DE10055499A1 - 6-heterocyclyl-3-oxo-3,4-dihydro-quinoxaline - Google Patents

Abstract

The invention relates to the compounds of the general formula (I), wherein R<1>, R<2>, R<3> and Z have the meanings indicated in the description. The invention also relates to a method and to the novel intermediates used for producing the novel compounds as well as to their use as plant treating agents, especially as herbicides.

Description

The invention relates to new 6-heterocyclyl-3-oxo-3,4-dihydro-quinoxaline, a Ver drive and new intermediates for their manufacture and their use as Plant treatment agents, in particular as herbicides.

There are already 6-heterocyclyl-3-oxo-1,2,3,4-tetrahydro-quinoxaline (see EP-A-420194) and 6-heterocyclyl-3-oxo-3,4-dihydro-quinoxalines, such as e.g. B. the Ver bonds 7- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazol-3-yl) -6-fluoro-2 (1H) - quinoxalinone (see US-A-5281571) and 7- (4-difluoromethyl-4,5-dihydro-5-oxo-3- propyl-1H-1,2,4-triazol-1-yl) -6-fluoro-1- (2-propynyl) -2 (1H) -quinoxalinone (see Pestic. Sci. 55 (1999), 281-287) with herbicidal properties (cf. also US-A-4670042, EP-A-311135).

However, the effect of these compounds is not satisfactory in all respects.

The new 6-heterocyclyl-3-oxo-3,4-dihydro-quinoxalines of the general formula (I) have now been

in which
R ^{1 represents} hydrogen or represents optionally substituted alkyl, alkylcarbonyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkenyl, alkenyloxy, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylthio, arylsulfinyl, arylsulfonyl or arylalkyl,
R ^{2 represents} hydrogen, cyano, halogen or optionally substituted alkyl,
R ^{3 represents} hydrogen or halogen, and
Z represents one of the heterocyclic groupings outlined below:

in which
Q ^{1 represents} O (oxygen) or S (sulfur),
Q ^{2 represents} O (oxygen) or S (sulfur),
R ⁴ for hydrogen, amino, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or for optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkoxycarbonyl, alkenyloxy, alkynyloxy, alkylthio, alkenylthio, alkynylthio, alkylamino, dialkylamino, cycloalkyl or Cyclo alkylalkyl stands, and
R ^{5 represents} hydrogen, hydroxy, amino, cyano, or optionally substituted alkyl, alkoxy, alkoxycarbonyl, alkylamino, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl or phenylalkyl,
found,
the known compounds 7- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazol-3-yl) -6-fluoro-2 (1H) -quinoxalinone (cf. US-A-5281571) and 7- (4-difluoro methyl-4,5-dihydro-5-oxo-3-propyl-1H-1,2,4-triazol-1-yl) -6-fluoro-1- (2-propynyl) -2 (1H ) -quinoxalinone (cf. Pestic. Sci. 55 (1999), 281-287) are excluded.

In the definitions are the hydrocarbon chains, such as alkyl, alkenyl or Alkynyl - also in combination with heteroatoms, such as in alkylamino - in each case straight chain or branched.

Preferred substituents or preferred ranges of the above and below Remaining existing formulas are defined below.

R ¹ preferably represents hydrogen, in each case optionally substituted by cyano, halogen, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkoxycarbonyl alkyl, alkylcarbonyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms in the alkyl groups, each for alkenyl, alkenyloxy or alkynyl optionally substituted by cyano or halogen, each having 3 to 6 carbon atoms, for cycloalkyl or cycloalkylalkyl each having 3 to 6 carbon atoms each optionally substituted by cyano, halogen or C ₁ -C ₄ -alkyl in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part, or for aryl, arylthio, arylsulfinyl, arylsulfonyl or arylalkyl each having 6 or 10 carbon atoms in the aryl group and optionally substituted by halogen and / or C ₁ -C ₄ alkyl 1 or 2 carbon atoms in the alkyl part.

R ² preferably represents hydrogen, cyano, halogen or optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy-substituted alkyl having 1 to 6 carbon atoms.

R ³ preferably represents hydrogen, fluorine or chlorine.

Z preferably represents one of the heterocyclic groupings outlined below

Q ¹ preferably represents O (oxygen).

Q ² preferably represents O (oxygen).

R ⁴ preferably represents hydrogen, amino, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, alkyl optionally substituted by cyano, halogen or C ₁ -C ₄ -alkoxy having 1 to 6 carbon atoms, in each case optionally substituted by halogen Alkenyl or alkynyl each having 2 to 6 carbon atoms, each for alkoxy or alkoxycarbonyl optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy or alkoxycarbonyl each having 1 to 6 carbon atoms in the alkyl groups, for each optionally substituted by halogen alkenyloxy or alkynyloxy each 3 to 6 carbon atoms, for alkylthio with 1 to 6 carbon atoms optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy, for each optionally substituted by halogen alkenylthio or alkynylthio each with 3 to 6 carbon atoms, for alkylamino or dialkylamino each Weil's 1 to 6 carbon atoms in the alkyl groups, or for each benenfa Is cycloalkyl or cycloalkylalkyl substituted by cyano, halogen or C ₁ -C ₄ alkyl, each having 3 to 6 carbon atoms in the cyclo alkyl groups and optionally 1 to 4 carbon atoms in the alkyl part.

R ⁵ preferably represents hydrogen, hydroxyl, amino, cyano, for alkyl, alkoxy, alkoxycarbonyl or alkylamino, each optionally optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy, each having up to 6 carbon atoms, each optionally by halogen substituted alkenyl or alkynyl each having up to 6 carbon atoms; for in each case optionally substituted by cyano, halogen or C ₁ -C ₄ -alkyl cycloalkyl or cycloalkylalkyl each having 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl part, or for in each case optionally by nitro, cyano, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ halo alkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy substituted phenyl or phenyl-C ₁ -C ₄ alkyl.

R ¹ particularly preferably represents hydrogen, in each case methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, acetyl which is optionally substituted by fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl , Propionyl, n- or i-butyroyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxy carbonyl, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or propylsulfonyl for propenyl optionally substituted by fluorine and / or chlorine, Butenyl, propenyloxy, butenyloxy, propynyl or butynyl, for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each optionally substituted by fluorine, chlorine or methyl, or for phenyl optionally substituted by fluorine, chlorine or methyl , Phe nylthio, phenylsulfinyl, phenylsulfonyl or benzyl.

R ² particularly preferably stands for hydrogen, cyano, fluorine, chlorine, bromine, or for methyl, ethyl, n- or i-propyl, n-, i-, s- or optionally substituted by fluorine, chlorine, methoxy or ethoxy t-butyl.

R ⁴ particularly preferably represents hydrogen, amino, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, and in each case methyl, ethyl, n- or i-propyl which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy , n-, i-, s- or t-butyl, for each optionally substituted by fluorine, chlorine or bromine, ethenyl, propenyl, butenyl, ethynyl, propynyl or butynyl, for each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy Methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, for propenyl oxy, butenyloxy, propynyloxy or butynyloxy, each optionally substituted by fluorine, chlorine or bromine, for each optionally by cyano, fluorine, chlorine , Methoxy or ethoxy substituted methylthio, ethylthio, n- or i-propylthio, for propenylthio optionally substituted by fluorine, chlorine or bromine, butenylthio, propinylthio or butinylthio, for methylamino, Ethylamino, n- or i-propylamino, dimethylamino or diethylamino, or for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl.

R ⁵ particularly preferably represents hydrogen, hydroxyl, amino, cyano, for each methyl, ethyl, n- or i-propyl, n-, optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylamino, ethylamino, n- or i-propylamino, each optionally with fluorine, chlorine or bromine-substituted propenyl, butenyl, propynyl or butynyl, for each cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl, or for each optionally by nitro, Cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, di fluoromethoxy or trifluoromethoxy substituted Phenyl, benzyl or phenylethyl.

R ¹ very particularly preferably represents hydrogen, in each case optionally substituted by fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl, methyl, ethyl, n- or i-propyl, acetyl, propionyl, methoxy, ethoxy, n- or i-propoxy , Methoxycarbonyl, ethoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, for propenyl, butenyl substituted by fluorine and / or chlorine, if appropriate , Propynyl or butynyl, for cyclopropyl optionally substituted by fluorine, chlorine or methyl, or for phenylthio, phenylsulfinyl, phenylsulfonyl or benzyl, each optionally substituted by chlorine or methyl.

R ² very particularly preferably represents hydrogen, fluorine, chlorine, bromine or methyl or ethyl which is in each case optionally substituted by fluorine and / or chlorine.

R ⁴ very particularly preferably represents hydrogen, cyano, carbamoyl, thio carbamoyl, fluorine, chlorine, bromine, in each case methyl, ethyl, n- or i-propyl optionally substituted by fluorine, chlorine, methoxy or ethoxy, in each case optionally by fluorine , Chlorine or bromine substituted ethenyl, propenyl, ethynyl or propynyl, each for methoxy, ethoxy, n- or i-propoxy optionally substituted by fluorine, chlorine, methoxy or ethoxy, for propenyloxy, butenyloxy each optionally substituted by fluorine, chlorine or bromine , Propinyloxy or butinyloxy, for each optionally substituted by fluorine and / or chlorine, methylthio, ethylthio, n- or i-propylthio, for each optionally substituted by fluorine, chlorine or bromine, propenylthio or propynylthio, for methylamino, ethylamino, n- or i -Propylamino, or for dimethylamino.

R ⁵ very particularly preferably represents hydrogen, each methyl, ethyl, n- or i-propyl optionally substituted by fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, and propenyl optionally substituted by fluorine and / or chlorine , Butenyl, propynyl or butynyl, or for cyclopropyl or cyclopropylmethyl which is optionally substituted by fluorine, chlorine or methyl.

The individual radicals R ⁴ and R ⁵ - insofar as they are connected to the same heterocyclic grouping more than once - can have the same or different meanings in the context of the definitions given above as preferred, particularly preferred or very particularly preferred.

A very particularly preferred group are those compounds of the formula (I) in which
R ¹ for hydrogen, for each methyl, ethyl, n- or i-propyl optionally substituted by fluorine, chlorine, methoxy or ethoxy, for propenyl, butenyl, propynyl or butinyl, optionally substituted by fluorine and / or chlorine, or for optionally cyclopropyl substituted by fluorine, chlorine or methyl,
R ^{2 represents} hydrogen or methyl optionally substituted by fluorine and / or chlorine,
R ^{3 represents} hydrogen, fluorine or chlorine,
Z represents the heterocyclic grouping outlined below:

in which
Q ^{1 represents} oxygen or sulfur,
Q ^{2 represents} oxygen or sulfur, and
R ⁵ represents methyl or ethyl optionally substituted by fluorine, chlorine, methoxy or ethoxy, or propenyl, butenyl, propynyl or butynyl optionally substituted by fluorine and / or chlorine, the two groups R ^{5 being} identical in each individual case or can be different.

Another very particularly preferred group are those compounds of the formula (I) in which
R ¹ for hydrogen, for each methyl, ethyl, n- or i-propyl optionally substituted by fluorine, chlorine, methoxy or ethoxy, for propenyl, butenyl, propynyl or butinyl, optionally substituted by fluorine and / or chlorine, or for optionally cyclopropyl substituted by fluorine, chlorine or methyl,
R ^{2 represents} hydrogen or methyl optionally substituted by fluorine and / or chlorine,
R ^{3 represents} hydrogen, fluorine or chlorine,
Z represents the heterocyclic grouping outlined below:

in which
Q ^{1 represents} oxygen or sulfur,
Q ^{2 represents} oxygen or sulfur,
R ^{4-1 represents} cyano or methyl or ethyl which is optionally substituted by fluorine and / or chlorine,
R ^{4-2 represents} hydrogen, fluorine, chlorine, bromine or in each case methyl or ethyl which is optionally substituted by fluorine and / or chlorine, and
R ^{5 stands} for amino or for methyl or ethyl which is in each case optionally substituted by fluorine, chlorine, methoxy or ethoxy or for propenyl, butenyl, propynyl or butinyl which is in each case optionally substituted by fluorine and / or chlorine.

The radicals listed above or listed in preferred areas definitions apply both to the end products of the formula (I) and correspondingly for the starting or intermediate products required for the production. This Residual definitions can be between themselves, that is, between the specified ones areas can be combined as required.

Those compounds of the formula (I) are preferred according to the invention which is a combination of the meanings listed above as preferred is present.

According to the invention, particular preference is given to those compounds of the formula (I) in which a combination of those listed as particularly preferred above Meanings exist.

According to the invention, those compounds of the Formula (I), in which a combination of the above is particularly preferred added listed meanings is present.

The new 6-heterocyclyl-3-oxo-3,4-dihydroquinoxalines of the general formula (I) have interesting biological properties. They stand out in particular from strong herbicidal activity.

The new 6-heterocyclyl-3-oxo-3,4-dihydroquinoxalines of the general formula (I) are obtained if 4-heterocyclyl-1,2-phenylene diamines of the general formula (II)

in which
R ¹ , R ³ and Z have the meanings given above,
with 2-oxocarboxylic acid esters of the general formula (III)

in which
R ^{2 has} the meaning given above and
R represents alkyl, preferably C ₁ -C ₄ alkyl (e.g. methyl or ethyl),
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
and, if appropriate, subsequently, in the usual way, as part of the definition of substituents, further chemical conversion reactions, such as, for. B. Oxida tion, reduction or substitution reactions.

If, for example, 1,2-dimethyl-4- (4-amino-2-chloro-5-ethylamino phenyl) -1,2,4-triazolidine-3,5-dione and methyl pyruvate are used as starting materials, then the The course of the reaction in the process according to the invention can be outlined by the following formula:

Formula (II) provides a general definition of the 4-heterocyclyl-1,2-phenylene diamines to be used as starting materials in the process according to the invention for the preparation of compounds of the general formula (I). In the general formula (II), R ¹ , R ³ and Z preferably have those meanings which are preferred, particularly preferred or very particularly preferred for R ¹ already in connection with the description of the compounds of the general formula (I) according to the invention , R ³ and Z have been specified.

The starting materials of the general formula (II) are not yet from the literature knows; as new substances, they are also the subject of the present application.

The new 4-heterocyclyl-1,2-phenylene diamines of the general formula (II) are obtained if 5-heterocyclyl-2-nitro-phenylamines of the general formula (IV)

in which
R ¹ , R ³ and Z have the meanings given above,
with a reducing agent, such as. B. iron, in the presence of a diluent, such as. B. acetic acid, at temperatures between 0 ° C and 100 ° C (see. The preparation examples).

Formula (IV) provides a general definition of the 5-heterocyclyl-2-nitro-phenylamines to be used as precursors. In the general formula (IV), R ¹ , R ³ and Z preferably have those meanings which are preferred, particularly preferred or very particularly preferred for R ¹ , R already in connection with the description of the compounds of the general formula (I) according to the invention ³ and Z have been specified.

The precursors of the general formula (IV) are not yet from the literature knows; as new substances, they are also the subject of the present application.

The new 5-heterocyclyl-2-nitro-phenylamines of the general formula (IV) are obtained if 2-halo-4-heterocyclyl-nitrobenzenes of the general formula (V)

in which
R ³ and Z have the meanings given above and
X ^{1 represents} halogen (in particular fluorine or chlorine),
with amino compounds of the general formula (VI)

H ₂ NR ¹ (VI)

in which
R ^{1 has} the meaning given above,
optionally in the presence of a reaction auxiliary, such as. As sodium hydride, and optionally in the presence of a diluent, such as. B. acetonitrile, at temperatures between 10 ° C and 150 ° C (see. The preparation examples).

The 2-halo-4-heterocyclyl-nitrobenzenes of the gen my formula (V) are known and / or can by known methods are produced (cf. Pestic. Sci. 30 (1999), 259-274; EP-A-438209, EP-A-597360, US-A-5378681, WO-A-85/01939, WO-A-96/18618, WO-A-99/55668, Her position examples).

The further amino compounds of the general formula required as precursors (VI) are known synthetic chemicals.

Formula (III) provides a general definition of the 2-oxocarboxylic acid esters to be used as starting materials in the process according to the invention for the preparation of compounds of the general formula (I). In the general formula (III), R ² preferably has the meaning which has already been given above in connection with the description of the compounds of the general formula (I) according to the invention as preferred, particularly preferred or very particularly preferred for R ² ; R preferably represents alkyl having 1 to 4 carbon atoms, in particular methyl or ethyl.

The starting materials of the general formula (III) are known organic synthesis chemicals.

The process according to the invention for the preparation of the compounds of the general Formula (I) is preferably carried out using a reaction aid guided. The usual reaction aids are generally the usual ones  organic or organic bases or acid acceptors. For this ge preferably hear alkali metal or alkaline earth metal acetate, amide, carbonate, -hydrogen carbonates, -hydrides, -hydroxides or -alkanolates, such as Sodium, potassium or calcium acetate, lithium, sodium, potassium or calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, Sodium, potassium or calcium hydroxide, sodium or potassium methanolate, -ethanolate, -n- or -i-propanolate, -n-, -i-, -s- or -t-butanolate; continue too basic organic nitrogen compounds, such as trimethylamine, tri ethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethyl-aniline, N, N-dimethyl-benzylamine, pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-di methyl, 2,6-dimethyl, 3,4-dimethyl and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2.2.2] - octane (DABCO), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), or 1,8-diazabicyclo- [5.4.0] -undec-7-en (DBU).

The process according to the invention for the preparation of the compounds of the general Formula (I) is preferably carried out using a diluent leads. Inert organic solutions are the main diluents medium into consideration. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as Petrol, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, Cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or -diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles, like Acetonitrile, propionitrile or butyronitrile; Amides, such as N, N-dimethylformamide, N, N- Dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethyl phosphoric triamide; Esters such as methyl acetate or ethyl acetate, Sulfoxides, such as dimethyl sulfoxide, alcohols, such as methanol, ethanol, n- or i-  Propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether.

The reaction temperatures can be carried out when carrying out the process according to the invention Process can be varied over a wide range. Generally you work at temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.

The process according to the invention is generally carried out under normal pressure leads. However, it is also possible to increase the process according to the invention or reduced pressure - generally between 0.1 bar and 10 bar to lead.

To carry out the process according to the invention, the starting materials in generally used in approximately equimolar amounts. However, it is also possible Lich to use one of the components in a larger excess. The order settlement is generally in a suitable diluent in the presence carried out a reaction auxiliary and the reaction mixture is in general mine stirred for several hours at the required temperature. The Aufar processing is carried out according to customary methods (cf. the manufacturing examples).

The active compounds according to the invention can be used as defoliants, desiccants, kraut tabs killers and especially used as a weed killer. Weeds in the broadest sense are understood to mean all plants that are found in places grow where they are undesirable. Whether the substances according to the invention as total or Selective herbicides act essentially depends on the amount used.

The active compounds according to the invention can, for. B. ver used in the following plants:
Dicotyledon weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Gupopsisia, Euphorbia , Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsesb, Senania, Senecio , Sida, Sinapis, Solantun, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.

Dicotyledon cultures of the genera: Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia.

Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.

Monocot cultures of the genera: Allium, Pineapple, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea.

However, the use of the active compounds according to the invention is by no means limited to these Limited genres, but extends in the same way to others Plants.

The active compounds according to the invention are suitable depending on the con center for total weed control, e.g. B. on industrial and track systems and on Because of and places with and without tree cover. Likewise, the fiction moderate active substances for weed control in permanent crops, e.g. B. forest, ornamental wood,  Fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, Berry fruit and hop plants, on ornamental and sports turf and pastures as well for selective weed control in annual crops.

The compounds of formula (I) according to the invention show strong herbicidal activity solvency and a wide range of effects when used on and on the floor aerial parts of plants. To a certain extent, they are also suitable for selective use Control of monocot and dicot weeds in monocot and di cotyledon cultures, both pre-emergence and post-emergence.

The active compounds according to the invention can be used in certain concentrations or Application rates also to control animal pests and fungal or bacterial plant diseases can be used. You let yourself be given if also as intermediates or precursors for the synthesis of other active ingredients put.

According to the invention, all plants and parts of plants can be treated. Under Plants are understood here as all plants and plant populations desired and undesirable wild plants or crops (including natural cultivated plants). Cultivated plants can be plants that are caused by conventional breeding and optimization methods or by biotechnological and obtained genetic engineering methods or combinations of these methods can be, including the transgenic plants and including by Plant variety rights of protectable or non-protectable plant varieties. Under Plant parts are said to be all above-ground and underground parts and organs of the Plants such as sprout, leaf, flower and root are understood to be exemplary Leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well Roots, tubers and rhizomes are listed. One of the plant parts also crops and vegetative and generative propagation material, for example wise cuttings, tubers, rhizomes, offshoots and seeds.  

The treatment according to the invention of the plants and parts of plants with the active ingredients substances takes place directly or by influencing their surroundings, living space or Storage room according to the usual treatment methods, e.g. B. by diving, spraying, Evaporation, misting, scattering, spreading and in the case of propagation material, in particular especially in the case of seeds, still by wrapping them in one or more layers.

The active ingredients can be converted into the usual formulations, such as Solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated nated natural and synthetic substances as well as very fine encapsulation in polymers Fabrics.

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients with extenders, i.e. liquid solvents and / or solid Carriers, optionally using surface-active agents, thus emulsifiers and / or dispersants and / or foam-producing Means.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable Oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as Acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar Solvents such as dimethylformamide and dimethyl sulfoxide, and water.

As solid carriers come into question: B. ammonium salts and natural Ge stone powders such as kaolins, clays, talc, chalk, quartz, attapulgite, Mont morillonite or diatomaceous earth and synthetic rock powder, such as highly disperse  Silicic acid, aluminum oxide and silicates, as solid carriers for granules come into question: z. B. broken and fractionated natural rocks such as calcite, Marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, Coconut shells, corn cobs and tobacco stems; as emulsifying and / or foam Generating funds are possible: z. B. non-ionic and anionic emuls gators, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as dispersants come into question: z. B. lignin sulfite and Methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospho lipids such as cephalins and lecithins and synthetic phospholipids. Further Additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, Molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their formulations also in a mixture with known herbicides and / or with substances which Improve crop tolerance ("safeners") for weed control ver can be used, whereby ready formulations or tank mixes are possible. It So mixtures with weed control agents are also possible, which a or contain several known herbicides and a safener.  

Known herbicides are suitable for the mixtures, for example Acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), Ametryne, Amicarbazone, Amidochlor, Amidosulfuron, Anilofos, Asulam, Atrazine, Azafenidin, Azimsulfuron, Beflubutamid, Benazolin (-ethyl), Benfuresate, Bensulf uron (-methyl), bentazone, benzfendizone, benzobicyclone, benzofenap, benzoylprop (-ethyl), bialaphos, bifenox, bispyribac (-sodium), bromobutide, bromofenoxime, Bromoxynil, Butachlor, Butafenacil (-allyl), Butroxydim, Butylate, Cafenstrole, Caloxydim, carbetamides, carfentrazone (-ethyl), chloromethoxyfen, chloramben, Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, Chlorsulfuron, Chlortoluron, Cini don (-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop (-propargyl), Clomazone, Clomeprop, Clopyralid, Clopyrasulfuron (-methyl), Clor ansulam (methyl), cumyluron, cyanazine, cybutryne, cycloate, cyclosulfamuron, Cycloxydim, Cyhalofop (-butyl), 2,4-D, 2,4-DB, Desmedipham, Diallate, Dicamba, Dichloroprop (-P), diclofop (-methyl), diclosulam, diethatyl (-ethyl), difenzoquat, Diflufenican, Diflufenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimetha metryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, Diuron, Dymron, Epropodan, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron (-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanide, fenoxaprop (-P-ethyl), fentrazamide, flamprop (-isopropyl, -isopropyl-L, -methyl), flazasulf uron, florasulam, fluazifop (-P-butyl), fluazolate, flucarbazone (-sodium), flufen acet, flumetsulam, flumiclorac (-pentyl), flumioxazin, flumipropyn, flumetsulam, Fluometuron, fluorochloridone, fluoroglycofen (-ethyl), flupoxam, flupropacil, Flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl), fluridone, fluroxypyr (-butoxypropyl, -meptyl), Flurprimidol, Flurtamone, Fluthiacet (-methyl), Fluthi amides, fomesafen, foramsulfuron, glufosinate (-ammonium), glyphosate (-iso propylammonium), halosafen, haloxyfop (-ethoxyethyl, -P-methyl), hexazinones, Imazamethabenz (-methyl), Imazamethapyr, Imazamox, Imazapic, Imazapyr, Imaza quin, imazethapyr, imazosulfuron, iodosulfuron (-methyl, -sodium), ioxynil, iso propalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, Lactofen, Lenacil, Linuron, MCPA, Mecoprop, Mefenacet, Mesotrione, Metamitron,  Metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-) metola chlorine, metosulam, metoxuron, metribuzin, metsulfüron (-methyl), molinate, mono linuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orben carb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, Paraquat, pelargonic acid, pendimethalin, pendralin, pentoxazone, phenmedipham, Picolinafen, Piperophos, Pretilachlor, Primisulfuron (-methyl), Profluazol, Prometryn, Propachlor, Propanil, Propaquizafop, Propisochlor, Propoxycarbazone (-sodium), propyzamide, prosulfocarb, prosulfuron, pyraflufen (-ethyl), pyrazogyl, Pyrazolates, pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxime, pyributicarb, pyri date, pyridatol, pyriftalid, pyriminobac (methyl), pyrithiobac (sodium), quin chlorac, quinmerac, quinoclamine, quizalofop (-P-ethyl, -P-tefuryl), rimsulfuron, Sethoxydim, Simazine, Simetryn, Sulcotrione, Sulfentrazone, Sulfometuron (-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, ter buthylazine, Terbutryn, Thenylchlor, Thiafluamide, Thiazopyr, Thidiazimin, Thifen sulfuron (-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallates, triasulfuron, Tribenuron (-methyl), triclopyr, tridiphane, trifluralin, trifloxysulfuron, triflusulf uron (methyl), tritosulfuron.

A mixture with other known active ingredients, such as fungicides, Insecticides, acaricides, nematicides, bird repellants, plants nutrients and soil structure improvers are possible.

The active substances can be used as such, in the form of their formulations or in the form thereof application forms prepared by further dilution, such as ready-to-use Solutions, suspensions, emulsions, powders, pastes and granules are used become. The application is done in the usual way, e.g. B. by pouring, spraying, Spray, sprinkle.

The active compounds according to the invention can be used both before and after emergence of the plants are applied. They can also be ground into the soil before sowing be prepared.  

The amount of active ingredient used can vary over a wide range. she depends essentially on the type of effect desired. In general the application rates are between 1 g and 10 kg of active ingredient per hectare of soil area, preferably between 5 g and 5 kg per ha.

The manufacture and use of the active compounds according to the invention start out the following examples.

Manufacturing examples

example 1

A mixture of 4.0 g (10 mmol) of 4- (4-amino-2-fluoro-5-i-propylamino-phenyl) -1- difluoromethyl-2-methyl-1,2,4-triazolidine-3,5-dione, 2.3 g (20 mmol) pyructs Acid ethyl ester, 1.0 g (10 mmol) of triethylamine and 100 ml of toluene is used for 15 hours heated to boiling under reflux. After cooling to room temperature Water jet vacuum was concentrated, the residue was taken up in methylene chloride, washed with water, dried with sodium sulfate and filtered. From the filtrate the solvent is distilled off carefully under reduced pressure and as Residual crude product remaining by column chromatography (silica gel, Methylene chloride / ethyl acetate, vol. 9: 1) cleaned.

1.0 g (26% of theory) of 1-difluoromethyl-4- (7-fluoro-4-isopropyl-2-methyl-3-oxo-3,4-dihydro-6-quinoxaliny1) -2-methyl-1 are obtained, 2,4-triazolidine-3,5-dione as an amorphous product.
logP = 2.39 ^a)

Analogously to Example 1 and in accordance with the general description of the production process according to the invention, the compounds of the general formula (I) listed in Table 1 below can also be prepared, for example.

Table 1

Examples of the compounds of the formula (I)

The logP values given in Table 1 were determined in accordance with EEC Directive 79/831 Annex V. A8 by HPLC (High Performance Liquid Chromato graphy) on a phase inversion column (C 18). Temperature: 43 ° C.

(a) Eluents for determination in the acidic range: 0.1% aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with ^a) .

(b) eluents for determination in the neutral range: 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with ^b) .

The calibration was carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values using the Retention times through linear interpolation between two consecutive Alkanones).

The lambda max values were determined using the UV spectra from 200 nm to 400 nm the maxima of the chromatographic signals determined.  

Starting materials of formula (II)

Example (II-1)

16.2 g (0.29 mol) of iron are placed in 100 ml of acetic acid and at 20 ° C to 50 ° C with a solution of 21 g (58 mmol) of 1-difluoromethyl-2-methyl-4- (2-fluoro-4- nitro-5-i-propylamino-phenyl) -1,2,4-triazolidin-3,5-dione in a mixture of Drop 80 ml of acetic acid and 150 ml of ethyl acetate with stirring puts. The reaction mixture is stirred for 60 minutes, then with 150 ml Ethyl acetate and 90 ml of water diluted, the organic phase separated, covered with 1200 ml of water and by adding sodium bicarbonate adjusted to pH = 8. The organic phase is separated off with sodium sulfate dries and filtered. The filtrate is concentrated in a water jet vacuum, the back stood digested with n-hexane and the crystalline product obtained by suction isolated.

17.4 g (91% of theory) of 4- (4-amino-2-fluoro-5-i-propylamino-phenyl) are obtained. 1-difluoromethyl-2-methyl-1,2,4-triazolidine-3,5-dione with a melting point of 135 ° C.  

Precursors of formula (IV)

Example (IV-1)

A mixture of 4.0 g (12.4 mmol) of 1-difluoromethyl-2-methyl-4- (2,5-difluoro-4- nitro-phenyl) -1,2,4-triazolidine-3,5-dione, 0.80 g (13.7 mmol) of isopropylamine, 0.50 g (13.7 mmol) sodium hydride and 120 ml acetonitrile is refluxed for 4 hours heated to boiling. After cooling, the mixture is about the same volume Poured water and then shaken with methylene chloride. The organic phase is separated off, washed with water, dried with sodium sulfate and filtered. The solvent is carefully removed from the filtrate under reduced pressure distilled.

4.2 g (94% of theory) of 1-difluoromethyl-2-methyl-4- (2-fluoro-4-nitro-5- i-propylamino-phenyl) -1,2,4-triazolidine-3,5-dione as an amorphous product.  

Precursors of formula (V)

Example (V-1)

step 1

A solution of 54.1 g (455 mmol) of ethyl 1-methyl-carbazate in 100 ml Toluene is at room temperature (about 20 ° C) with stirring in a solution of 70.5 g (455 mmol) of 2,5-difluorophenyl isocyanate in 700 ml of toluene and the Reak tion mixture is then heated to boiling under reflux for 3 hours. After Ab cool to room temperature, shake with 300 ml of diethyl ether and that crystalline product isolated by suction.

85.3 g (69% of theory) of 2 - [[(2,5-difluorophenyl) amino] carbonyl] -1-methyl-carbazinic acid ethyl ester are obtained.
logP = 1.79 ^a)

Level 2

A mixture of 85 g (0.31 mol) of 2 - [[(2,5-difluorophenyl) amino] carbonyl] -1- ethyl methyl carbazate, 12.5 g (0.31 mol) sodium hydride and 1 liter aceto Nitrile is heated to boiling under reflux for 15 hours. After concentration, the The residue was taken up in 1 liter of water and shaken with diethyl ether. The aqueous phase is then concentrated. Acidified hydrochloric acid and the crystalline falling product isolated by suction.

58.8 g (83.5% of theory) of 1-methyl-4- (2,5-difluorophenyl) -1,2,4-triazolidine-3,5-dione are obtained.
logP = 0.82 ^a)

level 3

A mixture of 29 g (128 mmol) of 1-methyl-4- (2,5-difluorophenyl) -1,2,4-triazoli din-3,5-dione, 35 g (256 mmol) potassium carbonate and 300 ml N, N-dimethylformamide is stirred at 65 ° C for 60 minutes. Then at 65 ° C chlorodifluoromethane three Introduced into this mixture for hours. Then the reaction poured mixture into 2 liters of water, with conc. Acidified hydrochloric acid and that crystalline product isolated by suction.  

39.8 g (56% of theory) of 1-difluoromethyl-2-methyl-4- (2,5-difluorophenyl) -1,2,4-triazolidine-3,5-dione are obtained.
logP = 2.14 ^a)

Level 4

A solution of 5.0 g (18 mmol) of 1-difluoromethyl-2-methyl-4- (2,5-difluorophenyl) - 1,2,4-triazolidine-3,5-dione in 30 ml conc. Sulfuric acid is cooled to 0 ° C and then dropwise with stirring with 12 g (18 mmol) nitric acid (100%) puts. The reaction mixture is stirred for 90 minutes at 0 ° C., then on Poured ice water and the crystalline product isolated by suction.

4.4 g (76% of theory) of 1-difluoromethyl-2-methyl-4- (2,5-difluoro-4- nitro-phenyl) -1,2,4-triazolidine-3,5-dione.  

Examples of use Example A Pre-emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

Seeds of the test plants are sown in normal soil. After 24 hours the soil is sprayed with the active ingredient preparation so that the desired one Active ingredient quantity is applied per unit area. The drug concentration in the spray liquor is chosen so that in 1000 liters of water per hectare each desired amount of active ingredient is applied.

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control. It means:
0% = no effect (like untreated control)
100% = total annihilation

In this test, for example, the compounds according to Preparation Example 1 are shown and 2 very strong action against weeds.  

Example B Post emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

With the active ingredient preparation, test plants are sprayed, which have a height of 5 to 15 cm have so that the desired amounts of active ingredient per unit area be applied. The concentration of the spray liquor is chosen so that in 1000 l water / ha the desired amounts of active ingredient are applied.

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.

It means:
0% = no effect (like untreated control)
100% = total annihilation

In this test, for example, the compounds according to Preparation Example 1 are shown and 2 very strong action against weeds.

Claims (13)

1. Compounds of formula (I)
in which
R ^{1 represents} hydrogen or represents optionally substituted alkyl, alkylcarbonyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkenyl, alkenyloxy, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylthio, arylsulfinyl, arylsulfonyl or arylalkyl,
R ^{2 represents} hydrogen, cyano, halogen or optionally substituted alkyl,
R ^{3 represents} hydrogen or halogen, and
Z represents one of the heterocyclic groupings outlined below:
in which
Q ^{1 represents} O (oxygen) or S (sulfur),
Q ^{2 represents} O (oxygen) or S (sulfur),
R ⁴ for hydrogen, amino, nitro, cyano, carboxy, carbamoyl, thio carbamoyl, halogen, or for optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkoxycarbonyl, alkenyloxy, alkynyloxy, alkylthio, alkenylthio, alkynylthio, alkylamino, di alkylamino, Cycloalkyl or cycloalkylalkyl, and
R ^{5 represents} hydrogen, hydroxy, amino, cyano, or optionally substituted alkyl, alkoxy, alkoxycarbonyl, alkylamino, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl or phenyl alkyl,
where the compounds 7- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazol-3-yl) -6-fluoro-2 (1H) -quinoxalinone and 7- (4-difluoromethyl-4,5-dihydro -5-oxo-3-propyl-1H-1,2,4-triazol-1-yl) -6-fluoro-1- (2-propynyl) -2 (1H) -quinoxalinone are excluded. 2. Compounds of formula (I) according to claim 1, characterized in that
R ¹ for hydrogen, for each alkyl, alkylcarbonyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl, each optionally substituted by cyano, halogen, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkoxycarbonyl, each having 1 to 6 carbon atoms in the Alkyl groups, each for alkenyl, alkenyloxy or alkynyl optionally substituted by cyano or halogen, each having 3 to 6 carbon atoms, for each cycloalkyl or cycloalkylalkyl optionally substituted by cyano, halogen or C ₁ -C ₄ alkyl, each having 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part, or for aryl, arylthio, arylsulfinyl, arylsulfonyl or arylalkyl each having 6 or 10 carbon atoms in the aryl group and optionally 1 or 2 each optionally substituted by halogen and / or C ₁ -C ₄ alkyl Carbon atoms in the alkyl part,
R ^{2 represents} hydrogen, cyano, halogen or alkyl having 1 to 6 carbon atoms which is optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy,
R ^{3 represents} hydrogen, fluorine or chlorine,
Q ^{1 stands} for O (oxygen),
Q ^{2 stands} for O (oxygen),
R ⁴ for hydrogen, amino, nitro, cyano, carboxy, carbamoyl, thio carbamoyl, halogen, for alkyl with 1 to 6 carbon atoms optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy, for each alkenyl optionally substituted by halogen or Alkynyl each having 2 to 6 carbon atoms, for alkoxy or alkoxycarbonyl each having 1 to 6 carbon atoms in the alkyl groups, optionally substituted by cyano, halogen or C ₁ -C ₄ -alkoxy, for each alkenyloxy or alkynyloxy optionally substituted by halogen, each having 3 to 6 carbon atoms, for alkylthio optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy having 1 to 6 carbon atoms, for each optionally substituted by halogen, alkenylthio or alkynylthio each having 3 to 6 carbon atoms, for alkylamino or dialkyl amino each 1 to 6 carbon atoms in the alkyl groups, or for each optionally by cyano , Halogen or C ₁ -C ₄ alkyl substituted cycloalkyl or cycloalkylalkyl each having 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl part, and
R ⁵ for hydrogen, hydroxyl, amino, cyano, for alkyl, alkoxy, alkoxycarbonyl or alkylamino, each optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy, each having up to 6 carbon atoms, for alkenyl optionally substituted by halogen or Alkynyl each having up to 6 carbon atoms, for each cycloalkyl or cycloalkylalkyl optionally substituted by cyano, halogen or C ₁ -C ₄ -alkyl, each having 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl part, or for each phenyl or phenyl-C ₁ -C ₄ - optionally substituted by nitro, cyano, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -haloalkoxy alkyl stands. 3. Compounds of formula (I) according to claim 1 or 2, characterized in that
R ^{1 is} hydrogen, for each methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, acetyl, propionyl which is optionally substituted by fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl, n- or i-butyroyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylthio, ethylthio, n- or i Propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or propylsulfonyl for propenyl, butenyl, propenyloxy optionally substituted by fluorine and / or chlorine, Butenyloxy, propynyl or butynyl, for each cyclo propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl optionally substituted by fluorine, chlorine or methyl, or for phenyl, phenylthio, phenylsulfinyl, each optionally substituted by fluorine, chlorine or methyl , P henylsulfonyl or benzyl,
R ² for hydrogen, cyano, fluorine, chlorine, bromine, or for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl which is optionally substituted by fluorine, chlorine, methoxy or ethoxy stands,
R ⁴ for hydrogen, amino, nitro, cyano, carboxy, carbamoyl, thio carbamoyl, fluorine, chlorine, bromine, for each methyl, ethyl, n- or i-propyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, n -, i-, s- or t-butyl, for ethenyl, propenyl, butenyl, ethynyl, propynyl or butynyl, optionally substituted by fluorine, chlorine or bromine, for methoxy optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy , Ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxy carbonyl, n- or i-propoxycarbonyl, for propenyloxy, butenyloxy, propynyloxy or butinyloxy, each optionally substituted by fluorine, chlorine or bromine, for each optionally substituted by cyano, fluorine, chlorine, Methoxy or ethoxy substituted methylthio, ethyl thio, n- or i-propylthio, for propenylthio, butenylthio, propynylthio or butinylthio optionally substituted by fluorine, chlorine or bromine, for methylamino, ethylamino, n- or i- Propyl amino, dimethylamino or diethylamino, or cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, which is optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl, and
R ⁵ for hydrogen, hydroxy, amino, cyano, for each methyl, ethyl, n- or i-propyl, n-, i-, optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxy carbonyl, n- or i-propoxycarbonyl, methylamino, ethylamino, n- or i-propylamino, each optionally with fluorine, chlorine or bromine substituted propenyl, butenyl, propynyl or butynyl, for each cyclopropyl, cyclobutyl, cyclopentyl, cyclo hexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl optionally substituted by cyano, fluorine, chlorine, bromine, methyl or ethyl, or for each optionally by nitro, cyano , Fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, di fluoromethoxy or trifluoromethoxy substituted phenyl , Benzyl or phenylethyl. 4. Compounds of formula (I) according to any one of claims 1 to 3, characterized in that
R ¹ for hydrogen, for each methyl, ethyl, n- or i-propyl, optionally substituted by fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl, acetyl, propionyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, Ethoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, for propylene, butenyl, each optionally substituted by fluorine and / or chlorine, Propynyl or butynyl, represents cyclopropyl optionally substituted by fluorine, chlorine or methyl, or represents phenylthio, phenylsulfinyl, phenylsulfonyl or benzyl which is optionally substituted by chlorine or methyl,
R ^{2 represents} hydrogen, fluorine, chlorine, bromine, or methyl or ethyl which is in each case optionally substituted by fluorine and / or chlorine,
R ⁴ for hydrogen, cyano, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, for each methyl, ethyl, n- or i-propyl optionally substituted by fluorine, chlorine, methoxy or ethoxy, for each optionally by fluorine, chlorine or bromine substituted ethenyl, propenyl, ethynyl or propynyl, each for methoxy, ethoxy, n- or i-propoxy optionally substituted by fluorine, chlorine, methoxy or ethoxy, for propenyloxy, butenyloxy, propynyloxy or butynyloxy each optionally substituted by fluorine, chlorine or bromine, for methylthio, ethylthio, n- or i-propylthio optionally substituted by fluorine and / or chlorine, for propenyl thio or propinylthio optionally substituted by fluorine, chlorine or bromine, for methylamino, ethylamino, n- or i-propylamino, or for Dimethylamino stands, and
R ⁵ for hydrogen, for each methyl, ethyl, n- or i-propyl optionally substituted by fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, for propenyl, butenyl, propynyl each optionally substituted by fluorine and / or chlorine or butinyl, or for cyclopropyl or cyclopropylmethyl which is optionally substituted by fluorine, chlorine or methyl. 5. Compounds of formula (I) according to any one of claims 1 to 4, characterized in that
Z represents one of the heterocyclic groupings outlined below:
6. Compounds of formula (I) according to any one of claims 1 to 4, characterized in that
R ¹ for hydrogen, for in each case optionally substituted by fluorine, chlorine, methoxy or ethoxy methyl, ethyl, n- or i-propyl, for in each case optionally substituted by fluorine and / or chlorine propenyl, butenyl, propynyl or butinyl, or for optionally by Fluorine, chlorine or methyl substituted cyclopropyl,
R ^{2 represents} hydrogen or methyl optionally substituted by fluorine and / or chlorine,
R ^{3 represents} hydrogen, fluorine or chlorine,
Z represents the heterocyclic grouping outlined below:
in which
Q ^{1 represents} oxygen or sulfur,
Q ^{2 represents} oxygen or sulfur, and
R ^{5 represents} in each case optionally substituted by fluorine, chlorine, methoxy or ethoxy, methyl or ethyl, or represents in each case optionally substituted by fluorine and / or chlorine propenyl, butenyl, propynyl or butinyl, the two R ⁵ groups being identical or different in each individual case could be. 7. Compounds of formula (I) according to any one of claims 1 to 4, characterized in that
R ¹ for hydrogen, for in each case optionally substituted by fluorine, chlorine, methoxy or ethoxy methyl, ethyl, n- or i-propyl, for in each case optionally substituted by fluorine and / or chlorine propenyl, butenyl, propynyl or butinyl, or for optionally by Fluorine, chlorine or methyl substituted cyclopropyl,
R ^{2 represents} hydrogen or methyl optionally substituted by fluorine and / or chlorine,
R ^{3 represents} hydrogen, fluorine or chlorine,
Z represents the heterocyclic grouping outlined below:
in which
Q ^{1 represents} oxygen or sulfur,
Q ^{2 represents} oxygen or sulfur,
R ^{4-1 represents} cyano or methyl or ethyl which is optionally substituted by fluorine and / or chlorine,
R ^{4-2 represents} hydrogen, fluorine, chlorine, bromine or in each case methyl or ethyl which is optionally substituted by fluorine and / or chlorine, and
R ^{5 stands} for amino or for methyl or ethyl substituted in each case optionally by fluorine, chlorine, methoxy or ethoxy or for propenyl, butenyl, propynyl or butynyl which is optionally substituted by fluorine and / or chlorine. 8. A process for the preparation of compounds of the formula (I) according to any one of claims 1 to 7, characterized in that compounds of the formula (II)
in which
R ¹ , R ³ and Z have the meanings given in one of claims 1 to 7,
with 2-oxocarboxylic acid esters of the formula (III)
in which
R ^{2 has} the meaning given in one of claims 1 to 4, 6 or 7 and
R represents alkyl,
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
and, if appropriate, thereafter, in the usual way in the context of the definition of substituents, further chemical conversion reactions, such as, for. B. oxidation, reduction or substitution reactions. 9. Compounds of formula (II)
in which
R ¹ , R ³ and Z have the meanings given in one of claims 1 to 7. 10. Compounds of the formula (IV)
in which
R ¹ , R ³ and Z have the meanings given in one of claims 1 to 7. 11. Agent, characterized by the content of at least one compound of Formula (I) according to one of claims 1 to 7 and extenders and / or surfactants. 12. Use of at least one compound of the formula (I) according to one of the Claims 1 to 7 or an agent according to claim 11 for combating of unwanted plants.   13. A method for controlling unwanted plants, characterized characterized in that at least one compound of formula (I) according to one of claims 1 to 7 or an agent according to claim 11 to undesirable Plants and / or their habitat can act.