WO2011039276A1 - Oxathiazinyl(het)arylsulfonylureas, processes and intermediates for preparation thereof and use thereof as crop protection agents and crop growth regulators - Google Patents

Abstract

The invention relates to novel oxathiazinyl(het)arylsulfonylureas of the formula (I), to processes for preparation thereof and to the use thereof as crop protection agents and crop growth regulators, where J is J-1 to J-4, where J-1 to J-4 are each defined as follows: and in which the arrow in each case represents a bond to the sulfonyl unit of the formula (I), E is a direct bond, alkylene, oxygen, alkylamino or sulfur, and in which A is N or CR¹¹, and where the R¹ to R¹¹ radicals are each as defined in the description.

Description

OXATHIAZINYL- (HET) ARYLSULFONYL HARVES, METHODS AND INTERMEDIATE PRODUCTS FOR THEIR PREPARATION AND THEIR USE AS PLANT PROTECTION AGENTS AND PULSE GROWTH REGULATORS

Description It is already known that certain N-azinyl-N'-arylsulphonylureas have been prepared with simple open-chain hydroxamic acid ester groups in the aryl moiety such as e.g. N- (4,6-dimethylpyrimidin-2-yl) -N '- (2-methoxyaminocarbonyl-phenylsulfonyl) urea and the corresponding - N' - (2-n-octyloxyaminocarbonylphenylsulfonyl) urea have herbicidal properties (cf. A-3 516 435 = EP-A-173 958 = US-4,704,158). However, the herbicidal action of these known compounds is not satisfactory in all respects.

Furthermore, certain herbicidally active N-azinyl-N'- (het) arylsulfonylureas have become known which are substituted in the (het) aryl moiety by o, o-dialkylated, likewise open-chain hydroxamic acid groups (cf EP-A-301 784). ; Corresponding cyclic hydroxamic acid derivatives (dihydrodoxazines) are also known, for example. in EP 0645386 = US 5476936.

Furthermore, substituted cyclic hydroxamic acid derivatives (dihydrodoxazines) have also been described (compare JP2007246477, JP2007217336, JP2007145792, WO2007046440, WO2005103044 = EP 1748047).

in welcher There have now been new oxathiazinyl (het) arylsulfonylureas of the general formula (I).

in which

 1 1

 A is nitrogen or a CR moiety

wherein R ^{11 is} hydrogen, alkyl, halogen and haloalkyl

R ^{1 is} hydrogen or an optionally substituted radical from the series alkyl, alkoxy, alkoxyalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aralkyl and

 Aryl stands,

R ^{2 is} hydrogen, halogen or each optionally halogen

 substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino having in each case 1 to 6 carbon atoms,

R ^{3 is} hydrogen, halogen or each optionally halogen

 substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino having in each case 1 to 6 carbon atoms,

 J is J-1 to J-4, wherein J-1 to J-4 have the following meanings:

J-1 J-2 J-3 J-4 wherein

the arrow is in each case a bond to the sulfonyl unit of the formula (I), represents a direct bond, alkylene, oxygen, alkylamino or sulfur,

 independently of one another are hydrogen, halogen, cyano, thiocyanato or in each case optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, alkylcarbonyl,

 Alkoxycarbonyl, alkylaminocarbonyl having in each case 1 to 3 carbon atoms,

is hydrogen or an optionally substituted radical from the series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aralkyl and aryl or a group C (= O) R ⁹ , where

 is hydrogen, optionally substituted alkyl, optionally substituted aryl, alkoxy, alkylamino or dialkylamino,

 independently of one another are hydrogen, halogen, cyano, thiocyanato, if appropriate

 halogen-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl,

 AI kylsulfonyl, alkylamino, alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl each having 1 to 3 carbon atoms, wherein in the aforementioned radicals the alkyl and alkylene groups each have 1 to 6 carbon atoms, the alkenyl and alkynyl groups each 2 to 6 carbon atoms, the

Cycloalkyl groups each 3 to 6 carbon atoms and the aryl groups may each contain 6 or 10 carbon atoms, as well as salts of compounds of formula (I) found.

A characteristic structural feature of the new sulfonylureas (I) is therefore the (5,6-dihydro- [1,2,2] oxathiazin-3-yl) radical as a novel heterocyclic substituent in the (het) aryl portion of the (het) arylsulfonylureas. The simple body of this class of compounds, such. As the (5,6-dihydro- [1, 4.2] -oxathiazin-3-yl) benzene, - thiazole or pyridine, are known (see, Brouwer, W.G., Blem, A. R. et al., EP

0104940 (Uniroyal Inc. 1983)).

The novel N-azinyl-N '- (het) arylsulfonyl-ureas of the general formula (I), if (a) (Het) arylsulfonamides of the general formula (II),

in welcher

in which

 J has the meanings given above, with

Azinyl carbamates of the formula (III),

in welcher

in which

A and R ¹ to R ^{3 have} the meanings given above and

R ^{12 is} alkyl or aryl,

if appropriate in the presence of a diluent and if appropriate the presence of a reaction auxiliary, or if

(b) (Het) arylsulfonyl isocyanates of the general formula (IV)

in welcher J die oben angegebenen Bedeutungen hat,

in which J has the meanings given above,

with aminoazines of the formula (V),

in welcher

in which

 1 3

 A and R to R have the meanings given above, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or if

(c) (Het) arylsulfonylcarbamates of the general formula (VI),

in welcher

in which

 12

 and R have the meanings given above, with aminoazines of the formula

in welcher

in which

A and R ¹ to R ^{3 have} the meanings given above, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, and, if appropriate, the products obtained by processes (a), (b) or (c) are converted into salts by customary methods.

The new oxathiazinyl (het) arylsulfonylureas of the formula (I) are distinguished by their strong herbicidal activity.

Surprisingly, the novel compounds of the formula (I) show considerably greater activity and / or increased selectivity than the compounds which are comparable in structure and activity profile N- (4,6-dimethylpyrimidin-2-yl) -N '- (2-methoxyaminocarbonyl-phenylsulfonyl ) urea and the corresponding -N '- (2-n-octyloxyaminocarbonyl-phenylsulfonyl) urea or dihydro-dioxazines as described in EP 0645386A1 (US 5476936).

The invention preferably compounds

of the formula (I) in which

 A is nitrogen or a CH group,

R ^{1 is} hydrogen or an optionally halogen-substituted radical from the series alkyl, alkoxy, alkoxyalkyl, alkenyl and alkynyl, each with up to

3 carbon atoms,

R ^{2 is} hydrogen, halogen or each optionally halogen

 substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino each with

1 to 3 carbon atoms in the alkyl radicals,

R ^{3 is} hydrogen, halogen or each optionally halogen

 substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino having in each case 1 to 3 carbon atoms in the alkyl radicals,

 J is J-1 to J-4, preferably J-2,

 E for a direct bond, methylene, oxygen, alkylamino with 1 to 3

 Carbon atoms or sulfur,

R ⁴ -R ⁷ independently of one another represent hydrogen, halogen, cyano, thiocyanato or in each case optionally halogen-substituted alkyl, alkoxy,

Alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, alkylcarbonyl, Alkoxycarbonyl or alkylaminocarbonyl each having 1 to 3

 Carbon atoms in the alkyl radicals,

R ⁸ is hydrogen or an optionally substituted radical from the series (dC ₄₎ -alkyl, (C ₃ -C ₆₎ -cycloalkyl, (C ₇ -CN) aralkyl and (C ₆ -C ₀₎ aryl, R ¹⁰ independently of one another represent hydrogen, halogen, cyano, thiocyanato or in each case optionally halogen-substituted alkyl, alkoxy,

 Alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, alkylcarbonyl,

 Alkoxycarbonyl or alkylaminocarbonyl each having 1 to 3

 Carbon atoms in the alkyl radicals.

The invention further preferably relates to salts which are obtained from compounds of the formula (I) and bases, such as, for example, sodium, potassium or calcium hydroxide, hydride, amide and carbonate, sodium or potassium (C 1 -C ₄ ) -alkanolaten, ammonia, (Ci-C ₄₎ - alkyl amines, di - ((Ci-C ₄₎ -alkyl) amines or tri - ((Ci-C ₄₎ alkyl) -amines, obtained by conventional methods.

The invention particularly relates to compounds of the formula (I)

in which

 A is nitrogen or a CH group,

R ^{1 is} hydrogen, methyl, ethyl, methoxy, methoxymethyl or ethoxy, R ^{2 is} hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy,

 Difluoromethoxy, methylthio, methylamino or dimethylamino,

R ^{3 is} hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy,

 Difluoromethoxy, methylthio, methylamino or dimethylamino,

J is J-1 to J-4, preferably J-2,

 E for a direct bond, methylene, oxygen, (Ci-C2) -alkylamino or

 Sulfur stands,

R ⁴ -R ⁷ independently of one another represent hydrogen, fluorine, chlorine, cyano, or in each case optionally substituted by chlorine or fluorine, methyl, methylthio, methylsulfinyl, methylsulfonyl, methoxycarbonyl and ethoxycarbonyl,

R ^{8 is} hydrogen, methyl, ethyl, phenyl or benzyl, R ^{10 is} independently of one another hydrogen, fluorine, chlorine, bromine, cyano or in each case optionally substituted by chlorine or fluorine methyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, methyl or dimethylamino.

The general or preferred ones listed above

Residue definitions apply both to the end products of the formula (I) and correspondingly to the starting or end preparation required in each case.

Intermediates. These remainder definitions can be combined with one another as desired, ie also between the specified preferred ranges.

The hydrocarbon radicals mentioned in the radical definitions, such as alkyl, alkenyl or alkynyl, even in combinations with heteroatoms, such as in alkoxy, alkylthio or alkylamino, are also straight-chain or branched, even if not expressly stated.

For example, for process variant (a), 2- (5,6-dihydro- [1,2,2] oxathiazin-3-yl) -benzenesulfonamide and (4,6-dimethoxypyrimidin-2-yl) -phenylcarbamate are used as starting materials , so the reaction course can be outlined by the following equation:

If, for example, for process variant (b) 2- (5,6-dihydro- [1, 4.2] - oxathiazin-3-yl) -benzenesulfonyl isocyanate and 2-amino-4,6-dimethoxypyrimidine as starting materials, the Reaction history are outlined by the following equation scheme:

Verwendet man beispielsweise für die Verfahrensvariante (c) N-(2-(5,6-Dihydro- [1 ,4,2]- oxathiazin-3-yl)-benzolsulfonyl)-phenylcarbamat und 2-Amino-4,6- dimethoxypyrimidin als Ausgangsstoffe, so kann der Reaktionsverlauf durch das folgende Formelschema skizziert werden:

For example, for process variant (c), use is made of N- (2- (5,6-dihydro- [1,2,2] oxathiazin-3-yl) -benzenesulfonyl) -phenylcarbamate and 2-amino-4,6-dimethoxypyrimidine as starting materials, the course of the reaction can be outlined by the following formula scheme:

The in process (a) for the preparation of compounds of formula (I) as starting materials to be used (Het) arylsulfonamide are generally defined by formula (II). In formula (II), J has the meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being particularly preferred for J.

Examples of the compounds of the formula (II) which may be mentioned are: 2- (5,6-dihydro [1,2,2] oxathiazin-3-yl) benzenesulfonamide, 2- (5,6-dihydro- [1, 4 , 2] -oxathiazin-3-yl) -6-methyl-benzenesulfonamide, 2- (5,6-dihydro- [1,2,2] -oxathiazin-3-yl) -phenylmethanesulfonamide, 3- (5,6- Dihydro- [1,2,2] oxathiazin-3-yl) -pyridine-2-sulfonamide, 2- (5,6-dihydro- [1,2,2] -oxathiazin-3-yl) -thiophene-3 sulfonamide, 1-methyl-4- (5,6-dihydro- [1,2,2] oxathiazin-3-yl) -pyrazole-5-sulfonamide, 1-methyl-3-chloro-4- (5, 6-dihydro- [1,2,2] oxathiazin-3-yl) -pyrazole-5-sulfonamide. The starting materials of the formula (II) are not yet known from the literature and as novel substances are also the subject of the present invention. Process for the preparation of the compounds of the formula (II) are described below [cf. Methods (d) and (e)].

The N-azinyl carbamates also to be used as starting materials in process (a) are generally defined by formula (III). In formula (III), A, R ¹ , R ² and R ³ preferably or in particular have those meanings which have already been mentioned above in connection with the description of the novel compounds

Compounds of formula (I) were preferably or as particularly preferred for A, R ¹ , R ² and R ^{3 were} specified. R ¹² is preferably (C 1 -C 6) -alkyl or (C 1 -C 5) -aryl, particularly preferably (C 1 -C ₄ ) -alkyl or phenyl.

The starting materials of the formula (III) are known and / or can be prepared by processes known per se (cf., EP-238 070).

The in process (b) for the preparation of compounds of formula (I) as starting materials to be used (Het) arylsulfonylisocyanate are generally defined by formula (IV). In formula (IV), J preferably has

in particular those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being particularly preferred for J.

Examples of starting materials of the formula (IV) which may be mentioned are: 2- (5,6-dihydro- [1,2,2] oxathiazin-3-yl) benzenesulfonyl isocyanate, 2- (5,6-dihydro- [1, 4,2] -oxathiazin-3-yl) -6-methyl-benzenesulfonyl isocyanate, 2- (5,6-dihydro- [1,2,2] -oxathiazin-3-yl) -phenylmethanesulfonyl isocyanate, 3- (5,6- Dihydro- [1,2,2] oxathiazin-3-yl) -pyridine-2-sulfonyl isocyanate, 2- (5,6-dihydro- [1,2,2] oxathiazin-3-yl) -thiophene-3 sulfonyl isocyanate, 1-methyl-4- (5,6-dihydro- [1,2,2] oxathiazin-3-yl) pyrazole-5-sulfonyl isocyanate, 1-methyl-3-chloro-4- (5, 6-dihydro- [1,2,2] oxathiazin-3-yl) pyrazole-5-sulfonyl isocyanate. The starting materials of the formula (IV) are not yet known from the literature and as novel substances are also the subject of the present invention. The novel (het) arylsulfonyl isocyanates of the formula (IV) are obtained by reacting (het) arylsulfonamides of the above formula (II) with phosgene in the presence of a diluent, such as, for example, chlorobenzene, and reaction auxiliaries, such as, for example, butyl isocyanate and diazabicyclooctane (DABCO), at temperatures between 0 ° C and 200 ° C, preferably between 20 ° C and 160 ° C, and then the volatile components are carefully distilled off under reduced pressure (see, EP 162 723).

The in process (b) for the preparation of compounds of formula (I) further required as starting materials aminoazines are generally defined by formula (V). In formula (V), A, R ¹ , R ² and R ^{3 are} preferably or

in particular those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being particularly preferred for R ¹ , R ² and R ³ . As examples of the starting materials of the formula (V) may be mentioned:

 2-amino-4,6-dimethoxypyrimidine,

 2-amino-4,6-diethoxypyrimidin,

 2-methylamino-4,6-dimethoxypyrimidine,

 2-methoxymethylamino-4,6-dimethoxypyrimidine,

2-amino-4,6-dimethylpyrimidine,

 2-amino-4,6-diethylpyrimidin,

 2-amino-4,6-bis pyrimidine (difluoromethoxy),

 2-amino-4,6-bis pyrimidine (dimethylamino)

 2-amino-4-methyl-6-ethylpyrimidine,

2-Am ino-4-methoxy-6-chloropyrim id in,

 2-amino-4-ethoxy-6-methylaminotriazin,

2-amino-4-methoxy-6-methyltriazin, 2-Amino-4-isopropoxy-6-chlorotriazine,

2-amino-4-methoxy-6-chlorotriazine,

2-Amino-4- (2,2,2-trifluoroethoxy) -6-dimethylaminotnazin,

2-amino-4-trifluornnethyl-6-nnethoxytriazin,

2-Amino-4-methylamino-6-chlorotriazine,

 2-amino-4-methoxy-6-dimethylaminotriazin,

2-amino-4,6-dimethoxytriazine,

2-amino-4,6-diethoxytriazin,

2-amino-4,6-dimethyltriazin,

2-amino-4-methyl-6-chloropyrimidine,

2-amino-4-methoxy-6-methylpyrimidine,

2-Amino-4-methoxy-6-ethoxypyrim id in,

2-amino-4-methoxy-6-dimethylaminopyrimidine,

2-amino-4-ethoxy-6-chloropyrimidine,

2-amino-4-ethoxy-6-dimethylaminopyrimidine,

2-amino-4-methyl-6-dimethylaminopyrimidine,

2-amino-4-methyl-6-isopropoxypyhmidin,

2-amino-4-dimethylamino-6-chloropyrimidine,

2-Amino-4- (2,2,2-thfluorethoxy) -6-chloropyrimidine,

2-Amino-4-methylamino-6-chloropyrimidine,

2-amino-4-d-isluoromethoxy-6-methylpyrimide in,

2-Amino-4- (2,2,2-thfluorethoxy) -6-methylpyrimidine.

The starting materials of the formula (V) are known and / or can be prepared by processes known per se (compare Huaxue Shijie, 32 (6), 254-7 (1991) JP-01 016 770, EP-246 984); some of these substances are commercially available synthetic chemicals.

The in process (c) for preparing compounds of formula (I) as starting materials to be used (Het) arylsulfonylcarbamate are generally defined by formula (VI). In formula (VI), J and R ¹² preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formulas (I) or (III) according to the invention preferably or as particularly preferred for J or R ^{12 were} given.

As examples of the starting materials of the formula (VI) may be mentioned:

N- (2- (5,6-dihydro- [1,2,2] oxathiazin-3-yl) benzenesulfonyl) -phenylcarbamate,

 N- (2- (5,6-Dihydro- [1,2,2] oxathiazin-3-yl) -6-methyl-benzenesulfonyl) -phenylcarbamate, N- (2- (5,6-dihydro- [1 , 4,2] -oxathiazin-3-yl) phenylmethanesulfonyl) -phenylcarbamate, N- (3- (5,6-dihydro- [1,2,2] -oxathiazin-3-yl) -pyridine-2-sulfonyl) - phenylcarbamate,

N- (2- (5,6-Dihydro- [1,2,2] oxathiazin-3-yl) thiophene-3-sulfonyl) -phenylcarbamate, N- (1-methyl-4- (5,6-dihydro - [1,2,2] oxathiazin-3-yl) pyrazole-5-sulfonyl) -phenylcarbamate, N- (1-methyl-3-chloro-4- (5,6-dihydro- [1, 4,2 ] -oxathiazin-3-yl) pyrazole-5-sulfonyl) -phenylcarbamate.

The starting materials of the formula (VI) are not yet known from the literature and as novel substances are also the subject of the present invention.

The novel (het) arylsulphonylcarbamates of the formula (VI) are obtained if

(Het) arylsulfonamides of the above formula (II) with chloroformate in

Presence of a diluent, e.g. Dioxane or acetone itril, and reaction auxiliaries, e.g. Pyridine, potassium or calcium carbonate, at

 Temperatures between 0 ° C and 120 ° C, preferably between 20 ° C and 100 ° C, reacted and then the volatile components are distilled off under reduced pressure carefully (see JP-04139170). The aminoazines of the formula (V) which are furthermore required as starting materials in process (c) according to the invention have already been described in more detail above in process (b).

in welcher The new starting and intermediate products of formulas (II), (IV) and (VI) described above and closely related may be collectively referred to as "(Het) arylsulfonyl compounds" and represented by the following formula (VII):

in which

 J has the meanings given above in formula (I) and

G is -NH ₂ , -N = C = O or -NH-COOR ¹² , wherein R ^{12 has} the meaning given above.

The in process (d) for the preparation of compounds of formula (II) as starting materials to be used N-hydroxy

(het) arylcarboxyimidoyl chlorides are generally defined by formula (VIII). In the formula (VIII), the group J preferably has those

Meanings which have already been mentioned above in connection with the description of the compounds of the formulas (I) or (II) according to the invention preferably or as particularly preferred for J.

As examples of the intermediates of the formula (VIII) may be mentioned:

2-bromo-N-hydroxybenzolcarboximidoylchlorid,

2-Bromo-N-hydroxy-3-methylbenzolcarboximidoylchlorid,

2- (bromomethyl) -N-hydroxybenzolcarboximidoylchlorid,

 2-bromo-N-hydroxypyridine-3-carboximidoyl chloride,

5-bromo-N-hydroxy-1-methyl-1H-pyrazole-4-carboximidoyl chloride,

5-bromo-3-chloro-N-hydroxy-1-methyl-1H-pyrazole-4-carboximidoyl chloride,

 3-bromo-N-hydroxythiophene-2-carboximidoyl chloride

The starting materials of the formula (VIII) are all known, some commercially available aldehydes, which can be converted by means of hydroxylamine first in their Carbaldoxime and then with chlorinating agents such as N-chlorosuccinimide or gaseous chlorine in the compounds of formula (VIII) , The new (het) arylsulfonamides of the formula (II) are obtained if (d) N-hydroxy- (het) arylcarboxyimidoyl chlorides of the formula (VIII)

in der Y für Wasserstoff oder Halogen (vorzugsweise für Wasserstoff oder Brom) steht,

in which Y is hydrogen or halogen (preferably hydrogen or bromine),

with an optionally substituted thioalkanol of the formula (IX),

in der

in the

R ⁴ - R ^{7 have} the meanings given above, if appropriate in the presence of an organic diluent and if appropriate in the presence of a reaction auxiliary.

The adduct thus obtained (X)

kann unter Einsatz geeigneter Reagentien zu Verbindungen der Formel (XI) cyclisiert werden. Geeignete Reagentien für eine Cyclisierung sind Azodicarbonsäuredialkylester in Verbindung mit Triphenylphosphin und Nitrophenolen als Katalysator (Mitsunobu- Bedingungen, s. auch Kai, Nakai Tetrahedron Lett. 42 (2001 ) 6895- 6897)

can be cyclized using suitable reagents to compounds of formula (XI). Suitable reagents for a cyclization are dialkyl azodicarboxylates in combination with triphenylphosphine and nitrophenols as catalyst (Mitsunobu conditions, see also Kai, Nakai Tetrahedron Lett., 42 (2001) 6895-6897)

(e) Alternatively, the novel (het) arylsulfonamides of the formula (II) are obtained if N-hydroxy- (Het) -arylcarboxyimidoyl chlorides of the formula (VIII)

in which Y is hydrogen or halogen (preferably hydrogen or bromine),

with an optionally substituted thiol of the formula (XII),

in der

in the

R ⁴ - R ^{7 have} the meanings given above, where X is halogen,

optionally substituted alkyl or arylcarboxynyloxy or -sulfonyloxy

(Preferably, chlorine, bromine, iodine, (Ci-Ce) alkyl or (C6-Ci2) -Arylcarbonyloxy or -sulfonyloxy), optionally in the presence of an organic

Diluent and optionally in the presence of a reaction auxiliary. The adduct thus obtained (XIII)

kann ebenfalls unter Einsatz geeigneter Basen, wie zum Beispiel Alkalimetallhydride, z.B. Natriumhydrid zu Verbindungen der Formel (XI) cyclisiert werden.

may also be cyclized to compounds of formula (XI) using appropriate bases, such as alkali metal hydrides, eg, sodium hydride.

From compounds of formula (XI) can be with suitable

Organometallic compounds, such as e.g. n-butyllithium, n-butylmagnesium chloride, n-butylmagnesium bromide, sec-butyllithium or tert-butyllithium, in the course of a halogen-metal exchange or e.g. with n-butyllithium, n-butylmagnesium chloride, n-butylmagnesium bromide, sec-butyllithium, tert-butyllithium,

 Lithium diisopropylamide, lithium hexamethyldisilazide or lithium tetramethylpiperidide in the course of deprotonation metallated derivatives of the formula (XIV) win, where M is an alkali or alkaline earth metal, preferably lithium or magnesium.

These metalated derivatives of the formula (XIV) can be reacted with suitable

Sulfonylating agents, such as gaseous sulfur dioxide on their Metal sulfinates, which are then oxidized with sulfuryl chloride, or directly with sulfuryl chloride in the chlorosulfones are transferred.

The chlorosulfones can then be treated with a suitable nitrogen source, e.g. gaseous ammonia or aqueous ammoniacal solutions into the desired compounds of formula (II).

8 10

Table A: Examples of the compounds of the formula (II) where R = CHs and R = H:

¹ H NMR data (400 MHz, solvent: DMSO-d ₆ , internal standard tetramethylsilane: d = 0.00 ppm) s = singlet, sbr = broad singlet, d = doublet, dd = double doublet, m = multiplet, q = Quartet, t = triplet)

A-1: (solvent: CDCl ₃ ) d = 8.15 - 8.05 ppm (m, 4H); 5.50 ppm (sbr, 2H); 4.35-4.25 ppm (m, 2H); 3.45-3.35 ppm (m, 2H)

 A-3: d = 8.85 - 8.75 ppm (s, 1H); 8.05-7.95 ppm (m, 1H); 7.75-7.65 ppm (m, 1H);

 7.45 ppm (s, 2H); 4.20 - 4.10 ppm (m, 2H); 3.45-3.35 ppm (m, 2H)

A-4: (solvent: CDCl ₃ ) d = 8.75 ppm (m, 1H); 7.95 ppm (m, 1H); 7.60 ppm (m, 1H);

 6.35 ppm (sbr, 2H); 4.20 ppm (m, 1H); 3.15 ppm (m, 2H); 1.49 ppm (d, 3H) A-5: d = 7.70 ppm (s, 1H); 7.30 ppm (s, 2H); 4.10-4.00 ppm (m, 2H); 4.05 ppm (s, 1H); 3.40-3.30 ppm (m, 2H)

 A-7: d = 7.80 ppm (d, 1H); 7.35 ppm (s, 2H); 7.20 ppm (d, 1H); 4.20 - 4.10 ppm (m,

2H) 3.50 - 3.40 ppm (m, 2H)

The processes (a), (b), (c) according to the invention for the preparation of the new

Compounds (I), the inventive method (d) and (e) for the preparation of new intermediates of formula (II) are preferably carried out using diluents. Suitable diluents are virtually all inert organic solvents. These include

preferably - aliphatic and aromatic, optionally halogenated

Hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride,

Chlorobenzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ether,

Glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as e.g. Acetonitrile and propionitrile, amides, e.g. Dimethylformamide, dimethylacetamide and N-methylpyrrolidone and dimethyl sulfoxide, tetramethylene sulfone and hexamethylphosphoric triamide.

The processes (a), (d) and (e) according to the invention are optionally carried out in the presence of a reaction auxiliary. These preferably include basic organic nitrogen compounds, e.g. Trimethylamine, triethylamine, N, N-dimethylaniline, Ν, Ν-dimethylbenzylamine, pyridine, 4-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) and diazabicycloundecene (DBU), as well as inorganic bases, e.g. Sodium hydride, potassium hydride,

Sodium carbonate, potassium carbonate, calcium carbonate, potassium hydroxide,

Sodium hydroxide, and calcium hydroxide.

 The inventive processes (b) and (c) are optionally carried out in the presence of a reaction auxiliary. Suitable for this purpose are preferably basic organic nitrogen compounds, e.g. Trimethylamine, triethylamine, N, N-dimethylaniline, Ν, Ν-dimethylbenzylamine, pyridine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) and diazabicycloundecene (DBU).

The reaction temperatures can in each case be varied within a relatively wide range in processes (a) to (e).

That's how you work

 - In process (a) generally at temperatures between 0 ° C and

150 ° C, preferably at temperatures between 10 ° C and 80 ° C;

 - In process (b) generally at temperatures between 0 ° C and

 150 ° C,

 preferably at temperatures between 20 ° C and 100 ° C;

 - in process (c) also generally at temperatures between 0 ° C and 150 ° C, preferably so at temperatures between 20 ° C and 100 ° C;

- in processes (d) and (e) generally at temperatures between -20 ° C and

 + 40 ° C, preferably at temperatures between -20 ° C and + 30 ° C.

The processes (a) to (e) are generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure. For carrying out the processes (a) to (e) according to the invention, the particular starting materials required in each case are used in approximately equimolar amounts. However, it is also possible to use one of the two components used in each case in a larger excess. The reactions are generally carried out in a suitable diluent and optionally with the addition of a reaction auxiliary, and the reaction mixture becomes several

 Stirred at the required temperature for hours. The workup is carried out in the inventive method in each case by conventional methods.

Salts may optionally be prepared from the compounds of the general formula (I) according to the invention. Such salts are obtained in a simple manner by customary salt formation methods, for example by dissolving or dispersing a compound of the formula (I) in a suitable manner

Diluents, such as methylene chloride, acetone, tert-butyl methyl ether or toluene, and addition of a suitable base. The salts can then be isolated by concentrating or filtering off, if appropriate after prolonged stirring (compare the preparation examples). The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and especially as weed killers. Weeds in the broadest sense are all plants that grow in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides essentially depends on the amount used.

The active compounds of the invention may e.g. used in the following plants:

Dicotyledonous weeds of the genera:

 Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea,

Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Dicotyledonous cultures of the genera:

 Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

Monocotyledonous weeds of the genera:

 Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine,

Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocotyl cultures of the genera:

Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium. However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants. The compounds are suitable depending on the concentration

 Total weed control e.g. on industrial and railway tracks and on paths and squares with and without tree cover. Similarly, the compounds for weed control in permanent crops, e.g. Forest, ornamental, fruit, wine, citrus, nut, banana, coffee, tea, gum, oil palm, cocoa, berry fruit and hop plants, on ornamental and sports turf and pasture and selective Weed control in one-year crops.

The compounds of the formula (I) according to the invention are suitable for the selective control of monocotyledonous and dicotyledonous weeds in different crops, in part e.g. in wheat, both pre-emergence and post-emergence.

The compounds of the invention may be in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or

Granules are used in the usual preparations. The invention therefore also relates to herbicidal and plant growth-regulating agents which contain the compounds according to the invention.

The compounds according to the invention can be formulated in various ways, depending on which biological and / or chemical-physical parameters are predetermined. As formulation options come

for example in question: wettable powder (WP), water-soluble powder (SP),

water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions,

Suspension concentrates (SC), 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 and will be known in principle

for example, described in: Winnacker-Kuchler, "Chemical Technology", Volume 7, C. Hanser Verlag Munich, 4th ed., 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd ed. 1979, G. Goodwin Ltd. London.

The necessary formulation auxiliaries such as inert materials, surfactants,

Solvents and 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, N.Y .; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers

Annual ", MC Publ. Corp., Ridgewood N.J .; Sisley and Wood," Encyclopedia of Surface Active Agents ", Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt,

 "Surface-active ethylene oxide adducts", Wiss. Publishing company, Stuttgart 1976;

Winnacker-Kuchler, "Chemische Technologie", Volume 7, C. Hanser Verlag Munich, 4th ed., 1986. On the basis of these formulations, it is also possible to use combinations with other pesticidally active substances, e.g. Insecticides, acaricides, herbicides,

Fungicides, as well as with safeners, fertilizers and / or growth regulators, e.g. in the form of a ready-made formulation or as a tank mix. Injectable powders are preparations which are uniformly dispersible in water and contain surfactants of the ionic and / or nonionic type (wetting agents, dispersants) in addition to the active ingredient except a diluent or inert substance. polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines,

Fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates,

lignosulfonic acid sodium, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, dibutylnaphthalene-sulfonic acid sodium or oleoylmethyltaurine acid. To prepare the wettable powders are the herbicidal active ingredients for example, finely ground in conventional equipment such as hammer mills, blower mills and air jet mills and at the same time or subsequently with the

Formulation aids mixed. Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyclohexanone, dimethylformamide, xylene or 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 suitable emulsifiers 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. Sorbitan fatty acid esters or polyoxethylenesorbitan esters such as e.g.

Polyoxyethylene.

Dusts are obtained by milling the active ingredient with finely divided solids, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

Suspension concentrates may be water or oil based. They can be prepared, for example, by wet grinding using commercially available bead mills and, if appropriate, addition of surfactants, as described, for example, in US Pat. upstairs with the others

Formulation types already listed are produced.

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

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 example polyvinyl alcohol, sodium polyacrylate or mineral oils, on the surface of carriers such as sand, 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 generally prepared by the usual methods such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.

For the preparation of plate, fluid bed, extruder and spray granules, see e.g.

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 Chemical Engineer's Handbook, 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.

For further details on the formulation of crop protection agents see, e.g. 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., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

The agrochemical preparations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of compounds according to the invention.

In wettable powders, the drug concentration is e.g. about 10 to 90 wt .-%, the balance to 100 wt .-% consists of conventional formulation ingredients. For emulsifiable concentrates, the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%. Dust-like 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

Granulation aids, fillers, etc. are used. In 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, antifreeze and solvent, fillers, carriers and dyes, antifoams,

Evaporation inhibitors and pH and viscosity affecting agents.

The following are some examples of possible drug formulations: a) A dust is obtained by mixing 10 parts by weight of a compound of formula (I) and / or salts thereof and 90 parts by weight of talc as an inert material and comminuted in a hammer mill. b) A wettable powder readily dispersible in water is obtained by reacting 25 parts by weight of a compound of the formula (I) and / or its salts,

64 parts by weight of kaolin-containing quartz as inert material, 10 parts by weight

 potassium lignosulfonate and 1 part by weight oleoylmethyltaurine sodium as wetting and dispersing agent and grinding in a pin mill.

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

 Parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to more than 277 C) and ground in a ball mill to a fineness of less than 5 microns.

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

 Compound of formula (I) and / or salts thereof, 75 parts by weight

 Cyclohexanone as a solvent and 10 parts by weight of ethoxylated

Nonylphenol as emulsifier. A water-dispersible granule is obtained by reacting 75 parts by weight of a compound of the formula (I) and / or salts thereof,

 10 parts by weight of lignosulfonic acid calcium,

 5 parts by weight of sodium lauryl sulfate,

 3 parts by weight of polyvinyl alcohol and

 7 parts by weight kaolin

 milled, ground on a pin mill and granulated the powder in a fluidized bed by spraying water as Granulierflüssigkeit.

A water-dispersible granule is also obtained by

25 parts by weight of a compound of the formula (I) and / or salts thereof,

 5 parts by weight of 2,2'-dinaphthylmethane-6,6'-disulfonate sodium

 2 parts by weight oleoylmethyltaurine acid sodium,

 1 part by weight of polyvinyl alcohol,

 17 parts by weight of calcium carbonate and

 50 parts by weight of water

 Homogenized on a colloid mill and pre-crushed, then grinded on a bead mill and the suspension thus obtained in a spray tower by means of a Einstoffdüse atomized and dried.

The active compounds according to the invention can be used as such or in their formulations also in mixture with known herbicides for controlling weeds, ready-to-use formulations or tank mixes being possible. As a combination partner for the compounds of the invention in

 Mixture formulations or in the tank mix are known, for example

Active substances which are based on an inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthetase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, protoporphyrinogen Oxidase based, for example, as described in Weed Research 26 (1986) 441 -445 or "The Pesticide Manual", 14th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2003 and cited there literature are described. Known herbicides or plant growth regulators which can be combined with the compounds according to the invention are, for example, the following active substances (which

Compounds are denoted either by the common name according to the International Organization for Standardization (ISO) or by the chemical name or by the code number) and always include all forms of use such as acids, salts, esters and isomers such as stereoisomers and optical isomers. Here are an example and partly also called several application forms:

Acetochlor, acibenzolar, acibenzolar-S-methyl, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn,

Amicarbazone, amidochlor, amidosulfuron, aminocyclopyrachlor, aminopyralid, amitrole, ammonium sulfamate, ancymidol, anilofos, asulam, atrazines, azafenidine, azimsulfuron, aziprotryn, BAH-043, BAS-140H, BAS-693H, BAS-714H, BAS-762H, BAS- 776H, BAS-800H, Beflubutamide, Benazoline, Benazolin-ethyl, Bencarbazone, Benfluralin, Benfuresate, Bensulide, Bensulfuron-methyl, Bentazone, Benzfendizone, Benzobicyclone, Benzofenap, Benzofluor, Benzoylprop, Bicyclopyrone, Bifenox, Bilanafos, Bilanafos-Sodium, Bispyribac, Bispyribac Sodium, Bromacil, Bromobutide, Bromofenoxime, Bromoxynil, Bromuron, Buminafos, Busoxinone, Butachlor,

Butafenacil, butamifos, butenachlor, butraline, butroxydim, butylates, cafenstrols, carbetamides, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, chloramben, chloroazifop, chlorazifop-butyl, chlorobromuron, chlorobufam, chlorfenac, chlorfenacsodium, chlorfenprop, chlorofluorol, chlorofluorol-nnethyl, Chloridazon, chlorimuron, chlorimuron-ethyl, chlormequat chloride, chloronitrofen, chlorophthalim, chlorothal-dimethyl, chlorotoluron, chlorosulfuron, cinidone, cinidon-ethyl, cinmethylin,

Cinosulfuron, clethodim, clodinafop clodinafop-propargyl, clofencet, clomazone, clomeprop, cloprop, clopyralid, cloransulam, cloransulam-methyl, cumyluron, cyanamides, cyanazines, cyclanilides, cycloates, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyhalofop-butyl, cyperquat, cyprazine , Cyprazole, 2,4-D, 2,4-DB, Daimuron / Dymron, Dalapon, Daminozide, Dazomet, n-Decanol, Desmedipham, Desmetryn, Detosyl-Pyrazolate (DTP), Diallate, Dicamba, Dichlobenil, Dichlorprop, Dichlorprop- P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, diethatyl, Diethatyl-ethyl, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron, dikegulac-sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipine, dimetrasulfuron, dinitramine, dinoseb, dinoterb, diphenamid, dipropetryn, Diquat, diquat-dibromide, dithiopyr, diuron, DNOC, eglinazine-ethyl, endothal, EPTC, esprocarb, etalfluralin, ethametsulfuron-n-ethyl, ethephon, ethidimuron, ethiozine, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanide, F-5331, ie N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo-1H-tetrazol-1-yl] -phenyl] -ethanesulfonamide,

Fenoprop, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fentrazamide, fenuron, flamprop, flamprop-M-isopropyl,

 Flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-p-butyl, fluazolates, flucarbazone, flucarbazone-sodium,

Flucetosulfuron, Fluchloralin, Flufenacet (Thiafluamide), Flufenpyr, Flufenpyr-ethyl, Flumetralin, Flumetsulam, Flumiclorac, Flumiclorac-pentyl, Flumioxazin,

Flumipropyne, fluometuron, fluorodifene, fluoroglycofen, fluoroglycofen-ethyl,

Flupoxam, flupropacil, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, flurenol, flurenol-butyl, fluridone, flurochloridone, fluroxypyr, fluroxypyr-meptyl, flurprimidol, flurtamone, fluthiacet, fluthiacet-methyl, fluthiamide, fomesafen, foramsulfuron, förch lorfenuron, fosamine , Furyloxyfen, gibberellin acid,

Glufosinate, L-glufosinate, L-glufosinate-ammonium, glufosinate-ammonium, glyphosate, glyphosate-isopropylammonium, H-9201, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfopethoxyethyl, haloxyfop-P-ethoxyethyl, Haloxyfop-methyl, Haloxyfop-P-methyl, Hexazinone, HNPC-9908, HOK-201, HW-02, Imazamethabenz, Imazamethabenz-methyl, Imazamox, Imazapic, Imazapyr, Imazaquin, Imazethapyr, Imazosulfuron, Inabenfide, Indanofan,

Indaziflam, indoleacetic acid (IAA), 4-indol-3-yl-butyric acid (IBA), iodosulfuron, iodosulfuron-methyl-sodium, loxynil, lecarbarbazonejsocarbamide, isopropalin, isoproturon, isourone, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, IDH-100, KUH 043, KUH-071, carbutilates, ketospiradox, lactofen, lenacil, linuron,

Maleic hydrazide, MCPA, MCPB, MCPB-methyl, -ethyl and -sodium, mecoprop, mecoprop-sodium, mecoprop-butotyl, mecoprop-p-butotyl, mecoprop-P-dimethylammonium, mecoprop-P-2-ethylhexyl, mecoprop-P potassium, mefenacet, Mefluidides, mepiquat chloride, mesosulfuron, mesosulfuron-methyl, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methazoles, methiozoline, methoxyphenones, methyldymrone, 1-methylcyclopropene, methylisothiocyanate, metobenzuron, metobenzuron, metobromuron, metolachlor, S- Metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinates, monalides, monocarbamides, monocarbamide dihydrogen sulfate,

Monolinuron, monosulfuron, monuron, MT 128, MT-5950, d. H. N- [3-chloro-4- (1-methylethyl) phenyl] -2-methylpentanamide, NGGC-01 1, naproanilides, napropamide, naptalam, NC-310, i. 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazoles, neburon, nicosulfuron, nipyraclofen, nitrite, nitrofen, nitrophenolate sodium

(Mixture of isomers), nitrofluorfen, nonanoic acid, norflurazon, orbencarb,

Orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paclobutrazole, paraquat, paraquat-dichloride, pelargonic acid

(Nonanoic acid), pendimethalin, pendralin, penoxsulam, pentanochlor, pentoxazone, perfluidone, pethoxamide, phenisopham, phenmedipham, phenmedipham-ethyl,

Pidoram, Picolinafen, Pinoxaden, Piperophos, Pirifenop, Pirifenopbutyl, Pretilachlor, Primisulfuron, Primisulfuron-methyl, Probenazole, Profluazole, Procyazine,

Prodiamines, prifluralins, profoxydim, prohexadione, prohexadione-calcium,

Prohydrojasmone, Prometon, Prometry, Propachlor, Propanil, Propaquizafop, Propazine, Prophet, Propisochlor, Propoxycarbazone, Propoxycarbazone Sodium, Propyrisulfuron, Propyzamide, Prosulfine, Prosulfocarb, Prosulfuron, Prynachlor, Pyraclonil, Pyraflufen, Pyraflufen-ethyl, Pyrasulfotole, Pyrazolynate (Pyrazolate) , Pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl,

Pyribenzoxim, Pyributicarb, Pyridafol, Pyridate, Pyriftalid, Pyriminobac, Pyriminobacmethyl, Pyrimisulfan, Pyrithiobac, Pyrithiobac Sodium, Pyroxasulfones, Pyroxsulam, Quinclorac, Quinmerac, Quinoclamine, Quizalofop, Quizalofop-ethyl, Quizalofop-P, Quizalofop-P-ethyl, Quizalofop P-tefuryl, rimsulfuron, saflufenacil, secbumetone, sethoxydim, siduron, simazine, simetryn, SN-106279, sulcotrione, sulfallates

(CDEC), sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosate (glyphosate trimesium), sulfosulfuron, SYN-523, SYP-249, SYP-298, SYP-300, tebutam, tebuthiuron, tecnazene, tefuryltrione, tembotrione, tepraloxydim, terbacil , Terbucarb, Terbuchlor, Terbumetone, Terbuthylazine, Terbutryn, TH-547, Thenylchloro, thiafluamides, thiazafluron, thiazopyr, thidiazimine, thidiazuron, thiencarbazones, thiencarbazone-n-ethyl, thifensulfuron, thifensulfuron-n-ethyl, thiobencarb, tiocarbazil, toramezone, tralkoxydim, triallate, triasulfuron, thaziflam, triazofenamide, tribenuron, tribenuron-methyl, trichloroacetic acid (TCA) , Triclopyr, Tridiphane, Trietazine, Trifloxysulfuron, Trifloxysulfuron-nathum, Trifluralin, Triflusulfuron, Triflusulfuron-methyl, Trimeturon, Trinexapac, Trinexapacethyl, Tritosulfuron, Tsitodef, Uniconazole, Uniconazole-P, Vernolate, ZJ-0166, ZJ-0270, ZJ -0543, ZJ-0862 and the following compounds

Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Fungiziden,

Also a mixture with other known active ingredients, such as fungicides,

Insecticides, acaricides, nematicides, bird repellents,

Plant nutrients and soil conditioners are possible.

The compounds according to the invention can also be used in combination with one or more compounds which act as safeners.

The safeners are preferably selected from the group consisting of S1) compounds of the formula (S1),

wobei die Symbole und Indizes folgende Bedeutungen haben:

where the symbols and indices have the following meanings:

n _A is a natural number from 0 to 5, preferably 0 to 3;

R _A ¹ is halogen, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkoxy, nitro or (C 1 -C ₄ ) -haloalkyl;

W _A is an unsubstituted or substituted divalent heterocyclic radical from the group of the unsaturated or unsaturated five-membered ring heterocycles having 1 to 3 hetero ring atoms from the group N and O, wherein 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 ),

A1) (W _A ² ) (W _A ³ ) (VV) m _A is 0 or 1;

R _A ² is OR _A ³ , SR _A ³ or NR _A ³ R _A ⁴ or a saturated or unsaturated 3- to 7-membered heterocycle having at least one N atom and up to 3 hetero atoms, preferably from the group O and S, who uses the N atom with the Carbonyl group in (S1) is connected and unsubstituted or by radicals from the group (Ci-C ₄ ) alkyl, (dC ₄ ) alkoxy or optionally

substituted phenyl, preferably a radical of the formula ORA ³ , NHR _a ⁴ or N (CH ₃ ) 2, in particular of the formula ORA ³ ;

R _a ³ is hydrogen or an unsubstituted or substituted aliphatic

 Hydrocarbon radical, preferably having a total of 1 to 18 carbon atoms;

R _A ⁴ is hydrogen, (C 1 -C 6) -alkyl, (C 1 -C 6) -alkoxy or substituted or

 unsubstituted phenyl;

R _A ⁵ is H, (C 1 -C ₈ ) -alkyl, (C 1 -C ₈ ) -haloalkyl, (C 1 -C ₄ ) -alkoxy- (C 1 -C ₈ ) -alkyl, cyano or COORA ⁹ , in which R _A ^{9 is} hydrogen, (C 1 -C ₈ ) -alkyl, (C 1 -C ₈ ) -haloalkyl, (C 1 -C ₄ ) -alkoxy- (C 1 -C ₄ ) -alkyl, (C ₁ -C ₆ ) -hydroxyalkyl, (C ₃ - Ci ₂₎ cycloalkyl or tri- (dC ₄₎ -alkyl-silyl;

R _A ^6, R _A ^7, RA ⁸ are identical or different hydrogen, (Ci-C ₈₎ alkyl, (CrC ₈₎ -Halo- alkyl, (C3-Ci2) -cycloalkyl or substituted or unsubstituted phenyl; preferably:

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

 1- (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylic acid 1- (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline Ethyl 3-carboxylate (S1-1) ("mefenpyr-diethyl"), and related compounds as described in WO-A-91/07874;

b) dichlorophenylpyrazolecarboxylic acid derivatives (S1 ^b), preferably compounds such as 1 - (2,4-dichlorophenyl) -5-methyl-pyrazol-3-carbonsäureethyl- ester (S1 -2), 1 - (2,4-dichlorophenyl) - Ethyl 5-isopropyl-pyrazole-3-carboxylate (S1-3), 1- (2,4-dichlorophenyl) -5- (1,1-dimethyl-ethyl) -pyrazole-3-carboxylic acid ethyl ester (S1- 4) and related compounds, as in

 EP-A-333,131 and EP-A-269,806 are described;

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 -chlorophenyl) -5-phenylpyrazole-3-carbonsäuremethylester (S1 -6) and related compounds as described, for example, in EP-A-268554;

Compounds of the type of triazolecarboxylic acids (S1 ^d ), preferably

 Compounds such as fenchlorazole (ethyl ester), i.

 1- (2,4-dichlorophenyl) -5-thchloromethyl- (1H) -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;

Compounds of the 5-benzyl- or carboxylic acid-5-phenyl-2-isoxazoline-3 or the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (S1 ^e), preferably compounds such as ethyl 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-91/08202, or 5,5-diphenyl-2-isoxazoline-carboxylic acid (S1 -10) or 5,5-diphenyl-2-isoxazoline-carboxylic acid ethyl ester (S1-1 1) ("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 are described.

Quinoline derivatives of the formula (S2)

where the symbols and indices have the following meanings:

R _B ¹ is halogen, ( _C ¹ -C ₄ ) -alkyl, ( _C ¹ -C ₄ ) -alkoxy, nitro or (C 1 -C ₄ ) -haloalkyl;

n _B is a natural number from 0 to 5, preferably 0 to 3;

R _B ² is OR _B ³ , SR _b ³ or NR _B ³ R _B ⁴ or a saturated one

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 with the carbonyl group in (S2) and unsubstituted or by radicals the group (Ci-C ₄ ) -alkyl, (Ci-C ₄ ) -alkoxy or optionally substituted phenyl, preferably one

Radical of the formula ORB ³ , NHR _b ⁴ or N (CH ₃ ) ₂ , in particular of the formula ORB ³ ; RB ³ is hydrogen or an unsubstituted or substituted aliphatic

 Hydrocarbon radical, preferably having a total of 1 to 18 carbon atoms;

RB ⁴ is hydrogen, (C 1 -C 6) alkyl, (C 1 -C 6) alkoxy or substituted or

 unsubstituted phenyl;

T _B is a (C 1 or C ₂ ) alkanediyl chain which is unsubstituted or substituted by one or two (C 1 -C ₄ ) -alkyl radicals or by [(C 1 -C 3) -alkoxy] -carbonyl; preferably:

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

 Allyl (5-chloro-8-quinolinoxy) acetates (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-A-0 492 366, 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) malonate 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-A-0 582 198 are described. S3) compounds of the formula (S3)

wobei die Symbole und Indizes folgende Bedeutungen haben:

where the symbols and indices have the following meanings:

Rc ¹ is (Ci-C ₄₎ alkyl, (Ci-C ₄₎ -haloalkyl, (C ₂ -C ₄₎ alkenyl, (C ₂ -C ₄₎ haloalkenyl,

_(C3-C7) -cycloalkyl, preferably dichloromethyl;

Rc ^2, rc ³ are identical or different hydrogen, (Ci-C ₄₎ -alkyl, _(C2-C4) -alkenyl, (C ₂ -C ₄₎ alkynyl, (Ci-C ₄₎ -haloalkyl, (C ₂ -C ₄₎ haloalkenyl, (dC ₄₎ - Al kylcarbamoyl- (Ci -C ₄₎ -alkyl, (C ₂ -C ₄₎ -alkyl kenylcarbamoyl- (Ci -C ₄₎ -alkyl, (Ci - C ₄ ) - alkoxy- (C 1 -C ₄ ) -alkyl, dioxolanyl- (C 1 -C ₄ ) -alkyl, thiazolyl, furyl, furylalkyl,

Thienyl, piperidyl, substituted or unsubstituted phenyl, or R _c ² and Rc ³ together form a substituted or unsubstituted one

 heterocyclic ring, preferably an oxazolidine, thiazolidine,

 Piperidine, morpholine, hexahydropyrimidine or benzoxazine ring; preferably:

 Active substances of the dichloroacetamide type, which are often used as pre-emergence safeners (soil-active safeners), such as. 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) of 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) Company Nitrokemia or Monsanto (S3-7),

 "TI-35" (1-dichloroacetyl-azepane) from TRI-Chemical RT (S3-8),

 "Diclonone" (dicyclonone) or "BAS145138" or "LAB145138" (S3-9) ((RS) -1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo [1,2-a] pyrimidin-6-one) from BASF .

 "Furilazole" or "MON 13900" ((RS) -3-dichloroacetyl-5- (2-furyl) -2,2-dimethyl-oxazolidine) (S3-10); and its (R) isomer (S3-1 1).

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

wherein the symbols and indices have the following meanings:

X _D is CH or N;

R _D ¹ is CO-NR _D ⁵ R _D ⁶ or NHCO-RD ⁷ ;

RD ² is halogen, (C 1 -C ₄ ) -haloalkyl, (C 1 -C ₄ ) -haloalkoxy, nitro, (C 1 -C ₄ ) -alkyl,

(dC ₄₎ alkoxy, (CrC ₄₎ alkylsulfonyl, (dC ₄₎ -alkoxycarbonyl or _(Ci-C4) - alkylcarbonyl;

R _D ³ is hydrogen, (C ₁ -C ₄ ) -alkyl, (C ₂ -C ₄ ) -alkenyl or (C ₂ -C ₄ ) -alkynyl;

R _D ⁴ is halogen, nitro, (dC ₄₎ -alkyl, (dC ₄₎ -haloalkyl, (dC ₄₎ haloalkoxy,

(C ₃ -C ₆₎ -cycloalkyl, phenyl, (dC ₄₎ alkoxy, cyano, (dC ₄₎ alkylthio, (dC ₄₎ - alkylsulfinyl, (CrC ₄₎ alkylsulfonyl, (dC ₄₎ -alkoxycarbonyl or ( C 1 -C ₄ ) - alkylcarbonyl;

R _D 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 -C ₆ ) ) -Cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl containing v _D heteroatoms from the group consisting of nitrogen, oxygen and

Sulfur, where the seven last-mentioned radicals are substituted by v _D substituents from the group halogen, (d-C6) alkoxy, (d-C6) -haloalkoxy, (dC ₂₎ alkylsulfinyl, _(Ci-C2) alkylsulfonyl, (C ₃ -C ₆₎ -cycloalkyl, (dC ₄₎ alkoxycarbonyl, (dC ₄₎ - Alkylcarbonyl and phenyl and in the case of cyclic radicals are also (C 1 -C ₄ ) -alkyl and (C 1 -C ₄ ) -haloalkyl substituted;

R _D ⁶ is hydrogen, (C ₁ -C ₆ ) -alkyl, (C ₂ -C ₆ ) -alkenyl or (C ₂ -C ₆ ) -alkynyl, where the three last-mentioned radicals are represented by v _D radicals from the group consisting of halogen, hydroxy , (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkoxy and (C 1 -C ₄ ) -alkylthio, or

RD ⁵ and RD ⁶ together with the nitrogen atom carrying them

 Pyrrolidinyl or piperidinyl moiety;

R _D ⁷ is hydrogen, (C 1 -C ₄ ) -alkylamino, di- (C 1 -C ₄ ) -alkylamino, (C ₁ -C ₆ ) -alkyl,

(C ₃ -C 6) -cycloalkyl, where the 2 last-mentioned radicals are substituted by v _D substituents from the group halogen, (dC ₄₎ alkoxy, (d-C6) haloalkoxy and (Ci-C ₄₎ -

Alkylthio and in the case of cyclic radicals also (C 1 -C ₄ ) -alkyl and (C 1 -C ₄ ) -

Haloalkyl are substituted;

n _D is 0, 1 or 2;

m _D is 1 or 2;

worin 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

RD ⁷ (CrC ₆₎ alkyl, (C ₃ -C 6) -cycloalkyl, where the 2 last-mentioned radicals are substituted by v _D substituents from the group halogen, (dC ₄₎ alkoxy, (d-C6) haloalkoxy and (Ci- C ₄ ) alkylthio and in the case of cyclic radicals are also (C 1 -C ₄ ) -alkyl and (C 1 -C ₄ ) -haloalkyl substituted;

R _D ^{4 is} halogen, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkoxy, CF _3;

m _D 1 or 2;

v _D 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,

e.g. such

R _D ⁵ = cyclopropyl and (R _D ⁴ ) = 2-OMe ("Cyprosulfamide", S4-1),

R _D ⁵ = cyclopropyl and (R _D ⁴ ) = 5-CI-2-OMe is (S4-2),

R _D ⁵ = ethyl and (R _D ⁴ ) = 2-OMe is (S4-3),

R _D ⁵ = isopropyl and (R _D ⁴ ) = 5-CI-2-OMe is (S4-4) and

R _D ⁵ = isopropyl and (R _D ⁴ ) = 2-OMe is (S4-5). such as

Compounds of the type of N-acylsulfamoylphenylureas of the formula (S4 ^C ) which are known, for example, from EP-A-365484,

wherein

RD ⁸ and RD ⁹ independently of one another are hydrogen, (C 1 -C 5 -alkyl, (C 3 -C 8) -cycloalkyl,

(C ₃ -C ₆ ) -alkynyl, (C ₃ -C ₆ ) -alkynyl,

R _D ^{4 is} halogen, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkoxy, CF ₃

m is _D 1 or 2; for example

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

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

 1 - [4- (N-4,5-dimethylbenzoylsulfamoyl) phenyl] -3-methylurea.

Active substances from the class of hydroxyaromatics and the aromatic-aliphatic carboxylic acid derivatives (S5), eg 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.

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-dihydroquinoxalin-2-one hydrochloride, 1- (2-methylsulfonylaminoethyl) -3- (2-thienyl) -1,2-dihydroquinoxaline-2 οη, as described in WO-A-2005/1 12630.

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, (C 1 -C 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, (dC ₄₎ -alkyl, (C2-C6) - alkenyl, (C ₂ -C ₄₎ alkynyl, cyanoalkyl, (dC ₄₎ -haloalkyl, phenyl,

Nitrophenyl, benzyl, halobenzyl, pyridinylalkyl and alkylammonium, n _E is 0 or 1

n _E ² , n _E ³ are each independently 0, 1 or 2, preferably:

 diphenylmethoxy,

 Diphenylmethoxyessigsäureethylester,

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

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

worin

wherein

X _F CH or N,

n _F 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,

R _F ^{1 is} halogen, (dC ₄₎ -alkyl, (dC ₄₎ -haloalkyl, (dC ₄₎ alkoxy, (dC ₄₎ -haloalkoxy, nitro, (dC ₄₎ alkylthio, (CrC ₄₎ alkylsulfonyl, ( dC ₄ ) alkoxycarbonyl, optionally substituted. Phenyl, optionally substituted phenoxy,

R _F ^{2 is} hydrogen or (C 1 -C ₄ ) -alkyl

R _F ^{3 is} hydrogen, (C ₁ -C ₈ ) -alkyl, (C ₂ -C ₄ ) -alkenyl, (C ₂ -C ₄ ) -alkynyl, or aryl, where each of the abovementioned C-containing radicals is unsubstituted or is replaced by one or more a plurality, preferably up to three, identical or different radicals from the group consisting of halogen and alkoxy, or their salts, preferably compounds, in which

X _F CH,

n _{F is} an integer from 0 to 2,

R _F ^{1 is} halogen, (dC ₄₎ -alkyl, (dC ₄₎ -haloalkyl, (dC ₄₎ alkoxy, (dC ₄₎ haloalkoxy, R ² is hydrogen or _F (dC ₄₎ -alkyl, R _F ^{3 is} hydrogen, (C ₁ -C ₈ ) -alkyl, (C ₂ -C ₄ ) -alkenyl, (C ₂ -C ₄ ) -alkynyl, or aryl, where each of the abovementioned C-containing radicals is unsubstituted or is replaced by one or more a plurality, preferably up to three, identical or different radicals from the group consisting of halogen and alkoxy is substituted, 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 Reg. No. 219479-18-2), 1, 2-dihydro-4-hydroxy-1 -methyl-3- (5-tetrazolylcarbonyl) -2-quinolone (CAS Reg. No. 95855-00-8), as described in the

 WO-A-1999/000020 are described.

S10) Compounds of the formulas (S10 ^a ) or (S10 ^b )

 as described in WO-A-2007/023719 and WO-A-2007/023764

(S10 ^a) (S10 ^b), wherein

R _G ^{1 is} halogen, (C ¹ -C ₄ ) -alkyl, methoxy, nitro, cyano, CF ₃ , OCF ₃

YG, Z _g independently of one another O or S,

n _{G is} an integer from 0 to 4,

R _G ^{2 is} (C ₁ -C ₆ ) -alkyl, (C ₂ -C ₆ ) -alkenyl, (C ₃ -C ₆ ) -cycloalkyl, aryl; benzyl,

 halobenzyl,

R _G ^{3 is} hydrogen or (Ci-C ₆ ) -alkyl.

S1 1) active ingredients of the type of oxyimino compounds (S1 1), which are known as seed dressing, such. B.

"Oxabetrinil" ((Z) -1, 3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile) (S1 1 -1), which is known as a seedling safener for millet against damage from metolachlor,

 "Fluxofenim" (1- (4-chlorophenyl) -2,2,2-trifluoro-1-ethanone-O- (1,3-dioxolan-2-ylmethyl) -oxyn) (S1 1 -2), which was used as seed dressing -Safener for millet is known against damage from metolachlor, and

 "Cyometrinil" or "CGA-43089" ((Z) -cyanomethoxyimino (phenyl) acetonitrile) (S1 1 -3), which is known as a seed dressing safener for millet against damage by metolachlor.

S12) Isothiochromanone (S12) class agents, e.g. Methyl - [(3-oxo-1H-2-benzothiopyran-4 (3H) -ylidene) methoxy] acetate (CAS Reg.

 205121 -04-6) (S12-1) and related compounds of WO-A-1998/13361

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

 "Naphthalene anhydride" (1,8-naphthalenedicarboxylic anhydride) (S13-1), which is known as

Seed pickling safener for maize known for damage from thiocarbamate herbicides

 "Fenclorim" (4,6-dichloro-2-phenylpyrimidine) (S13-2), known as safener for pretilachlor in sown rice,

 "Flurazole" (benzyl-2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (S13-3) used as a seed dressing safener for millet against damage by alachlor and

 Metolachlor is known

 "CL 304415" (CAS 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) (S13-9).

S14) active substances, in addition to a herbicidal activity against harmful plants and safener action on crop plants such as rice, such as. B.

 "Dimepiperate" or "MY-93" (S-1-methyl-1-phenylethyl-piperidine-1-carbothioate) 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) which can be used as safener for rice against damage of some herbicides is known

 "Methoxyphenone" or "NK 049" (3,3'-dimethyl-4-methoxy-benzophenone), which is known as safener for rice against damage of some herbicides,

"COD" (1-Bromo-4- (chloromethylsulfonyl) benzene) from Kumiai, (CAS Registry No. 54091-06-4), which is known as a safener against damage of some herbicides in rice. S15) active substances, which are primarily used as herbicides, but also

 Safeners on crops, 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,

 Of 4- (4-chlorophenoxy) butyric acid,

 3,6-dichloro-2-methoxybenzoic acid (Dicamba),

1 - (ethoxycarbonyl) ethyl 3,6-dichloro-2-methoxybenzoate (lactidichloroethyl). The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The application is done in the usual way, for example by pouring, spraying; Spraying, sprinkling.

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 lie.

Preference is given to the use of the compounds of the 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,

Manioc and maize or also crops of sugar beet, cotton, soya, rapeseed,

Potato, tomato, pea and other vegetables.

 Preferably, the compounds of formula (I) as herbicides in

Crop plants are used, which are resistant to the phytotoxic effects of herbicides or have been made genetically resistant. Conventional ways of producing new plants that have modified properties compared to previously occurring plants exist

for example, in classical breeding methods and the generation of mutants. Alternatively, new plants with altered properties can help

Genetic engineering methods are produced (see, for example, EP-A-0221044, EP-A-0131624). For example, several cases have been described

 genetic engineering of crops for modification of the starch synthesized in the plants (eg WO 92/1 1376, WO 92/14827, WO 91/19806),

transgenic crops which are resistant to certain herbicides of the

 Glufosinate (see, for example, EP-A-0242236, EP-A-242246) or glyphosate

 (WO 92/00377) or the sulfonylureas (EP-A-0257993, US-A-5013659) are resistant,

 Transgenic crops, such as cotton, with the ability to produce Bacillus thuringiensis toxins (Bt toxins), which the

 Make plants resistant to certain pests (EP-A-0142924, EP-A-0193259).

 Transgenic crop plants with modified fatty acid composition (WO 91/13972).

- genetically modified crops with new content or

 Secondary materials z. B. new phytoalexins, which increased one

 Disease resistance cause (EPA 309862, EPA0464461)

 genetically modified plants with reduced photorespiration, which have higher yields and higher stress tolerance (EPA 0305398).

- Transgenic crops that produce pharmaceutically or diagnostically important proteins ("molecular pharming")

 transgenic crops characterized by higher yields or better

 To distinguish quality

transgenic crops characterized by a combination z. B. 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 can 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 Edition Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Genes and Clones", VCH Weinheim 2nd edition 1996

The production of plant cells with a reduced activity of a

Gene product can be obtained, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to obtain a

Cosuppressionseffekt.es or the expression of at least one appropriately engineered ribozyme, specifically transcripts of the above

Gene product splits.

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. Also possible is the use of DNA sequences that encode a high degree of homology to those

Have 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 of skill 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, the 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 (I) according to the invention can be used in transgenic cultures which are resistant to growth substances, such as. B. Dicamba or against herbicides, the essential plant enzymes, eg. Acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate

Dioxygenases (HPPD) inhibit or are resistant to herbicides from the group of sulfonylureas, the glyphosate, glufosinate or benzoylisoxazole and analogues.

In the application of the active compounds according to the invention in transgenic cultures, in addition to the effects to be observed in other cultures

Harmful plants often have effects that are specific for application in the particular transgenic culture, for example a modified or specific one extended weed spectrum that can be controlled, changed effort amounts that 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 formula (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.

The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be incorporated into the soil before sowing. The amount of active ingredient used can vary within a substantial range. It depends essentially on the type of effect desired. In general, the application rates are between 10g and 10kg of active ingredient per hectare

Soil area, preferably between 50 g and 5 kg per hectare. The preparation and the use of the active compounds according to the invention are evident from the following examples.

Preparation Examples:

Example 1 -1

2- (5,6-Dihydro-1,2,2-oxathiazin-3-yl) -N - [(4,6-dimethoxypyrimidin-2-yl) carbamoyl] benzenesulfonamide

(Method (a)) To a solution of 1, 292 g (5.00 mmol) of 2- (5,6-dihydro [1,2,2] oxathiazin-3-yl) benzenesulfonamide and 1.377 g (5.00 mmol) of 2 - (N-Phenoxycarbonylamino) -4,6-dimethoxypyrimidine in 25 ml acetonitrile is added at 0 ° C 0.16 g (5.15 mmol) 80% sodium hydride suspension. After 4 h stirring at RT is evaporated in vacuo, the residue dissolved in water and acidified with phosphoric acid to about pH 3. The precipitate is filtered off with suction and dried. Yield of N- (4,6-

Dimethoxypyrimidin-2-yl) -N '- (2- (5,6-dihydro [1,2,2] oxthiazin-3-yl) benzenesulfonyl) urea: 1.9 g (87%). ¹ H-NMR (DMSO-d ₆ ): δ = 8.20 ppm (d, 1 H); 7.80 ppm (tr, 1H); 7.75 ppm (tr, 1H); 7.60 ppm (d, 1H); 6.00 ppm (s, 1H); 4.10 ppm (tr, 2H); 3.90 ppm (s, 6H); 3.30 ppm (tr, 2H)

Analogously to Example 1 -1 and according to the general description of

For example, the other compounds of formula (I) listed in Tables 1, 2, 3 and 4 below can also be prepared.

( ⁺ )

Abbreviations: Mp .: = melting point Zers. or Z. = with decomposition = The stated melting point (mp) refers in each case to the corresponding sodium salt.

(J-1)

4 5 6 7

Table 1: Examples of the compounds of the formula (I) where R = R = R = R = H

10

 and R = H:

¹ H-NMR data (400 MHz, solvent: DMSO-d ₆ , internal standard tetramethylsilane: d = 0.00 ppm) s = singlet, sbr = broad singlet, d = doublet, dd = double doublet, m = multiplet, q = Quartet, t = triplet)

1 -2: d = 8.20 ppm (d, 1 H); 7.80 ppm (tr, 1H); 7.70 ppm (tr, 1H); 7.55 ppm (d, 1H);

 7.00 ppm (s, 1H); 4.15 ppm (tr, 2H); 3.35 ppm (tr, 2H); 2.50 ppm (s, 6H) 1-5: d = 8.15 ppm (d, 1H); 7.80 ppm (tr, 1H); 7.75 ppm (tr, 1H); 7.60 ppm (d, 1H)

6.85 ppm (s, 1H); 4.10 ppm (tr, 2H); 4ppm (s, 3H); 3.35ppm (tr, 2H) 1 -6: (250MHz) d = 8.20ppm (d, 1H); 7.85 ppm (tr, 1H); 7.75 ppm (tr, 1H); 7.60 ppm (d, 1H); 5.90 ppm (s, 1H); 4.35 ppm (q, 4H); 4.10 ppm (dd, 2H); 3.30 ppm (dd, 2H); 1.35 ppm (tr, 6H)

 1 -9: d = 8.20 ppm (d, 1H); 7.80 ppm (tr, 1H); 7.75 ppm (tr, 1H); 7.55 ppm (d, 1H);

 7.35 ppm (s, 1H); 4.10 ppm (dd, 2H), 3.40 ppm (dd, 2H) 2.50 ppm (s, 3H) 1 -10: δ = 8.20 ppm (d, 1H); 7.80 ppm (tr, 1H); 7.75 ppm (tr, 1H); 7.55 ppm (d, 1H);

 6.55 ppm (s, 1H); 4.10 ppm (dd, 2H); 3.90 ppm (s, 3H); 3.35 ppm (dd, 2H);

2.40 ppm (s, 3H)

 1 -12: d = 8.20 ppm (d, 1H); 7.85 ppm (tr, 1H); 7.75 ppm (tr, 1H); 7.60 ppm (d, 1H);

 4.10 ppm (tr, 2H); 4.00 ppm (s, 3H); 3.40 ppm (tr, 2H); 2.50 ppm (s, 3H) 1-15: δ = 8.20 ppm (d, 1H); 7.85 ppm (tr, 1H); 7.75 ppm (tr, 1H); 7.55 ppm (d, 1H);

 4.10 ppm (tr, 2H); 4.00 ppm (s, 6H); 3.35 ppm (tr, 2H)

 1 -18: d = 8.20 ppm (d, 1H); 7.85 ppm (tr, 1H); 7.75 ppm (tr, 1H); 7.60 ppm (d, 1H);

4.20 ppm (tr, 2H); 3.40 ppm (tr, 2H); 2.50 ppm (s, 6H) Example 2-1

 3- (5,6-Dihydro-1,2,2-oxathiazin-3-yl) -N - [(4,6-dimethoxypyrimidin-2-yl) carbamoyl] pyridine-2-sulfonamide

2-Bromo-pyridin-3-carbaldoxinn

To a mixture of 8.22 g (0.1 18 mol) of hydroxylamine hydrochloride and 9.70 g (0.1 18 mol) of sodium acetate in 170 ml of methanol and 22 ml of water is portioned at room temperature a total of 20.00 g (0.108 mol) of 2-bromo-3-pyridincaboxaldehyde. It is allowed to stir for 3 hours at room temperature.

Subsequently, 300 ml of ice water are added. The precipitated product is filtered off with suction, washed with water and dried.

This gives 17 g (78% of theory) of 2-bromo-pyridine-3-carbaldoxime

as a solid of melting point: 184 ° C. 2-Bromo-N-hydroxy-thionicotinimidic acid 2-hydroxyethyl ester

17.00 g (0.085 mol) of 2-bromo-pyridine-3-carbaldoxime are introduced together with 4.00 g (0.030 mol) of N-chlorosuccinimide at a maximum of 40 ° C in 52 ml of dimethylformamide. The remaining 9.55 g (0.072 mol) of N-chlorosuccinimide are portioned in such a way that the reaction starts and proceeds at 35-40 ° C.

It is stirred for 1 hour. (Yield about 75%)

 The reaction solution thus obtained is cooled to 10 ° C and treated with 0.57 ml (0.004 mol) of triethylamine in 3 ml of dimethylformamide. Subsequently, 1 .43 ml

(0.020 mol) of 2-mercaptoethanol in 3 ml of dimethylformamide is slowly added dropwise, then 2.28 ml (0.016 mol) of triethylamine are added.

The resulting suspension is stirred for a further 2 hours.

It is mixed with water, extracted with ethyl acetate. The organic phase is dried and concentrated. The residue is taken up with a little ethyl acetate and precipitated with n-hexane.

 This gives 0.5 g (92%, 69% over both stages) of 2-bromo-N-hydroxy-thionicotinimidate 2-hydroxyethyl ester as a solid of melting point: 138 ° C.

3- (2-Bromo-pyridin-3-yl) -5,6-dihydro-1,2,2-oxathiazine

24.00 g (0.056 mol) of 2-hydroxyethyl 2-bromo-N-hydroxy-thionicotinamide are treated with 1 .566 g (0.01 1 mol) of 4-nitrophenol and 14.76 g (0.056 mol)

Triphenylphosphine in 50ml tetrahydrofuran submitted. 9.97 ml (0.051 mol) of diisopropyl azodicarboxylate are slowly added dropwise and the mixture is stirred in for 5 hours

Room temperature after. It is allowed to stand overnight, added again 2.21 ml (0.001 mol) of diisopropyl azodicarboxylate and stirred for a further 6 hours

The mixture is concentrated on a rotary evaporator and the residue is chromatographed with a mixture of ethyl acetate / n-heptane 6: 4.

This gives a solid of mp 1 18 ° C (yield 75%). 3- (5,6-Dihydro-1,2,2-oxathiazin-3-yl) -pyridine-2-sulfonic acid anide

Unter Stickstoffatmosphäre werden bei -10°C 5.6 ml (0.01 1 Mol, 2.1 Äquivalente) einer 2M n-Butylmagnesiumchlorid-Lösung in 85ml Tetrahydrofuran vorgelegt und tropfenweise mit 4.5 ml einer 2.5M n-Butyllithium-Lösung (2 Äquivalente) versetzt. Man rührt 30 min bei -5° bis 0°C nach, kühlt auf -10°C und tropft dann 1 .40 g (0.005 Mol) 3-(2-Bromo-pyridin-3-yl)-5,6-dihydro-1 ,4,2-oxathiazin, gelöst in wenig

Under a nitrogen atmosphere, 5.6 ml (0.01 1 mol, 2.1 equivalents) of a 2M n-butylmagnesium chloride solution in 85 ml of tetrahydrofuran are initially charged at -10 ° C. and admixed dropwise with 4.5 ml of a 2.5M n-butyllithium solution (2 equivalents). The mixture is stirred for 30 min at -5 ° to 0 ° C, cooled to -10 ° C and then dripping 1.40 g (0.005 mol) of 3- (2-bromo-pyridin-3-yl) -5,6-dihydro -1,4,2-oxathiazine dissolved in a little

Tetrahydrofuran, too. The reddish-brown solution is at -5 to 0 ° C for 30 min

stirred, with the solution slowly clouding. It is then cooled to -50 ° C and initiates sulfur dioxide gas until a pH paper indicates no more basicity. The now clarified solution is allowed to warm to -10 ° C within 30 min and then treated dropwise with 0.61 ml (0.008 mol) of sulfuryl chloride in 3 ml of n-heptane. The mixture is stirred for 1 hour at 0 ° C.

 9 ml of a 35% strength aqueous ammonia solution are then added dropwise at -10 ° C., the mixture is checked whether the solution remains alkaline, and the yellow suspension is stirred at room temperature for 3 hours.

It is concentrated in vacuo, mixed with drying agent and digested the mixture vigorously with ethyl acetate. It is filtered off with suction and the residue is washed twice with ethyl acetate. The combined filtrates are concentrated, and the residue thus obtained is crystallized with a little diethyl ether. This gives 1 .48g (52% yield) of a solid, mp 174 ° C. 3- (5,6-Dihydro-1,2,2-oxathiazin-3-yl) -N - [(4,6-dimethoxypyrimidin-2-yl) -carbamoyl] -pyridine-2-sulfonan-1-one (Ex. 1 )

To a solution of 0.18 g (0.69 mmol) of 3- (5,6-dihydro-1,2,2-oxathiazin-3-yl) -pyridine-2-sulfonic acid amide and 0.19 g (0.69 mmol) of 2- (N-phenoxycarbonylamino ) - 4,6-dimethoxypyrimidine in 25 ml of acetonitrile is added at RT 0.24 g (1 .60 mmol) of 1, 8-diazabicyclo [5.4.0] undec-7-ene. After 2 h stirring at RT is in vacuo

concentrated, the residue taken up in a little water and with 6M

 Hydrochloric acid acidified. The precipitate is filtered off with suction and dried. Yield of 3- (5,6-dihydro-1,2,2-oxathiazin-3-yl) -N - [(4,6-dimethoxypyrimidin-2-yl) carbamoyl] pyridine-2-sulfonamide: 0.21 g (69 %).

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ = 8.75 ppm (m, 1H); 8.10 ppm (m, 1H); 7.80 ppm (m, 1H), 6.00 ppm (s, 1H); 4.15 ppm (tr, 2H); 3.90 ppm (s, 6H); 3.40 ppm (tr, 2H)

Sodium - {[3- (5,6-dihydro-1, 4,2-oxathiazin-3-yl) pyridin-2-yl] sulfonyl} [(4,6-dimethoxypyrimidin-2-yl) carbamoyl] azanide (Ex No. 2-1 Na ⁺ )

0.10g (0.2mmol) 3-(5,6-Dihydro-1 ,4,2-oxathiazin-3-yl)-N-[(4,6-dimethoxypyrimidin-2- yl)carbamoyl]pyridin-2-sulfonannid werden in 5ml Methylenchlorid gelöst, mit einem Tropfen Wasser und 8mg (0.2mmol) Natriumhydroxid versetzt und 1 h bei RT gerührt.

0.10 g (0.2 mmol) of 3- (5,6-dihydro-1,2,2-oxathiazin-3-yl) -N - [(4,6-dimethoxypyrimidin-2-yl) carbamoyl] pyridine-2-sulfonanide dissolved in 5 ml of methylene chloride, treated with a drop of water and 8mg (0.2mmol) of sodium hydroxide and stirred for 1 h at RT.

 It is concentrated in vacuo, the resulting salt in acetone / toluene and concentrated in vacuo (twice).

 Yield of sodium - {[3- (5,6-dihydro-1, 4,2-oxathiazin-3-yl) pyridin-2-yl] sulfonyl} [(4,6-dimethoxypyrimidin-2-yl) carbamoyl] azanide : 88mg (95%)

1H-NMR (400 MHz, CDCl ₃ ): 8.10 ppm (sbr); 7.70 ppm (sbr), 7.60 ppm (dbr, 1H); 7.10 ppm (trbr); 5.55 ppm (s, 1H); 4.35 ppm (sbr, 2H); 3.75 ppm (s, 6H), 3.40 ppm (sbr, 2H)

By way of example, the further compounds of the formula (I) listed in Tables 2 and 3 below can also be prepared analogously to Example 2-1.

4 5 6 7

 Table 2 Examples of the compounds of formula (I) where R = R = R = R = H;

 10

 R = H:

1H-NMR-Daten (400 MHz, Solvens: DMSO-d₆, interner Standard Tetramethylsilan: d = 0,00 ppm) s = Singulett, sbr = breites Singulett, d = Dublett, dd = Doppeldublett, m = Multiplett, q = Quartett, t = Triplett)

1H-NMR data (400 MHz, solvent: DMSO-d ₆ , internal standard tetramethylsilane: d = 0.00 ppm) s = singlet, sbr = broad singlet, d = doublet, dd = double doublet, m = multiplet, q = Quartet, t = triplet)

2-2: d = 8.75 ppm (m, 1H); 8.10 ppm (m, 1H); 7.80 ppm (m, 1H); 7.00 ppm (s, 1H);

 4.15 ppm (tr, 2H); 3.40 ppm (tr, 2H): 2.50 ppm (s, 6H)

 2-4: d = 8.80 ppm (m, 1H); 8.10 ppm (m, 1H); 7.80 ppm (m, 1H); 5.95 ppm (s, 1H);

 4.30 ppm (m, 4H); 4.15 ppm (tr, 2H); 3.40 ppm (tr, 2H); 1.30 ppm (m, 6H) 2-7: d = 8.75 ppm (m, 1H); 8.10 ppm (m, 1H); 7.80 ppm (m, 1H); 4.15 ppm (tr, 2H);

4.00 ppm (s, 3H); 3.40 ppm (tr, 2H); 2.45 ppm (s, 3H)

 (J-2)

 6 4 5 7

Table 3 Examples of the compounds of the formula (I) where R = Me; R = R = R =

 10

 H and R = H:

¹ H-NMR data (400 MHz, solvent: DMSO-d ₆ , internal standard tetramethylsilane: d = 0.00 ppm) s = singlet, sbr = broad singlet, d = doublet, dd = double doublet, m = multiplet, q = Quartet, t = triplet) 1: d = 8.70 ppm (m, 1H); 7.90 ppm (m, 1H); 7.55 ppm (m, 1H); 5.80 ppm (s, 1H);

4.20 ppm (m, 1H); 3.95 ppm (s, 6H); 3.15 ppm (m, 2H); 1.49 ppm (d, 3H) 7: d = 8.70 ppm (m, 1H); 7.90 ppm (m, 1H); 7.55 ppm (m, 1H, pyridine-H); 4.20 ppm (m, 1H); 4.05 ppm (s, 3H); 3.15 ppm (m, 2H); 2.55 ppm (s, 3H); 1, 49 ppm

(d, 3H)

Example 4-1

 4- (5,6-Dihydro-1,2,2-oxathiazin-3-yl) -N - [(4,6-dimethoxypyrimide

2-yl) carbamoyl] -1-methyl-1H-pyrazole-5-sulfonamide

2-chloroethanethiol

In a solution of 200 g (3.33 mol) of thiirane (ethylene sulfide) in 3.4 l of ether is passed at -6 to -9 ° C 1 .5 h of hydrogen chloride. It is allowed to rise slowly to RT and stirred overnight. The ether is distilled off at atmospheric pressure via a Vigreux column. The residue is distilled in vacuo (bp _50.80 = 48-50 ° C) and stored in the freezer. Yield: 88.2 g (27.4%). ¹ H-NMR (CDCl ₃ ): d = 1.75 ppm (tr, 1H), 2.90 ppm (dtr, 2H), 3.65 ppm (tr, 2H).

N-hydroxy-1-methyl-1H-pyrazole-4-carboximidoyl chloride

In einer Lösung von 75.28 g (0.602 mol) 1 -Methyl-1 H-pyrazol-4-carbaldehydoxim in 1 .5 I Chloroform leitet man bei -15°C einen Überschuß Chlor ein. Man rührt 3 h bei - 15 °C und vertreibt anschließend das überschüssige Chlor mit Argon. Nach Rühren über Nacht wird das Produkt abgesaugt. Ausbeute: 75.9 g (96.1 %). ¹H-NMR

In a solution of 75.28 g (0.602 mol) of 1-methyl-1 H-pyrazole-4-carbaldehydoxim in 1 .5 I chloroform is passed at -15 ° C, an excess of chlorine. The mixture is stirred for 3 h at - 15 ° C and then expels the excess chlorine with argon. After stirring overnight, the product is aspirated. Yield: 75.9 g (96.1%). ¹ H-NMR

 (DMSO-de): d = 3.90ppm (s, 3H), 7.70ppm and 8.10ppm (2s, 2H), 10.4ppm (sbr, 1H).

2-chloroethyl-N-hydroxy-1-methyl-1H-pyrazole-4-carbimidothioate

To a solution of 39.85 g (250 mmol) of N-hydroxy-1-methyl-1H-pyrazole-4-carboximidoyl chloride in 600 ml of ether is pumped at 5-10 ° C within one hour synchronously by means of two syringe pumps 48.45 g (500 mmol ) 2-chloroethanethiol in 70 ml of ether and 27.82 g (275 mmol) of triethylamine in 218 ml of ether. Then it is stirred for 3 days at RT. Since it. DC still starting material is present, a further 12.1 1 g (125 mmol) 2-Chlorethanethiol and 6.96 g (63 mmol) of triethylamine are injected in the same manner. After stirring for four hours, this addition is repeated and stirring is continued overnight. It is suctioned off, the filtrate is evaporated and the residue is dried under high vacuum. Yield: 48.6 g (88.5%). ¹ H-NMR (DMSO-d ₆ ): d = 3.20 ppm and 3.60 ppm (2tr, 4H), 3.85 ppm (s, 3H), 7.60 ppm and 7.95 ppm (2s, 2H), 12.60 ppm (s, 1H ). 3- (1-Methyl-1H-pyrazol-4-yl) -5,6-dihydro-1,2,2-oxathiazine

7.9 g (263 mmol) of 80 are added in portions to a solution of 48.6 g (221 mmol) of 2-chloroethyl-N-hydroxy-1-methyl-1H-pyrazole-4-carbimidothioate in 0.16 l of DMF at 20 ° C. under argon % sodium hydride suspension. The mixture is stirred overnight at RT, then poured into ice-water and extracted three times with methylene chloride. The combined extracts are dried and evaporated in vacuo. The residue is chromatographed (eluent: cyclohexane / ethyl acetate 1: 3). Yield: 1 1 .2 g (27%).

H NMR (CDCl ₃ ): d = 3.25 ppm - 3.35 ppm and 4.10 ppm - 4.20 ppm (2m, 4H); 3.90 ppm (s, 1H); 7.65 ppm and 7.75 ppm (2s, 2H).

4- (5,6-Dihydro-1,2,2-oxathiazin-3-yl) -1-methyl-1H-pyrazole-5-sulfonamide

Zu einer Lösung von 0.92 g (5.0 mmol) 3-(1 -Methyl-1 H-pyrazol-4-yl)-5,6-dihydro- 1 ,4,2-oxathiazin in 10 ml Ether tropft man unter Argon bei -70°C eine Lösung von Lithiumdiisopropylamid (hergestellt durch Zusatz von 3.6 ml (9 mmol) 2.5 M n- Butyllithium in Hexan zu 1 .12 ml (8 mmol) Diisopropylamin in 5 ml Ether bei -60°C) und rührt 2 h bei -70°C. Anschließend spritzt man 0.80 ml (10 mmol) Sulfurylchlorid in 3 ml Hexan vorgekühlt zu und leitet sofort danach einen geringen

A solution of 0.92 g (5.0 mmol) of 3- (1-methyl-1H-pyrazol-4-yl) -5,6-dihydro-1,2,2-oxathiazine in 10 ml of ether is added dropwise under argon. 70 ° C, a solution of lithium diisopropylamide (prepared by adding 3.6 ml (9 mmol) of 2.5 M n-butyl lithium in hexane to 1 .12 ml (8 mmol) of diisopropylamine in 5 ml of ether at -60 ° C) and stirred for 2 h -70 ° C. Subsequently, 0.80 ml (10 mmol) of sulfuryl chloride in 3 ml of hexane are injected precooled and immediately afterward led to a small amount

 Ammonia excess. The solution is evaporated in vacuo and the

Residue between methylene chloride and 25% Sodium dihydrogen phosphate solution distributed. The aqueous phase is extracted twice with methylene chloride. The combined organic phases are dried, evaporated in vacuo and chromatographed (eluent ethyl acetate / cyclohexane 1: 9). Yield: 23 mg (1 .8%). ¹ H-NMR (DMSO-d ₆ ): d = 3.30 ppm - 3.40 ppm and 4.00 ppm - 4.10 ppm (2m, 4H); 4.05 ppm (s, 1H), 7.70 ppm (s, 1H); 7.30 ppm (s, 2H).

4- (5,6-Dihydro-1,2,2-oxathiazin-3-yl) -N - [(4,6-dimethoxypyrimidin-2-yl) carbamoyl] -1-methyl-1H-pyrazole-5- sulfonamide (Ex 4-1)

To a solution of 262 mg (1 .00 mmol) of 4- (5,6-dihydro-1,2,2-oxathiazin-3-yl) -1-methyl-1H-pyrazole-5-sulfonamide and 276 mg ( 1 .00 mmol) of 2- (N-phenoxycarbonylamino) -4,6-dimethoxypyrimidine in 3 ml of acetonitrile are added at 0 ° C 32 mg (1 .06 mmol) 80% sodium hydride suspension. After stirring at RT for 5 h, the mixture is evaporated in vacuo and the residue is dissolved in a little water. This solution is extracted with methylene chloride (the extract becomes

discarded), acidified to pH 2 with phosphoric acid and again with

Extracted methylene chloride. The combined extracts of the acidic solution are dried and evaporated in vacuo. Yield: 294 mg (66%). ¹ H-NMR (400 MHz, DMSO-de): d = 7.85 ppm (s, 1H); 6.00 ppm (s, 1H); 4.20 ppm (s, 3H); 3.95 ppm (m, 2H); 3.90 ppm (s, 6H); 3.30 ppm (m, 2H)

Table 4 Examples of the compounds of formula (I) where R = R = R = R = H; R

 10

= CH ₃ and R = H:

¹ H-NMR data (400 MHz, solvent: DMSO-d ₆ , internal standard tetramethylsilane: d = 0.00 ppm) s = singlet, sbr = broad singlet, d = doublet, dd = double doublet, m = multiplet, q = Quartet, t = triplet)

4-2: d = 7.80 ppm (s, 1H); 7.00 ppm (s, 1H); 4.20 ppm (s, 3H); 4.00 ppm (m, 2H);

 3.30 ppm (m, 2H); 2.40 ppm (s, 6H)

 4-3: d = 7.80 ppm (s, 1H); 6.85 ppm (s, 1H); 4.20 ppm (s, 3H); 4.00 ppm (m, 2H);

4.00 ppm (s, 3H); 3.30 ppm (m, 2H) 4-4: d = 7.85 ppm (s, 1H); 5.95 ppm (s, 1H); 4.30 ppm (m, 2H); 4.20 ppm (s, 3H);

4.00 ppm (m, 2H); 3.30 ppm (m, 2H); 1.30 ppm (s, 6H)

 4-8: (250 MHz) d = 7.85 ppm (s, 1H); 4.20 ppm (s, 3H); 4.00 ppm (m, 2H); 3.95 ppm

(s, 6H); 3.30 ppm (m, 2H)

According to the general description of the invention

 Manufacturing process, for example, the other, in the

 Table 5 listed compounds of formula (I) are prepared.

(J-4)

4 5 6 7

 Table 5 Examples of the compounds of formula (I) where R = R = R = R = H;

 10

 R = H:

¹ H-NMR data (400 MHz, solvent: DMSO-d ₆ , internal standard tetramethylsilane: d = 0.00 ppm) s = singlet, sbr = broad singlet, d = doublet, dd = double doublet, m = multiplet, q = Quartet, t = triplet)

5-1: d = 7.85 ppm (d, 1H); 7.55 ppm (d, 1H); 6.00 ppm (s, 1H); 4.05 ppm (m, 2H);

 3.90 ppm (s, 3H); 3.35 ppm (m, 2H)

Application Examples: Example A

1 . Pre-emergence herbicidal action

Seeds of monocotyledonous or dicotyledonous weeds are cultivated in

 Wood fiber pots laid in sandy loam soil and covered with soil. The test compounds formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then applied to the surface of the cover soil as an aqueous suspension with an application rate of 800 l / ha with the addition of 0.2% wetting agent.

After about 3 weeks life of the test plants in the greenhouse under optimal growth conditions, the effect of the preparations is visually in Compared to untreated controls scored (herbicidal activity in percent (%): 100% effect = plants have died, 0% effect = like control plants).

The following are the efficiencies of some of the claimed compounds on various weeds tested.

It means:

 ALOMY Alopecurus myosuroides

 AMARE Ambrosia artemisiifolia

 ECHCG Echinochloa crus-galli

 LOLMU Lolium multiflorum

 MATIN MATRICARIA INDODORA

 SETVI Setaria viridis

 STEME Stellaria media

 VIOTR viola tricolor

Connection Application A A E L M S s V

 g ai / ha L M C O A E T I

 O A H L T T E O

M R C M I V M T

Y E G U N I E R

2-1 80 80 80 90 80 90 90 90 100 Connection application ALMS

 g ai / ha L O A T

 O L T E

M M I M

Y U N E

3-1 80 90 90 90 80

In this test, for example, the compounds 2-1 and 3-1 show a very strong action against weeds with partially good compatibility with crops.

Example B

2. Post-emergence herbicidal action

Seeds of monocotyledonous or dicotyledonous weeds are cultivated in

Wood fiber pots laid in sandy loam soil, 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. In the form of wettable powders (WP) or as emulsion concentrates (EC)

formulated test compounds are then sprayed onto the green parts of plants as an aqueous suspension with a water application rate of about 800 l / ha with the addition of 0.2% wetting agent. After about 3 weeks of service life of

Test plants in the greenhouse under optimal growth conditions, the effect of the preparations is scored visually compared to untreated controls (herbicidal action in percent (%): 100% effect = plants are dead, 0% effect = as control plants).

The following are the efficiencies of some of the claimed compounds on various weeds tested. Where:

 ABUTH Abutilon theophrasti

 AMARE Ambrosia artemisiifolia

 ECHCG Echinochloa crus-galli

 LOLMU Lolium multiflorum

 MATIN Mairicaria indodora

 PHBPU Ipomoea purpurea

 SETVI Setaria viridis

 STEME Stellaria media

 VIOTR viola tricolor

Connection Application A E L M P S s V g ai / ha M C O A H E T I

 A H L T B T E O

R C M I P V M T

E G U N U I R E

2-1 Na ⁺ 80 100 90 90 90 80 90 100 90 Connection application AALMSV

 g ai / ha B M O A T I

 U A L T E O

T R M I M T

H E U N E R

3-1 80 90 90 80 80 90 90

In this test, for example, the compounds 2-1, 2-1 show its Na ⁺ salt and 3-1 with some good compatibility with crop plants very strong action against weeds.

Claims

claims  1 . Oxathiazinyl (het) arylsulfonylureas of the formula (I),

in which  1 1  A is nitrogen or a CR moiety, wherein  1 1  R is hydrogen, alkyl, halogen and haloalkyl,  1  R is hydrogen or an optionally substituted radical from the series  Alkyl, alkoxy, alkoxyalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aralkyl and aryl,  2  R is hydrogen, halogen or in each case optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino having in each case 1 to 6 carbon atoms,  3  R is hydrogen, halogen or in each case optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino having in each case 1 to 6 carbon atoms,  J is J-1 to J-4, wherein J-1 to J-4 have the following meanings:

J-1 J-2 J-3 J-4 wherein the arrow is in each case a bond to the sulfonyl unit of the formula (I), E is a direct bond, alkylene, oxygen, alkylamino or sulfur,  4 7  R-R independently of one another are hydrogen, halogen, cyano, thiocyanato or in each case halogen-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, alkylcarbonyl,  Alkoxycarbonyl, alkylaminocarbonyl having in each case 1 to 3 carbon atoms,  8th  R is hydrogen or an optionally substituted radical of the  Series alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aralkyl and aryl  9 9  or a group C (= O) -R, where R is hydrogen,  optionally substituted alkyl, optionally substituted aryl, Alkoxy, alkylamino or dialkylamino,  10  R independently of one another are hydrogen, halogen, cyano, thiocyanato or, if appropriate, in each case  halogen-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl,  Alkylsulfonyl, alkylamino, alkylcarbonyl, alkoxycarbonyl,  Alkylaminocarbonyl each having 1 to 3 carbon atoms, where in the abovementioned radicals the alkyl and alkylene groups each have 1 to 6 C atoms, the alkenyl and alkynyl groups each have 2 to 6 C atoms, the Cycloalkyl groups each 3 to 6 carbon atoms and the aryl groups may each contain 6 or 10 carbon atoms, as well as salts of compounds of the formula (I). 2. sulfonylureas of the formula (I) according to claim 1, characterized characterized in that A is nitrogen or a CH group, R ^{1 is} hydrogen or optionally substituted by halogen Radical from the series alkyl, alkoxy, alkoxyalkyl, alkenyl and alkynyl having in each case up to 3 carbon atoms, R ^{2 is} hydrogen, halogen or in each case optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino having in each case 1 to 3 carbon atoms in the alkyl radicals, R ^{3 is} hydrogen, halogen or in each case optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino having in each case 1 to 3 carbon atoms in the alkyl radicals, J stands for J-1 to J-4,  E for a direct bond, methylene, oxygen, alkylamino with 1 to 3  Carbon atoms or sulfur, R ⁴ -R ⁷ independently of one another represent hydrogen, halogen, cyano, thiocyanato or in each case optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, alkylcarbonyl, Alkoxycarbonyl or alkylaminocarbonyl each having 1 to 3  Carbon atoms in the alkyl radicals,  8th  R is hydrogen or an optionally substituted radical of the Series (dC ₄₎ -alkyl, (C ₃ -C ₆₎ -cycloalkyl, (C ₇ -CN) aralkyl and (C ₆ -C ₀₎ -aryl,  10  R independently of one another are hydrogen, halogen, cyano, thiocyanato or, if appropriate, in each case  halogen-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, alkylcarbonyl, alkoxycarbonyl or  Alkylaminocarbonyl each having 1 to 3 carbon atoms in the Alkyl radicals is. 3. sulfonylureas of the formula (I) according to claim 1, characterized characterized in that A is nitrogen or a CH group,  1  R is hydrogen, methyl, ethyl, methoxy, methoxymethyl or ethoxy stands, is hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, methylamino or dimethylamino, is hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, methylamino or dimethylamino, for J -1 to J-4,  is a direct bond, methylene, oxygen, Ci-C2-alkylamino or sulfur,  independently of one another is hydrogen, fluorine, chlorine, cyano, or in each case optionally substituted by chlorine or fluorine, methyl, methylthio, methylsulfinyl, methylsulfonyl, methoxycarbonyl and ethoxycarbonyl,  is hydrogen, methyl, ethyl, phenyl or benzyl,  independently of one another for hydrogen, fluorine, chlorine, bromine, cyano or for each optionally  methyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, methyl- or dimethylamino-substituted by chlorine or fluorine. 4. A process for the preparation of N-azinyl-N '- (het) arylsulfonylureas of the formula (I) according to claim 1, characterized in that  (a) (Het) arylsulfonamides of the general formula (II),

in which J has the meanings given in claim 1, with N-azinyl carbamates of the formula (III)

in which  1 3  A and R - R have the meanings given in claim 1, and  12 R is AI kyl or aryl, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or in that (b) (Het) arylsulfonyl isocyanates of the general formula (IV),

has the meanings given above, with aminoazines of the formula (V),

in which  1 3 A and R - R have the meanings given above, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary, or in that (c) N- (Het) arylsulfonylcarbamates of the general formula (VI)

in which  12  J and R have the meanings given above, with aminoazines of the formula (V),

in which  1 3  A and R - R have the meanings given above,  optionally in the presence of a diluent and optionally in the presence of a  Reaction auxiliaries,  and, if appropriate, the products obtained by processes (a), (b) or (c) are converted into salts by customary methods. 5. A herbicidal composition, characterized by a content of at least one compound of formula (I) according to claim 1. 6. Use of compounds of general formula (I) according to claim 1 for controlling unwanted plant growth. 7. A method for controlling weeds, characterized in that one lets compounds of general formula (I) according to claim 1 act on the weeds or their habitat. 8. A process for the preparation of herbicidal agents, characterized in that compounds of the general formula (I) according to claim 1 with Extenders and / or surface-active agents mixed. 9. (Het) arylsulfonyl compounds of the formula (VII)

which one  J has the meanings given above in formula (I) and G is -NH ₂ , -N = C = O or -NH-COOR ¹² , where R ^{12 is} the one above  Meaning has.