EP2225234A1 - Herbicidal compounds based on n-azinyl-n'-pyridylsulphonylureas - Google Patents

Abstract

What are described are compounds of the general formula (I) in which the particular substituents are each defined as specified in the description. The compounds of the general formula (I) can be used as herbicides and crop growth regulators.

Description

 description

Herbicidal compounds based on N-azinyl-N'-pyridylsulfonylureas

The present invention relates to N-azinyl-N'-pyridylsulfonylureas. Another

The present invention relates to mixtures of the aforementioned urea derivatives with other herbicides and / or safeners. Moreover, the present invention relates to processes for the preparation of the aforementioned urea derivatives and the use of these compounds as herbicides and plant growth regulators alone and in admixture with safeners and / or in admixture with other herbicides, in particular their use for plant control in specific crops or as crop protection regulators ,

It is already known that certain N-azinyl-N'-arylsulphonylureas are linked to simple open-chain hydroxamic acid ester groups in the aryl part, e.g. N- (4,6-dimethylpyrimidin-2-yl) -N '- (2-methoxyaminocarbonyl-phenylsulfonyl) -urea and the corresponding N42-n-octyloxyaminocycloconphenylsulfonyl) -urea have herbicidal properties (compare DE 3 516 435 A, EP 0173958 A, US 4,704,158).

Furthermore, certain herbicidally active N-azinyl-N'-hetarylsulfonylureas are known which are substituted in the hetaryl by O.N-dialkylated, also open-chain hydroxamic acid groups (see, EP 0 301 784 A); corresponding cyclic hydroxamic acid derivatives, however, have not previously been described.

The active compounds already known according to the abovementioned publications have disadvantages in their application, be it

(a) they have no or only insufficient herbicidal activity against harmful plants, (b) that only too low a spectrum of harmful plants can be fought, or

(c) that they have too low a selectivity in crops.

It is therefore desirable to provide alternative chemical agents based on corresponding urea derivatives which can be used as herbicides or plant growth regulators and which have certain advantages over prior art systems.

Thus, it is generally the object of the present invention to provide corresponding alternative urea derivatives which are used as herbicides or plant growth regulators, in particular with a satisfactory herbicidal activity against harmful plants, with a broad spectrum against harmful plants and / or with a high selectivity in crops can be. These urea derivatives should preferably have a better property profile, in particular a better herbicidal action against harmful plants, a broader spectrum of harmful plants and / or a higher selectivity in crops than the urea derivatives known from the prior art.

There have now been new N-azinyl-N'-pyridylsulfonylureas of the general formula (I),

in which V, W, X and Y are chosen such that one of these indices is nitrogen and the remaining indices are carbon atoms which unsubstituted or may be substituted with the illustrated R ⁸ ;

A is selected from the group consisting of nitrogen and CR ⁹ ; in which

R ^{9 is} selected from the group consisting of hydrogen, alkyl, halo and haloalkyl;

R ^{1 is} selected from the group consisting of hydrogen and an optionally substituted radical from the series alkyl, alkoxy, alkoxyalkyl,

Alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aralkyl and aryl;

R ^{2 is} selected from the group consisting of hydrogen, halogen, optionally substituted by halogen alkyl, optionally substituted by halogen alkoxy, optionally substituted by halogen

Alkylthio, optionally substituted by halogen alkylamino or optionally substituted by halogen dialkylamino;

R ^{3 is} selected from the group consisting of hydrogen, halogen, optionally halogen-substituted alkyl, optionally

Halogen-substituted alkoxy, optionally halogen-substituted alkylthio, optionally halogen-substituted alkylamino or optionally halogen-substituted dialkylamino,

R ⁴ to R ⁷ , each independently, are selected from the group consisting of hydrogen, halogen, cyano, alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl or dialkylaminocarbonyl, the radicals being unsubstituted or one or more radicals selected from the group consisting of halogen, cyano, alkoxy and

Alkylthio, or R ⁴ and R ⁶ or R ⁵ and R ^{7 is} an optionally interrupted by oxygen or sulfur alkylidene Represent group,

R ^{8 is} selected from the group consisting of hydrogen, halogen,

Cyano, thiocyanato, nitro, alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl,

Alkylaminocarbonyl, or dialkylaminocarbonyl, where the radicals may be unsubstituted or may carry one or more radicals selected from the group consisting of halogen, cyano, alkoxy and alkylthio. 0

Q is selected from the group consisting of oxygen or sulfur, in particular oxygen,

and salts of compounds of the formula (I). 5

A first embodiment of the present invention comprises compounds of the general formula (I) in which

A is preferably selected from the group consisting of nitrogen and CH.0

A second embodiment of the present invention comprises compounds of the general formula (I) in which

R ^{1 is} preferably selected from the group consisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, alkenyl and alkynyl, where the radicals may be unsubstituted or may carry one or more halogen atoms,

R ^{1 is} particularly preferably selected from the group consisting of

Hydrogen, methyl, ethyl, methoxy, methoxymethyl and ethoxy, o

R ^{1 is} particularly preferably selected from the group consisting of hydrogen and methyl, and

R ^{1 is} particularly preferably hydrogen.

A third embodiment of the present invention comprises compounds of the general formula (I) in which

R ^{2 is} preferably selected from the group consisting of hydrogen, halogen,

Alkyl, alkoxy, alkylthio, alkylamino and dialkylamino, where the radicals may be unsubstituted or may carry one or more halogen atoms,

R ^{2 is} particularly preferably selected from the group consisting of hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoroethoxy, difluoromethoxy, methylthio, methylamino and dimethylamino,

and

R ^{2 is} particularly preferably selected from the group consisting of hydrogen, chlorine, methyl, methoxy, methylthio and dimethylamino.

A fourth embodiment of the present invention comprises compounds of the general formula (I) in which

R ^{3 is} preferably selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, alkylthio, alkylamino and dialkylamino, where the radicals may be unsubstituted or may carry one or more halogen atoms,

R ^{3 is} particularly preferably selected from the group consisting of hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoroethoxy, difluoromethoxy, methylthio, methylamino or dimethylamino

and R ^{3 is} particularly preferably selected from the group consisting of methyl, methoxy and trifluoroethoxy.

A fifth embodiment of the present invention comprises compounds of the general formula (I) in which

R ⁴ to R ⁷ , each independently of one another, are preferably selected from the group consisting of hydrogen, halogen, cyano,, alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino,

Alkylcarbonyl, alkoxycarbony, alkylaminocarbonyl or dialkylamino, where the radicals may be unsubstituted or may carry one or more halogen atoms,

R ⁴ to R ⁷ , each independently of one another, are particularly preferably selected from the group consisting of hydrogen, fluorine, chlorine, cyano, methyl, ethyl, propyl, isopropyl, cyclopropyl, n-, i- s- or tertertert. Butyl, methylthio, methylsulfinyl, methylsulfonyl, methoxycarbonyl and ethoxycarbonyl, where the radicals may be unsubstituted or may carry one or more halogen atoms, and R ⁴ and R ⁶ or R ⁵ and R ^{7 is} a CH ₂ -CH ₂ -CH ₂ group, a CH ₂ -CH ₂ -CH ₂ -CH ₂ -GrUpPe, a CH ₂ -O-CH ₂ -group, CH ₂ -S-CH ₂ -group, a CH ₂ -O-CH ₂ -CH ₂ -group, represents a CH ₂ -CH ₂ -O-CH ₂ group or CH ₂ -CH ₂ -O-CH ₂ -CH ₂ group,

and

R ⁴ to R ⁷ , in each case independently of one another, are particularly preferably selected from the group consisting of hydrogen, methyl, ethyl, propyl and isopropyl, or R ⁴ and R ⁶ or R ⁵ and R ^{7 is} a CH ₂ -CH ₂ - CH ₂ -group, a CH ₂ -CH ₂ -CH ₂ -CH ₂ -group, a CH ₂ -O-CH ₂ -group, CH ₂ -S-CH ₂ - group, a CH ₂ -O-CH ₂ -CH ₂ group, a CH ₂ -CH ₂ -O-CH ₂ group or CH _{2 is} -CH ₂ -O-CH ₂ -CH ₂ -GrUpPe.

A sixth embodiment of the present invention comprises compounds of the general formula (I) in which

R ^{8 is} preferably selected from the group consisting of hydrogen, halogen, cyano, thiocyanato, nitro, alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl and dialkylaminocarbonyl, where the radicals may be unsubstituted or can carry one or more halogen atoms,

R ^{8 is} particularly preferably selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, cyano, methyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, methylamino and dimethylamino, where the radicals are unsubstituted may be or may carry one or more halogen atoms,

and

R ^{8 is} particularly preferably hydrogen.

Within the scope of these embodiments of the present invention, it is possible to arbitrarily combine the individual general, preferred and particularly preferred meanings for the substituents R ¹ to R ⁸ , Q and A. That is, compounds of the general formula (I) are encompassed by the present invention in which, for example, the substituent R ^{1 has} a preferred meaning and the substituents R ² to R ^{8 have} the general meaning or, for example, the substituent R ^{2 is} a preferred one Substituent R ^{3 has} a particularly preferred meaning, which and the other substituents have the general meaning. These individual combinations are not expressis verbis called for clarity, but are included within the scope of the present invention. The heterocycle of compounds of the general formula (I) directly connected to the dihydroisoxazole ring

has a nitrogen atom, ie, a group selected from the group consisting of V, W, X and Y, corresponds to a nitrogen atom. The remaining three radicals have the meaning of a carbon atom, wherein the carbon atoms may optionally be substituted by the radical R ⁸ .

In a particular embodiment of the present invention, the compound of the general formula (I) therefore has the following structure (Ia) in which V has the meaning of a nitrogen atom:

In a still further embodiment of the present invention, the compound of the general formula (I) therefore has the following structure (Ib), in which W has the meaning of a nitrogen atom:

In a still further embodiment of the present invention, the compound of the general formula (I) therefore has the following structure (Ic) in which X has the meaning of a nitrogen atom:

In a still further embodiment of the present invention, the compound of the general formula (I) therefore has the following structure (Id), in which Y has the meaning of a nitrogen atom:

In each of these four embodiments, the individual radicals R ¹ to R ⁸ , A and Q may be the general, preferred and particularly preferred ones defined above Have meanings.

Among these four embodiments, those compounds are particularly preferred according to the invention in which V, W and Y have the meaning of nitrogen (compounds of the general formula (Ia), (Ib), (Id)).

Particular preference is given to those compounds of the formula (I) in which V and Y have the meaning of nitrogen (compounds of the general formula (Ia), (Id))

Very particular preference is given to those compounds of the formula (I) in which V is nitrogen (compounds of the general formula (Ia)

In the compounds of the general formula (I), the substituents and radicals R ¹ to R ⁸ , Q and A have the above general, preferred, particularly preferred, especially preferred and in particular very preferred meanings.

The present invention preferably also provides the lithium, sodium, potassium, magnesium, calcium, ammonium, C 1 -C ₄ -alkyl ammonium, di- (C 1 -C ₄ -alkyl) -ammonium, tri- (C 1 -C ₄ -alkyl) ammonium Ci-C ₄ -alkyl) -ammonium, tetra- (-C ₄ alkyl) - ammonium-, tri _{(Ci-C4-alkyl)} sulfonium, C ₅ - or Cβ cycloalkyl-ammonium, di- ( -C ₂ - alkyl) -benzyl-ammonium, and tri (Ci-C ₂ alkyl) -benzyl-ammonium salts of compounds of formula (I) in which R ¹ to R ^8, A and Q have the general above preferred , Particularly preferred and particularly preferred meanings and which can be prepared by generally conventional methods.

The compounds of the general formula (I) can furthermore, if appropriate, be prepared by addition of a suitable inorganic or organic acid, such as, for example, HCl, HBr, H ₂ SO ₄ or HNO ₃ , but also oxalic acid or sulfonic acids to a basic group, such as, for example, As amino or alkylamino, salts. Suitable substituents which are present in deprotonated form, such as, for example, sulfonic acids or carboxylic acids, can form internal salts with groups which can themselves be protonated, such as amino groups. Salts can also be formed by having suitable substituents, such as. As sulfonic acids or carboxylic acids, the hydrogen is replaced by a cation suitable in the agrochemical field. These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or else ammonium salts, salts with organic amines or quaternary (quaternary) ammonium salts with cations of the formula [NRR ¹ R ¹¹ R ¹¹¹ J ⁺ , where R to R ¹ each independently represent an organic radical, in particular alkyl, aryl, aralkyl or alkylaryl.

In general formula (I) and all other formulas in the present invention, the radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino, alkylthio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylsulfinyl and haloalkylsulfonyl, as well as the corresponding unsaturated and / or substituted radicals in the Carbon skeleton in each case be straight-chain or branched. Unless specifically stated, these radicals are the lower carbon skeletons, e.g. with 1 to 6 C atoms, in particular 1 to 4 C atoms, or in unsaturated groups having 2 to 6 C atoms, in particular 2 to 4 C atoms, is preferred. Alkyl radicals, also in the composite meanings such as alkoxy, haloalkyl, etc., mean e.g. Methyl, ethyl, propyls such as n- or i-propyl, butyls such as n-, iso- or tert-butyl, pentyls such as n-pentyl, isopentyl or neo-pentyl, hexyls such as n-hexyl, i-hexyl, 3-methylpentyl, 2,2-dimethylbutyl or 2,3-dimethylbutyl, heptyls such as n-heptyl, 1-methylhexy or 1, 4-dimethylpentyl; Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; wherein at least one double bond or triple bond, preferably a double bond or triple bond is included. Alkenyl means e.g. Vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methyl-but-2-en-1-yl; Alkynyl means e.g. Ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl and 1-methyl-but-3-yn-1-yl.

Cycloalkyl groups are, for. Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,

Cycloheptyl and cyclooctyl. The cycloalkyl groups can occur in bi- or tri-cyclic form. When haloalkyl groups and haloalkyl radicals of haloalkoxy, haloalkylthio, haloalkenyl, haloalkynyl, etc. are indicated, these radicals are the lower carbon skeletons, e.g. B. with 1 to 6 carbon atoms or 2 to 6, in particular 1 to 4 carbon atoms or preferably 2 to 4 carbon atoms, and the corresponding unsaturated and / or substituted radicals in the carbon skeleton in each case straight-chain or branched. Examples are difluoromethyl, 2,2,2-trifluoroethyl, trifluoroallyl, 1-chloroprop-1-yl-3-yl. The term "halo" is used according to the invention synonymously with "halogen".

Alkylene groups in these residues are the lower carbon skeletons, e.g. B. with 1 to 10 C-atoms, in particular 1 to 6 C-atoms or preferably 2 to 4 C-atoms (unless otherwise defined), and the corresponding unsaturated and / or substituted radicals in the carbon skeleton, which are each straight-chain or branched can. Examples are methylene, ethylene, n- and i-propylene and n-, s-, i-, t-butylene.

Hydroxyalkyl groups in these residues are the lower carbon skeletons, e.g. B. with 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms, and the corresponding unsaturated and / or substituted radicals in the carbon skeleton, which may each be straight-chain or branched. Examples of these are 1, 2-dihydroxyethyl and 3-hydroxypropyl.

Halogen is fluorine, chlorine, bromine or iodine. Haloalkyl, alkenyl and alkynyl are halogen, preferably fluorine, chlorine or bromine, in particular by fluorine and / or chlorine, partially or completely substituted alkyl, alkenyl or alkynyl, for example monohaloalkyl (= monohaloalkyl), perhaloalkyl, CF ₃ , CHF ₂ , CH ₂ F, CF ₃ CF ₂ , CH ₂ FCHCl, CCI ₃ , CHCl ₂ , CH ₂ CH ₂ Cl; 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 Cl; the same applies to haloalkenyl and other halogen-substituted radicals.

Aryl means a mono-, bi- or polycyclic aromatic system, for example phenyl or naphthyl, preferably phenyl. Unless defined otherwise, the definition "substituted by one or more radicals" means one or more identical or different radicals.

The exemplified substituents ("first substituent level"), if they contain hydrocarbon-containing moieties, may optionally be further substituted there ("second substituent plane"), for example by one of the substituents as defined for the first substituent level. Corresponding further substituent levels are possible. Preferably, the term "substituted radical" includes only one or two substituent levels.

For radicals with C atoms, those having 1 to 6 C atoms, preferably 1 to 4 C atoms, in particular 1 or 2 C atoms, are preferred. Preference is generally given to substituents from the group halogen, for example fluorine and chlorine, (C 1 -C ₄ ) -alkyl, preferably methyl or ethyl, (C 1 -C ₄ ) -haloalkyl, preferably trifluoromethyl, (C 1 -C ₄ ) -alkoxy, preferably methoxy or ethoxy, (CrC ₄ ) haloalkoxy, nitro and cyano.

If an aryl radical is substituted, it may preferably be phenyl which is one or more times, preferably up to three times, by identical or different radicals from the group consisting of halogen, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) alkoxy, (C ₁ -C ₄₎ - haloalkyl, (CrC ₄₎ -haloalkoxy, cyano and nitro, for example o-, m- and p-tolyl, di-methylphenyle, 2-, 3- and 4-chlorophenyl , 2-, 3- and 4-trifluoromethyl and 2-, 3- and 4-trichloromethyl-phenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.

Depending on the nature and linkage of the substituents, the compounds of the general formula (I) can exist as stereoisomers. The possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers, Z and E isomers, are all encompassed by the formula (I).

If, for example, one or more alkenyl groups are present, diastereomers (Z and E isomers) can occur. For example, one or more Asymmetric carbon atoms present, so enantiomers and diastereomers can occur. Stereoisomers can be obtained from the resulting mixtures in the preparation by conventional separation methods. Similarly, stereoisomers can be selectively prepared by using stereoselective reactions using optically active sources and / or adjuvants. The invention thus also relates to all stereoisomers which comprises the general formula (I) but are not specified with their specific stereoform, and mixtures thereof.

Preparation of the compounds of the general formula (I) according to the invention

Another object of the present invention are methods for preparing corresponding compounds of general formula (I) and / or salts thereof.

In a first embodiment of the present invention, the compounds of the general formula (I) are prepared by reacting (4,5-dihydroisoxazol-3-yl) pyridine-sulfonamides of the general formula (II)

with a heterocyclic (thio) carbamate of the general formula (III)

wherein R ^{12 is} a substituted or unsubstituted (C ₁ -C ₂₀ ) hydrocarbon radical such as aryl or alkyl, preferably optionally substituted phenyl or optionally substituted (C ₁ -C ₄ ) -alkyl, and wherein V, W, X, Y, R ¹ to R ⁸ , Q and A are as defined above.

The compounds of general formula (II) can be obtained by reacting the compounds of general formula (X) with a chlorinating agent such as chlorine gas and ammonia solution according to the following reaction scheme:

The compounds of the general formula (X) can in turn be obtained by reacting compounds of the general formula (XI) with benzylmercaptan according to the following reaction scheme starting from the compounds of the general formula (XI):

The compounds of general formula (XI) can in turn be obtained by ring closure and construction of the heterocycle starting from compounds of general formula (XII) according to the following reaction scheme:

2-chloronicotinaldehyde oxime and substituted 2-chloronicotinaldehyde oximes are known, for example, from the prior art and can be prepared by methods known to the person skilled in the art (cf., WO 2003/090539, Helvetica Chimica Acta 59, 211-21 (1976), EP 0 012 158).

In a second embodiment of the present invention, the compounds of the general formula (I) are prepared by (4,5-

Dihydroisoxazol-3-yl) pyridine-sulfonic acid iso (thio) cyanates of the general formula (IV)

with an aminoheterocycle of the general formula (V)

wherein V, W, X, Y, R ¹ to R ⁸ , Q and A are as defined above.

In a third embodiment of the present invention, the compounds of general formula (I) are prepared by reacting sulfonyl (thio) carbamates of general formula (VI)

wherein R ¹² is a substituted or unsubstituted (CrC ₂ O) hydrocarbon radical such as aryl or alkyl, preferably optionally substituted phenyl or optionally substituted (DCO-alkyl, with an amino heterocycle of the general formula (V)

wherein V, W, X, Y, R ¹ to R ⁸ , Q and A are as defined above.

In a fourth embodiment of the present invention, the compounds of the general formula (I) are prepared by reacting (4,5-dihydroisoxazol-3-yl) pyridine-sulfonamides of the general formula (II)

with an iso (thio) cyanate of the general formula (VII)

optionally in the presence of a reaction auxiliary, wherein R ^{1 is} hydrogen and R ² to R ⁸ , V, W, X, Y, Q and A have the above significance.

In a fifth embodiment of the present invention, the production takes place the compounds of the general formula (I) in that an aminoheterocycle of the general formula (V)

initially base catalysed with a carbonic acid ester, e.g. Diphenyl carbonate, and the intermediate formed of the general formula (IM)

in a one-pot reaction with a (4,5-dihydroisoxazol-3-yl) pyridine-sulfonamide of the general formula (II)

(see JP1989221366), wherein V, W, X, Y, R) 1 ¹ ub: i'st R-) 8 ^ö , Q and A have the above significance.

In a sixth embodiment of the present invention, the preparation of the compounds of general formula (I) is carried out by (4,5- Dihydroisoxazol-3-yl) pyridine-sulfonic acid halides of the general formula (VIII)

wherein Hal is a halogen atom, preferably chlorine, with a (thio) cyanate, for example a metal (thio) cyanate, in particular an alkali metal (thio) cyanate, such as sodium (thio) cyanate, to a iso (thio) cyanate of Formula (IV)

or a solvated (stabilized) derivative thereof, and then with an amino heterocycle of the general formula (V)

wherein V, W, X, Y, R ¹ to R ⁸ , Q and A are as defined above.

In a seventh embodiment of the present invention, the production takes place of the compounds of the general formula (I) where Q = oxygen by reacting (4,5-dihydroisoxazol-3-yl) pyridine-sulfonic acid amides of the general formula (II)

with a heterocyclic bis-carbamate of the general formula (IX),

in which R ^{12 is} a substituted or unsubstituted (C 1 -C ₂ 0) -hydrocarbon radical such as aryl or alkyl, preferably optionally substituted phenyl or optionally substituted (dCO-alkyl, in the presence of a basic reaction auxiliary, wherein V, W, X, Y, R ¹ to R ⁸ and A have the above significance.

In an eighth embodiment of the present invention, the compounds of the general formula (I) are prepared by reacting (4,5-dihydroisoxazol-3-yl) pyridine-sulfonic acid amides of the general formula (II)

initially base catalysed with a carbonic acid ester, e.g. Diphenyl carbonate, and reacting the intermediate formed of the general formula (VI)

in a one-pot reaction with an aminoheterocycle of the general formula (V)

wherein V, W, X, Y, R ¹ to R ⁸ , Q and A are as defined above.

All of these processes lead to compounds of the general formula (I) according to the invention.

In each of the above-mentioned process variants, inert solvents are used in each case. Under inert solvents are used in the sense of the present This invention means solvents which are inert under the respective reaction conditions, ie in particular do not react with the educts, but need not be inert under any reaction conditions.

Examples of organic solvents which can be used in the present invention are aromatic or aliphatic solvents, such as benzene, toluene, xylene, mesitylene, hexane, heptane, octane, cyclohexane; aliphatic and aromatic halogenated hydrocarbons, such as methylene chloride, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, ethers, such as diethyl ether, dibutyl ether, diisobutyl ether, methyl tert-butyl ether,

Isopropyl ethyl ether, diisopropyl ether, tetrahydrofuran, and dioxane; furthermore also dimethyl sulfoxide, and acid amide derivatives, such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone, and also carboxylic esters, such as ethyl acetate, or else diglyme, dimethyl glycol; Nitriles such as acetonitrile, propionitrile or butyronitrile and ketones such as acetone, methyl ethyl ketone or

Cyclohexanone. Particularly preferred are toluene, xylene, dichlorobenzene, chlorobenzene, acetonitrile, acetone, butyronitrile or ethyl acetate. However, the present invention is not limited to the solvents exemplified above.

The reaction temperature at which the reactions according to the above embodiments can be carried out can vary within wide ranges. For example, the reactions at a temperature of 0 to 100 ⁰ C, preferably 20 to 70 ° C, are performed.

The implementations of the present invention are generally disclosed

Normal pressure performed. However, it is also possible to work under elevated pressure or reduced pressure, generally between 0.1 bar and 10 bar.

If appropriate, the processes for preparing the N-azinyl-N'-pyridylsulfonylureas of the general formula (I) according to the invention are carried out in the presence of a basic reaction auxiliary. As such, all customary inorganic or organic bases are suitable. These include, for example, alkali metal or alkaline earth metal hydrides, hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates, such as lithium, sodium, potassium or calcium hydride, lithium, sodium or potassium amide, sodium or Potassium methoxide, sodium or potassium ethylate, sodium or potassium propylate, aluminum isopropylate, sodium or potassium tert-butoxide, sodium or potassium hydroxide, ammonium hydroxide, sodium, potassium or calcium acetate, ammonium acetate, sodium, potassium or calcium carbonate, ammonium carbonate , Sodium or potassium bicarbonate, as well as basic organic

Nitrogen compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldiisopropylamine, NN-dimethylcyclohexylamine, dicyclohexylamine, ethyldicyclohexylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, 2-methyl, 3-methyl and 4-methylpyridine , 2,4-dimethyl, 2,6-dimethyl, 3,4-dimethyl and 3,5-dimethylpyridine, 5-ethyl-2-methylpyridine, N-methylpyridine, 4- (N ₁ N-

Dimethylamino) -pyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

Intermediate

Another object of the present invention are also certain intermediates, which are run in accordance with the synthetic routes shown above in the preparation of the compounds of general formula (I) according to the invention.

Accordingly, in a first embodiment of the intermediates, the present invention also relates to compounds of the general formula (II)

in which the radicals V, W, X, Y, R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 have} the general, preferred and particularly preferred meanings given above.

Another object of the present invention are in a second embodiment of the intermediates and compounds of general formula (IV)

in which the radicals V, W, X, Y, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and Q have the general, preferred and particularly preferred meanings given above.

Another object of the present invention are in a third

Embodiment of the intermediates also compounds of the general formula (X)

in which the radicals V, W, X ₁ Y, R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 have} the general, preferred and particularly preferred meanings given above.

A further subject matter of the present invention, in a fourth embodiment of the intermediates, is also compounds of the general formula (XI)

in which the radicals V, W, X, Y, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and Hal have the general, preferred and particularly preferred meanings given above.

A further subject matter of the present invention, in a fifth embodiment of the intermediates, is also compounds of the general formula (VIII)

in which the radicals V, W, X, Y, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and Hal have the general, preferred and particularly preferred meanings given above.

A further subject matter of the present invention, in a sixth embodiment of the intermediates, is also compounds of the general formula (VI)

in which the radicals V, W, X, Y, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ R ¹² and Q have the general, preferred and particularly preferred meanings given above.

Libraries of compounds of formula (I) and / or their salts, which can be synthesized after the above reactions, can also be prepared in a parallelized manner, which can be done in a manual, partially automated or fully automated manner. It is possible, for example, to automate the reaction procedure, the work-up or the purification of the products or intermediates. Overall, this is understood to mean a procedure as described, for example, by D. Tiebes in Combinatorial Chemistry - Synthesis, Analysis, Screening (publisher Günther Jung), Verlag Wiley 1999, on pages 1 to 34.

For parallelized reaction performance and work-up a number of commercially available devices may be used, for example, Calypso reaction blocks (Caylpso reaction blocks) from Barnstead International, Dubuque, Iowa 52004-0797, USA or reaction stations from Radleys, Shirehill, Saffron Waiden, Essex, CB 11 3AZ, England or MultiPROBE Automated Workstations of Perkin Elmar, Waltham, Massachusetts 02451, USA. For the parallelized purification of compounds of the general formula (I) and their salts or of the intermediates obtained during the preparation, inter alia

Chromatographieapparaturen available, for example, the company ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, United States.

The listed equipment leads to a modular procedure, in which the individual work steps are automated, but between the work steps, manual operations must be performed. This can be circumvented by the use of partially or fully integrated automation systems in which the respective automation modules are operated, for example, by robots. Such automation systems can be obtained, for example, from Caliper, Hopkinton, MA 01748, USA.

The implementation of single or multiple synthetic steps can be supported by the use of polymer-supported reagents / Scavanger resins. A number of experimental protocols are described in the literature, for example in ChemFiles, Vol. 1, Polymer-Supported Scavengers and Reagents for Solution Phase Synthesis (Sigma-Aldrich).

In addition to the methods described herein, the preparation of compounds of general formula (I) and their salts can be carried out fully or partially by solid-phase assisted methods. For this purpose, individual intermediates or all intermediates of the synthesis or adapted for the appropriate approach synthesis are bound to a synthetic resin. Solid-phase assisted synthesis methods are well described in the literature, eg Barry A. Bunin in "The Combinatorial Index", Academic Press, 1998 and Combinatorial Chemistry - Synthesis, Analysis, Screening (published by Günther Jung), published by Wiley, 1999. Use Solid-phase assisted synthesis methods allow a series of protocols known from the literature, which in turn can be performed manually or automatically. For example, the "teabag method" (Houghten, US 4,631,211; Houghten et al., Proc. Natl. Acad. Sei., 1985, 82, 5131-5135) can be used with products of IRORI, 11149 North Torrey Pines Road, La JoIIa, CA 92037, USA. The automation of solid phase assisted parallel synthesis succeeds, for example, by equipment of the companies Argonaut Technologies, Inc., 887 Industrial Road, San Carlos, CA 94070, USA or MultiSynTech GmbH, Wullener Feld 4, 58454 Wirten, Germany. The reactions can also be carried out, for example, by means of IRORI technology in microreactors from Nexus Biosystems, 12140 Community Road, Poway, CA92064, USA.

Both solid and liquid phases can be supported by the implementation of single or multiple synthetic steps through the use of microwave technology. A number of experimental protocols are described in the specialist literature, for example in Microwaves in Organic and Medicinal Chemistry (publishers C. O. Kappe and A. Stadler), Verlag Wiley, 2005.

The preparation according to the methods described herein provides compounds of formula (I) and their salts in the form of substance collections called libraries. The present invention also provides libraries containing at least two compounds of formula (I) and their salts.

Another object of the invention is due to the herbicidal property of the compounds of general formula (I), the use of the compounds of general formula (I) according to the invention as herbicides for controlling harmful plants.

Another object of the invention is due to the herbicidal property of the compounds of general formula (I), the use of the compounds of general formula (I) according to the invention as herbicides for controlling harmful plants.

With the external conditions such as temperature, humidity, the type of herbicide used, among other things, the required application rate of the compounds of the formula (I) varies. It can vary within wide limits, for example between 0.001 and 10000 g / ha or more of active substance, but is preferably between 0.5 and 5000 g / ha, preferably between 0.5 and 1000 g / ha and most preferably between 0.5 and 500 g / ha.

The compounds of the formula (I) according to the invention and their salts, also referred to below together as compounds of the formula (I), have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. Even difficult to control perennial weeds, which expel from rhizomes, rhizomes or other permanent organs, are well detected by the active ingredients. It does not matter whether the substances are applied in the pre-sowing, pre-emergence or postemergence process.

In the individual examples may be mentioned some representatives of the monocotyledonous and dicotyledonous weed flora, which can be controlled by the compounds of the general formula (I) according to the invention, without the intention of limiting them to certain species.

On the side of monocotyledonous weed species, for. B. Agrostis, Alopecurus, Apera, Avena, Brachicaria, Bromus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Festuca, Fimbristylis, ischemic, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Sagittaria, Scirpus, Setaria,

Sphenoclea, as well as Cyperusarten mainly from the annuelle group and on the part of the perennial species Agropyron, Cynodon, Imperata and Sorghum and also perennial Cyperusarten well grasped.

In dicotyledonous weed species, the spectrum of activity extends to species such. Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida on the annall side as well as Convolvulus, Cirsium, Rumex and Artemisia in perennial weeds. In addition, herbicidal activity in dicotyledonous weeds such as Ambrosia, Anthemis, Carduus, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Emex, Galeopsis, Galinsoga,

Lepidium, Lindernia, Papaver, Portlaca, Polygonum, Ranunculus, Rorippa, Rotala, Seneceio, Sesbania, Solanum, Sonchus, Taraxacum, Trifolium, Urtica and Xanthium observed.

If the compounds of the general formula (I) according to the invention are applied to the surface of the earth prior to germination, either the emergence of the weed seedlings is completely prevented or the weeds grow up to the cotyledon stage, but then cease their growth and finally die after the lapse of three to three weeks four weeks completely off.

When the active compounds of the general formula (I) are applied to the green plant parts in the postemergence process, a drastic growth arrest also occurs very rapidly after the treatment and the weed plants remain in the growth stage present at the time of application or die completely after a certain time, so that This way, a weed competition that is harmful to cultivated plants is eliminated very early and sustainably.

Although the compounds of general formula (I) according to the invention have excellent herbicidal activity against mono- and dicotyledonous weeds, crops of economically important crops such. As wheat, barley, rye, rice, corn, sugar beet, cotton, oilseed rape and soy only insignificant or not at all damaged. For these reasons, the present compounds are very well suited for the selective control of undesired plant growth in agricultural crops.

In addition, the substances of the general formula (I) according to the invention have excellent growth-regulatory properties in crop plants. They regulate the plant's metabolism and can thus be used to specifically influence plant constituents and to facilitate harvesting, such as, for example, B. be used by triggering desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of unwanted vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous cultures as it reduces or completely eliminates storage can be.

Due to their herbicidal and plant growth regulatory properties, the active compounds can also be used for controlling harmful plants in crops of known or yet to be developed genetically modified plants. The transgenic plants are usually characterized by particular advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.

Other special properties relate to z. B. the crop in terms of quantity, quality, shelf life, composition and special ingredients. Thus, transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known. Other special properties may be in a tolerance or resistance to abiotic stressors z. As heat, cold, drought, salt and ultraviolet radiation.

Preference is given to the use of the compounds of the general formula (I) according to the invention or salts thereof in economically important transgenic crops of useful and ornamental plants, eg. As cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn or cultures of sugar beet, cotton, soy, rape, potato, tomato, pea and other vegetables.

Preferably, the compounds of general formula (I) can be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made genetically resistant.

Conventional ways of producing new plants which have modified properties in comparison to previously occurring plants consist, for example, in classical breeding methods and the production of mutants. Alternatively, new plants with altered properties can be generated by means of genetic engineering methods (see, for example, EP 0221044, EP 0131624). For example, genetic modifications of crop plants have been described in several cases for the purpose of modifying the starch synthesized in the plants (eg WO 92/011376, WO 92/014827, US Pat.

WO 91/019806), transgenic crops which are resistant to certain glufosinate-type herbicides (cf., for example, EP 0242236, EP 0242246) or glyphosate (WO 92/000377) or the sulfonylureas (EP 0257993, US Pat. No. 5,013,659), Transgenic crops, such as cotton, with the ability to produce Bacillus thuringiensis toxins (Bt toxins), which make the plants resistant to certain pests (EP 0142924, EP 0193259). Transgenic crop plants with modified fatty acid composition (WO 91/013972). genetically modified crops with new content or secondary substances z. B. new phytoalexins that cause increased disease resistance (EP 0309862, EP 0464461) genetically modified plants with reduced photorespiration, which have higher yields and higher stress tolerance (EP 0305398) transgenic crops, the pharmaceutically or diagnostically important

Produce proteins ("molecular pharming") transgenic crops that are characterized by higher yields or better quality - transgenic crops which are characterized by a combination of, for example, the above-mentioned new properties ("gene stacking")

Numerous molecular biology techniques that can be used to produce novel transgenic plants with altered properties are known in principle; see, for. BI Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg, or Christou, "Trends in Plant Science" 1 (1996) 423-431). For such genetic engineering, nucleic acid molecules can be introduced into plasmids that allow mutagenesis or sequence alteration by recombination of DNA sequences. With the help of standard methods z. For example, base substitutions are made, partial sequences are removed, or natural or synthetic sequences are added. For the connection of the DNA fragments with one another adapters or linkers can be attached to the fragments, see, for example, US Pat. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. CoId Spring Harbor Laboratory Press, ColD Spring Harbor, NY; or Winnacker "Genes and Clones", VCH Weinheim 2nd edition 1996

The production of plant cells having 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 obtain a cosuppression effect or the expression of at least one appropriately engineered ribozyme which specifically cleaves transcripts of the above gene product.

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

In the expression of nucleic acid molecules in plants, the synthesized protein may be located in any compartment of the plant cell. But to achieve the localization in a particular compartment, z. For example, the coding region can be linked to DNA sequences that ensure localization in a particular compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad., U.S.A. 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). The expression of the nucleic acid molecules can also take place in the organelles of the plant cells.

The transgenic plant cells can be regenerated to whole plants by known techniques. The transgenic plants may, in principle, be plants of any plant species, that is, both monocotyledonous and dicotyledonous plants.

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

Preferably, the compounds of the general formula (I) according to the invention can be used in transgenic cultures which are resistant to growth substances, such. B. Dicamba or against herbicides, the essential plant enzymes, eg. As acetolactate synthases (ALS), EPSP synthases, glutamine synthase (GS) or Hydoxyphenylpyruvat dioxygenases (HPPD) inhibit or herbicides from the group of sulfonylureas, the glyphosate, glufosinate or benzoylisoxazole and analogues, are resistant.

In the application of the active compounds of the general formula (I) according to the invention in transgenic cultures, in addition to the effects observed in other cultures against harmful plants, effects which are specific for the application in the respective transgenic culture often occur, for example a modified or specially extended weed spectrum, that can be combated, changed application rates, which can be used for the application, preferably good compatibility with the herbicides to which the transgenic culture is resistant, and influencing the growth and yield of the transgenic crops.

The invention therefore also relates to the use of Compounds of the general formula (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.

The compounds of the general formula (I) can be formulated in various ways, depending on which biological and / or chemical-physical parameters are predetermined. Possible formulation options are, for example: wettable powder (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions , Suspension concentrates (SC), oil or water based dispersions, oil miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for litter 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-Kuchler, "Chemische Technologie", Volume 7, C. Hanser Verlag Munich, 4th ed. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY , 1973; K. Martens, "Spray Drying" Handbook, 3rd ed. 1979, G. Goodwin Ltd. London.

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 Insecticides Dust Diluents and Carriers", 2nd ed., Darland Books, Caldwell N.J., H.v. 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; Schonfeldt, "Grenzwerte-Aktiv Ethylene Oxide Adducts", Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Kuchler, "Chemische Technologie", Volume 7 , C. Hanser Verlag Munich, 4th ed. 1986. On the basis of these formulations can also be combinations with others Pesticide-active substances, such. As insecticides, acaricides, herbicides, fungicides, and with safeners, fertilizers and / or growth regulators produce, for. B. in the form of a finished formulation or as a tank mix.

Injection powders are preparations which are uniformly dispersible in water and, in addition to the active ingredient, also contain ionic and / or nonionic surfactants (wetting agent, dispersant) in addition to a diluent or inert substance, eg. Example, polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, 2,2'-dinaphthylmethane-6,6 ^I -disulfonsaures sodium, dibutylnaphthalene-sulfonic acid sodium or oleoylmethyltaurinsaures sodium. To prepare the wettable powders, the herbicidal active compounds are finely ground, for example, in customary apparatus such as hammer mills, blower mills and air-jet mills and mixed simultaneously or subsequently with the formulation auxiliaries.

Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent z. B. butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers). Examples of emulsifiers which may be used are: alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide / ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as e.g. B. sorbitan fatty acid esters or Polyoxethylenensorbitanester such. B. Polyoxyethylensorbitanfettsäureester.

Dusts are obtained by grinding the active ingredient with finely divided solids, eg. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth. Suspension concentrates may be water or oil based. You can, for example, by wet grinding using commercially available bead mills and optionally added surfactants, such as. B. are already listed above in the other formulation types, are produced. 5

Emulsions, eg. As oil-in-water emulsions (EW) can be, for example, by means of stirring, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as. B. are already listed above in the other formulation types, produce.0

Granules can be prepared either by spraying the active ingredient on adsorptive, granulated inert material or by applying active substance concentrates by means of adhesives, for. As polyvinyl alcohol, polyacrylic acid sodium or mineral oils, on the surface of carriers such as sand, 5 kaolinites or granulated inert material. It is also possible to granulate suitable active ingredients in the manner customary for the production of fertilizer granules, if desired in admixture with fertilizers.

Water-dispersible granules are usually by the usual Verfahren0 such as spray drying, fluidized bed granulation, plate granulation, mixing with

High-speed mixers and extrusion produced without solid inert material.

For the preparation of plate, fluidized bed, extruder and spray granules see, for. B.

Process in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J.E.

Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff; "Perry's! 5 Chemical Engineer's Handbook," 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.

For more details on pesticide formulation see, e.g. B.G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., O Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

The agrochemical preparations usually contain 0.1 to 99 wt .-%, in particular 0.1 to 95 wt .-%, active ingredient of the formula (I).

In wettable powders, the active ingredient concentration z. B. about 10 to 90 wt .-%, the remainder to 100 wt .-% consists of conventional formulation components. For emulsifiable concentrates, the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%. Dusty formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% of active ingredient. In the case of water-dispersible granules, the active ingredient content depends, in part, on whether the active compound is liquid or solid and which granulating aids, fillers and the like are present. be used. In the case of the water-dispersible granules, the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

In addition, the active substance formulations mentioned optionally contain the customary adhesion, wetting, dispersing, emulsifying, penetrating, preserving, antifreezing and solvent-based agents, fillers, carriers and colorants, defoamers, evaporation inhibitors and the pH value and Viscosity-influencing agent.

The compounds of the general formula (I) or salts thereof can be used as such or in the form of their preparations (formulations) with other pesticidal substances, such. As insecticides, acaricides, nematicides, herbicides, fungicides, safeners, fertilizers and / or growth regulators can be used in combination, eg. B. as a ready-made formulation or as tank mixes. As a combination partner for the active compounds of the general formula (I) according to the invention in mixed formulations or in the tank mix, for example, known active compounds which are based on an inhibition of, for example

Acetolactate synthase, acetyl coenzyme A carboxylase, PS I, PS II, HPPDO, phytoene desaturase, protoporphyrinogen oxidase, glutamine synthetase, 5

Enolpyruvylshikimat-3-phosphate synthetase or cellulose biosynthesis are used. Such compounds and other usable compounds with teilwiese unknown or other mechanism of action are z. In Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 11th edition 1997 (hereinafter also "PM" for short) and 12th edition 2000, The British Crop Protection Council and the Royal Soc. of Chemistry (publisher) and literature cited therein. As literature-known herbicides, which can be combined with the compounds of formula (I), z. The following compounds are to be mentioned (note: the compounds are denoted either by the "common name" according to the International Organization for Standardization (ISO) or by the chemical name, if appropriate together with a customary code number):

acetochlor; acifluorfen (-sodium); aclonifen; AKH 7088, i. [[[1 - [5- [2-chloro-4-

(trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidene] amino] oxy] acetic acid and acetic acid methyl ester; acrolein; alachlor; alloxydim (-sodium); ametryn; amicarbazone, amidochlor, amidosulfuron; aminopyralid, amitrole; AMS, i. ammonium sulfamate; anilofos; asulam; atraton; atrazine; azafenidin, azimsulfuron

(DPX-A8947); aziprotryn; barban; BAS 516H, i. 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; BCPC; beflubutamide, benazoline (-ethyl); benfluralin; benfuresate; bensulfuron (-methyl); bensulide; bentazone; benzfendizone; benzobicyclone, benzofenap; benzofluor; benzoylprop (-ethyl); benzthiazuron; bifenox; bialaphos; bifenox; bispyribac (-sodium), borax; bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butafenacil, butamifos; butenachlor; buthidazole; butraline; butroxydim, butylate; cacodylic acid; calcium chlorates; cafenstrole (CH-900); carbetamide; carfentrazone (-ethyl); caloxydim,

CDAA, ie 2-chloro-N, N-di-2-propenylacetamide; CDEC, ie diethyldithiocarbamic acid 2-chloroallyl ester; chlorofluorol (-methyl); chlomethoxyfen; clethodim; clomeprop; chloramben; chlorazifop-butyl, chloromesulon; chlorbromuron; chlorbufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron (-ethyl); chloroacetic acid; chlornitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlorthal (dimethyl); chlorthiamid; chlorotoluron, cinidone (-methyl and -ethyl), cinmethylin; cinosulfuron; cisanilide; clefoxydim, clethodim; clodinafop and its ester derivatives (eg clodinafop-propargyl); clomazone; clomeprop; cloproxydim; clopyralid; clopyrasulfuron (-methyl); cloransulam (-methyl), cresol; cumyluron (JC 940); cyanamide; cyanazine; cycloate; Cyclosulfamuron (AC 104); cycloxydim; cycluron; cyhalofop and its ester derivatives (eg butyl ester, DEH

112); cyperquat; cyprazine; cyprazole; daimuron; 2,4-D, 2,4-DB, 3,4-DA, 3,4-DB,

2,4-DEB, dalapon; dazomed; desmedipham; Desmetryn; di-allate; dicamba; dichlobenil; ortho-dichlorobenzene; para-dichlorobenzene; dichloφrop; dichlorprop-

P; diclofop and its esters such as diclofop-methyl; diclosulam, diethatyl (-ethyl); difenoxuron; difenzoquat; difenzoquat methylsulphate; diflufenican; diflufenzopyr, dimefuron; dimepiperate, dimethachlor; dimethametryn; dimethenamid (SAN-582H); dimethenamid-P; dimethazone, dimexyflam, dimethipine; di-methylarsinic acid; dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; diquat-dibromide; dithiopyr; diuron; DNOC; 3,4-DP; DSMA; EBEP; eglinazine-ethyl; EL77, i.

5-cyano-1- (1, 1-dimethylethyl) -N-methyl-1H-pyrazole-4-carboxamide; endothal; epoprodan, EPTC; esprocarb; ethalfluralin; ethametsulfuron (-methyl); Ethidimuron; ethiozin; ethofumesate; ethoxyfen and its esters (eg ethyl ester, HN-252); ethoxysulfuron, etobenzanide (HW 52); F5231, ie N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo-1H-tetrazol-1-yl] -phenyl] -ethanesulfonamide; fenoprop; fenoxan, fenoxaprop and fenoxaprop-P and their esters, eg. Fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim; fentrazamide, fenuron; -ferrous sulphate; flamprop (-methyl or -isopropyl or -isopropyl-L); flazasulfuron; floazulate, florasulam, fluazifop and fluazifop-P and their esters, e.g. Fluazifop-butyl and fluazifop-p-butyl; fluazolate; flucarbazone (-sodium), flucetosulfuron; fluchloralin; flufenacet; flufenpyr (-ethyl); flumetsulam; flumeturon; flumiclorac (pentyl), flumioxazine (S-482); flumipropyn; fluometuron, fluorochloridone, fluorodifen; fluoroglycofen (-ethyl); flupoxam (KNW-739); flupropacil (UBIC-4243); flupropanate, flupyrsulfuron (-methyl or -sodium), flurenol (-butyl), fluridone; flurochloridone; fluroxypyr (-meptyl); fluφrimidol; flurtamone; fluthiacet (-methyl) (KIH-9201); fluthiamide; fomesafen; foramsulfuron; fosamine; furyloxyfen; glufosinate (- ammonium); glyphosate (-isopropylammonium); halo safen; halosulfuron (-methyl) and its esters (eg, methyl ester, NC-319); haloxyfop and its esters; haloxyfop-P (= R-haloxyfop) and its esters; HC-252; hexazinone; imazamethabenz (-methyl); imazapyr; imazaquin and salts such as the ammonium salt; imazamethapyr, imazamox, imazapic, imazethamethapyr; imazethapyr; imazosulfuron; indanofan, iodomethane; iodosulfuron (methylsodium); ioxynil; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxachlortole, isoxaflutole, isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MAA; MUMMY; MCPA; MCPA-2-ethylhexyl; MCPA-thioethyl; MCPB; mecoprop; mecoprop-P; mefenacet; mefluidide; mesosulfuron (-methyl); mesotrione, metamifop; metamitron; metazachlor; methabenzthiazuron; metham; methazole; methoxyphenone; methylarsonic acid; methyldymron; methyl isothiocyanate; metabenzuron, metamifop; methobenzuron; metobromuron; (Alpha-) metolachlor;

S-metolachlor; metosulam (XRD 511); metoxuron; metribuzin; metsulfuron-methyl;

MK-616; MH; molinate; monalide; monocarbamide dihydrogen sulfates; monolinuron; monuron; monosulfuron; MSMA; MT 128, i. 6-chloro-N- (3-chloro-2-propenyl) -5-methyl-N-phenyl-3-pyridazineamine; MT 5950, i. N- [3-chloro-4- (1-methylethyl) phenyl] -2-methylpentanamide; naproanilide; napropamide; naptalam; NC 310, i.

4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazol; neburon; nicosulfuron; nipyraclophen; nitralin; nitrofen; nitrofluorfen; nonanoic acid; norflurazon; Oleic acid (fatty acid); orbencarb; orthosulfamuron; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxasulfuron, oxaziclomefone, oxyfluorfen; paraquat; paraquat-dichloride; pebulate; pelargonic acid, pendimethalin; penoxsulam; pentachlorophenol; Pentanochlor; pentoxazone, perfluidone; phenisopham; phenmedipham (ethyl); pethoxamid; picloram; picolinafen, pinoxaden, piperophos; piributicarb; pirifenopbutyl; pretilachlor; primisulfuron (-methyl); potassium arsenite; potassium azide; procarbazone- (sodium), procyazine; prodi amines; profluazol; profluralin; profoxydim; proglinazine (-ethyl); prometon; prometryne; propachlor; propanil; propaquizafop and its esters; propazine; propham; propisochlor; propoxycarbazone (-sodium) (BAY MKH 6561); Propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA-152005); prynachlor; pyraclonil; pyraflufen (-ethyl), pyrasulfotole; pyrazolinate; pyrazon; pyrazosulfuron (-ethyl); pyrazoxyfen; pyribambenz-isopropyl; pyribenzoxime, pyributicarb, pyridafol, pyridate; pyriftalid; pyrimidobac (-methyl), pyrimisulfan, pyrithiobac (-sodium) (KIH-2031); pyroxasulfone; pyroxofop and its esters (eg propargyl esters); pyroxsulam (triflosulam); quinclorac; quinmerac; quinoclamine, quinofop and its ester derivatives, quizalofop and quizalofop-P and their ester derivatives z. Eg 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; saflufenacil (CAS RN: 372137-35-4); secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, ie 2 - [[7- [2-chloro-4- (trifluoromethyl) phenoxy] -2-naphthalenyl] oxy] propanoic acid and methyl ester; SMA; sodium arsenite; sodium azide; sodium chlorates; sulcotrione, sulfentrazone (FMC-97285, F-6285); sulfazuron; sulfometuron (-methyl); sulfosate (ICI-A0224); sulfosulfuron, 2,3,6-TBA; TCA (sodium); tebutam (GCP-5544); tebuthiuron; tefuryltrione, tembotrione, tepraloxydim, 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); thiafluamide, thiazafluron; thiazopyr (Mon-13200); thidiazimin (SN-24085); thiencarbazone-methyl, thifensulfuron (-methyl); thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triaziflam, triazofenamide; tribenuron (-methyl); tricamba; triclopyr; tridiphane; trietazine; trifloxysulfuron (sodium); trifluralin; triflusulfuron-methyl and esters (eg, methyl ester, DPX-66037); trihydroxytriazine; trimeturon; tritosulfuron; tropramezone; tsitodef; vernolate; [3- [2-chloro-4-fluoro-5- (1-methyl-6-trifluoromethyl) -1-dioxo-1 ', 5'-tetrahydropyrimidine-S-y-phenoxy-pyridyloxy-acetic acid ethyl ester, WL 110547, ie 5 Phenoxy-1- [3- (trifluoromethyl) phenyl] -1H-tetrazole; UBH-509; D-489; LS 82-556, ie, [(S) -3-N- (methylbenzyl) carbamoyl-5- propionyl-2,6-lutidine]; KPP-300; NC-324; NC-330; KH-218; DPX-N8189; SC-0774; DOWCO-535; DK-8910; V-53482; PP-600; MBH Ethyl- [2-chloro-5- (4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -4-fluoro-phenoxy] -acetate KIH-6127, ie pyriminobac-methyl; KIH-2023, ie bispyribac sodium; and SYP-249, ie ethyl 2- {2-nitro-5 - [(2-chloro-4-trifluoromethyl) phenoxy] benzoxy} 3-methyl-3-butenoates; SYN-523.

Of particular interest is the selective control of harmful plants in crops of commercial and ornamental plants. Although the compounds of the general formula (I) according to the invention already have very good to sufficient selectivity in many cultures, phytotoxicities on the crop plants can in principle occur in some crops and, above all, in the case of mixtures with other herbicides which are less selective. In this regard, combinations of compounds of the general formula (I) of of particular interest, which contain the compounds of the general formula (I) or their combinations with other herbicides or pesticides and safeners. The safeners, which are used in an antidote effective content, reduce the phytotoxic side effects of the herbicides / pesticides used, eg. B. in economically important crops such as cereals (wheat, barley, rye, corn, rice, millet), sugar beet, sugar cane, rapeseed, cotton and soybeans, preferably cereals. The following groups of compounds are suitable, for example, as safeners for the compounds (I), alone or in combinations thereof with other pesticides:

The safeners are preferably selected from the group consisting of:

S1) compounds of the formula (S1),

where the symbols and indices have the following meanings: ΠA is a natural number from 0 to 5, preferably 0 to 3; RA ¹ is halogen, (C _r C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, nitro or (dC ₄ ) haloalkyl; W _A is an unsubstituted or substituted divalent heterocyclic radical selected from the group consisting of the pentally unsaturated or aromatic five-membered heterocycles having 1 to 3 hetero ring atoms from the group consisting of N and O, where at least one

N atom and at most one O atom is contained in the ring, preferably a radical from the group (W _A ¹ ) to (W _A ⁴ ),

ITIA is 0 or 1; RA ² is ORA ³ , SRA ³ or NRA ³ RA ⁴ or a saturated or unsaturated 3- to 7-membered heterocycle having at least one N atom and up to 3 heteroatoms, preferably from the group O and S, which is bonded via the N- Atom is connected to the carbonyl group in (S1) and is unsubstituted or substituted by radicals from the group (CrC ₄ ) alkyl, (Ci-C ₄ ) AIkOXy or optionally substituted phenyl, preferably a radical of the formula OR _A ³ , NHRA ⁴ or N (CH ₃ ) ₂ , in particular the formula OR _A ³ ;

RA ³ is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having in total 1 to 18 carbon atoms; RA ⁴ is hydrogen, (CRCE) -alkyl ₁ (CrCβJAlkoxy or substituted or unsubstituted phenyl;

RA ⁵ is H ₁ (Ci-C ₈₎ alkyl, (C _r C ₈₎ haloalkyl, (d ^ Alkoxytd-CsJAlkyl, cyano or COOR ^9, wherein R _A ⁹ is hydrogen, (C _r C ₈₎ alkyl, (CrC ₈ is) haloalkyl, (CrC ₄₎ alkoxy (CrC ₄₎ alkyl, (CrC ₆₎ hydroxyalkyl, (C ₃ -C ₁₂₎ cycloalkyl or tri- (C _r C ₄₎ -alkyl-silyl;

RA ⁶ , RA ⁷ , RA ⁸ are identical or different hydrogen, (C 1 -C ₈ ) alkyl,

(dC ₈₎ haloalkyl, _(C3-Ci2) cycloalkyl or substituted or unsubstituted phenyl;

preferably: a) compounds of the type of dichlorophenylpyrazoline-3-carboxylic acid (S1 ^a ), preferably compounds such as

1- (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylic acid, 1- (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2- pyrazoline-3-carboxylic acid ethyl ester (S1-1) ("mefenpyr-diethyl") and related compounds as described in WO-A-91/07874; b) Derivatives of dichlorophenylpyrazolecarboxylic acid (S1 ^b ), preferably compounds such as ethyl 1- (2,4-dichlorophenyl) -5-methyl-pyrazole-3-carboxylate (S1 -2), 1 - ^^ - dichlorophenyl-δ-isopropyl pyrazole-S-carboxylic acid ethyl ester (S1-3), 1- (2,4-dichlorophenyl) -5- (1, 1-dimethyl-ethyl) -pyrazole-3-carboxylic acid ethyl ester (S1-4) and related compounds as described in EP-A-333,131 and EP-A-269,806; c) derivatives of 1, 5-diphenylpyrazole-3-carboxylic acid (S1 ^C), preferably compounds such as 1 - (2,4-dichlorophenyl) -5-phenylpyrazole-3-carbonsäureethyl- ester (S1 -5), 1 - (2 -Chloφhenyl) -5-phenylpyrazole-3-carbonsäuremethylester

(S 1-6) and related compounds as described, for example, in EP-A-268554; d) compounds of the type of triazolecarboxylic acids (S1 ^d ), preferably compounds such as fenchlorazole (ethyl ester), ie

1- (2,4-dichlorophenyl) -5-trichloromethyl- (1 H) -1, 2,4-triazole-3-carboxylic acid ethyl ester (S1-7), and related compounds as described in EP-A-174 562 and EP-A-346 620; e) Compounds of the 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (S1 ^e), preferably compounds such as 5- (2, 4-dichlorobenzyl) -2-isoxazoline-3-carboxylic acid ethyl ester (S1-8) or 5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-9) and related compounds as described in WO-A-

Or 5,5-diphenyl-2-isoxazoline-carboxylic acid (S1-10) or 5,5-diphenyl-2-isoxazoline-carboxylic acid ethyl ester (S1-11) ("isoxadifen-ethyl") or n-propyl ester (S1-12) or 5- (4-fluorophenyl) -5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-13), as described in the patent application WO-A-95/07897.

S2) quinoline derivatives of the formula (S2)

where the symbols and indices have the following meanings: RB ¹ is halogen, (CrC ₄₎ alkyl, (C _r C ₄₎ alkoxy, nitro or (C _r C ₄₎ haloalkyl; n _B is a natural number from 0 to 5, preferably 0 to 3; RB ² is ORB ³ , SR _B ³ or NR ₆ ³ RB ⁴ or a saturated or unsaturated 3- to 7-membered heterocycle having at least one N atom and up to 3 heteroatoms, preferably from the group O and S, which is connected via the N atom to the carbonyl group in (S2) and unsubstituted or by radicals from the group (C 1 -C ₄ ) alkyl, (C 1 -C ₄ ) Alkoxy or optionally substituted phenyl is substituted, preferably a radical of the formula OR ₈ ³ , NHR ₆ ⁴ or N (CH ₃ ) ₂ , in particular the formula OR ₈ ³ ;

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

RB ⁴ is hydrogen, (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) alkoxy or substituted or unsubstituted phenyl; TB is a (Ci or C2) alkanediyl chain which is unsubstituted or substituted by one or two (CrC ₄ ) alkyl radicals or by [(CrC ₃ ) alkoxy] carbonyl;

preferably: a) Compounds of the 8-quinolinoxyacetic acid (S2 ^a), preferably (5-chloro-8-quinolinoxy) acetic acid (1 -methylhexyl) ester ( "cloquintocet-mexyl")

(S2-1),

(5-Chloro-8-quinolinoxy) acetic acid (1, 3-dimethylbut-1-yl) ester (S2-2), (5-chloro-8-quinolinoxy) acetic acid 4-allyloxy-butyl ester (S2- 3), (5-chloro-8-quinolinoxy) acetic acid 1-allyloxy-prop-2-yl ester (S2-4), (5-chloro-8-quinolinoxy) acetic acid ethyl ester (S2-5),

(5-chloro-8-quinolinoxy) acetic acid methyl ester (S2-6), (5-chloro-8-quinolinoxy) allyl acetate (S2-7), (5-chloro-8-quinolinoxy) acetic acid 2- (2-propylidene) iminoxy) -1-ethyl ester (S2-8), (5-chloro-8-quinolinoxy) acetic acid 2-oxo-prop-1-yl ester (S2-9) and related compounds as described in EP-A-86,750 , EP-A-94 349 and

EP-A-191 736 or EP-AO 492 366, and (5-chloro-8-quinolinoxy) acetic acid (S2-10), their hydrates and salts, for example their lithium, sodium, potassium, calcium, Magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts as described in WO-A-2002/34048; b) compounds of the (5-chloro-8-quinolinoxy) malonic acid type (S2 ^b ), preferably compounds such as (5-chloro-8-quinolinoxy) malonic acid diethyl ester, (5-chloro-8-quinolinoxy) malonic acid diallyl ester, (5-chloro-8-quinolineoxy) malonic acid methyl ethyl ester and related compounds, as described in EP-AO 582 198.

S3) compounds of the formula (S3)

wherein the symbols and indices have the following meanings: Rc ¹ is (C _r C ₄ ) alkyl, (CrC ₄ ) haloalkyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) haloalkenyl, (C ₃ -C ₇ ) Cycloalkyl, preferably dichloromethyl; Rc ^2, rc ³ are identical or different hydrogen, (CrC ₄₎ alkyl, (C ₂ -C ₄₎ -alkenyl AI,

(C ₂ -C ₄₎ alkynyl, (C _{r C4)} haloalkyl, (C ₂ -C ₄₎ haloalkenyl, (C _r C ₄₎ alkylcarbamoyl (CrC ₄₎ alkyl, (C ₂ -C ₄₎ Alkenylcarbamoyl- ( Ci-C ₄₎ alkyl, (C _{r C4)} alkoxy- _(Ci-C4) alkyl, dioxolanyl (CrC ₄₎ alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or Rc ² and Rc ³ together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine, piperidine, morpholine, hexahydropyrimidine or benzoxazine ring;

preferably: active agents of the dichloroacetamide type, often as pre-emergence safeners

(soil-active safeners) are used, such. B.

"Dichloromid" (N, N-diallyl-2,2-dichloroacetamide) (S3-1),

"R-29148" (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer

(S3-2), "R-28725" (3-dichloroacetyl-2,2, -dimethyl-1,3-oxazolidine) from Stauffer

(S3-3),

"Benoxacor" (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4),

"PPG-1292" (N-allyl-N - [(1,3-dioxolan-2-yl) -methyl] -dichloroacetamide) from the company PPG Industries (S3-5),

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

"AD-67" or "MON 4660" (3-dichloroacetyl-1-oxa-3-aza-spiro [4,5] decane) from Nitrokemia or Monsanto (S3-7),

"TI-35" (1-dichloroacetyl-azepane) from TRI-Chemical RT (S3-8), "diclonone" (dicyclonone) or "BAS145138" or "LAB145138" (S3-9) (3-dichloroacetyl-2, 5,5-trimethyl-1,3-diazabicyclo [4.3.0] nonane) from BASF, "furilazole" or "MON 13900" ((RS) -3-dichloroacetyl-5- (2-furyl) -2,2 dimethyl oxazolidine) (S3-10); and its (R) isomer (S3-11).

S4) N-acylsulfonamides of the formula (S4) and their salts,

wherein the symbols and indices have the following meanings: X ₀ is CH or N; R ₀ ¹ is CO-NRD ⁵ RD ⁶ or NHCO-RD ⁷ ;

RD ² is halogen, (C _r C ₄ ) haloalkyl, (C _r C ₄ ) haloalkoxy, nitro, (C _r C ₄ ) alkyl, (Ci-C ₄ ) alkoxy, (Ci-C ₄ ) alkylsulfonyl, (C _r C ₄ ) alkoxycarbonyl or

(C _r C ₄ ) alkylcarbonyl;

R ₀ ³ is hydrogen, (C _r C ₄ ) alkyl, (C ₂ -C ₄ ) alkenyl or (C ₂ -C ₄ ) alkynyl; RD ⁴ is halogen, nitro, (Ci-C ₄₎ alkyl, (dC ₄₎ haloalkyl, (C _{r C4)} haloalkoxy,

(C ₃ -C ₆₎ cycloalkyl, phenyl, (Ci-C ₄₎ alkoxy, cyano, (C _{r C4)} alkylthio, (Ci-C ₄₎ alkylsulfinyl, (C _r C ₄₎ alkylsulfonyl, (C _r C ₄ ) Alkoxycarbonyl or

(C _r C ₄ ) alkylcarbonyl; R ₀ ⁵ is hydrogen, (C ₁ -C ₆ ) alkyl, (C ₃ -C ₆ ) cycloalkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl,

(C ₅ -Co) CyClOa I kenyl, phenyl or 3- to 6-membered heterocyclyl containing VD heteroatoms from the group nitrogen, oxygen and sulfur, where the seven last-mentioned radicals are substituted by v _D substituents from the group halogen, (C _{r C6)} alkoxy, (Ci-C ₆₎ haloalkoxy, (CrC ₂₎ alkylsulfinyl, (CrC ₂ ) Alkylsulfonyl, (C ₃ -C ₆ ) cycloalkyl, (C ₁ -C ₄ ) alkoxycarbonyl, (C ₁ -C ₄ ) alkylcarbonyl and phenyl and in the case of cyclic radicals also (C ₁ -C ₄ )

Alkyl and (dC ₄ ) haloalkyl;

R ₀ ⁶ is hydrogen, (Ci-C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl or (C ₂ -C ₆ ) alkynyl, where the three latter radicals by v _D radicals from the group halogen, hydroxy, (CrC ₄ ) alkyl, (C 1 -C ₄ ) alkoxy and (C 1 -C ₄ ) alkylthio, or RD ⁵ and RD ⁶ together with the nitrogen atom bearing them form a pyrrolidinyl or piperidinyl radical;

R ⁷ ₀ is hydrogen, (Ci-C ₄₎ alkylamino, di (Ci-C ₄₎ alkylamino, (CrC ₆₎ alkyl,

(C ₃ -C ₆ ) cycloalkyl, where the 2 latter radicals by VD substituents selected from the group consisting of halogen, (CrC ₄ ) alkoxy, (CrC ₆ ) haloalkoxy and (C _r C ₄ ) alkylthio and in the case of cyclic radicals also (C _r C ₄ ) alkyl and

(CrC ₄ ) haloalkyl are substituted; n _D is O, 1 or 2; m _D is 1 or 2; v _D is 0, 1, 2 or 3;

preferred are compounds of the type of N-acylsulfonamides, for example the following formula (S4 ^a ), the z. B. are known from WO-A-97/45016

wherein R ₀ ⁷ (CrC ₆ ) alkyl, (C ₃ -C ₆ ) cycloalkyl, where the latter two radicals by v _D

Substituents from the group halogen, (Ci -C ₄ ) Al koxy, (CrCβJHaloalkoxy and (C-ι-C ₄ ) alkylthio and in the case of cyclic radicals also (CrC ₄ ) alkyl and (CrC ₄ ) haloalkyl are substituted; R ₀ ⁴ halogen, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, CF _3; limit 1 or 2;

V ₀ is 0, 1, 2 or 3;

such as

Acylsulfamoylbenzoesäureamide, for example, the following formula (S4 ^b ), for example, are known from WO-A-99/16744,

for example, those in which RD ⁵ = cyclopropyl and (R _D ⁴ ) = 2-OMe ("Cyprosulfamide", S4-1), R _D ⁵ = cyclopropyl and (R ₀ ⁴ ) = 5-CI-2-OMe (S4 -2), R _D ⁵ = ethyl and (R ₀ ⁴ ) = 2-OMe is (S4-3), R _D ⁵ = isopropyl and (R _D ⁴ ) = 5-CI-2-OMe (S4-4 ) and R _D ⁵ = isopropyl and (R ₀ ⁴ ) = 2-OMe (S4-5).

such as

N-acylsulfamoylphenyl urea compounds of formula (S4), e.g. are known from EP-A-365484,

wherein

R _{0 8>} u _ln DR _D ndj 9 are independently hydrogen, (CrCβ) alkyl, (C ₃ -C ₈₎ cycloalkyl, (C ₃ -C ₆ ) alkenyl, (C ₃ -C ₆ ) alkynyl, RD ⁴ halogen, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, CF ₃ m _D 1 or 2;

for example

1- [4- (N-2-Methoxybenzoylsulfamoyl) phenyl] -3-methyl-urea,

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

1- [4- (N-4,5-Dimethylbenzoylsulfamoyl) phenyl] -3-methyl-urea.

S5) Active ingredients from the class of hydroxyaromatics and aromatic-aliphatic carboxylic acid derivatives (S5), e.g.

3,4,5-triacetoxybenzoic acid ethyl ester, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicyclic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid, as described in US Pat WO-A-2004/084631, WO-A-2005/015994, WO-A-2005/016001.

56) Agents from the class of 1, 2-dihydroquinoxaline-2-ones (S6), e.g. 1-Methyl-3- (2-thienyl) -1,2-dihydroquinoxalin-2-one, 1-methyl-3- (2-thienyl) -1,2-dihydroquinoxaline-2-thione, 1- (2-aminoethyl ) -3- (2-thienyl) -1,2-dihydroquinoxaline-2-one hydrochloride, 1- (2-methylsulfonylaminoethyl) -3- (2-thienyl) -1, 2-dihydroquinoxaline-2 on, as described in WO-A-2005/112630.

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

wherein the symbols and indices have the following meanings:

RE ^1, RE ² are independently halogen, (CrC ₄₎ alkyl, (C ₁ -C ₄₎ -alkoxy, (C 1 -C ₄ ) haloalkyl, (C 1 -C ₄ ) alkylamino, di (C 1 -C ₄ ) alkylamino, nitro; A _E is COORE ³ or COSR _E ⁴

RE ³ , RE ⁴ are independently hydrogen, (CrC ₄ ) AIKyI,

(C ₂ -C ₆ ) alkenyl, (C ₂ -C ₄ ) alkynyl, cyanoalkyl, (C _r C ₄ ) haloalkyl, phenyl, nitrophenyl, benzyl, halobenzyl, pyridinylalkyl and alkylammonium, n _E ¹ is 0 or 1 n _E ² , nε ³ are independently 0, 1 or 2, preferably:

Diphenylmethoxyacetic acid, ethyl diphenylmethoxyacetate,

Methyl diphenylmethoxyacetate (CAS No. 41858-19-9) (S7-1).

S8) compounds of the formula (S8) as described in WO-A-98/27049

wherein

XF CH or N, _nF for the case that X _F = N, an integer from 0 to 4 and for the case that X _F = CH, an integer from 0 to 5, RF ¹ halogen, ( C _r C ₄ ) alkyl, (dC ₄ ) haloalkyl, (C _r C ₄ ) alkoxy, (C _r C ₄ ) haloalkoxy,

Nitro, (dC ₄ ) alkylthio, (C _r C ₄ ) -alkylsulfonyl, (C _r C ₄ ) alkoxycarbonyl, optionally substituted. Phenyl, optionally substituted phenoxy, RF ² hydrogen or (dC ₄ ) alkyl

RF ^{3 is} hydrogen, (C _r C ₈ ) alkyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) alkynyl, or aryl, wherein each of the aforementioned C-containing radicals is unsubstituted or substituted by one or more, preferably to to three equal or different residues from the

A group consisting of halogen and alkoxy is substituted; mean, or their salts,

preferably compounds wherein

XF CH,

ΠF is an integer from 0 to 2,

RF ¹ halogen, (C _r C ₄ ) alkyl, (C _r C ₄ ) haloalkyl, (C ₁ -C ₄ ) alkoxy, (C _r C ₄ ) haloalkoxy, RF ² hydrogen or (C _r C ₄ ) alkyl, RF ^{3 is} hydrogen, (C ₁ -C ₈ ) alkyl, (C ₂ -C ₄ ) alkynyl, (C ₂ -C ₄ ) alkynyl, or aryl, where each of the abovementioned C-containing radicals is unsubstituted or by one or more, preferably up to three the same or different radicals from the group consisting of halogen and alkoxy is substituted, mean, or their salts.

S9) Agents from the class of 3- (5-tetrazolylcarbonyl) -2-quinolones (S9), e.g. 1, 2-dihydro-4-hydroxy-1-ethyl-3- (5-tetrazolylcarbonyl) -2-quinolone (CAS

Registration number. 219479-18-2), 1, 2-dihydro-4-hydroxy-1-methyl-3- (5-tetrazolylcarbonyl) -2-quinolone (CAS Reg. No. 95855-00-8), as described in WO-A-1999/000020.

S10) compounds of the formulas (S10 ^a ) or (S10 ^b ) as described in WO-A-2007/023719 and WO-A-2007/023764

wherein

RG ¹ halogen, (C _r C ₄ ) alkyl, methoxy, nitro, cyano, CF ₃ , OCF ₃ YG, Zcunabhängig each other O or S, n _{G is} an integer from 0 to 4,

RG ² (C ₁ -C ₁₆ ) Al kVl, (C ₂ -C ₆ ) alkynyl, (C ₃ -C ₆ ) cycloalkyl, aryl; Benzyl, halobenzyl,

RG ^{3 is} hydrogen or (C 1 -C 6 -alkyl.

S11) oxyimino compound type compounds (S11) known as seed dressings, such as those described in US Pat. B.

"Oxabetrinil" ((Z) -1, 3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile) (S11-1), which is known as a seed dressing safener for millet against damage by metolachlor, "Fluxofenim" (1- (4 -Chlorophenyl) -2,2,2-trifluoro-1-ethanone O- (1,3-dioxolan-2-ylmethyl) -oxime) (S11-2), which has been disclosed as a seed dressing safener for millet against damage by metolachlor is and

"Cyometrinil" or "CGA-43089" ((Z) -cyanomethoxyimino (phenyl) acetonitrile)

(S11-3), known as millet safener for millet against damage from metolachlor.

512) Class I) isothiochromanone (S12) actives, e.g. Methyl - [(3-oxo-1H-2-benzothiopyran-4 (3H) -ylidene) methoxy] acetate (CAS No. 205121-04-6) (S12-1) and related compounds of WO-A -1998 / 13361.

513) One or more compounds from group (S13):

"Naphthalene anhydride" (1,8-naphthalenedicarboxylic anhydride) (S13-1), which is known as a corn seed safener for corn against damage by thiocarbamate herbicides, "fenclorim" (4,6-dichloro-2-phenylpyrimidine) (S13-2) as a safener for

Pretilachlor is known in sown rice,

"Flurazole" (benzyl-2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (S13-3), which is known as a seed dressing safener for millet against damage by alachlor and metolachlor, "CL 304415" (CAS Reg. No. 31541 -57-8)

(4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4) from American Cyanamid, used as safener for maize against damage of Imidazolinones are known

"MG 191" (CAS Reg. No. 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia, which is known as safener for corn, " MG-838 "(CAS Reg. No. 133993-74-5) (2-propenyl 1-oxa-4-azaspiro [4.5] decane-4-carbodithioate) (S13-6) of the company

Nitrokemia,

"Disulfonone" (O, O-diethyl S-2-ethylthioethyl phosphorodithioate) (S13-7), "dietholate" (O, O-diethyl-O-phenyl phosphorotioate) (S13-8), "mephenate" (4-chlorophenyl) methylcarbamate) (S 13-9).

514) active substances which, in addition to a herbicidal activity against harmful plants, also have safener action on crops such as rice, such as, for example, rice. "Dimepiperate" or "MY-93" (S-1-methyl-1-phenylethyl-piperidine-1-carbothioate), which is known as a safener for rice against damage by the herbicide Molinate,

"Daimuron" or "SK 23" (1- (1-methyl-1-phenylethyl) -3-p-tolyl-urea) known as safener for rice against damage of the herbicide imazosulfuron, "cumyluron" = "JC-" 940 "(3- (2-chlorophenylmethyl) -1- (1-methyl-1-phenylethyl) urea, see JP-A-60087254) known as safener for rice against damage of some herbicides,

"Methoxyphenone" or "NK 049" (3,3'-dimethyl-4-methoxybenzophenone) known as safener for rice against damage of some herbicides, "COD" (1-bromo-4- (chloromethylsulfonyl) benzene) by Kumiai, (CAS Reg. No. 54091-06-4), which is known as safener against damage of some herbicides in rice.

515) active substances primarily used as herbicides, but also having safener action on crop plants, e.g. (2,4-dichlorophenoxy) acetic acid (2,4-D), (4-chlorophenoxy) acetic acid,

(R, S) -2- (4-chloro-o-tolyloxy) propionic acid (mecoprop), 4- (2,4-dichlorophenoxy) butyric acid (2,4-DB), (4-chloro-o-tolyloxy) acetic acid (MCPA), 4- (4-chloro-o-tolyloxy) butyric acid, 4- (4-chlorophenoxy) butyric acid, 3,6-dichloro-2-methoxybenzoic acid (Dicamba), 1 - (ethoxycarbonyl) ethyl 3,6-dichloro-2-methoxybenzoate (lactidichloroethyl).

Preferred herbicide-safener combinations comprising (A) a herbicidally effective amount of one or more compounds of formula (I) or their salts, and (B) an antidote effective amount of one or more safeners.

In the context of the invention, herbicidally effective amount means an amount of one or more herbicides which is suitable for negatively influencing plant growth. Antidote effective amount in the sense of the invention means an amount of one or more safeners which is suitable for reducing the phytotoxic effect of crop protection active ingredients (eg of herbicides) on crop plants.

Some of the safeners are already known as herbicides and therefore, in addition to the herbicidal effect on harmful plants, also have a protective effect on the crop plants.

The weight ratio of herbicide (mixture) to safener generally depends on the application rate of herbicide and the effectiveness of the particular safener and can vary within wide limits, for example in the range from 200: 1 to 1: 200, preferably 100: 1 to 1: 100, in particular 20: 1 to 1:20. The safeners can be formulated analogously to the compounds of the formula (I) or mixtures thereof with further herbicides / pesticides and provided and used as finished formulation or tank mixture with the herbicides.

For use, the formulations present in commercially available form are optionally diluted in a customary manner, for. As in wettable powders, emulsifiable Concentrates, dispersions and water-dispersible granules by means of water. Dust-like preparations, ground or scattered granules and 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, u.a. varies the required application rate of the compounds of general formula (I). It can vary within wide limits, eg. B. between 0.001 and 10.0 kg / ha or more active substance, but it is preferably between 0.005 and 5 kg / ha.

The present invention will be explained in more detail by means of the following examples, which by no means limit the invention.

A. Synthesis Examples

1. N - [(4-Chloro-6-methoxypyrimidin-2-yl) carbamoyl] -3- (4,5-dihydroisoxazol-3-yl) -pyridine-2-sulfonamide (1a-1):

230 mg (1 mmol) of 3- (4,5-dihydroisoxazol-3-yl) -pyridine-2-sulfonamide (IIa-1) are dissolved in 10 ml of acetonitrile and treated with 400 mg (1 mmol) of diphenyl- (4-chloro) 6-methoxypyrimidin-2-yl) imidodicarbonate (cf. WO 1996/022284). With stirring, 160 mg (1 mmol) of DBU (diazabicyclo-undecene) are added dropwise. After standing for 1 hour at 20 ⁰ C is poured onto a mixture of methylene chloride and aqueous hydrochloric acid (5%). The organic phase is washed twice with water and once with saturated brine. After drying with magnesium sulfate, the organic phase is concentrated in vacuo. The residue is triturated in diethyl ether and filtered off with suction. The resulting crystals are stirred in isopropanol, filtered off with suction and dried. 200 mg (0.45 mmol) of N - [(4-chloro-6-methoxypyrimidin-2-yl) carbamoyl] -3- (4,5-dihydroisoxazol-3-yl) pyridine-2-sulfonamide (Ia-1) are obtained. from the purity content (HPLC) 92.8%.

The compounds of general formula (I) described in the following tables are obtained according to or analogously to the synthesis example described above: Table 1a: Compounds of the formula (Ia)

¹ H NMR data (400 MHz, solvent: CD ₃ CN, internal standard: tetramethylsilane δ = 0.00 ppm, s = singlet, br s = broad singlet, d = doublet, dd = double doublet, m = multiple, q = quartet, t = triplet)

la-1: δ = 3.44 (t, 2H); 4.01 (s, 6H); 4.47 (t, 2H); 6.62 (s, 1H); 7.68 (dd, 1H); 7.99 (dd,

1H); 8.39 (brs s, 1H); 8.68 (dd, 1H); 12.2 (brs s, 1H) ppm la-2: δ = 3.44 (t, 2H); 3.94 (s, 6H); 4.46 (t, 2H); 5.87 (s, 1H); 7.67 (dd, 1H); 7.98 (dd,

1H); 8.14 (brs s, 1H); 8.66 (dd, 1H); 12.8 (brs s, 1H) ppm la-3: δ = 2.42 (s, 6H); 3.45 (t, 2H); 4.46 (t, 2H); 6.90 (s, 1H); 7.66 (dd, 1H); 7.97 (dd, 1H); 8.06 (brs s, 1 H); 8.66 (dd, 1H); 13.3 (brs s, 1 H) ppm la-4: δ = 2.55 (s, 3H); 3.45 (t, 2H); 3.94 (s, 3H); 4.47 (t, 2H); 6.42 (s, 1H); 7.67 (dd,

1H); 7.98 (dd, 1H); 8.18 (brs s, 1H); 8.67 (dd, 1H); 12.9 (br s, 1H) ppm la-5: δ = 3.45 (t, 2H); 3.97 (s, 3H); 4.46 (t, 2H); 6.54 (d, 1H); 7.66 (dd, 1H); 7.97 (dd,

1H); 8.1-8.4 (br.1H); 8.29 (d, 1H); 8.66 (dd, 1H); 13.1 (br s, 1H) ppm la-6: δ = 3.44 (t, 2H); 4.03 (s, 6H); 4.47 (t, 2H); 7.68 (dd, 1H); 7.99 (dd, 1H); 8.4 (brs s, 1H); 8.67 (dd, 1H); 12.5 (brs s, 1H) ppm la-7: δ = 2.49 (s, 3H); 3.44 (t, 2H); 4.02 (s, 3H); 4.47 (t, 2H); 7.68 (dd, 1H); 8.00 (dd,

1H); 8.4 (br., 1H); 8.67 (dd, 1H); 12.6 (br, s, 1H) ppm la-8: δ = 3.16 (s, 3H); 3.19 (s, 3H); 3.44 (t, 2H); 4.47 (t, 2H); 4.87 (q, 2H); 7.67 (dd, 1H); 7.98 (dd, 1H); 8.14 (brs s, 1H); 8.67 (dd, 1H); 12.9 (br s, 1H) ppm la-9: δ = 3.43 (s, 3H); 3.45 (t, 2H); 3.95 (s, 3H); 4.46 (t, 2H); 6.40 (s, 1H); 7.66 (dd,

1H); 7.97 (dd, 1H); 8.0-8.25 (br., 1H); 8.66 (dd, 1H); 13.4 (br s, 1H) ppm la-10: δ = 0.95 (d, 3H); 1.01 (d, 3H); 3.18 (dd, 1H); 3.45 (dd, 1H); 3.87 (m, 1H); 3.94

(s, 6H); 4.49 (m, 1H); 5.86 (s, 1H); 7.66 (dd, 1H); 7.97 (dd, 1H); 8.2 (brs s, 1H); 8.65 (dd, 1H); 12.8 (br s, 1H) ppm la-11: δ = 1.40 (d, 3H); 3.07 (dd, 1H); 3.54 (dd, 1H); 3.94 (s, 6H); 4.89 (m, 1H); 5.87

(s, 1H); 7.66 (dd, 1H); 7.98 (dd, 1H); 8.18 (brs s, 1H); 8.65 (dd, 1H); 12.8 (br s, 1H) ppm la-12: δ = 1.47 (s, 6H); 2.49 (s, 3H); 3.24 (s, 2H); 4.02 (s, 3H); 7.67 (dd, 1H); 7.99 (dd, 1H); 8.45 (brs s, 1H); 8.64 (dd, 1H); 12.6 (br, s, 1H) ppm la-13: δ = 1.47 (s, 6H); 3.25 (s, 2H); 3.94 (s, 6H); 5.86 (s, 1H); 7.66 (dd, 1H); 7.99

(dd, 1H); 8.16 (brs s, 1H); 8.64 (dd, 1H); 12.8 (brs s, 1H) ppm la-14: δ = 1.47 (s, 6H); 3.25 (s, 2H); 4.00 (s, 3H); 6.61 (s, 1H); 7.67 (dd, 1H); 7.99

(dd, 1H); 8.38 (brs s, 1H); 8.65 (dd, 1H); 12.2 (br, s, 1H) ppm la-15: δ = 1.40 (d, 3H); 2.39 (s, 3H); 3.08 (dd, 1H); 3.55 (dd, 1H); 3.94 (s, 3H); 4.89

(m, 1H); 6.40 (s, 1H); 7.65 (dd, 1H); 7.96 (dd, 1H); 8.0-8.3 (br., 1 H); 8.64 (dd, 1H); 13.4 (br, 1H) ppm la-16: δ = 1.40 (d, 3H); 3.07 (dd, 1H); 3.54 (dd, 1H); 4.01 (s, 3H); 4.90 (m, 1H); 6.62

(s, 1H); 7.67 (dd, 1H); 7.99 (dd, 1H); 8.40 (brs s, 1H); 8.66 (dd, 1H); 12.2 (brs s, 1H) ppm la-17: δ = 0.97 (t, 3H); 1.4-1.55 (m, 2H); 1.6-1.7 (m, 1H); 1.72-1.82 (m, 1H); 2.39 (s, 3H); 3.11 (dd, 1H); 3.51 (dd, 1H); 3.95 (s, 3H); 4.75 (m, 1H); 6.40 (s, 1H); 7.65 (dd,

1H); 7.97 (dd, 1H); 8.05-8.25 (br., 1 H); 8.64 (dd, 1H); 13.4 (brs s, 1H) ppm la-18: δ = 0.99 (t, 3H); 1.65-1.85 (m, 2H); 2.50 (s, 3H); 3.11 (dd, 1H); 3.49 (dd, 1H);

4.02 (S, 3H); 4.71 (m, 1H); 7.68 (dd, 1H); 7.99 (dd, 1H); 8.42 (brs s, 1H); 8.66 (dd,

1H); 12.6 (br s, 1H) ppm la-19: δ = 0.98 (t, 3H); 1.65-1.85 (m, 2H); 2.39 (s, 3H); 3.12 (dd, 1H); 3.51 (dd, 1H);

3.95 (s, 3H); 4.70 (m, 1H); 6.40 (s, 1H); 7.65 (dd, 1H); 7.96 (dd, 1H); 8.13 (brs s, 1H);

8.65 (dd, 1H); 13.4 (br s, 1H) ppm la-20: δ = 0.99 (t, 3H); 1.65-1.85 (m, 2H); 3.11 (dd, 1H); 3.50 (dd, 1H); 4.01 (s, 3H);

4.70 (m, 1H); 6.62 (s, 1H); 7.67 (dd, 1H); 7.98 (dd, 1H); 8.39 (brs s, 1H); 8.66 (dd, 1H); 12.2 (br, s, 1H) ppm la-21: δ = 0.98 (t, 3H); 1.40-1.55 (m, 2H); 1.6-1.7 (m, 1H); 1.7-1.85 (m.1 H); 3.11 (dd,

1H); 3.51 (dd, 1H); 3.94 (s, 6H); 4.75 (m, 1H); 5.86 (s, 1H); 7.66 (dd, 1H); 7.97 (dd,

1H); 8.13 (brs s, 1H); 8.64 (dd, 1H); 12.8 (br.s, 1H) ppm la-22: δ = 0.95 (d, 3H); 1.00 (d, 3H); 2.39 (s, 3H); 3.18 (dd, 1H); 3.46 (dd, 1H); 3.95 (s, 3H); 4.50 (m, 1H); 6.40 (s, 1H); 7.65 (dd, 1H); 7.96 (dd, 1H); 8.05-8.25 (br., 1 H);

8.65 (dd, 1H); 13.4 (br s, 1 H) ppm la-23: δ = 0.97 (t, 3H); 1.35-1.55 (m, 2H); 1.6-1.7 (m, 1H); 1.72-1.83 (m, 1H); 2.50 (s,

3H); 3.10 (dd, 1H); 3.50 (dd, 1H); 4.02 (s.3H); 4.78 (m, 1H); 7.67 (dd, 1H); 7.99 (dd,

1H); 8.44 (brs s, 1 H); 8.65 (dd, 1H); 12.6 (br s, 1 H) ppm la-24: δ = 0.98 (t, 3H); 1.63-1.86 (m, 2H); 3.12 (dd, 1H); 3.50 (dd, 1H); 3.94 (s, 6H);

4.70 (m, 1H); 5.87 (s, 1H); 7.66 (dd, 1H); 7.97 (dd, 1H); 8.15 (brs s, 1H); 8.65 (dd,

1H); 12.8 (brs s, 1H) ppm Table 1b: Compounds of the formula (Ib)

Table 1c: Compounds of the formula (Ic)

Table 1d: Compounds of the formula (Id)

2. 3- (4,5-Dihydroisoxazol-3-yl) pyridine-2-sulfonamide (IIa-1)

2.7 g (10 mmol) of 2- (benzylthio) -3- (4,5-dihydroisoxazol-3-yl) pyridine (Xa-1) are taken up in a mixture of 50 ml of glacial acetic acid and 25 ml of water. In the resulting suspension is introduced at 0 ⁰ C chlorine gas until a faint yellowing occurs. The clear solution is extracted three times with methylene chloride. The combined organic phases are washed with water and brine, dried with magnesium sulfate and concentrated in vacuo. The result is an oily substance, the compound of formula (VIIIa-1), which is used without further purification in the subsequent reaction.

The crude sulfochloride (VIIIa-1) is taken up in 10 ml of acetonitrile and treated dropwise with 26% aqueous ammonia solution until a sample shows basic reaction. The mixture is concentrated and taken up in methylene chloride. Insoluble salts are filtered off. The filtrate is washed with water, dried and concentrated, the residue triturated with diethyl ether. This gives 1.3 g (5.5 mmol) of 3- (4,5-dihydroisoxazol-3-yl) pyridine-2-sulfonamide (IIa-1) of purity (HPLC) 96.1% in the form of colorless crystals, mp 155-156 ⁰ C. ,

Analog can be produced: Table 2a: Compounds of the formula (Villa)

Table 2b: Compounds of the formula (VIIIb)

Table 2c: Compounds of the formula (VIIIc)

Table 2d: Compounds of the formula (VIIId)

Table 3a: Compounds of the formula (IIa)

Table 3b: Compounds of the formula (IIb)

Table 3c: Compounds of the formula (Mc)

Table 3d: Compounds of the formula (Md)

3. 2- (Benzylthio) -3- (4,5-dihydroisoxazol-3-yl) pyridine (Xa-1)

In 600 ml of absolute N, N-dimethylformamide 2.86 g (0.11 mol) of sodium hydride (95%) are suspended. While stirring, 13.64 g (0.11 mol) of benzylmercaptan are added dropwise, with heating taking place.

18.3 g (0.1 mol) of 2-chloro-3- (4,5-dihydroisoxazol-3-yl) pyridine (Xla-1) dissolved in 30 ml of N, N-dimethylformamide are added in portions to the clear solution, and the mixture is stirred for 3 hours stirred at 20 ° C. The solution is concentrated, the residue taken up in methylene chloride and washed several times with water. After drying with magnesium sulfate, filtration and concentration, the residue is crystallized in diisopropyl ether. This gives 23.8 g (87.4 mmol) of 2- (benzylthio) -3- (4,5-dihydroisoxazol-3-yl) pyridine (Xa-1) of purity (HPLC) 99.3% in the form of colorless crystals, mp 97-98 ⁰ C.

Analog can be produced:

Table 4a: Compounds of the formula (Xa)

¹ H NMR data (400 MHz, solvent: CD ₃ CN, internal standard: tetramethylsilane δ = 0.00 ppm, s = singlet, br s = broad singlet, d = doublet, dd = double doublet, m = multiple, q = quartet, t = triplet)

Xa-6: δ = 0.96 (t, 3H); 1.6-1.8 (m, 2H); 3.02 (dd, 1H); 3.41 (dd, 1H); 4.45 (s, 2H); 4.62 (m, 1H); 7.14 (dd, 1H); 7.15-7.33 (m, 3H); 7.40-7.48 (m, 2H); 7.65 (dd, 1H); 8.45 (dd, 1H) ppm

Table 4b: Compounds of the formula (Xb)

Table 4c: Compounds of the formula (Xc)

Table 4d: Compounds of the formula (Xd)

4. 2-chloro-3- (4,5-dihydroisoxazol-3-yl) pyridine (Xla-1)

22.5 g (0.14 mol) of 2-chloronicotinaldehyde oxime are dissolved in 1650 ml of methylene chloride in a pressure vessel. The autoclave is closed and rendered inert with nitrogen. Ethylene is pressed on until 5 bar are reached. With good stirring, 279 g (231.3 ml) of sodium hypochlorite solution (10-13%) are pumped in in the course of 1 hour at 20 ⁰ C. After dosing, stirring is continued for 15 hours at room temperature. After releasing the pressure vessel, excess ethylene is blown out with nitrogen. The organic phase is separated, washed with water and dried with Baylith TE 144. After removal of the solvent in vacuo, 23.8 g of 2-chloro-3- (4,5-dihydroisoxazol-3-yl) pyridine (Xla-1) of purity (HPLC) 98.1%, logp = 0.97.

Analog can be produced:

Table 5a: Compounds of the formula (XIa)

¹ H NMR data (400 MHz, solvent: CD ₃ CN, internal standard: tetramethylsilane δ = 0.00 ppm, s = singlet, br s = broad singlet, d = doublet, dd = double doublet, m = multiple, q = quartet, t = triplet)

Xla-2: δ = 1.38 (d, 3H); 3.07 (dd, 1H); 3.54 (dd, 1H); 4.88 (m, 1H); 7.38 (dd, 1H); 7.96 (dd, 1H); 8.40 (dd, 1H) ppm

Xla-3: δ = 0.95 (d, 3H); 0.99 (d.3H); 3.19 (dd, 1H); 3.44 (dd, 1H); 4.52 (m, 1H); 7.38 (dd, 1H); 7.94 (dd, 1H); 8.40 (dd, 1H) ppm

Table 5b: Compounds of the formula (XIb)

Table 5c: Compounds of the formula (XIc)

Table 5d: Compounds of the formula (XId)

1 H-NMR data (400 MHz, solvent: CD ₃ CN, internal standard: tetramethylsilane δ • 0.00 ppm; s = singlet, br. S = broad singlet, d = doublet, dd = double doublet, m = multiple «, q = quartet, t = triplet)

Xld-1: δ = 3.47 (t, 2H); 4.40 (t, 2H); 7.39-7.44 (m, 1H); 7.58-7.63 (m, 1H); 8.46 (m, 1H) ppm

B. Formulation Examples

a) A dust is obtained by mixing 10 parts by weight of a compound of formula (I) and 90 parts by weight of talc as an inert material and comminuted in a hammer mill.

b) A readily dispersible in water, wettable powder is obtained by reacting 25 parts by weight of a compound of formula (I), 64 parts by weight of kaolinhaltigen quartz as inert material, 10 parts by weight of lignosulfonate and 1 part by weight oleoylmethyltaurinsaures sodium as net and

Dispersant mixed and ground in a pin mill.

c) A dispersion concentrate readily dispersible in water is obtained by reacting 20 parts by weight of a compound of the formula (I) with 6 parts by weight of alkylphenol polyglycol ether (© Triton X 207), 3 parts by weight

Isotridecanolpolyglykolether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to about 277 ⁰ C) mixed and milled in a ball mill to a fineness of less than 5 microns.

d) An emulsifiable concentrate is obtained from 15 parts by weight of a

Compound of formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.

e) A water-dispersible granule is obtained by reacting 75 parts by weight of a compound of the formula (I)

10 "lignosulfonic acid calcium,

5 "sodium lauryl sulfate,

3 "polyvinyl alcohol and

7 "kaolin mixed, ground on a pin mill and the powder in a fluidized bed through

Spraying of water as granulating liquid granulated. f) A water-dispersible granules are also obtained by 25 parts by weight of a compound of formula (I), 5 "2,2'-dinaphthylmethane-6,6 ^l -disulfonate sodium,

2 "oleoylmethyl tauric acid sodium,

1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and

Homogenized 50 ° "water on a colloid mill and pre-crushed, then grinded on a bead mill and the resulting suspension in a spray tower by means of a single-fluid nozzle atomized and dried.

C. Biological examples

1. Herbicidal action or crop plant compatibility in the pre-emergence

Seeds of monocotyledonous or dicotyledonous weeds are cultivated in

Wood fiber pots laid in sandy loam soil and covered with soil. The compounds of the invention formulated in the form of wettable powders (WP) are then applied to the surface of the cover soil as an aqueous suspension or emulsion having a water application rate of 600 l / ha, with the addition of 0.2% wetting agent.

After the treatment, the pots are placed in the greenhouse and kept under good growth conditions for the test plants. After approx. 3 weeks, the effect of the preparations is scored visually in comparison to untreated controls (herbicidal action in percent (%): 100% action = plants have died, 0% action = like control plants).

As the results show, compounds of the invention have a good herbicidal pre-emergence activity against a broad spectrum of grass weeds and weeds. The compounds of the invention have for example a very good herbicidal activity against harmful plants such as Alopecurus myosuroides, Matricaria inodora and Stellaria media pre-emergence in a Application rate of 0.08 kg and less active substance per hectare.

The following results were achieved with the compounds according to the invention in pre-emergence:

In the table, the individual cultures have the following abbreviations: ALOMY: Field Foxtail (gras) (Alopecurus myosuroides) MATIN: Odorless Chamomile (Matricaria inodora) STEME: Chickweed (Stellaria media)

2. Post-emergence herbicidal action Seeds of monocotyledonous or dicotyledonous crops are laid out in sandy loam soil in wood fiber pots, covered with soil and grown in the greenhouse under good growth conditions. 2 to 3 weeks after sowing, the test plants are treated in the single leaf stage. The compounds of the invention formulated in the form of wettable powders (WP) are then sprayed onto the green plant parts as an aqueous suspension or emulsion having a water application rate of 600 l / ha with the addition of 0.2% wetting agent. After about 3 weeks of life of the test plants in the greenhouse under optimal growth conditions, the effect of the preparations is scored visually compared to untreated controls (herbicidal activity in percent (%): 100% effect = plants are dead, 0% effect = like control plants).

As the results show, compounds according to the invention have a good herbicidal postemergence activity against a broad spectrum of grass weeds and weeds. For example, the compounds of the invention have a very good herbicidal activity against harmful plants such as Alopecurus myosuroides, Echinochloa crus-galli, Lolium multiflorum, Abutilon theophrasti, Amaranthus retroflexus, Pharitis purpurea, Stellaria media and Viola tricolor postemergence at an application rate of 0.08 kg and less active substance per hectare.

The following results were achieved with the compounds according to the invention in postemergence:

In the table, the individual cultures have the following abbreviations:

ALOMY: Field Foxtail (Alopecurus myosuroides.)

ECHCG: Barnyardgrass (Echinochloa crus-galli)

LOLMU: Many-flowered Lolch (Lolium multiflorum)

ABUTH: Velvet Poplar (Abutilon theophrasti) AMARE: Curved Foxtail (Amaranthus retroflexus)

PHBPU: Purple Glory (Pharbitis / Ipomoea purpurea)

STEME: Chickweed (Stellaria media)

VIOTR: Wild Pansy (Viola tricolor)

Claims

claims

1. N-azinyl-N'-pyridylsulfonylureas of the general formula (I)

in which

V, W, X and Y are chosen such that one of these indices is nitrogen and the remaining indices are carbon atoms which may be unsubstituted or substituted with the represented R ⁸ ;

A is selected from the group consisting of nitrogen and CR ⁹ ; in which

R ^{9 is} selected from the group consisting of hydrogen, alkyl, halo and haloalkyl;

R ^{1 is} selected from the group consisting of hydrogen and an optionally substituted radical from the series alkyl, alkoxy,

Alkoxyalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aralkyl and aryl;

R ^{2 is} selected from the group consisting of hydrogen, halogen, optionally halogen-substituted alkyl, optionally halogen-substituted alkoxy, optionally substituted by halogen alkylthio, optionally substituted by halogen alkylamino or optionally substituted by halogen dialkylamino: R ^{3 is} selected from the group consisting of hydrogen, halogen, optionally halogen-substituted alkyl, optionally halogen-substituted alkoxy, optionally halogen-substituted alkylthio, optionally substituted by halogen alkylamino or optionally substituted by halogen

dialkylamino;

R ⁴ to R ⁷ , each independently of one another, are selected from the group consisting of hydrogen, halogen, cyano, alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino,

Dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl or dialkylaminocarbonyl, where the radicals may be unsubstituted or may carry one or more radicals selected from the group consisting of halogen, cyano, alkoxy or alkylthio, or R ⁴ and R ⁶ or R ⁵ and R ^{7 represents} an alkylidene group optionally interrupted by oxygen or sulfur;

R ^{8 is} selected from the group consisting of hydrogen, halogen, cyano, thiocyanato, nitro, alkyl, alkoxy, alkylthio, alkylsulfinyl,

Alkylsulfonyl, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, or dialkylaminocarbonyl, wherein the radicals may be unsubstituted or may bear one or more radicals selected from the group consisting of halogen, cyano, alkoxy and alkylthio;

Q is selected from the group consisting of oxygen, or sulfur

and salts of compounds of the formula (I).

2. N-azinyl-N'-pyridylsulfonyl-ureas according to claim 1, characterized in that the substituent A is selected from the group consisting of nitrogen and CH.

3. N-azinyl-N'-pyridysulfonylureas according to claim 1 or 2, characterized in that the substituent R ^{1 is} selected from the group consisting of hydrogen, optionally halogen-substituted alkyl, optionally halogen-substituted alkoxy, optionally Halogen-substituted alkoxyalkyl, optionally halogen-substituted alkenyl and optionally halogen-substituted alkynyl.

4. N-azinyl-N'-pyridylsulfonyl-urea according to one of claims 1 to 3, characterized in that the substituent R ^{2 is} selected from the group consisting of hydrogen, halogen, optionally substituted by halogen alkyl, optionally substituted by halogen Alkoxy, optionally substituted by halogen alkylthio, optionally substituted by halogen alkylamino and optionally substituted by halogen dialkylamino.

5. N-azinyl-N'-pyridysulfonyl-urea according to one of claims 1 to 4, characterized in that the substituent R ^{3 is} selected from the group consisting of hydrogen, halogen, optionally substituted by halogen alkyl, optionally substituted by halogen Alkoxy, optionally substituted by halogen alkylthio, optionally substituted by halogen alkylamino and optionally substituted by halogen dialkylamino.

6. N-azinyl-N'-pyridysulfonyl-ureas according to any one of claims 1 to 5, characterized in that the substituents R ⁴ to R ⁷ , each independently of one another, are selected from the group consisting of hydrogen,

Halogen, cyano, thiocyanato, optionally halogen-substituted alkyl, optionally halogen-substituted alkoxy, optionally alkylthio substituted by halogen, optionally substituted by halogen alkylsulfinyl, optionally substituted by halogen alkylsulfonyl, optionally substituted by halogen alkylamino, optionally substituted by halogen alkylcarbonyl, optionally substituted by halogen alkoxycarbonyl or optionally by

Halogen substituted alkylaminocarbonyl.

7. N-azinyl-N'-pyridysulfonylureas according to any one of claims 1 to 6, characterized in that the substituent R ^{8 is} selected from the group consisting of hydrogen, halogen, cyano, thiocyanato, optionally halogen-substituted alkyl, optionally substituted by halogen alkoxy, optionally substituted by halogen alkylthio, optionally substituted by halogen alkylsulfinyl, optionally substituted by halogen alkylsulfonyl, optionally substituted by halogen alkylamino, optionally substituted by halogen

Alkylcarbonyl, optionally substituted by halogen alkoxycarbonyl and optionally substituted by halogen alkylaminocarbonyl.

8. A process for the preparation of N-azinyl-N'-pyridylsulfonylureas according to any one of claims 1 to 7, characterized by one of the following

Steps:

(a) Reaction of (4,5-dihydroisoxazol-3-yl) pyridine-sulfonamides of the general formula (II)

with a heterocyclic (thio) carbamate of the general formula (III)

wherein R ^{12 is} a substituted or unsubstituted (dC ₂ o) hydrocarbon radical such as aryl or alkyl, preferably optionally substituted phenyl or optionally substituted (CiCO-alkyl and wherein V, W, X, Y, R ¹ to R ⁸ , Q and A has the meaning of any one of claims 1 to 7; or

(b) Reaction of (4,5-dihydroisoxazol-3-yl) pyridine-sulfonic acid iso (thio) cyanates of the general formula (IV)

with an aminoheterocycle of the general formula (V)

wherein V, W, X, Y, R ¹ to R ⁸ , Q and A have the meaning of any one of claims 1 to 7; or

(c) Reaction of (4,5-dihydroisoxazol-3-yl) pyridine-sulfonyl (thio) carbamates of the general formula (VI)

wherein R ¹² is a substituted or unsubstituted (C1-C2 ₀₎ - hydrocarbon radical such as aryl or alkyl, preferably optionally substituted phenyl or optionally substituted (dC ₄₎ -alkyl, with an amino heterocycle of the general formula (V)

wherein V, W, X, Y, R ¹ to R ⁸ , Q and A have the meaning of any one of claims 1 to 7; or

(d) Reaction of (4,5-dihydroisoxazol-3-yl) pyridine-sulfonamides of the general formula (II)

with an iso (thio) cyanate of the general formula (VII)

optionally in the presence of a reaction auxiliary, wherein R ^{1 is} hydrogen and V, W, X, Y, R ² to R ⁸ , Q and A have the meaning of any one of claims 1 to 7; or

(e) Reaction of an aminoheterocycle of the general formula (V)

initially base-catalyzed with a carbonic acid ester and the intermediate formed of the general formula (III)

in a one-pot reaction with a (4,5-dihydroisoxazol-3-yl) pyridinesulfonamide of the general formula (II)

wherein V, W, X, Y, R ¹ to R ⁸ , Q and A have the meaning of any one of claims 1 to 7; or

(f) Reaction of (4,5-dihydroisxazol-3-yl) pyridine-sulfonic acid halides of the general formula (VIII)

wherein Hal is a halogen atom with a (thio) cyanate to an iso (thio) cyanate of the general formula (IV)

or a solvated (stabilized) derivative, and then with an amino heterocycle of general formula (V)

wherein V, W, X, Y, R ¹ to R ⁸ , Q and A have the meaning of any one of claims 1 to 7; or

(g) reacting (4,5-dihydroisoxazol-3-yl) pyridine-sulfonic acid amides of the general formula (II) with a heterocyclic bis-carbamate of the general formula (IX)

wherein R ^{12 is} a substituted or unsubstituted (C ₁ -C _{2 0} ) - hydrocarbon radical, in the presence of a basic reaction auxiliary, wherein Q is oxygen and V, W, X, Y, R ¹ to R ⁸ , and A has the meaning according to one of Claims 1 to 7; or (h) Reaction of (4,5-dihydroisoxazol-3-yl) pyridine-sulfonic acid amides of the general formula (II)

base catalysis with a carbonic acid ester and reaction of the intermediate formed of the general formula (VI)

in a one-pot reaction with an aminoheterocycle of the general formula (V)

wherein V, W, X, Y, R ¹ to R ⁸ , Q and A are as defined in any of

Claims 1 to 7 have.

9. Compounds of the general formula (II)

in which the radicals V, W, X, Y, R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 have} the meanings according to one of claims 1 to 7.

10. Compounds of the general formula (VIII)

in which the radicals V, W, X, Y, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and Hal have the meanings according to one of claims 1 to 7.

11. Compounds of the general formula (XI)

in which the radicals V, W, X, Y, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and Hal have the meanings according to one of claims 1 to 7.

12. Compounds of the general formula (X)

in which the radicals V, W, X, Y, R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 have} the meanings according to one of claims 1 to 7.

13. Compositions containing at least one compound of general formula (I) according to one of claims 1 to 7.

14. The composition according to claim 13, characterized in that the composition comprises at least one further active ingredient which is selected from the group consisting of at least one further herbicide and at least one safener.

15. Use of the compounds of general formula (I) according to one of claims 1 to 7 as herbicides and plant growth regulators.

16. Use of the compositions according to claim 14 or 15 as herbicides and plant growth regulators.

17. Use according to claim 15 or 16 for plant control in specific crops or as a plant protection regulator.