EP1758877A1 - Substituted benzoylcyclohexandiones for use as herbicides - Google Patents

Abstract

The invention relates to the derivatives of the benzoylcyclohexandiones of formula (I), wherein R1 and R2 represent different groups and Het represents a saturated heterocyclic group containing oxygen and carbon atoms, and to their use as herbicides.

Description

description

Substituted benzoylcyclohexanediones as herbicides

The invention relates to the technical field of herbicides, in particular that of herbicides from the group of benzoylcyclohexanediones for the selective control of weeds and weeds in crops of useful plants, in particular in rice crops.

From various publications it is already known that certain benzoyl derivatives have herbicidal properties. For example, WO 99/10327 and WO 99/10328 disclose benzoylcyclohexanediones and benzoyipyrazolones which carry a heterocyclyl or heteroaryl radical bonded via a polyatomic bridge in the 3-position of the phenyl ring. The earlier priority, not prepublished German patent application No. DE 103 01 110.2 describes benzoylcyclohexanediones and which, in the 3-position of the phenyl ring, carry a heterocyclyl radical bonded via an oxymethyl or thiomethyl bridge.

However, the compounds known from these publications frequently show an insufficient herbicidal activity.

The object of the present invention is to provide further herbicidally active compounds having improved herbicidal properties compared to the compounds disclosed in the prior art.

It has now been found that benzoylcyclohexanediones which, in the 3-position of the phenyl ring, carry a heterocyclyl radical bonded via a three-atom bridge are particularly suitable as herbicides. The present invention therefore relates to compounds of the formula (I) or their salts

where the residues and indices have the following meanings:

R ¹ , R ² independently of one another denote hydrogen, mercapto, nitro, halogen, cyano, rhodano, (dC-βJ-alkyl, (CC ₆ ) haloalkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) - haloalkenyl, (C ₂ -C ₆ ) alkynyl, (C ₃ -C ₆ ) haloalkynyl, (C ₃ -C ₆ ) cycloalkyl, OR ⁴ , OCOR ⁴ , OSO ₂ R ⁴ , S (0) _n R ⁴ , SO ₂ OR ⁴ , SO ₂ N (R ⁴ ) ₂ , NR ⁴ SO ₂ R ⁴ , NR ⁴ COR ⁴ , (CC ₆ ) - alkyl-S (O) _n R ⁴ , (CC ₆ ) alkyl -OR ⁴ , (-CC ₆ ) -alkyl-OCOR ⁴ , (C ₁ -C ₆ ) -alkyl-OSO ₂ R ⁴ , (CC ₆ ) -alkyl-SO ₂ OR ⁴ , (C ₁ -C ₆ ) -Alkyl-SO ₂ N (R ⁴ ) ₂ or (C ₁ -C ₆ ) -alkyl-NR ⁴ COR ⁴ ;

R ^{3 represents} hydrogen, (CC ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl or (C ₂ -C ₆ ) alkynyl;

R ⁴ is hydrogen, _(Cι-C6) alkyl, (C ₂ -C ₆₎ alkenyl, (C ₂ -C ₆₎ -alkynyl, (C ₃ -C ₆₎ - cycloalkyl, phenyl or phenyl- (Cι -C ₆ ) -alkyl, the six last-mentioned residues by s residues from the group hydroxy, mercapto, amino, cyano, nitro, rhodano, OR ³ , SR ³ , N (R ³ ) ₂ , NOR ³ , OCOR ³ , SCOR ³ , NR ³ COR ³ , CO ₂ R ³ , COSR ³ , CON (R ³ ) ₂ , (dC ₄ ) - alkyliminooxy, (Cι-C) alkoxyamino, (CrC ^ alkylcarbonyl, (C ₁ -C) alkoxy - (C ₂ -C ₆ ) - Alkoxycarbonyl and (-C-C) alkylsulfonyl are substituted;

Het denotes a completely saturated heterocyclic group, the ring atoms of which consist of 2 oxygen and 2, 3, 4 or 5 carbon atoms and Het is substituted by n radicals R ⁵ ;

n represents 0, 1 or 2;

s represents 0, 1, 2 or 3; R ⁵ means hydroxy, mercapto, amino, cyano, nitro, halogen, formyl, (C-ι-C ₆ ) - alkylamino, (Cι-C ₆ ) -dialkylamino, (Cι-C ₆ ) -alkoxycarbonyl, (Cι-Ce ) -Alkylcarbonyl, (CrC ₄ ) -alkylcarbonyloxy, (C ₁ -C ₆ ) -alkyl, (Cι-C ₆ ) -haloalkyl, (CC ₆ ) -alkylthio, (d- C ₆ ) -haloalkylthio, (Cι-C ₆ ) alkoxy, (-C-C ₆ ) haloalkoxy or R ⁵ together with the carbon atom to which it is attached forms a carbonyl group, or two R ⁵ together with the carbon atom to which they are attached form a 3- up to 6-part spiroring;

Depending on external conditions, such as solvent and pH, the compounds of the formula (I) according to the invention can occur in different tautomeric structures:

Depending on external conditions, such as solvent and pH, the compounds of the formula (I) according to the invention can occur in different tautomeric structures. Depending on the nature of the substituents, the compounds of the formula (I) contain an acidic proton which can be removed by reaction with a base. Suitable bases are, for example, hydrides, hydroxides and Carbonates of alkali and alkaline earth metals, such as lithium, sodium, potassium, magnesium and calcium, as well as ammonia and organic amines such as triethylamine and pyridine. Such salts are also the subject of the invention.

In formula (I) and all subsequent formulas, alkyl radicals with more than two carbon atoms can be straight-chain or branched. Alkyl radicals mean e.g. Methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl and 1, 3-dimethylbutyl.

If a group is substituted several times by radicals, this means that this group is substituted by one or more identical or different of the radicals mentioned.

Cycloalkyl means a carbocyclic, saturated ring system with three to nine carbon atoms, e.g. Cyclopropyl, cyclopentyl or cyclohexyl. Analogously, cycloalkenyl means a monocyclic alkenyl group with three to nine carbon ring members, e.g. Cyclopropenyl, cyclobutenyl, cyclpentyl and cyclohexenyl, where the double bond can be located at any position. In the case of composite radicals, such as cycloalkylalkenyl, the former radical can be in any position of the latter.

The heterocyclic group Het includes residues such as 1,3-dioxetan-2-yl, 1,3-dioxolan-2-yl, 1,3-dioxolan-4-yl, 1,3-dioxan-2-yl, 1,1 3-dioxan-4-yl, 1, 3-dioxan-5-yl, 1, 4-dioxan-2-yl, 1, 3-dioxepan-2-yl, 1, 3-dioxepan-4-yl, 1, 3-Dioxepan-5-yl, 1,4-dioxepan-2-yl, 1,4-dioxepan-5-yl and 1,4-dioxepan-6-yl.

In the case of a doubly substituted amino group, such as dialkylamino, these two substituents can be the same or different.

Halogen means fluorine, chlorine, bromine or iodine. Haloalkyl, -alkenyl and -alkynyl are partially or completely substituted alkyl by halogen, preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine, Alkenyl or alkynyl, for example CF ₃ , CHF ₂ , CH ₂ F, CF ₃ CF ₂ , CH ₂ FCHCI, CCI ₃ , CHCI ₂ , CH ₂ CH ₂ CI, CH = CHCI, CH = CCI ₂ , CsCCH ₂ CI; Haloalkoxy is, for example, OCF ₃ , OCHF ₂ , OCH ₂ F, CF ₃ CF ₂ O, OCH ₂ CF ₃ and OCH ₂ CH ₂ CI; the same applies to haloalkenyl and other halogen-substituted radicals.

If a group is substituted several times, this means that when combining the various substituents the general principles of the structure of chemical compounds must be observed, i.e. that no compounds are formed which the person skilled in the art knows that they are chemically unstable or not possible.

Depending on the nature and linkage of the substituents, the compounds of the formula (I) can be present as stereoisomers. If, for example, one or more asymmetric carbon atoms are present, enantiomers and diastereomers can occur. Stereoisomers can be obtained from the mixtures obtained in the preparation by customary separation methods, e.g. obtained by chromatographic separation processes. Likewise, stereoisomers can be produced selectively by using stereoselective reactions using optically active starting materials and / or auxiliary substances. The invention also relates to all stereoisomers and their mixtures which are encompassed by the general formula (I) but are not specifically defined.

Compounds of the formula (I) have proven to be advantageous in which R ¹ , R ² independently of one another are hydrogen, nitro, halogen, (CC) alkyl, (CrC ^ haloalkyl, (C ₂ -C ₆ ) alkenyl, ( C ₂ -C ₆ ) haloalkenyl, (C ₂ -C ₆ ) alkynyl, (C ₂ -C ₆ ) haloalkynyl, (C ₃ -C ₆ ) cycloalkyl, -OR ⁴ , S (O) _n R ⁴ , SO ₂ OR ⁴ , SO ₂ N (R ⁴ ) ₂ , NR ⁴ SO ₂ R ⁴ or (-C-C ₆ ) alkyl-S (O) _n R ⁴ ;

R ^{4 represents} hydrogen, (CC ₄ ) alkyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) alkynyl, (C ₃ -C ₆ ) cycloalkyl, phenyl or phenyl- (CrC ₄ ) alkyl, the six last-mentioned radicals being substituted by s radicals from the group cyano, nitro, R ³ , OR ³ , SR ³ or N (R ³ ) ₂ , and the other substituents and indices each have the meanings given above.

Preferred compounds of the general formula (I) are those in which R ³ denotes hydrogen or methyl;

R ⁵ means cyano, nitro, halogen, (-C-C ₄ ) alkoxycarbonyl, (C-ι ~ C ₄ ) -

Alkylcarbonyl, _(Cι-C4) alkylcarbonyloxy, _(Cι-C4) alkyl, (CrC ₄₎ haloalkyl, (C1-C4) -

Alkylthio, (CrC _^ haloalkylthio, (CrC ₆ ) alkoxy, (C ₁ -C ₆ ) haloalkoxy, or R ⁵ together with the carbon atom to which it is attached form one

Carbonyl group, or two R ⁵ together with the carbon atom to which they are attached form a 5-6-membered spiro ring, and the other substituents and indices in each case those mentioned above

Have meanings.

Compounds of the general formula (I) in which

R ^{5 represents} methyl, methoxy, ethyl, hexyl or chloromethyl, or R ⁵ together with the carbon atom to which it is attached forms one

Carbonyl group, or two R ⁵ together with the carbon atom to which they are attached form a 5-6 membered spiro ring, and the other substituents and indices each have the meanings given above.

Compounds of the general formula (I) in which

R ^{1 represents} chlorine, bromine, iodine, nitro, methyl or thiomethyl;

R ^{2 represents} chlorine, methylsulfonyl or ethylsulfonyl, and the other substituents and indices in each case those mentioned above

Have meanings.

In all of the formulas mentioned below, unless otherwise defined, the substituents and symbols have the same meaning as described under formula (I). Compounds according to the invention can be prepared, for example, by the base-catalyzed reaction of a compound of the formula (purple), in which T represents halogen, hydroxy or alkoxy, with a cyclohexanedione (II) in the presence of a source of cyanide by the method given in scheme 1. Such methods are described for example in EP-A 0 369 803 and EP-B 0 283 261. Scheme 1:

(II) (purple) (la)

Compounds of the formula (purple), in which T represents OH, can be prepared, for example, according to scheme 2 from compounds of the formula (Via), in which shark represents halogen. Scheme 2:

(Via) (Va) lla)

Compounds of the general formula (purple) can also be obtained by reactions according to Scheme 3. Scheme 3:

(Vlb) (Vb) (purple)

Compounds of the formulas (Via) and (VIb) are known from the literature or can be prepared by known methods, as are described, for example, in WO 96/26200 and in the older and not prepublished German patent application No. 10144412.5. Compounds of the formulas (Va) and (Vb) are known to the person skilled in the art or can be prepared by methods known to the person skilled in the art.

The compounds of formula (I) according to the invention have excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants. Perennial weeds that are difficult to control and that sprout from rhizomes, rhizomes or other permanent organs are also well captured by the active ingredients. It is usually irrelevant whether the substances are applied by pre-sowing, pre-emergence or post-emergence. Some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned in detail, which can be controlled by the compounds according to the invention without the name being intended to restrict them to certain species. On the monocotyledon weed species, for example, Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria and Cyperus species from the annual group and on the perennial species Agropyron, Cynodon, Imperata and Sorghum as well as perennial Cyperus species are well recorded. In the case of dicotyledon weed species, the spectrum of activity extends to species such as Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Sida, Matricaria and Abutilon on the annual side as well as Convolvulus, Cirsium, Rumex and Artemisia in perennial weeds. Harmful plants occurring in the rice under the specific culture conditions, such as, for example, Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus, are also excellently combated by the active compounds according to the invention. If the compounds according to the invention are applied to the surface of the earth before germination, either the weed seedlings emerge completely or the weeds grow to the cotyledon stage, but then stop growing and finally die completely after three to four weeks. When the active ingredients are applied to the green parts of the plant in the post-emergence process, there is also a drastic growth stop very quickly after the treatment and the weed plants remain in the growth stage at the time of application or die completely after a certain time, so that one for the crop plants harmful weed competition is eliminated very early and sustainably. In particular, the compounds according to the invention show an excellent action against Amaranthus retroflexus, Avena sp., Echinochloa sp., Cyperus serotinus, Lolium multiflorum, Setaria viridis, Sagittaria pygmaea, Scirpus juncoides, Sinapis sp. and Stellaria media.

Although the compounds of the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops such as e.g. Wheat, barley, rye, rice, corn, sugar beet, cotton and soy are only slightly or not at all damaged. They are particularly well tolerated in wheat, corn and rice. For these reasons, the present compounds are very suitable for the selective control of undesired plant growth in agricultural crops or in ornamental crops.

Because of their herbicidal properties, the active compounds can also be used to control harmful plants in crops of known or still to be developed genetically modified plants. The transgenic plants are generally distinguished by special advantageous properties, for example by resistance to certain ones Pesticides, especially certain herbicides, resistance to plant diseases or pathogens such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties concern e.g. B. the crop in terms of quantity, quality, shelf life, composition and special ingredients. Transgenic plants with an increased starch content or altered starch quality or with a different fatty acid composition of the crop are known.

Preferred is the use of the compounds of formula (I) according to the invention or their salts in economically important transgenic crops of useful and ornamental plants, for. B. of cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn or also crops of sugar beet, cotton, soybean, rapeseed, potato, tomato, pea and other vegetables. The compounds of the formula (I) can preferably be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been rendered genetically resistant.

Conventional ways of producing new plants which have modified properties in comparison to previously occurring plants are, for example, classic breeding methods and the generation of mutants. Alternatively, new plants with modified properties can be produced using genetic engineering methods (see, for example, EP-A-0221044, EP-A-0131624). In several cases, for example, genetic engineering modifications of crop plants have been described in order to modify the starch synthesized in the plants (e.g. WO 92/11376, WO 92/14827, WO 91/19806), transgenic crop plants which are active against certain herbicides of the glufosinate type ( see, for example, EP-A-0242236, EP-A-242246) or glyphosate (WO 92/00377) or sulfonylureas (EP-A-0257993, US-A-5013659) are resistant, transgenic crop plants, for example cotton , with the ability to produce Bacillus thuringiensis toxins (Bt toxins) which the plants make resistant to certain pests (EP-A-0142924, EP-A-0193259). transgenic crop plants with modified fatty acid composition (WO 91/13972).

In principle, numerous molecular biological techniques with which new transgenic plants with modified properties can be produced are known; see e.g. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. Gold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Gene and Clones", VCH Weinheim 2nd edition 1996 or Christou, "Trends in Plant Science" 1 (1996) 423-431).

For such genetic engineering manipulations, nucleic acid molecules can be introduced into plasmids which allow mutagenesis or a sequence change by recombining DNA sequences. With the help of the standard procedures mentioned above, e.g. B. base exchanges, partial sequences removed or natural or synthetic sequences added. To connect the DNA fragments to one another, adapters or linkers can be attached to the fragments.

The production of plant cells with a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to achieve a cosuppression effect or the expression of at least one appropriately constructed ribozyme which specifically cleaves transcripts of the above-mentioned gene product.

For this purpose, DNA molecules can be used that comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules that only comprise parts of the coding sequence, these parts having to be long enough to be in the cells to cause an antisense effect. It is also possible to use DNA sequences that have a high degree of homology to the coding sequences of a gene product, but are not completely identical.

When nucleic acid molecules are expressed in plants, the synthesized protein can be located in any compartment of the plant cell. However, in order to achieve localization in a particular compartment, z. B. the coding region can be linked to DNA sequences that ensure localization in a particular compartment. Such sequences are known to the person skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1: 95-106 (1991).

The transgenic plant cells can be regenerated into whole plants using known techniques. The transgenic plants can in principle be plants of any plant species, i.e. both monocot and dicot plants.

Thus, transgenic plants are available which have changed properties due to overexpression, suppression or inhibition of homologous (= natural) genes or gene sequences or expression of heterologous (= foreign) genes or gene sequences.

When the active compounds according to the invention are used in transgenic crops, in addition to the effects on harmful plants which can be observed in other crops, effects often occur which are specific to the application in the respective transgenic culture, for example a changed or specially expanded weed spectrum which can be controlled changed Application rates that can be used for the application, preferably good combinability with the herbicides to which the transgenic culture is resistant, and influencing the growth and yield of the transgenic crop plants. The invention therefore also relates to the use of the compounds according to the invention as herbicides for controlling harmful plants in transgenic crop plants. In addition, the substances according to the invention have excellent growth-regulating properties in crop plants. They intervene regulating the plant's own metabolism and can thus be used to influence plant constituents in a targeted manner and to facilitate harvesting, for example by triggering desiccation and stunted growth. Furthermore, they are also suitable for general control and inhibition of undesirable vegetative growth without killing the plants. Inhibiting vegetative growth plays a major role in many monocotyledonous and dicotyledonous crops, as this can reduce or completely prevent storage.

The compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations. The invention therefore also relates to herbicidal compositions which comprise compounds of the formula (I). The compounds of the formula (I) can be formulated in various ways, depending on which biological and / or chemical-physical parameters are specified. Possible formulation options include, for example: wettable powder (WP), water-soluble powder (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions , Suspension concentrates (SC), dispersions based on oil or water, oil-miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for spreading and soil application, granules (GR) in the form of micro, spray , Elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes. These individual formulation types are known in principle and are described, for example, in: Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th Edition 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY , 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London. The necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell NJ, Hv Olphen, "Introduction to Clay Colloid Chemistry "; 2nd Ed., J. Wiley & Sons, NY; C. Marsden, "Solvent Guide"; 2nd Ed., Interscience, NY 1963; McCutcheon's Detergents and Emulsifiers Annual, MC Publ. Corp., Ridgewood NJ; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., NY 1964; Schönfeldt, "Interface-active ethylene oxide adducts", Wiss. Publishing company, Stuttgart 1976; Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.

Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, contain not only a diluent or an inert substance, but also ionic and / or nonionic surfactants (wetting agents, dispersing agents), e.g. polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, ligninsulfonic acid sodium, dibutylnaphthaiine sulfonic acid sodium or sodium sulfonic acid also contain sodium. To produce the wettable powders, the herbicidal active ingredients are, for example, finely ground in customary apparatuses such as hammer mills, fan mills and air jet mills and are mixed simultaneously or subsequently with the formulation auxiliaries.

Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or even higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents with the addition of one or more ionic and / or nonionic surfactants (emulators). Examples of emulsifiers which can be used: calcium alkylarylsulfonates such as Ca dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid, alkyl aryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensate sationsprodukte, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters or polyoxyethylene such as polyoxyethylene -sorbitanfettsäureester. Dusts are obtained by grinding the active substance with finely divided solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

Suspension concentrates can be water or oil based. You can, for example, by wet grinding using commercially available bead mills and optionally adding surfactants, such as those e.g. already listed above for the other types of formulation.

Emulsions, e.g. Oil-in-water emulsions (EW) can, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as those e.g. already listed above for the other types of formulation.

Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.

Water-dispersible granules are generally produced using the customary methods, such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.

For the production of plate, fluidized bed, extruder and spray granules, see, for example, the process in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; JE 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 on 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., Blackwel! Scientific Publications, Oxford, 1968, pages 101-103.

The agrochemical preparations generally contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of active ingredient of the formula (I). The active substance concentration in wettable powders is e.g. about 10 to 90 wt .-%, the rest of 100 wt .-% consists of conventional formulation components. In the case of emulsifiable concentrates, the active substance concentration can be about 1 to 90, preferably 5 to 80,% by weight. Dust-like formulations contain 1 to 30% by weight of active ingredient, preferably mostly 5 to 20% by weight of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50% by weight of active ingredient. In the case of water-dispersible granules, the active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulating aids, fillers, etc. are used. The active ingredient content of the water-dispersible granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

In addition, the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreezes and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and the pH and Agents influencing viscosity.

Based on these formulations, combinations with other pesticidally active substances, e.g. Manufacture insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers and / or growth regulators, e.g. in the form of a finished formulation or as a tank mix.

Known active ingredients, such as those described, for example, in Weed Research 26, 441-445 (1986) or "The Pesticide Manual", can be used as combination partners for the active ingredients according to the invention in mixture formulations or in the tank mix. 11th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 1997 and the literature cited therein. Known herbicides which can be combined with the compounds of the formula (I) are, for example, the following active substances (note: the compounds are either with the "common name" according to the International Organization for Standardization (ISO) or with the chemical name , possibly together with a usual code number): acetochlor; acifluorfen; aclonifen; AKH 7088, ie [[[1- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidene] amino] oxy] acetic acid and methyl acetate; alachlor; alloxydim; ametryn; amidosulfuron; amitrol; AMS, ie ammonium sulfamate; anilofos; asulam; atrazine; azimsulfurone (DPX-A8947); aziprotryn; barban; BAS 516 H, ie 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluralin; benfuresate; bensulfuron-methyl; bensulide; bentazone; benzofenap; benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox; bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butamifos; butenachlor; buthidazole; butraline; butylate; cafenstrole (CH-900); carbetamide; cafentrazone (ICI-A0051); CDAA, ie 2-chloro-N, N-di-2-propenylacetamide; CDEC, ie 2-chloroallyl ester of diethyldithiocarbamic acid; chlomethoxyfen; chloramben; chlorazifop-butyl, chloromesulone (ICI-A0051); chlorbromuron; chlorbufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron ethyl; chlornitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlorthal-dimethyl; chlorthiamid; cinmethylin; cinosulfuron; clethodim; clodinafop and its ester derivatives (eg clodinafop-propargyl); clomazone; clomeprop; cloproxydim; clopyralid; cumyluron (JC 940); cyanazine; cycloate; cyclosulfamuron (AC 104); cycloxydim; cycluron; cyhalofop and its ester derivatives (eg butyl ester, DEH-112); cyperquat; cyprazine; cyprazole; daimuron; 2,4-DB; dalapon; desmedipham; Desmetryn; di-allate; dicamba; dichlobenil; dichloroprop; diclofop and its esters such as diclofop-methyl; diethatyl; difenoxuron; difenzoquat; diflufenican; dimefuron; dimethachlor; dimethametryn; dimethenamid (SAN-582H); dimethazone, clomazone; dimethipin; dimetrasulfuron, dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 77, ie 5-cyano-1- (1, 1-dimethylethyl) -N-methyl-1 H-pyrazole-4- carboxamide; endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl; Ethidimuron; ethiozin; ethofumesate; F5231, ie N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo-1H-tetrazol-1-yl] phenyl] ethanesulfonamide; ethoxyfen and its esters (eg ethyl ester, HN-252); etobenzanide (HW 52); fenoprop; fenoxan, fenoxaprop and fenoxaprop-P and their esters, for example fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim; fenuron; flamprop-methyl; flazasulfuron; fluazifop and fluazifop-P and their esters, for example fluazifop-butyl and fluazifop-P-butyl; fluchloralin; flumetsulam; flumeturon; flumiclorac and its esters (eg pentyl ester, S-23031); flumioxazin (S-482); flumipropyn; flupoxam (KNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil (UBIC-4243); fluridone; flurochloridone; fluroxypyr; flurtamone; fomesafen; fosamine; furyloxyfen; glufosinate; glyphosate; halo safen; halosulfuron and its esters (eg methyl ester, NC-319); haloxyfop and its esters; haloxyfop-P (= R-haloxyfop) and its esters; hexazinone; imazapyr; imazamethabenz-methyl; imazaquin and salts such as the ammonium salt; ioxynil; imazethamethapyr; imazethapyr; imazosulfuron; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidide; mesotrione; metamitron; metazachlor; metham; methabenzthiazuron; methazole; methoxyphenone; methyldymron; metabenzuron, methobenzuron; metobromuron; metolachlor; metosulam (XRD 511); metoxuron; metribuzin; metsulfuron-methyl; MH; molinate; monalide; monolinuron; monuron; monocarbamide dihydrogen sulfates; MT 128, ie 6-chloro-N- (3-chloro-2-propenyl) -5-methyl-N-phenyl-3-pyridazinamine; MT 5950, ie N- [3-chloro-4- (1-methylethyl) phenyl] -2-methylpentanamide; naproanilide; napropamide; naptalam; NC 310, ie 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitralin; nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxyfluorfen; paraquat; pebulate; pendimethalin; perfluidone; phenisopham; phenmedipham; picloram; piperophos; piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl; procyazine; prodi amines; profluralin; proglinazine-ethyl; prometon; prometryne; propachlor; propanil; propaquizafop and its esters; propazine; propham; propisochlor; Propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA-152005); prynachlor; pyrazolinate; pyrazon; pyrazosulfuron-ethyl; pyrazoxyfen; pyridate; pyrithiobac (KIH-2031); pyroxofop and its esters (eg propargyl esters); quinclorac; quinmerac; quinofop and its ester derivatives, quizalofop and quizalofop-P and their ester derivatives, for example quizalofop-ethyl; quizalofop-P-tefuryl and ethyl; renriduron; rimsulfuron (DPX-E 9636); S 275, ie 2- [4-chloro-2-fluoro-5- (2-propynyloxy) phenyl] -4,5,6,7-tetrahydro-2H-indazole; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, ie 2 - [[7- [2-chloro-4- (trifluoromethyl) phenoxy] -2-naphthalenyl] oxy] propanoic acid and methyl ester; suclotrione; sulfentrazone (FMC-97285, F-6285); sulfazuron; sulfometuron-methyl; sulfosate (ICI-A0224); TCA; tebutam (GCP-5544); tebuthiuron; terbacil; terbucarb; terbuchlor; terbumeton; Terbuthylazine; terbutryn; TFH 450, ie N, N-diethyl-3 - [(2-ethyl-6-methylphenyl) sulfonyl] -1 H-1, 2,4-triazole-1-carboxamide; thenylchlor (NSK-850); thiazafluron; thiazopyr (Mon-13200); thidiazimin (SN-24085); thiobencarb; thifensulfuron-methyl; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide; tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin; triflusulfuron and esters (e.g. methyl ester, DPX-66037); trimeturon; tsitodef; vernolate; WL 110547, ie 5-phenoxy-1- [3- (trifluoromethyl) phenyl] -1 H-tetrazole; UBH-509; D-489; LS 82-556; KPP-300; NC-324; NC-330; KH-218; DPX-N8189; SC-0774; Dowco-535; DK-8910; V-53482; PP-600; MBH-001; KIH-9201; ET-751; KIH-6127 and KIH-2023.

For use, the formulations available in commercial form are usually diluted in e.g. for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules using water. Preparations in the form of dust, ground granules or granules as well as sprayable solutions are usually no longer diluted with other inert substances before use. With the external conditions such as temperature, humidity, the type of herbicide used, etc. the required application rate of the compounds of formula (I) varies. It can fluctuate within wide limits, e.g. between 0.001 and 1.0 kg / ha or more active substance, but is preferably between 0.005 and 750 g / ha.

The following examples illustrate the invention. A. Chemical examples

Preparation of 2- [2-chloro-3 - ({[2- (chloromethyl) -2-methyl-1, 3-dioxolan-4-yl] methoxy} methyl) -4- (methylsulfonyl) benzoyl] cyclohexane-1, 3-dione (table example no.1.1)

Step 1: 2-chloro-3 - ({[2- (chloromethyl) -2-methyl-1, 3-dioxolan-4-yl] methoxy} methy!) - 4- (methylsulfonyl) benzoic acid 5 ml DMF and 3.58 g (22 mmol) of 2- (chloromethyl) -2-methyl-1,3-dioxolan-4-yl] methanol were initially taken at RT and 0.85 g (21 mmol) of 60% NaH were added. The mixture was stirred for an hour and then 3 g (11 mmol) of 3-bromomethyl-2-chloro-4-methylsulfonyl-benzoic acid were added. Then stirring was continued for 1 hour. The mixture was diluted with 50 ml of water, acidified with KHSO ₄ solution and extracted with chloroform. The organic phases were dried with MgSO ₄ , filtered and concentrated. 3,568 g of viscous oil were obtained as a crude product which was purified by chromatography. Yield 1.28 g (3.5 mmol) 32% as a colorless oil with a purity of 91% according to HPLC.

¹ H NMR: δ [CDCI ₃ ] 1.45 and 1.5 (2s, 3H), 3.3 (s, 3H), 3.5 (m, 2H), 3.8 (m, 3H), 4.15 (m, 1H), 4.45 (m, 1H), 5.25 (s, 2H), 7.98 (d, 1H), 8.08 (d, 1H)

Step 2: 3-oxocyclohex-1-en-1-yl 2-chloro-3 - ({[2- (chloromethyl) -2-methyl-1, 3-dioxolan-4-yl] methoxy} methyl) -4- (methylsulfonyl) benzoate 0.58 g crude 2-chloro-3 - ({[2- (chloromethyl) -2-methyl-1,3-dioxolan-4-yl] methoxy} methyl) -4- (methylsulfonyl) benzoic acid, 0.496 g (4 mmol) of cyclohexanedione and 0.364 g (2 mmol) of N- (3-dimethylaminopropyl) -N ^, -ethylcarbodiimd hydrochloride were dissolved in 5 ml of CH ₂ CI ₂ and stirred at RT for 4 h. The mixture was then washed with water and NaHCO ₃ solution, dried over MgSO ₄ , suction filtered through silica gel and concentrated. Yield 0.428 g (0.9 mmol) 52% as a yellow oil with a purity of 80% according to HPLC.

¹ H-NMR: δ [CDCI ₃ ] 1, 45 and 1.5 (2s, 3H), 2.15 (m, 2H), 2.5 (t, 2H), 2.7 (m, 2H), 3.3 (s, 3H), 3.5 (m, 2H), 3.8 (m, 3H), 4.15 (m, 1H), 4.45 (m, 1 H), 5.25 (s, 2H), 6.1 (s, 1 H), 7.9 (d, 1H), 8.09 (d, 1H) Step 3: 2- [2-chloro-3 - ({[2- (chloromethyl) -2-methyl-1, 3-dioxolan-4-yl] methoxy} methyl) -4- (methylsulfonyl) benzoyl] cyclohexane-1 , 3-dione 0.385 g (1 mmol) 3-oxocyclohex-1-en-1-yl 2-chloro-3 - ({[2- (chloromethyl) -2-methyl-1, 3-dioxolan-4-yl] methoxy} methyl) -4- (methylsulfonyl) benzoate were dissolved in 5 ml of CH ₃ CN and 0.123 g (1 mmol) of NEt ₃ and 0.006 g of acetone cyanohydrin and 0.017 g of KCN were added with stirring. The mixture was stirred at RT for 40 hours and then rotated in. It was acidified with KHSO solution and extracted with CH CI ₂ . The organic solution was dried with MgSO ₄ , filtered and evaporated. The crude product was purified by chromatography. Yield 0.247 g (0.53 mmol) 77% colorless oil with a purity of 97% according to HPLC. ¹ H NMR: δ [CDCI ₃ ] 1.45 and 1.5 (2s, 3H), 2.05 (m, 2H), 2.4 (t, 2H), 2.8 (m, 2H), 3.3 (s, 3H), 3.5 (m, 2H), 3.75 (m, 3H), 4.1 (m, 1H), 4.4 (m, 1H), 5.2 (s, 2H), 7.3 (d, 1H), 8.1 (d, 1H), 16.98 ( s, 1H)

The abbreviations used here mean: cPr = cyclo-propyl nPr = n-propyl nBu = n-butyl Et = ethyl Me = methyl Ph = phenyl RT = room temperature

Table: Compounds of the formula (I) according to the invention, in which n is 0

B. Formulation Examples 1. Dusts A dusts are obtained by mixing 10 parts by weight of a compound of the general formula (I) and 90 parts by weight of talc as an inert substance and comminuting them in a hammer mill.

2. Dispersible powder A wettable powder which is readily dispersible in water is obtained by adding 25 parts by weight of a compound of the general formula (I), 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of oleoylmethyl tauric acid sodium as the wetting agent. and dispersant mixes and grinds in a pin mill. 3. Dispersion concentrate

A dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of a compound of the general formula (I), 6 parts by weight of alkylphenol polyglycol ether (© Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight. Mixes parts of paraffinic mineral oil (boiling range approx. 255 to above 277 ° C) and grinds to a fineness of less than 5 microns in a attritor.

4. Emulsifiable concentrate

An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the general formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated nonylphenol as emulsifier.

5. Water-dispersible granules

A water-dispersible granulate is obtained by

75 parts by weight of a compound of the general formula (I),

Mix 10 "calcium lignosulfonate, 5" sodium lauryl sulfate, 3 "polyvinyl alcohol and 7" kaolin, grind them on a pin mill and mix the powder in a fluidized bed

Spraying water granulated as granulating liquid.

A water-dispersible granulate is also obtained by

25 parts by weight of a compound of the general formula (I), 5 "2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, 2" oleoylmethyl tauric acid sodium, 1 "polyvinyl alcohol, 17" calcium carbonate and

50 "water homogenized and pre-comminuted on a colloid mill, then ground on a bead mill and the suspension thus obtained is atomized and dried in a spray tower using a single-component nozzle.

C. Biological examples

1. Pre-emergence weed action

Seeds of monocotyledonous and dicotyledonous weed plants are laid out in sandy loam in cardboard pots and covered with soil. The compounds according to the invention formulated in the form of wettable powders or emulsion concentrates are then applied as an aqueous suspension or emulsion with a water application rate of the equivalent of 600 to 800 l / ha in various dosages to the surface of the covering earth. After the treatment, the pots are placed in the greenhouse and kept under good growth conditions for the weeds. After the test plants have emerged, the optical damage to the plants or the emergence damage is assessed after a test period of 3 to 4 weeks in comparison to untreated controls. After the test plants have stood in the greenhouse for 3 to 4 weeks under optimal growth conditions, the activity of the compounds is rated. The compounds according to the invention have excellent activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants. For example, the compounds according to the invention No. 1.43 and 1.64 at a dosage of 320 g / ha show at least 80% activity against the harmful plants Sinapis arvensis, Stellaria media and Amaranthus retroflexus. The compound of No. 1.1 according to the invention has an at least 90% activity against the harmful plants Lolium multiflorum and Stellaria media at a dosage of 320 g / ha.

2. Post-emergence herbicidal activity against harmful plants

Seeds of monocotyledonous and dicotyledonous harmful plants are grown in sandy pots in cardboard pots

Clay soil laid out, covered with earth and in the greenhouse under good ones Growth conditions attracted. Two to three weeks after sowing, the test plants are treated in a three-leaf study. The compounds according to the invention formulated as wettable powder or as emulsion concentrates are sprayed onto the surface of the green parts of the plant in various dosages at a rate of water equivalent to 600 to 800 l / ha. After the test plants have stood in the greenhouse for 3 to 4 weeks under optimal growth conditions, the activity of the compounds is rated. The compounds according to the invention have excellent activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants. For example, the compounds according to the invention Nos. 1.1, 1.43 and 1.106 at a dosage of 320 g / ha show an at least 80% activity against the harmful plants Sinapis arvensis and Stellaria media.

3. Crop tolerance

In further experiments in the greenhouse, seeds of barley and monocotyledonous and dicotyledonous harmful plants are laid out in sandy loam soil, covered with soil and placed in the greenhouse until the plants have developed two to three real leaves. Treatment with the compounds of the formula (I) according to the invention is then carried out as described under item 2 above. Four to five weeks after application and standing in the greenhouse, it is determined by means of an optical evaluation that the compounds according to the invention have excellent compatibility with important crop plants, in particular wheat, maize and rice.

Claims

claims:

1. Compounds of formula (I) or their salts

where the residues and indices have the following meanings:

R ^1, R ² independently of one another are hydrogen, mercapto, nitro, halogen, cyano, thiocyanato, (CC ₆₎ alkyl, (CrC ₆₎ -haloalkyl, (C ₂ -C ₆₎ alkenyl, (C ₂ -C ₆ ) - haloalkenyl, (C ₂ -C ₆ ) alkynyl, (C ₃ -C ₆ ) haloalkynyl, (C ₃ -C ₆ ) cycloalkyl, OR ⁴ , OCOR ⁴ , OSO ₂ R ⁴ , S (O) _n R ⁴ , SO ₂ OR ⁴ , SO ₂ N (R ⁴ ) ₂ , NR ⁴ SO ₂ R ⁴ , NR ⁴ COR ⁴ , (C ^ -C ₆ ) - alkyl-S (O) _n R ⁴ , (d- CeJ-alkyl-OR ⁴ , (CC ₆ ) -alkyl-OCOR ⁴ , (-C-C ₆ ) -alkyl-OSO ₂ R ⁴ , (Cι-C ₆ ) -alkyl-SO ₂ OR ⁴ , (CC ₆ ) - Alkyl-SO ₂ N (R ⁴ ) ₂ or (CC ₆ ) -alkyl-NR ⁴ COR ⁴ ;

R ^{3 represents} hydrogen, (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl or (C ₂ -C ₆ ) alkynyl;

R ⁴ is hydrogen, (-C ₆ ) -alk l. (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, (C ₃ -C ₆ ) - cycloalkyl, phenyl or phenyl- (-C-C ₆ ) alkyl, the six last-mentioned radicals by s Radicals of the group hydroxy, mercapto, amino, cyano, nitro, rhodano, OR ³ , SR ³ , N (R ³ ) ₂ , NOR ³ , OCOR ³ , SCOR ³ , NR ³ COR ³ , CO ₂ R ³ , COSR ³ , CON (R ³ ) ₂ , (CC ₄ ) - alkyliminooxy, (Cι-C ₄ ) alkoxyamino, (Cι-C) alkylcarbonyl, (Cι-C ₄ ) alkoxy- (C ₂ -C ₆ ) - alkoxycarbonyl and (-C-C) alkylsulfonyl are substituted;

Het denotes a fully saturated heterocyclic group, the ring atoms of which consist of 2 oxygen and 2, 3, 4 or 5 carbon atoms, and Het is substituted by n radicals R ⁵ ;

n represents 0, 1 or 2;

s represents 0, 1, 2 or 3; R ⁵ means hydroxy, mercapto, amino, cyano, nitro, halogen, formyl, (-C-C ₆ ) alkylamino, (Cι-C ₆ ) -dialkylamino, (CrC ₆ ) -alkoxycarbonyl, (CrC ₆ ) -alkylcarbonyl, ( Cι-C ₄₎ alkylcarbonyloxy, _(Cι-C6) alkyl, (Cι-C ₆₎ -haloalkyl, (CC ₆₎ alkylthio, (CrC ₆₎ haloalkylthio, _(Cι-C6) alkoxy, or R ⁵ together with the carbon atom to which it is attached form a carbonyl group, or two R ⁵ together with the carbon atom to which they are attached form a 3- to 6-membered spiro ring.

2. Compounds according to claim 1, wherein

R ¹ , R ² independently of one another are hydrogen, nitro, halogen, (dC ₄ ) - alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) haloalkenyl, (C ₂ -C ₆ ) alkynyl, (C ₂ -C ₆ ) haloalkynyl, (C ₃ -C ₆ ) cycloalkyl, -OR ⁴ , S (O) _n R ⁴ , SO ₂ OR ⁴ , SO ₂ N (R ⁴ ) ₂ , NR ⁴ SO ₂ R ⁴ or (C ₁ -C ₆ ) alkyl-S (O) _n R ⁴ ;

R ⁴ is hydrogen, (dC ^ alkyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) alkynyl, (C ₃ -C ₆ ) - cycloalkyl, phenyl or phenyl- (-C-C ₄ ) -alkyl, the six latter radicals being substituted by s radicals from the group cyano, nitro, R ³ , OR ³ , SR ³ or N (R ³ ) ₂ .

3. Compounds according to claim 1 or 2, wherein R ^{3 represents} hydrogen or methyl;

R ⁵ means cyano, nitro, halogen, (-C-C) ~ alkoxycarbonyl, (C-ι-C) -

Alkylcarbonyl, (dC ^ alkylcarbonyloxy, (dC ^ alkyl, (-C-C ₄ ) haloalkyl, (CC ₄ ) -

Alkylthio, (CrO -haloalkylthio, (d-Ce ^ alkoxy, (-C-C ₆ ) -haloalkoxy, or R ⁵ forms together with the carbon atom to which it is attached

Carbonyl group, or two R ⁵ together with the carbon atom to which they are attached form a 5-6 membered spiro ring.

4. Compounds according to any one of claims 1 to 3, wherein R ⁵ is methyl, methoxy, ethyl, hexyl or chloromethyl, or R ⁵ together with the carbon atom to which it is attached forms one

Carbonyl group, or two R ⁵ together with the carbon atom to which they are attached form a 5-6 membered spiro ring.

5. Compounds according to any one of claims 1 to 4, wherein R ^{1 represents} chlorine, bromine, iodine, nitro, methyl or thiomethyl; R ^{2 represents} chlorine, methylsulfonyl or ethylsulfonyl.

6. Herbicidal agents, characterized by a herbicidally active content of at least one compound of the general formula (I) according to one of claims 1 to 5

7. Herbicidal compositions according to claim 6 in a mixture with formulation auxiliaries.

8. A method for controlling unwanted plants, characterized in that an effective amount of at least one compound of the general formula (I) according to one of claims 1 to 5 or a herbicidal composition according to claim 6 or 7 on the plants or on the location of the unwanted Applied plant growth.

9. Use of compounds of general formula (I) according to one of claims 1 to 5 or of herbicidal compositions according to claim 6 or 7 for combating undesirable plants.

10. Use according to claim 9, characterized in that the compounds of general formula (I) are used to control unwanted plants in crops of useful plants.

11. Use according to claim 10, characterized in that the crop plants are transgenic crop plants.