcarbonyl) - 2-quinolones (S9), for example, 1,2-dihydro-4-hydroxy-1-ethyl-3- (5-tetrazolylcarbonyl ) -2-quinolone (CAS Reg. No .: 219479-18-2), 1,2-dihydro-4-hydroxy-1-methyl-3- (5-tetrazolylcarbonyl) -2-quinolone (CAS Reg No .: 95855-00-8), as described in WO-A- 1999/000020.

[116] S10) Compounds of the formula (S10a) or (S10b) as described in WO-A-2007/023719 and WO-A-2007/023764 O 3

The ZG RG

O 1 2 1 (RG) nG N YG RG (RG) nG O O

Y Y N RG 2

The H

O O (S10a) (S10b) where

[117] RG1 is halogen, (C1-C4) -alkyl, methoxy, nitro, cyan, CF3, OCF3,

[118] YG, ZG independently of each other are O or S,

[119] nG is an integer from 0 to 4,

[120] RG2 is (C1-C16) -alkyl, (C2-C6) -alkenyl, (C3-C6) -cycloalkyl, aryl, benzyl or halobenzyl,

[121] RG3 is hydrogen or (C1-C6) -alkyl.

[122] S11) Active compounds of the oxy-imine (S11) type of compounds, which are known as seed coatings, such as "oxabetrinyl" ((Z) -1,3-dioxolan-2-ylmethoxy) imino (phenyl) acetonitrile) (S11-1), which is known as a seed coating protector for millet against damage to metachlor, "fluxofenim" (1- (4-chlorophenyl) -2,2,2-trifluoro-1- ethanone O- (1,3-dioxolan-2-ylmethyl) oxime) (S11-2), which is known as a millet seed coating protector against damage from metolachlor and "ciometrinil" or "CGA-43089" (( Z) -cyanomethoxy-imino (phenyl) acetonitrile) (S11-3), which is well known as a seed coating protector for millet against damage from metolachlor.

[123] S12) Active compounds of the class of isothiocromanones (S12), such as, for example, methyl [(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.

[124] S13) One or more compounds in the group (S13): "naphthalic anhydride" (1,8-naphthalene carboxylic anhydride) (S13-1), which is known as a corn seed coating protector against herbicide damage of thiocarbamate, "fenclorim" (4,6-dichloro-2-phenylpyrimidine) (S13-2), which is known as a protector for pretilachlor in seeded rice, "flurazole" (benzyl 2-chloro-4-trifluoromethyl-1,3 -thiazole-5-carboxylate) (S13-3), which is well known as a seed coating protector for millet against damage by alachlor and metolachlor, "CL 304415" (CAS Reg. No .: 31541 -57 -8) ( American Cyanamid 4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid (S13-4), which is known as a protector for corn against imidazolinone damage, "MG 191" ( CAS Reg. No .: 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia, which is known as protector for corn, "MG 838" (CAS Reg No .: 133993-74-5) (2-propenyl 1-oxa-4-azaspiro [4.5] decane-4-carbodithioate) (S13-6) from Nitrokem ia, "disulfoton" (O, O-diethyl S-2-ethylthioethyl phosphorodithioate) (S13-7), "dietolate" (O, O-diethyl O-phenyl phosphorothioate) (S13-8), "mefenate" (4- chlorophenyl methylcarbamate) (S13-9).

[125] S14) Active compounds that, in addition to having a herbicidal effect against harmful plants, also have a protective effect on crop plants, such as rice, for example, "dimepiperate" or "MY-93" (S-1-methyl -1-phenylethyl piperidine-1-carbothioate), which is known as a protector for rice against damage by herbicide molinate, “daimuron” or “SK 23” (1- (1-methyl-1-phenylethyl) -3-p-tolylurea ), which is known as a protector for rice against damage from the herbicide imazosulfuron,

"cumiluron" = "JC-940" (3- (2-chlorophenylmethyl) -1- (1-methyl-1-phenylethyl) urea, see JP-A-60087254), which is known as a protector for rice from damage by some herbicide, "methoxyphenone" or "NK 049" (3,3'-dimethyl-4-methoxybenzenophenone), which is known to protect against damage to some herbicides, "CSB" (1-bromo-4- (chloromethylsulfonyl) benzene ) from Kumiai, (CAS reg. no. 54091-06-4), which is known as a protector against damage by some herbicides in rice.

[126] S15) Compounds of the formula (S15) or their tautomers,

O 2 4

RH RH

N 3 (S15) 1 RH

N THE RH

H which are known, for example, in WO-A-2008/131861 and WO-A-2008/131860. on what

[127] RH1 is (C1-C6) -haloalkyl,

[128] RH2 is hydrogen or halogen,

[129] RH3, RH4 independently of one another are hydrogen, (C1- C16) -alkyl, (C2-C16) -alkenyl or (C2-C16) -alkynyl, where each of the last 3 radicals is unsubstituted or replaced by one or more radicals in the halogen group, 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, (C3-C6) -cycloalkyl which is unsubstituted or substituted, phenyl which is unsubstituted or substituted and heterocyclyl that is unsubstituted or substituted, or (C3-C6) -cycloalkyl, (C4-C6) -cycloalkenyl, (C3-C6) -cycloalkyl that is in a condensed ring location with a saturated carbocyclic ring or 4 to 6-membered unsaturated or (C4-C6) -cycloalkenyl which is in a condensed ring location with a 4 to 6-membered saturated or unsaturated carbocyclic ring, where each of the last 4 radicals is unsubstituted or substituted by one or more radicals in the group consisting of halogen ene, hydroxy,

cyano, (C1-C4) -alkyl, (C1-C4) -haloalkyl, (C1-C4) -alkoxy, (C1-C4) - haloalkoxy, (C1-C4) -alkylthio, (C1-C4) -alkylamino, di [(C1-C4) - alkyl] amino, [(C1-C4) -alkoxy] carbonyl, [(C1-C4) - haloalkoxy] carbonyl, (C3-C6) -cycloalkyl, unsubstituted or substituted phenyl and non-heterocyclyl replaced or replaced; or

[130] RH3 is (C1-C4) -alkoxy, (C2-C4) -alkenyloxy, (C2-C6) - alkynyloxy or (C2-C4) -haloalkoxy and

[131] RH4 is hydrogen or (C1-C4) -alkyl or

[132] RH3 and RH4 together with the directly attached N atom are a 4- to 8-membered heterocyclic ring, which may contain hetero ring atoms in addition to the N atom, preferably up to two hetero ring atoms from the group consisting in N, O and S and that is unsubstituted or substituted by one or more radicals in the group consisting of halogen, cyano, nitro, (C1-C4) -alkyl, (C1-C4) -haloalkyl, (C1-C4) -alkoxy, (C1-C4) -haloalkoxy and (C1-C4) -alkylthio.

[133] S16) Active compounds that are used mainly as herbicides, but also have a protective effect on cultivated plants, for example (2,4-dichlorophenoxy) acetic acid (2,4-D), (4-chlorophenoxy) acetic acid, (R, S) -2- (4-chloro-o-tolyloxy) propionic acid (mecoprop), 4- (2,4-dichlorophenoxy) butyric acid (2,4-DB), (4-chloro-o-tolyloxy ) acetic acid (MCPA), 4- (4-chloro-o-tolyloxy) butyric acid, 4- (4-chlorophenoxy) butyric acid, 3,6-dichloro-2-methoxybenzoic acid (dicamba), 1- (ethoxycarbonyl) ethyl 3,6-dichloro-2-methoxybenzoate (lactidichlorethyl). Preparation

[134] The synthesis of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethylisoxazolidin-3-one is known in the United States patent

4,405,357.

Claims (9)

Claims 1. A compound of the formula (I), 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one, in crystalline form, characterized by the fact that the X-ray powder diffractogram with the use of Cu Kα radiation at 25 ° C has at least 3 of the following values 2Θ (2 theta) (modification A): values 2Θ (2 theta) in ° 10.5 14.2 18.5 19.8 21, 8 23.2 24.3 24.9 2. 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one according to claim 1, characterized by the fact that the X-ray powder diffractogram using radiation from Cu Kα at 25 ° C has at least 4, preferably 6, more preferably all the values of 2Θ (2 theta) specified in claim 1. 3. 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one according to claim 1 or 2, characterized by the Raman spectrum having at least the following ranges: Maximum range [cm -1] 3059 2989 2970 2934 1694 1588 719 706 4. Composition, characterized by the fact that it comprises the compound of formula (I) in modification A, according to any one of claims 1 to 3 in a total amount of at least 5% by weight, based on the total amount of 2- [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one present in the composition and one or more substances selected from groups (i) and / or (ii): (i) one or more substances agrochemically active, preferably selected from the group consisting of herbicides, insecticides, acaricides, nematicides, fungicides, protectors, fertilizers and / or growth regulators, (ii) one or more usual formulation aids in plantation protection. Composition according to Claim 4, characterized in that it comprises 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one in modification A in a total amount of at least 50% by weight, based on the total amount of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one present in the composition. Composition according to Claim 4, characterized in that it comprises 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one in modification A in a total amount of at least 80% by weight, based on the total amount of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one present in the composition. Composition according to Claim 4, characterized in that it comprises 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one in modification A in a total amount of at least 95% by weight, based on the total amount of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one present in the composition. 8. Use of compositions according to claims 4 to 7, characterized by being for the control of harmful plants or to regulate the growth of plants. 9. Method to control harmful plants or to regulate plant growth, characterized by an efficient amount - of 2 - [(2,4-dichlorophenyl) methyl] -4,4-dimethyl-isoxazolidin-3-one according to any one of claims 1 to 3, or - a composition according to any of claims 4 to 7 be applied to plants, seeds of soil plants on which or on which the plants grow or in the area under cultivation.