WO2019030177A1

WO2019030177A1 - Crystal forms of 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one

Info

Publication number: WO2019030177A1
Application number: PCT/EP2018/071279
Authority: WO
Inventors: Britta Olenik; Bernd Rösler
Original assignee: Bayer Aktiengesellschaft
Priority date: 2017-08-09
Filing date: 2018-08-06
Publication date: 2019-02-14
Also published as: BR112020002715A2; EP3665160A1; CL2020000334A1; AU2018314741A1; CN111051290A

Abstract

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

Description

Crystal forms of 2-r(2,4-dichlorophenyl)methyl1-4,4-dimethyl-isoxazolidin-3-one

The present invention relates to the crystal forms of 2-[(2,4-dichlorophenyl)mefhyl]-4,4-dimefhyl- isoxazolidin-3-one, a method for preparing these crystal forms, use thereof in agrochemical formulations and also particular compositions, mixtures or agrochemical formulations comprising these crystal forms. 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one of formula (I) and its herbicidal activity is known from US patent 4,405,357.

(I)

It is also known that 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one of formula (I) and salts thereof may be used in combination with other herbicidal active ingredients and/or with safener described in WO 2012/148689 (Al).

2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one has the empirical formula G2H13CI2NO2. The CAS number is 81777-95-9.

Compound of formula (I) can be prepared by the methods described in US patent 4,405,357. The crystal form of 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one which is present after preparation without any further crystallization/recrystallization steps has been characterized for the first time and is referred to hereinafter as crystal form A or modification A.

The following 2Θ (2 theta) values (table 1) are measured for crystal form A of 2- [(2,4- dichlorophenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one using Cu Ka radiation at 25°C (X-ray powder diffractometry):

Table 1 :

Crystal form A is characterized in that the X-ray powder diffractogram using Cu Ka radiation at 25°C has at least 3, preferably at least 4, more preferably at least 6, particularly preferably all of the most intensive 2Θ (2 theta) signals specified in table 2.

Table 2:

All X-ray powder diffractometry data stated in the present text refers to the following measurement parameters:

Scan axis gonio

Scan Mode transmission

Start Position [°2theta] 2.0066 End Position [°2theta] 37.9906

Anode material Cu

Wavelength K-alphal [A] 1.54060

Wavelength K-alpha2 [A] 1.54443 Wavelength K-beta [A] 1.39225

K-A2 / K-Al ratio 0.50000

Generator 40 mA, 40 kV

Incident Beam Monochromator focusing X-ray mirror

Spinning yes 2Θ (2 theta) values + 0.2°

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

Crystal forms A is further characterized by Raman spectra. All Raman spectroscopy data given in the present text refer to the following measurement parameters, in which the position of the band maxima of the wave number are in each case stated in cm^"1:

Instrument Bruker Raman RFS 100/S Number of scans 64 Resolution 2 - 4 cm^-1 Laser power 50 mW Laser wavelength 1064 nm

The following bands are measured doing Raman spectroscopy for crystal form A of 2- [(2,4- dichlorophenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one (table 3, figure 2):

Band maximum [cm ¹]

2989

2978

2970

2961

2934

2905

2875

2865

2842

2762

2719

2683

1694

1588

1567

1468

1460

1441

1385

1352

1293

1262

1225

1210

1179

1145

1121

1106

1051

1025

1010

976

964

952

894

857 Band maximum [cm ¹]

756

719

706

661

604

555

Table 3:

Crystal form A is preferably characterized in that the Raman spectrum thereof has at least the following bands (table 4):

Band maximum [cm^" ]

3059

2989

2970

2934

1694

1588

719

706

Table 4:

Compound of formula (I), 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one, crystallizes in three modifications. The above described one (herein referred to as modification A/crystal form A) has a melting point of 82°C, modification B has got a melting point of 72°C and modification C has got a melting point of 44°C. Compound of formula (I) may appear in amorphous form at room temperature, however, it has a great tendency to recrystallize. Modification A seems to be the thermodynamically stablest form.

In a further aspect, the present invention relates to a herbicidal composition, characterized in that said composition comprises compound of formula (I), and one or more further substances selected from groups (i) and/or (ii):

(i) one or more further agrochemically active substances, preferably selected from the group consisting of herbicides, insecticides, acaricides, nematicides, fungicides, safeners, fertilizers and/or further growth regulators,

(ii) one or more formulation auxiliaries customary in crop protection.

Composition comprising modification A of 2-[(2,4-dichlorophenyl)methyl]-4,4-dimefhyl-isoxazolidin- 3-one 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.

Preferred is 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, based on the total amount of 2-[(2,4- dichlorophenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one present in the composition. More preferred is a composition comprising modification A of 2-[(2,4-dichlorophenyl)methyl]-4,4- dimethyl-isoxazolidin-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.

Most preferred is a composition comprising modification A of 2-[(2,4-dichlorophenyl)methyl]-4,4- dimethyl-isoxazolidin-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.

Compound of formula (I) and/or salts thereof can be formulated in various ways according to which biological and/or physicochemical parameters are required. 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- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusting products (DP), seed-dressing products, granules for broadcasting and soil application, 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. These individual formulation types are known in principle and are described, for example, in: Winnacker-Kiichler, "Chemische Technologie" [Chemical technology], volume 7, C. Hanser Verlag Munich, 4th ed. 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd ed. 1979, G. Goodwin Ltd. London.

The necessary formulation auxiliaries, such as inert materials, surfactants, solvents and further additives are likewise known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt, "Grenzflachenaktive Athylenoxidaddukte" [Interface- active Ethylene Oxide Adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Kiichler, "Chemische Technologie", volume 7, C. Hanser Verlag Munich, 4th ed. 1986. Wettable powders are preparations which can be dispersed uniformly in water and, as well as the active compound, apart from a diluent or inert substance, also comprise surfactants of the ionic and/or nonionic type (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulphates, alkanesulphonates, alkylbenzenesulphonates, sodium lignosulphonate, sodium 2,2'-dinaphthylmethane-6,6'-disulphonate, sodium dibutylnaphthalenesulphonate or else sodium oleoylmethyltaurinate. To prepare the wettable powders, the herbicidally active compounds are ground finely, for example in customary apparatus such as hammer mills, blower mills and air -jet mills, and simultaneously or subsequently mixed with the formulation assistants.

Emulsifiable concentrates are produced by dissolving the active compound in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or else relatively high-boiling aromatics or hydrocarbons or mixtures of the organic solvents, with addition of one or more surfactants of the ionic and/or nonionic type (emulsifiers). The emulsifiers used may, for example, be: alkylarylsulphonic calcium salts, such as calcium dodecylbenzenesulphonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, such as, for example, sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, such as, for example, polyoxyethylene sorbitan fatty acid esters.

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

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

Granules can be produced either by spraying the active compound onto adsorptive granulated inert material or by applying active compound concentrates by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or mineral oils, to the surface of carrier substances, such as sand, kaolinites or of granulated inert material. Suitable active compounds can also be granulated in the manner customary for the production of fertilizer granules - if desired as a mixture with fertilizers. Water-dispersible granules are produced generally by the customary processes such as spray-drying, fluidized bed granulation, pan granulation, mixing with high-speed mixers and extrusion without solid inert material.

For the production of pan granules, fluidized bed granules, extruder granules and spray granules, see, for example, processes in "Spray-Drying Handbook" 3rd 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, pp. 8-57.

For further details regarding the formulation of crop protection agents, see, for example, G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

The agrochemical formulations comprise generally from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of active compound of the formula (I) and/or salts thereof.

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

In addition, the active compound formulations mentioned optionally comprise the respective customary tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and agents which influence the pH and the viscosity. Examples of formulation auxiliaries are described, inter alia, in "Chemistry and Technology of Agrochemical Formulations", ed. D. A. Knowles, Kluwer Academic Publishers (1998).

Compound of formula (I) and/or salts thereof can be employed as such or in the form of their preparations (formulations) combined with other pesticidally active compounds, such as, for example, insecticides, acaricides, nematicides, herbicides, fungicides, safeners, fertilizers and/or growth regulators, for example as finished formulation or as tank mixes. The combination formulations can be prepared on the basis of the abovementioned formulations, while taking account of the physical properties and stabilities of the active compounds to be combined. The weight ratios of herbicide (mixture) to safener depend generally on the herbicide application rate and the efficacy of the safener in question and may vary within wide limits, for example in the range from 200: 1 to 1 :200, preferably 100: 1 to 1: 100, in particular 20: 1 to 1:20. Analogously to compound of formula (I), the safeners can be formulated with further herbicides/pesticides and be provided and em- ployed as a finished formulation or tankmix with the herbicides.

For application, the herbicide or herbicide/safener formulations present in commercial form are, if appropriate, diluted in a customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules with water. Preparations in the form of dusts, granules for soil application or granules for broadcasting and sprayable solutions are usually not diluted further with other inert substances prior to application.

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

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

The application as culm stabilizer may take place at various stages of the growth of the plants. Preferred is, for example, the application after the tillering phase, at the beginning of the longitudinal growth.

As an alternative, application as plant growth regulator is also possible by treating the seed, which in- eludes various techniques for dressing and coating seed. Here, the application rate depends on the particular techniques and can be determined in preliminary tests.

Components which can be used in combination with the active compounds according to the invention in mixed formulations or in tank mix are, for example, known active compounds as they are described in, for example, Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 16th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2006, and the literature cited therein, and which for example act as inhibitor of acetolactate synthase, acetyl-CoA-carboxylase, cellulose-synthase, enolpyruvylshikimat-3-phosphat-synthase, glutamin-synthetase, p-hydroxyphenylpyruvat-dioxygenase, phytoendesaturase, photosystem I, photosystem II, and/or protoporphyrinogen-oxidase.

Examples of active compounds which may be mentioned as herbicides or plant growth regulators which are known from the literature and which can be combined with the compounds according to the invention are the following (compounds are either described by "common name" in accordance with the International Organization for Standardization (ISO) or by chemical name or by a customary code number), and always comprise all applicable forms such as acids, salts, ester, or modifications such as iso- mers, like stereoisomers and optical isomers. As an example at least one applicable form and/or modifications can be mentioned.

Examples for herbicides are:

Acetochlor, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim- sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3- methylphenyl)-5-fluoropyridine-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyrachlor- potassium, aminocyclopyrachlor-methyl, aminopyralid, amitrole, ammoniumsulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin, benazolin-ethyl, benfluralin, ben- furesate, bensulfuron, bensulfuron-methyl, bensulide, bentazone, benzobicyclon, benzofenap, bicyclo- pyron, bifenox, bilanafos, bilanafos-sodium, bispyribac, bispyribac-sodium, bromacil, bromobutide, bromofenoxim, bromoxynil, bromoxynil-butyrate, -potassium, -heptanoate, and -octanoate, busoxinone, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chlorbromuron, chlorfenac, chlorfenac- sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlo- rophthalim, chlorotoluron, chlorthal-dimethyl, chlorsulfuron, cinidon, cinidon-ethyl, cinmethylin, cino- sulfuron, clacyfos, clethodim, clodinafop, clodinafop-propargyl, clomazone, clomeprop, clopyralid, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cycloate, cyclopyrimorate, cy- closulfamuron, cycloxydim, cyhalofop, cyhalofop-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 (dymron), dalapon, dazomet, n-decanol, desmedipham, detosyl-pyrazolate (DTP), dicamba, dichlobenil, 2-(2,4-dichlorobenzyl)-4,4-dimethyl-l,2-oxazolidin-3- one, 2-(2,5-dichlorobenzyl)-4,4-dimethyl-l,2-oxazolidin-3-one, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr- sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimetrasulfuron, dinitramine, dinoterb, diphenamid, diquat, diquat-dibromid, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyfen, ethoxyf en-ethyl, ethoxysulfuron, etobenzanid, F-9600, F-5231, i.e. N-{2- chloro-4-fluoro-5-[4-(3-fluoropropyl)-5-oxo-4,5-dihydro-lH-tetrazol-l-yl]phenyl}ethanesulfonamide, F-7967, i. e. 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-lH-benzimidazol-4-yl]-l-methyl-6- (trifluoromethyl)pyrimidine-2,4(lH,3H)-dione, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxa- prop-P-ethyl, fenoxasulfone, fenquinotrione, fentrazamide, flamprop, flamprop-M-isopropyl, flamprop- M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-P-butyl, flucarba- zone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazin, fluometuron, flurenol, flurenol-butyl, - dimethylammonium and -methyl, fluoroglycofen, fluoroglycofen-ethyl, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone, flurochloridone, fluroxypyr, fluroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, fosamine, glufosinate, glufosinate-ammonium, glufosinate-P-sodium, glufosinate-P-ammonium, glufosinate-P- sodium, glypho- sate, glyphosate-ammonium, -isopropylammonium, -diammonium, -dimethylammonium, -potassium, - sodium, and -trimesium, H-9201, i.e. 0-(2,4-dimethyl-6-nitrophenyl) O-ethyl isopropylphosphorami- dothioate, halauxifen, halauxifen-methyl ,halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, ha- loxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, hexazinone, HW-02, i.e. l-(dimethoxyphosphoryl) ethyl-(2,4-dichlorophenoxy)acetate, imaza- methabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic- ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-immonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron-methyl- sodium, ioxynil, ioxynil-octanoate, -potassium and -sodium, ipfencarbazone, isoproturon, isouron, isox- aben, isoxaflutole, karbutilate, KUH-043, i.e. 3-({ [5-(difluoromethyl)-l-methyl-3-(trifluoromethyl)-lH- pyrazol-4-yl]methyl } sulfonyl)-5,5-dimethyl-4,5-dihydro- 1 ,2-oxazole, ketospiradox, lactofen, lenacil, linuron, MCPA, MCPA-butotyl, -dimethylammonium, -2-ethylhexyl, -isopropylammonium, -potassium, and -sodium, MCPB, MCPB-methyl, -ethy,l and -sodium, mecoprop, mecoprop-sodium, and -butotyl, mecoprop-P, mecoprop-P-butotyl, -dimethylammonium, -2-ethylhexyl, and -potassium, mefenacet, mefluidide, mesosulfuron, mesosulfuron-methyl, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methiopyrsulfuron, methiozolin, methyl isothiocyanate, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsul- furon, metsulfuron-methyl, molinat, monolinuron, monosulfuron, monosulfuron-ester, MT-5950, i.e. N- (3-chloro-4-isopropylphenyl)-2-methylpentan amide, NGGC-011, napropamide, NC-310, i.e. [5- (benzyloxy)-l -methyl- lH-pyrazol-4-yl](2,4-dichlorophenyl)methanone, neburon, nicosulfuron, nonano- ic acid (pelargonic acid), norflurazon, oleic acid (fatty acids), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefon, oxyfluorfen, paraquat, paraquat dichloride, pebu- late, pendimethalin, penoxsulam, pentachlorphenol, pentoxazone, pethoxamid, petroleum oils, phen- medipham, picloram, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron- methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole, pyrazolynate (pyrazo- late), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyri- bambenz-propyl, pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac- methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quin- merac, quinoclamine, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P- tefuryl, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, SL-261, sulcotrion, sulfen- trazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, SYN-523, SYP-249, i.e. l-efhoxy-3-mefhyl- l-oxobut-3-en-2-yl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, SYP-300, i.e. l-[7-fluoro- 3-oxo-4-(prop-2-yn-l-yl)-3,4-dihydro-2H-l,4-benzoxazin-6-yl]-3-propyl-2-thioxoimidazolidine-4,5- dione, 2,3,6-TBA, TCA (trichloroacetic acid), TCA-sodium, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumeton, terbuthylazin, terbutryn, thenylchlor, thiazopyr, thien- carbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tribenu- ron-methyl, triclopyr, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazin, trifluralin, triflusulfuron, triflusulfuron-methyl, tritosulfuron, urea sulfate, vernolate, XDE-848, ZJ-0862, i.e. 3,4- dichloro-N- { 2- [(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl } aniline, and the following compounds :

Examples for plant growth regulators are:

Acibenzolar, acibenzolar-S-methyl, 5-aminolevulinic acid, ancymidol, 6-benzylaminopurine, Brassinolid, catechine, chlormequat chloride, cloprop, cyclanilide, 3-(cycloprop-l-enyl) propionic acid, daminozide, dazomet, n-decanol, dikegulac, dikegulac- sodium, endothal, endothal- dipotassium, -disodium, and -mono(N,N-dimethylalkylammonium), ethephon, flumetralin, flurenol, flurenol-butyl, flurprimidol, forchlorfenuron, gibberellic acid, inabenfide, indol-3-acetic acid (IAA), 4- indol-3-ylbutyric acid, isoprothiolane, probenazole, jasmonic acid, maleic hydrazide, mepiquat chloride, 1-methylcyclopropene, methyl jasmonate, 2-(l-naphthyl)acetamide, 1-naphthylacetic acid, 2- naphthyl- oxyacetic acid, nitrophenolate-mixture, paclobutrazol, N-(2-phenylethyl)-beta-alanine, N-phenyl- phthalamic acid, prohexadione, prohexadione-calcium, prohydrojasmone, salicylic acid, strigolactone, tecnazene, thidiazuron, triacontanol, trinexapac, trinexapac-ethyl, tsitodef, uniconazole, uniconazole-P.

The safeners are preferably selected from the group consisting of: si) compounds of the formula (S I)

where the symbols and indices have the following meanings: n_A is a natural number from 0 to 5, preferably from 0 to 3;

R_A ¹ is halogen, (G-C -alkyl, (G-C -alkoxy, nitro or (G-C -haloalkyl;

W_A is an unsubstituted or substituted divalent heterocyclic radical from the group consisting of partially unsaturated or aromatic five-membered heterocycles having 1 to 3 hetero ring atoms from the group consisting of N and O, where at least one nitrogen atom and at most one oxygen atom is present in the ring, preferably a radical from the group consisting of (W_A ¹) to (W_A ⁴),

(W_A ¹) (W_A ²) (W_A ³) (W_A ⁴) is 0 or 1 ;

R_A ² is OR_A ³, SR_A ³ or NR_A ³R_A ⁴ 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 attached via the nitrogen atom to the carbonyl group in (S I) and which is unsubstituted or substituted by radicals from the group consisting of (G-C -alkyl, (G-C -alkoxy and optionally substituted phenyl, preferably a radical of the formula OR_A ³, NHR_A ⁴ or N(C1¾)2, in particular of the formula OR_A ³;

R_A ³ is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical having preferably a total of 1 to 18 C-atoms;

R_A ⁴ is hydrogen, (Ci-Ce)-alkyl, (Ci-Ce)-alkoxy or substituted or unsubstituted phenyl;

R_A ⁵ is H, (Ci-C₈)-alkyl, (G-C₈)-haloalkyl, (Ci-C₄)-alkoxy-(Ci-C₈)-alkyl, cyano or COOR_A ⁹ where R_A ⁹ is hydrogen, (G-C₈)-alkyl, (Ci-C₈)-haloalkyl, (Ci-C₄)-alkoxy-(Ci-C₄)-alkyl, (G-C₆)- hydroxyalkyl, (C3-Ci2)-cycloalkyl or tri-(Ci-C4)-alkylsilyl; R_A ⁶, R_A ⁷, R_A ⁸ are identical or different and are hydrogen, (Ci-Cs)-alkyl, (Ci-C8)-haloalkyl, (C3-C12)- cycloalkyl or substituted or unsubstituted phenyl; preferably: a) compounds of the type of the dichlorophenylpyrazoline-3-carboxylic acid (S l ), preferably compounds such as l-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-mefhyl-2-pyrazoline-3- carboxylic acid, ethyl l-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-mefhyl-2-pyrazoline-3- carboxylate (S l-1) ("mefenpyr(-diethyl)"), and related compounds, as described in WO-A- 91/07874; b) derivatives of dichlorophenylpyrazolecarboxylic acid (S l^b), preferably compounds such as ethyl l-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S I -2), ethyl l-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (S I -3), ethyl l-(2,4-dichlorophenyl)-5-(l,l-dimethylethyl)pyrazole-3-carboxylate (S l-4) and related compounds, as described in EP-A-333 131 and EP-A-269 806; c) derivatives of l,5-diphenylpyrazole-3-carboxylic acid (S l^c), preferably compounds such as ethyl l-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S I -5), methyl l-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (S l-6) and related compounds, as described, for example, in EP-A-268554; d) compounds of the type of the triazolecarboxylic acids (S l^d), preferably compounds such as fenchlorazole(-ethyl), i.e. ethyl l-(2,4-dichlorophenyl)-5-trichloromethyl-(lH)-l,2,4-triazole-3- carboxylate (S l-7), and related compounds, as described in EP-A-174 562 and EP-A-346 620; e) compounds of the type of the 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or the 5,5- diphenyl-2-isoxazoline-3-carboxylic acid (S T), preferably compounds such as ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (S 1-8) or ethyl 5-phenyl-2-isoxazoline-3- carboxylate (S l-9) and related compounds, as described in WO-A-91/08202, or 5,5-diphenyl-2- isoxazolinecarboxylic acid (S l-10) or ethyl 5,5-diphenyl-2-isoxazolinecarboxylate (S l-11) ("isoxadifen-ethyl") or n-propyl 5,5-diphenyl-2-isoxazolinecarboxylate (S I- 12) or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (S l-13), as described in the patent application WO-A-95/07897.

S2) Quinoline derivatives of the formula (S2)

where the symbols and indices have the following meanings:

RB¹ is halogen, (Ci-C -alkyl, (Ci-C -alkoxy, nitro or (Ci-C -haloalkyl; ne is a natural number from 0 to 5, preferably from 0 to 3;

RB² is ORB³, SRB³ or NR_B ³R_B ⁴ or a saturated or unsaturated 3- to 7-membered heterocycle having at least one nitrogen atom and up to 3 het- eroatoms, preferably from the group consisting of O and S, which is attached via the nitrogen atom to the carbonyl group in (S2) and which is unsubstituted or substituted by radicals from the group consisting of (Ci-C -alkyl, (Ci-C -alkoxy and optionally substituted phenyl, preferably a radical of the formula ORB³, NHRB⁴ or N(C1¾)2, in particular of the formula ORB³;

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

RB⁴ is hydrogen, (Ci-Ce)-alkyl, (Ci-Ce)-alkoxy or substituted or unsubstituted phenyl;

TB is a (Ci- or C₂)-alkanediyl chain which is unsubstituted or substituted by one or two (C₁-C4)- alkyl radicals or by [(Ci-C3)-alkoxy]carbonyl; preferably: a) compounds of the type of the 8 -quinolinoxy acetic acid (S2 ), preferably 1-methylhexyl (5-chloro-8-quinolinoxy)acetate (common name "cloquintocet-mexyl" (S2- 1),

1,3-dimethyl-but-l-yl (5-chloro-8-quinolinoxy)acetate (S2-2), 4-allyloxybutyl (5 -chloro- 8 -quinolinoxy) acetate (S2-3), l-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), allyl (5-chloro-8-quinolinoxy)acetate (S2-7),

2-(2-propylideneiminoxy)- l -ethyl (5-chloro-8-quinolinoxy)acetate (S2-8), 2-oxo-prop-l-yl (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, magne- sium, aluminium, iron, ammonium, quaternary ammonium, sulphonium or phosphonium salts, as described in WO-A-2002/34048; compounds of the type of the (5-chloro-8-quinolinoxy)malonic acid (S2^b), 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.

S3) Compounds of the formula (S3)

where the symbols and indices have the following meanings:

Rc¹ is (Ci-C₄)-alkyl, (Ci-C₄)-haloalkyl, (C₂-C₄)-alkenyl, (C₂-C₄)-haloalkenyl, (C₃-C₇)-cycloalkyl, preferably dichloromethyl;

Rc², Rc³ are identical or different and are hydrogen, (Ci-C₄)-alkyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (Ci- C )-haloalkyl, (C₂-C )-haloalkenyl, (Ci-C )-alkylcarbamoyl-(Ci-C )-alkyl, (C2-C4)- alkenylcarbamoyl-(Ci-C₄)-alkyl, (Ci-C₄)-alkoxy-(Ci-C₄)-alkyl, dioxolanyl-(Ci-C₄)-alkyl, thia- zolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or Rc² and Rc³ together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, fhiazoli- dine, piperidine, morpholine, hexahydropyrimidine or benzoxazine ring; preferably: active compounds of the type of the dichloroacetamides which are frequently used as pre- emergence safeners (soil-acting safeners), such as, for example, "dichlormid" (N,N-diallyl-2,2-dichloroacetamide) (S3-1),

"R-29148" (3-dichloroacetyl-2,2,5-trimethyl-l,3-oxazolidine) from Stauffer (S3-2), "R-28725" (3-dichloroacetyl-2,2-dimethyl-l,3-oxazolidine) from Stauffer (S3-3), "benoxacor" (4-dichloroacetyl-3,4-dihydro-3-methyl-2H- 1,4-benzoxazine) (S3-4),

"PPG-1292" (N-allyl-N-[(l,3-dioxolan-2-yl)methyl]dichloroacetamide) from PPG Industries (S3-5),

"DKA-24" (N-allyl-N-[(allylaminocarbonyl)methyl]dichloroacetamide) from Sagro-Chem (S3- 6),

"AD-67" or "MON 4660" (3-dichloroacetyl-l-oxa-3-aza-spiro[4,5]decane) from Nitrokemia or Monsanto (S3-7), "TI-35" (1-dichloroacetylazepane) from TRI-Chemical RT (S3-8) "diclonon" (dicyclonon) or "BAS 145138" or "LAB 145138" (S3-9) (3-dichloroacetyl-2,5,5- trimethyl-l,3-diazabicyclo[4.3.0]nonane) from BASF,

"furilazole" or "MON 13900" ((RS)- l-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[l,2- a]pyrimidin-6-one) (S3-10) and also its (R)-isomer (S3-11).

N-Acylsulphonamides of the formula (S4) and their salts

where the symbols and indices have the following meanings: A_D is S0₂-NR_D ³-CO or CO-NR_D ³-S0₂; X_D is CH or N;

RD¹ is CO-NR_D ⁵RD⁶ or NHCO-RD⁷;

RD² is halogen, (Ci-C4)-haloalkyl, (Ci-C4)-haloalkoxy, nitro, (Ci-C4)-alkyl, (Ci-C4)-alkoxy, (C₁ -C4)- alkylsulphonyl, (Ci-C4)-alkoxycarbonyl or (Ci-C4)-alkylcarbonyl;

RD³ is hydrogen, (Ci-C4)-alkyl, (C₂-C4)-alkenyl or (C₂-C4)-alkynyl;

RD⁴ is halogen, nitro, (Ci-C4)-alkyl, (Ci-C4)-haloalkyl, (Ci-C4)-haloalkoxy, (C3-C6)-cycloalkyl, phenyl, (Ci-C4)-alkoxy, cyano, (Ci-C4)-alkylthio, (Ci-C4)-alkylsulphinyl, (Ci-C4)-alkylsulphonyl, (Ci-C4)-alkoxycarbonyl or (Ci-C4)-alkylcarbonyl;

RD⁵ is hydrogen, (G-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl, (C₅-C₆)- cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl which contains VD heteroatoms from the group consisting of nitrogen, oxygen and sulphur, where the seven last-mentioned radicals are substituted by VD substituents from the group consisting of halogen, (Ci-Ce)-alkoxy, (Ci-Ce)- haloalkoxy, (Ci-C₂)-alkylsulphinyl, (Ci-C₂)-alkylsulphonyl, (C3-C6)-cycloalkyl, (C₁-C4)- alkoxycarbonyl, (Ci-C4)-alkylcarbonyl and phenyl and, in the case of cyclic radicals, also (Ci- C₄)-alkyl and (Ci-C₄)-haloalkyl;

RD⁶ is hydrogen, (Ci-Ce)-alkyl, (C₂-Ce)-alkenyl or (C₂-Ce)-alkynyl, where the three last-mentioned radicals are substituted by VD radicals from the group consisting of halogen, hydroxy, (C₁ -C4)- alkyl, (Ci-C4)-alkoxy and (Ci-C4)-alkylthio, or

RD⁵ and RD⁶ together with the nitrogen atom carrying them form a pyrrolidinyl or piperidinyl radical; RD⁷ is hydrogen, (Ci-C -alkylamino, di-(Ci-C4)-alkylamino, (Ci-Ce)-alkyl, (C3-C6)-cycloalkyl, where the 2 last-mentioned radicals are substituted by VD substituents from the group consisting of halogen, (Ci-C4)-alkoxy, halo-(Ci-C6)-alkoxy and (Ci-C4)-alkylthio and, in the case of cyclic radicals, also (Ci-C4)-alkyl and (Ci-C4)-haloalkyl; no is 0, 1 or 2; mo is 1 or 2;

VD is 0, 1, 2 or 3; from among these, preference is given to compounds of the type of the N-acylsulphonamides, for example of the formula (S4 ) below, which are known, for example, from WO-A- 97/45016

in which

RD⁷ is (Ci-C6)-alkyl, (C3-C6)-cycloalkyl, where the 2 last-mentioned radicals are substituted by VD substituents from the group consisting of halogen, (Ci-C4)-alkoxy, halo-(Ci-C6)-alkoxy and (Ci- C4)-alkylthio and, in the case of cyclic radicals, also (Ci-C4)-alkyl and (Ci-C4)-haloalkyl;

RD⁴ is halogen, (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy, CF_3; mo is 1 or 2;

VD is 0, 1, 2 or 3; and also acylsulphamoylbenzamides, for example of the formula (S4^b) below, which are known, for example, from WO-A-99/16744,

for example those in which RD⁵ = cyclopropyl and (R_D ⁴) = 2-OMe ("cyprosulphamide", S4-1), RD⁵ = cyclopropyl and (R_D ⁴) = 5-Cl-2-OMe (S4-2), RD⁵ = ethyl and (RD⁴) = 2-OMe (S4-3), RD⁵ = isopropyl and (RD⁴) = 5-Cl-2-OMe (S4-4) and RD⁵ = isopropyl and (RD⁴) = 2-OMe (S4-5) and also compounds of the type of the N-acylsulphamoylphenylureas of the formula (S4^C), which are known, for example, from EP-A-365484,

in which

RD⁸ and RD⁹ independently of one another are hydrogen, (Ci-Cs alkyl, (C3-Cs)-cycloalkyl, (C3-C6)- alkenyl, (C3-C6)-alkynyl,

RD⁴ is halogen, (G-C₄)-alkyl, (Ci-C₄)-alkoxy, CF₃, mo is 1 or 2; for example

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

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

l-[4-(N-4,5-dimethylbenzoylsulphamoyl)phenyl]-3-methylurea, and also N-phenylsulphonylterephthalamides of the formula (S4^d), which are known, for example, from

CN 101838227,

e.g. such compounds in which

RD⁴ is halogen, (Ci-C₄)-alkyl, (Ci-C₄)-alkoxy, CF₃; mo is 1 or 2;

RD⁵ is hydrogen, (Ci-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C2-C₆)-alkenyl, (C2-C₆)-alkynyl, (C₅-C₆)- cycloalkenyl.

55) Active compounds from the class of the hydroxyaromatics and aromatic- aliphatic carboxylic acid derivatives (S5), for example ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicyclic acid, 2 -hydroxy cinnamic acid, 2,4- dichlorocinnamic acid, as described in WO-A-2004/084631, WO-A-2005/015994, WO-A- 2005/016001.

56) Active compounds from the class of the l,2-dihydroquinoxalin-2-ones (S6), for example l-methyl-3-(2-thienyl)-l,2-dihydroquinoxalin-2-one, l-methyl-3-(2-thienyl)-l,2- dihydroquinoxaline-2-thione, l-(2-aminoethyl)-3-(2-thienyl)-l,2-dihydroquinoxalin-2-one hydrochloride, l-(2-methylsulphonylaminoethyl)-3-(2-thienyl)-l,2-dihydroquinoxalin-2-one, as described in WO-A-2005/112630.

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

where the symbols and indices have the following meanings:

RE¹, RE² independently of one another are halogen, (Ci-C -alkyl, (Ci-C -alkoxy, (C₁-C₄)- haloalkyl, (Ci-C₄)-alkylamino, di-(Ci-C₄)-alkylamino, nitro; is COORE³ or COSRE⁴

RE³, RE⁴ independently of one another are hydrogen, (Ci-C₄)-alkyl, (C₂-Ce)-alkenyl, (C₂-C₄)- alkynyl, cyanoalkyl, (Ci-C₄)-haloalkyl, phenyl, nitrophenyl, benzyl, halobenzyl, pyridi- nylalkyl or alkylammonium, nE is 0 or 1; ΠΕ², ΠΕ³ independently of one another are 0, 1 or 2, preferably:

diphenylmethoxyacetic acid, ethyl diphenylmethoxyacetate, methyl diphenylmethoxyacetate (CAS Reg. No.: 41858- 19-9) (S7-1). S8) Compounds of the formula (S8), as described in WO- A-98/27049,

in which

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

RF¹ is halogen, (Ci-C -alkyl, (Ci-C -haloalkyl, (Ci-C -alkoxy, (Ci-C -haloalkoxy, nitro, (C₁-C4)- alkylthio, (Ci-C4)-alkylsulphonyl, (Ci-C4)-alkoxycarbonyl, optionally substituted phenyl, optionally substituted phenoxy,

RF² is hydrogen or (Ci-C₄)-alkyl, RF³ is hydrogen, (Ci-Cs)-alkyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl or aryl, where each of the carbon- containing radicals mentioned above is unsubstituted or substituted by one or more, preferably by up to three, identical or different radicals from the group consisting of halogen and alkoxy; or salts thereof, preferably compounds in which X_F is CH, nF is an integer from 0 to 2,

RF¹ is halogen, (Ci-C4)-alkyl, (Ci-C4)-haloalkyl, (Ci-C4)-alkoxy, (Ci-C4)-haloalkoxy,

RF² is hydrogen or (Ci-C₄)-alkyl, RF³ is hydrogen, (Ci-Cs)-alkyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl or aryl, where each of the carbon- containing radicals mentioned above is unsubstituted or substituted by one or more, preferably by up to three, identical or different radicals from the group consisting of halogen and alkoxy; or salts thereof,

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

S 10) Compounds of the formula (S10^a) or (S 10^b) as described in WO-A-2007/023719 and WO-A- 2007/023764

(S10^a) (S10^b) in which

R_G ¹ is halogen, (Ci-C -alkyl, methoxy, nitro, cyano, CF₃, OCF₃ YG, G independently of one another are O or S, no is an integer from 0 to 4,

R_G ² is (Ci-Ci6)-alkyl, (C₂-Ce)-alkenyl, (C₃-Ce)-cycloalkyl, aryl; benzyl, halobenzyl, R_G ³ is hydrogen or (Ci-C6)-alkyl.

S l l) Active compounds of the type of the oxyimino compounds (S l l), which are known as seed dressings, such as, for example, "oxabetrinil" ((Z)-l,3-dioxolan-2-ylmethoxyimino- (phenyl)acetonitrile) (S I 1-1), which is known as seed dressing safener for millet against metolachlor damage,

"fluxofenim" ( 1 -(4-chlorophenyl)-2,2,2-trifluoro- 1 -ethanone 0-( 1 ,3-dioxolan-2- ylmethyl)oxime) (S I 1-2), which is known as seed dressing safener for millet against metolachlor damage, and "cyometrinil" or "CGA-43089" ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S I 1-3), which is known as seed dressing safener for millet against metolachlor damage.

512) Active compounds from the class of the isothiochromanones (S 12), such as, for example, methyl [(3-oxo- lH-2-benzothiopyran-4(3H)-ylidene)methoxy] acetate (CAS Reg. No.: 205121-04-6) (S 12- 1) and related compounds from WO-A-1998/13361.

513) One or more compounds from group (S 13):

"naphthalic anhydrid" (1,8-naphthalenedicarboxylic anhydride) (S 13-1), which is known as seed dressing safener for corn against thiocarbamate herbicide damage,

"fenclorim" (4,6-dichloro-2-phenylpyrimidine) (S 13-2), which is known as safener for preti- lachlor in sown rice,

"flurazole" (benzyl 2-chloro-4-trifluoromethyl-l,3-thiazole-5-carboxylate) (S I 3-3), which is known as seed dressing safener for millet against alachlor and metolachlor damage,

"CL 304415" (CAS Reg. No.: 31541-57-8) (4-carboxy-3,4-dihydro-2H-l-benzopyran-4-acetic acid) (S I 3-4) from American Cyanamid, which is known as safener for corn against imidazoli- none damage,

"MG 191 " (CAS Reg. No.: 96420-72-3) (2-dichloromethyl-2-methyl-l,3-dioxolane) (S 13-5) from Nitrokemia, which is known as safener for corn,

"MG 838" (CAS Reg. No.: 133993-74-5) (2-propenyl l-oxa-4-azaspiro[4.5]decane-4- carbodithioate) (S 13-6) from Nitrokemia,

"disulphoton" (0,0-diethyl S-2-ethylthioethyl phosphorodithioate) (S I 3-7), "dietholate" (Ο,Ο-diethyl O-phenyl phosphorothioate) (S I 3-8), "mephenate" (4-chlorophenyl methylcarbamate) (S I 3-9).

514) Active compounds which, besides a herbicidal effect against harmful plants, also have a safener effect on crop plants such as rice, such as, for example, "dimepiperate" or "MY-93" (S-l -methyl- 1 -phenylethyl piperidine-l-carbothioate), which is known as safener for rice against molinate herbicide damage,

"daimuron" or "SK 23" (l-(l-methyl-l-phenylethyl)-3-p-tolylurea), which is known as safener for rice against imazosulphuron herbicide damage,

"cumyluron" = "JC-940" (3-(2-chlorophenylmethyl)- l-(l-methyl-l-phenylethyl)urea, see JP-A- 60087254), which is known as safener for rice against some herbicide damage, "methoxyphenone" or "NK 049" (3,3'-dimefhyl-4-mefhoxybenzophenone), which is known as safener for rice against some herbicide damage,

"CSB" (l-bromo-4-(chloromethylsulphonyl)benzene) from Kumiai, (CAS Reg. No. 54091-06- 4), which is known as safener against some herbicide damage in rice. S 15) Compounds of the formula (S 15) or its tautomers,

which are known, for example, from WO-A-2008/131861 and WO-A-2008/131860, in which

RH¹ is (Ci-C₆)-haloalkyl,

RH² is hydrogen or halogen, RH³, RH⁴ independently of one another are hydrogen, (Ci-Ci6)-alkyl, (C₂-Ci6)-alkenyl or

(C2-C₁₆)-alkynyl, where each of the 3 last-mentioned radicals is unsubstituted or substituted by one or more radicals from the group consisting of halogen, hydroxy, cyano, (Ci-C -alkoxy, (Ci-C -haloalkoxy, (Ci-C₄)-alkylthio, (Ci-C₄)-alkylamino, di-[(Ci-C₄)-alkyl]-amino, [(Ci-C₄)-alkoxy] -carbonyl, [(Ci-C₄)-haloalkoxy]-carbonyl, unsubstituted or substituted

(C₃-Ce)-cycloalkyl, unsubstituted or substituted phenyl, and unsubstituted or substituted heterocyclyl; or (C₃-Ce)-cycloalkyl, (C₄-Ce)-cycloalkenyl, (C3-C6)- cycloalkyl which is at one site of the ring condensed with a 4 to 6-membered saturated or unsaturated carbocyclic ring , or (C4-C6)- cycloalkenyl which is at one site of the ring condensed with a 4 to 6-membered saturated or unsaturated carbocyclic ring, where each of the 4 last-mentioned radicals is unsubstituted or substituted by one or more radicals from the group consisting of halogen, hydroxy, cyano, (Ci-C4)-alkyl, (Ci-C₄)-haloalkyl, (Ci-C₄)-alkoxy, (Ci-C₄)-haloalkoxy, (Ci-C₄)-alkylthio, (G-C₄)- alkylamino, di-(Ci-C₄)-alkyl]-amino, [(Ci-C₄)-alkoxy] -carbonyl, [(Ci-C₄)-haloalkoxy]- carbonyl, unsubstituted or substituted (C₃-Ce)-cycloalkyl, unsubstituted or substituted phenyl, and unsubstituted or substituted heterocyclyl; or RH³ is (Ci-C4)-alkoxy, (C₂-C4)-alkenyloxy, (C₂-Ce)-alkynyloxy or (C₂-C4)-haloalkoxy, and RH⁴ is hydrogen or (Ci-C4)-alkyl, or_

RH³ and RH⁴ together with the directly bound N-atom are a 4 to 8-membered heterocyclic ring, which can contain further hetero ring atoms besides the N-atom, preferably up to two further hetero ring atoms from the group consisting of N, O and S, and which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, cyano, nitro, (Ci-C4)-alkyl, (Ci-C₄)-haloalkyl, (Ci-C₄)-alkoxy, (Ci-C₄)-haloalkoxy, and (Ci-C₄)-alkylthio.

S 16) Active compounds which are primarily used as herbicides, but also have safener effect on crop 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), l-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate (lactidichlor-ethyl).

Preparation The synthesis of 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one is known from US patent 4,405,357.

Claims

1. Compound of formula (I), 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one, in crystalline form, characterized in that the X-ray powder diffractogram using Cu Ka radiation at 25°C has at least 3 of the following 2Θ (2 theta) values (modification A):

2Θ (2 theta) values in

10,5

14,2

18,5

19,8

21,8

23,2

24,3

2. 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one according to Claim 1, characterized in that the X-ray powder diffractogram using Cu Ka radiation at 25°C has at least 4, preferably at least 6, more preferably all of the 2Θ (2 theta) values specified in Claim 1.

3. 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one according to Claim 1 or 2, char- acterized in that the Raman spectrum thereof has at least the following bands:

Band maximum [cm ¹]

3059

2989

2970

2934

1694

1588

719

706

4. Composition , characterized in that it comprises compound of formula (I) in modification A, according to any 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 com- position and one or more further substances selected from groups (i) and/or (ii):

(i) one or more further agrochemically active substances, preferably selected from the group consisting of herbicides, insecticides, acaricides, nematicides, fungicides, safeners, fertilizers and/or further growth regulators, (ii) one or more formulation auxiliaries customary in crop protection.

5. Composition according to claim 4 comprising 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.

6. Composition according to claim 4 comprising 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.

7. Composition according to claim 4 comprising 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 for controlling harmful plants or for regulating the growth of plants.

9. Method for controlling harmful plants or for regulating the growth of plants, characterized in that an effective amount of 2-[(2,4-dichlorophenyl)methyl]-4,4-dimethyl-isoxazolidin-3-one according to any of claims 1 to 3, or - a composition according to any of claims 4 to 7 is applied to the plants, seeds of plants, the soil in which or on which the plants grow or the area under cultivation.