DE19921732A1 - New 2-benzoyl-1,3-cyclohexanedione derivatives useful as herbicides, especially for selective weed control in monocot crops, e.g. maize - Google Patents

Abstract

2-Benzoyl-1,3-cyclohexanedione derivatives (I) are new. 2-Benzoyl-1,3-cyclohexanedione derivatives of formula (I) and their tautomers and salts are new: m, n = 0-3; A = a single bond or alkylene; R<1> = H or optionally substituted alkyl or alkoxycarbonyl; R<2> = optionally substituted alkyl; R<3> = H, NO2, CN, COOH, CONH2, CSNH2, halogen or optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino or dialkylsulfamoyl; R<4> = NO2, CN, COOH, CONH2, CSNH2, halogen or optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino or dialkylsulfamoyl; Z' = optionally substituted, (un)saturated, mono- or bicyclic heterocyclyl containing 1-4 heteroatoms (up to 4 N and optionally one O, S, SO or SO2) and 1-3 C=O and/or C=S groups; alternatively R<1>+R<2> = alkylene when m = 1. Independent claims are also included for the following: (A) a process for preparing (I); and (B) benzoic acid derivatives of formula (III), other than 2-(5-carboxy-2,4-dichlorophenyl)-4-difluoromethyl-5-methyl-2,4-dihydro -3H-1,2,4-triazol-3-one and 2-(5-carboxy-2,4-dichlorophenyl)-4,5-dimethyl-2,4-dihydro-3H-1,2,4-tri azol-3-one.

Description

The invention relates to new substituted benzoylcyclohexanediones, processes for their Production and their use as herbicides.

It is already known that certain substituted benzoylcyclohexanediones have herbicidal properties (cf. EP-A-090262, EP-A-135191, EP-A-186118, EP-A-186119, EP-A-186120, EP-A-319075, WO-A-96/26200, WO-A-97/46530 WO-A-99/07688). However, the action of these compounds is not in all Be long satisfactory.

The new substituted benzoylcyclohexanediones of the general formula (I)

in which
m represents the numbers 0, 1, 2 or 3,
n represents the numbers 0, 1, 2 or 3,
A represents a single bond or alkanediyl (alkylene)
R ^{1 represents} hydrogen or optionally substituted alkyl or alkoxycarbonyl,
R ^{2 stands} for optionally substituted alkyl, or together with R ^{1 stands} for alkanediyl (alkylene), in which case m stands for 1 and R ¹ and R ² on the same carbon atom ("geminal") or on two adjacent carbon atoms ("vicinal ") stand,
R ^{3 represents} hydrogen, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or each optionally substituted alkyl, alkoxy, alkyl thio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino or dialkyl aminosulfonyl,
R ^{4 is} nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or represents optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino or dialkylaminosulfonyl, and
Z represents an optionally substituted 4- to 12-membered, saturated or unsaturated, monocyclic or bicyclic, heterocyclic grouping which has 1 to 4 heteroatoms (up to 4 nitrogen atoms and optionally - alternatively or additively - an oxygen atom or a sulfur atom, or one Contains SO group or an SO _{2 group} ), and which additionally contains one to three oxo groups (C = O) and / or thioxo groups (C = S) as constituents of the heterocycle,
- Including all possible tautomeric forms of the compounds of the general formula (I) and the possible salts of the compounds of the general formula (I) - found.

In the definitions, the hydrocarbon chains, such as alkyl or alkanediyl - are also in connection with heteroatoms, such as in alkoxy - in each case straight-chain or ver branches.  

In addition to the compounds of the general formula (I) - above - can also always the corresponding tautomeric forms - as an example below shown - available.

Preferred substituents of those listed in the formulas shown above Leftovers are explained below:

m preferably represents the numbers 0, 1 or 2.

n preferably represents the numbers 0, 1 or 2.

A preferably represents a single bond or alkanediyl (alkylene) with 1 up to 4 carbon atoms.

R ¹ preferably represents hydrogen, alkyl optionally substituted by halogen, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkylsulfinyl or C ₁ -C ₄ -alkylsulfonyl having 1 to 6 Carbon atoms or for alkoxycarbonyl with up to 6 carbon atoms.

R ² preferably represents alkyl optionally substituted by halogen with 1 to 6 carbon atoms, or together with R ^{1 represents} alkanediyl (alkylene) with 2 to 5 carbon atoms, in which case m stands for 1 and R ¹ and R ² on the same carbon atom ( "geminal") or on two adjacent carbon atoms ("vicinal").

R ³ preferably represents hydrogen, nitro, cyano, carboxy, carbamoyl, thio carbamoyl, halogen, in each case optionally by halogen, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkylsulfinyl or C ₁ -C ₄ alkylsulfonyl substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having up to 4 carbon atoms in the alkyl groups, or for alkyl amino, dialkylamino or dialkylamino sulfonyl each having up to 4 carbon atoms in the alkyl groups.

R ⁴ preferably represents nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, in each case optionally by halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl or C ₁ -C ₄ -Alkylsulfonyl substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, each with up to 4 carbon atoms in the alkyl groups, or for alkylamino, dialkyl amino or dialkylaminosulfonyl, each with up to 4 carbon atoms in the alkyl groups.

Z preferably represents one of the heterocyclic groupings below

in which the bond shown in dashed lines is a single bond or a double bond,
Q represents oxygen or sulfur,
R ⁵ for hydrogen, hydroxy, mercapto, cyano, halogen, for each ge optionally by cyano, halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl thio, C ₁ -C ₄ alkylsulfinyl or C ₁ - C ₄ -Alkylsulfonyl substituted alkyl, alkylcarbonyl, alkoxy, alkoxycarbonyl, alkylthio, alkyl sulfinyl or alkylsulfonyl, each with up to 6 carbon atoms in the alkyl groups, for propadienylthio, for each optionally substituted by halogen alkylamino or dialkylamino, each with up to 6 carbon atoms in the alkyl groups , for alkenyl, alkynyl, alkenyloxy, alkenylthio or alkenylamino each optionally substituted by halogen, each having up to 6 carbon atoms in the alkenyl or alkynyl groups, for cycloalkyl, cycloalkyl oxy, cycloalkylthio, cycloalkylamino, cycloalkylalkyl, cycloalkyl alkoxy, each optionally substituted by halogen, Cycloalkylalkylthio or Cycloalkylalkylamino each with 3 to 6 carbon atoms in the cycloalkyl groups and given enen if up to 4 carbon atoms in the alkyl part, or for phenyl, phenyloxy, phenylthio, phenylamino, benzyl, benzyloxy, benzylthio or benzylamino optionally substituted by halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy , stands for pyrrolidino, piperidino or morpholino, or - in the event that two adjacent residues R ⁵ and R ⁵ are on a double bond - together with the adjacent residue R ⁵ also represents a benzo group, and
R ^{6 represents} hydrogen, hydroxyl, amino, alkylidene amino with up to 4 carbon atoms, for alkyl, alkoxy, alkylamino, dialkyl amino or alkanoylamino, each optionally substituted by halogen or C ₁ -C ₄ alkoxy, each having up to 6 carbon atoms in the alkyl groups, for alkenyl, alkynyl or alkenyloxy optionally substituted by halogen, each having up to 6 carbon atoms in the alkenyl or alkynyl groups, for cycloalkyl, cycloalkyl alkyl or cycloalkylamino, each optionally substituted by halogen, each having 3 to 6 carbon atoms in the cycloalkyl groups and optionally to to 3 carbon atoms in the alkyl part, or for phenyl or benzyl optionally substituted by halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, or together with an adjacent radical R ⁵ or R ⁶ for GE if necessary by Halogen or C ₁ -C ₄ alkyl substituted alkane diyl having 3 to 5 carbon atoms,
where the individual radicals R ⁵ and R ⁶ - if several of them are bound to the same heterocyclic groupings, may have the same or different meanings within the scope of the above definition.

A particularly preferably represents a single bond, methylene, ethylidene (Ethane-1,1-diyl) or dimethylene (ethane-1,2-diyl).

R ¹ particularly preferably represents hydrogen, in each case optionally by fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl , Ethylsulfonyl, n- or i-propylsulfonyl substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, or for methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl.

R ² particularly preferably represents methyl, ethyl, n- or i-propyl, or together with R ^{1 represents} methylene, ethane-1,1-diyl (ethylidene, -CH (CH ₃ ) -), ethane-1,2- diyl (dimethylene, -CH ₂ CH ₂ -), propane-1,3-diyl (trimethylene, -CH ₂ CH ₂ CH ₂ -), butane-1,4-diyl (tetramethylene, -CH ₂ CH ₂ CH ₂ CH ₂ -) or pentane-1,5-diyl (pentamethylene, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -), in which case m stands for 1 and R ¹ and R ² on the same carbon atom ("geminal") or on two adjacent carbon atoms ("vicinal").

R ³ particularly preferably represents hydrogen-nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, iodine, in each case optionally by fluorine and / or chlorine, methoxy, ethoxy, n- or i-propoxy, methylthio, Ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally with fluorine and / or chlorine , Methoxy, ethoxy, n- or i-propoxy substituted methoxy, ethoxy, n- or i-propoxy, for each methylthio, ethylthio, n- or i-propylthio optionally substituted by fluorine and / or chlorine, methylsulfinyl, ethyl sulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, or for methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, dimethylaminosulfonyl or diethylamino sulfonyl.

R ⁴ particularly preferably represents nitro, cyano, carboxy, carbamoyl, thio carbamoyl, fluorine, chlorine, bromine, in each case optionally by fluorine and / or chlorine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally with fluorine and / or chlorine, methoxy, ethoxy , n- or i-Propoxy substituted methoxy, ethoxy, n- or i-propoxy, for each methyl thio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i- substituted by fluorine and / or chlorine Propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, or for methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, dimethylaminosulfonyl or diethylaminosulfonyl.

Z particularly preferably represents the following heterocyclic grouping

R ⁵ particularly preferably represents hydrogen, hydroxyl, mercapto, cyano, fluorine, chlorine, bromine, iodine, in each case optionally by fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-Butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl substituted Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, Ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, for methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, di-n-propylamino or di-i-propylamino, for ethenyl optionally substituted by fluorine and / or chlorine, Propenyl, butenenyl, ethynyl, propynyl, butynyl , Propyleneyloxy, butenyloxy, propenylthio, butenylthio, propenylamino or butenylamino, for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutylthio, cyclopentylthio, cycloputylthio, cycloputylthio, cycloputylthio, cycloputylthio, cycloputylthio cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutyl methoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopropylmethylthio, Cyclobutylmethylthio, Cyclopentylmethylthio, cyclohexylmethylthio, cyclo Propylmethylamino, Cyclobutylmethylamino, cyclopentylmethylamino or cyclohexylmethylamino, or represents in each case optionally substituted by fluorine, chlorine , Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy substituted phenyl, phenyloxy, phenylthio, phenylamino, benzyl, benzyloxy, benzylthio or Benzylamino , or - in the event that two adjacent radicals R ⁵ and R ⁵ are located on a double bond - together with the adjacent radical R ⁵ also for a benzo group.

R ⁶ particularly preferably represents hydrogen, hydroxyl, amino, in each case optionally substituted by fluorine and / or chlorine, methoxy or ethoxy, methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, methoxy, Ethoxy, n- or i-propoxy, methylamino, ethylamino or dimethylamino, for each optionally substituted by fluorine and / or chlorine, ethenyl, propenyl, ethynyl, propynyl or propenyloxy, for cyclopropyl, cyclobutyl, each optionally substituted by fluorine and / or chlorine, Cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or for each optionally by fluorine, chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy substituted phenyl or benzyl, or together with an adjacent radical R ⁵ or R ^6, each propane-1,3-diyl (trimethylene), butane-1,4-diyl optionally substituted by methyl and / or ethyl (Tetramethylene) or pentane-1-5- diyl (pentamethylene),
where the individual radicals R ⁵ and R ⁶ - if several of them are bound to the same heterocyclic groupings, may have the same or different meanings within the scope of the above definition.

A very particularly preferably represents a single bond or methylene.

R ¹ very particularly preferably represents hydrogen, methyl, ethyl, n- or i-propyl.

R ² very particularly preferably represents methyl.

R ³ very particularly preferably represents hydrogen nitro, cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthio methyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, di fluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, Ethyl sulfinyl, methyl sulfdnyl, ethyl sulfonyl or dimethylaminosulfonyl.

R ⁴ very particularly preferably represents nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinyl methyl, methylsulfonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methyl sulfonyl, ethylsulfonyl or dimethylaminosulfonyl.

R ⁵ very particularly preferably represents hydrogen, hydroxyl, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, Fluorodichloromethyl, fluoroethyl, chloroethyl, difluoroethyl, dichloroethyl, fluoro-n-propyl, fluoro-i-propyl, chloro-n-propyl, chloro-i-propyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, fluoroethoxy, chloroethoxy, difluoroethoxy, dichloroethoxy, trifluoroethoxy, trichloroethoxy, chlorofluoroethoxy, chlorodi fluoroethoxy, fluorodichloroethoxy, methylthio, ethylthio, n- or i-propylthio, fluoroethylthio , Chloroethylthio, difluoroethylthio, dichloroethylthio, chlorofluoroethylthio, chlorodifluoroethylthio, fluorodichloroethylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, dimethylamio, propenyl, propyl, propylsulfonyl, dimethylamino, propenyl, propylsulfonyl, dimethylamino, propenyl clopropylmethyl, cyclopropylmethoxy, phenyl or phenoxy.

R ⁶ very particularly preferably represents amino, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylamino, dimethylamino, cycloproypyl or cyclopropylmethyl, or together with R. ⁵ for propane-1,3-diyl (trimethylene), butane-1,4-diyl (tetramethylene) or pentane-1,5-diyl (pentamethylene).

A most preferably represents methylene.

The invention preferably relates to the sodium, potassium, magnesium, calcium, ammonium, C ₁ -C ₄ alkyl ammonium, di (C ₁ -C ₄ alkyl) ammonium, tri ( C ₁ -C ₄ alkyl) ammonium, tetra (C ₁ -C ₄ alkyl) ammonium, tri (C ₁ -C ₄ alkyl) sulfonium, C ₅ or C ₆ cycloalkyl -ammonium- and di- (C ₁ -C ₂ alkyl) -benzyl ammonium salts of the compounds of formula (I), in which m, n, A, R ¹ , R ² , R ³ , R ⁴ and Z the have the meanings given above.

According to the invention, preference is given to the compounds of the formula (I) in which one A combination of the meanings listed above as preferred is present.

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

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

Compounds of the following general formulas (IA), (IB) and (IC) are particularly emphasized as according to the invention:

in which
m represents the numbers 0, 1 or 2,
n represents the numbers 0, 1 or 2,
A particularly preferably represents a single bond or methylene.

Q represents oxygen or sulfur,
R ^{1 represents} hydrogen, methyl, ethyl, n- or i-propyl,
R ^{2 represents} methyl,
R ³ for hydrogen nitro, cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfyl, ethylsulfyl, ethylsulfyl, methylsulfinyl sulfonyl or dimethylaminosulfonyl,
R ⁴ for nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, meth oxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonylylmethylsulfonyl stands,
R ⁵ for hydrogen, hydroxy, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, fluoroethyl, Chloroethyl, di fluoroethyl, dichloroethyl, fluoro-n-propyl, fluoro-i-propyl, chloro-n-propyl, chloro-i-propyl, methoxymethyl, ethoxymethyl, methoxycthyl, ethoxycthyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, fluoroethoxy, chloroethoxy, difluoroethoxy, dichloroethoxy, trifluoroethoxy, trichloroethoxy, chlorofluoroethoxy, chlorodifluoroethoxy, fluorodichloroethoxy, methylthio, ethylthio, n- or i-propylthio, fluoroethylthio, chloroethylthio, chloroethylthio, chloroethylthio , Chlorofluoroethylthio, chlorodifluoroethylthio, fluorine dichloroethylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, dimethylamino, propenylthio, butenylthio, propynyl propyl, cycloethyl, cyclo-propylthylmethyl, cyclo-methylethyl, cyclo-propylthyl, cyclo-methyl, cyclo-propyl-thyl, xy, phenyl or phenoxy, and
R ^{6 represents} amino, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylamino, dimethylamino, cycloproypyl or cyclopropyl methyl, or together with R ^{5 stands} for propane -1,3-diyl (trimethylene), butane-1,4-diyl (tetramethylene) or pentane-1,5-diyl (pentamethylene).

The compounds of formula (IA) in which A represents methylene are particularly emphasized here.

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

Examples of the compounds of the general formula (I) according to the invention are listed in the groups below.

Group 1

R ³ , (R ⁴ ) _n , R ⁵ and R ⁶ have, for example, the meanings given in the table below:

Group 2

R ³ , (R ⁴ ) _n , R ⁵ and R ⁶ have, for example, the meanings given in the table below:

Group 3

R ³ , (R ⁴ ) _n , R ⁵ and R ⁶ have, for example, the meanings given above in Group 1.

Group 4

R ³ , (R ⁴ ) _n , R ⁵ and R ⁶ have, for example, the meanings given above in Group 2.

The new substituted benzoylcyclohexanediones of the general formula (I) are characterized by strong and selective herbicidal activity.

The new substituted benzoylcyclohexanediones of the general formula (I) are obtained if 1,3-cyclohexanedione or its derivatives of the general formula (II)

in which
m, R ¹ and R ^{2 have} the meaning given above,
with substituted benzoic acids of the general formula (III),

in which
n, A, R ³ , R ⁴ and Z have the meaning given above,
in the presence of a dehydrating agent, if appropriate in the presence of one or more reaction auxiliaries and if appropriate in the presence of a diluent,
and, if appropriate, subsequently carrying out the compounds of the formula (I) thus obtained within the scope of the definition of the substituent in a customary manner, electrophilic or nucleophilic or oxidation or reduction reactions, or converting the compounds of the formula (I) into salts in the customary manner.

The compounds of the formula (I) can be converted by conventional methods into other compounds of the formula (I) as defined above, for example by nucleophilic substitution (for example R ⁵ : Cl → OC ₂ H ₅ , SCH ₃ ) or by oxidation (e.g. R ⁵ : CH ₂ SCH ₃ → CH ₂ S (O) CH ₃ ).

The compounds of general formula (I) can in principle also as in The following are schematically synthesized:

Reaction of 1,3-cyclohexanedione or its derivatives of the general formula (II) - above - with reactive derivatives of the substituted benzoic acids of the general formula (III) - above - in particular with corresponding carboxylic acid chlorides, carboxylic acid anhydrides, carboxylic acid cyanides, carboxylic acid methyl esters or -ethyl esters - optionally in the presence of reaction auxiliaries, such as. B. triethylamine (and optionally additionally zinc chloride), and optionally in the presence of a diluent, such as. B. Methylene chloride:

(Y e.g. CN, Cl).

In the implementations outlined above for producing the connections of the general My formula (I) generally occurs in addition to the desired C-benzoyly tion on cyclohexanedione also leads to O-benzoylation - cf. below Formula scheme (see Synthesis 1978, 925-927; Tetrahedron Lett. 37 (1996), 1007-1009,  WO-A-91/05469). The O-benzoyl compounds formed here are however under the reaction conditions of the process according to the invention corresponding C-benzoyl compounds of formula (I) isomerized.

If, for example, 1,3-cyclohexanedione and 2- (3-carboxy-5-fluorobenzyl) -5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazole-3- are used on as starting materials, the course of the reaction in the process according to the invention can be outlined using the following formula:

The cyclohexanediones to be used as starting materials in the process according to the invention for the preparation of compounds of the formula (I) are generally defined by the formula (II). In the formula (II), m, R ¹ and R ² preferably have those meanings which are preferred above, in connection with the description of the compounds of the formula (I) according to the invention, particularly before or very particularly preferred for m, R ¹ and R ^{2 were} specified.

The starting materials of the general formula (II) are known and / or can be according to known processes are produced.

Formula (III) provides a general definition of the substituted benzoic acids to be used as starting materials in the process according to the invention for the preparation of compounds of formula (I). In the formula (III), n, A, R ³ , R ⁴ and Z preferably have those meanings which are already preferred, particularly preferred, very particularly preferred or most in connection with the description of the compounds of the formula (I) according to the invention were preferably given for n, A, R ³ , R ⁴ and Z.

With the exception of 2- (5-car boxy-2,4-dichlorophenyl) -4-difluoromethyl-5-methyl-2,4-dihydro-3H-1,2,4-tri azol-3-one - also known as 2,4-dichloro-5- (4-difluoromethyl-4,5-dihydro-3-me thyl-5-oxo-1H-1,2,4-triazol-1-yl) benzoic acid (CAS Reg. No. 90208-77-8) and 2- (5-carboxy-2,4-di chlorophenyl) -4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazol-3-one - alias 2,4-di chloro-5- (4,5-dihydro-3,4-dimethyl-5-oxo-1H-1,2,4-triazol-1-yl) benzoic acid (CAS Reg.No. 90208-76-7) - not yet known from the literature. They are with the exception of 2- (5-carboxy-2,4-dichlorophenyl) -4-difluoromethyl-5-methyl-2,4-dihydro-3H-1,2,4-tri azol-3-one and 2- (5-carboxy-2,4-dichlorophenyl) -4,5-dimethyl-2,4-dihy dro-3H-1,2,4-triazol-3-one (cf. JP-A-58225070 - cited in Chem. Abstracts 100: 209 881, JP-A-02 015 069 - cited in Chem. Abstracts 113: 23929) as new substances also counter stood the present application.

The new substituted benzoic acids of the general formula (III) are obtained if benzoic acid derivatives of the general formula (IV)

in which
n, A, R ³ and R ⁴ and Z have the meaning given above, and
Y represents cyano, carbamoyl, halocarbonyl or alkoxycarbonyl,
with water, optionally in the presence of a hydrolysis aid, such as. B. sulfuric acid, at temperatures between 50 ° C and 120 ° C (see. Her position examples).

The benzoic acid derivatives of the general formula (IV) required as precursors are known and / or can be produced by methods known per se (see DE-A-3839480, DE-A-4239296, EP-A-597360, EP-A-609734, DE-A-4303676, EP-A-617026, DE-A-4405614, US-A-5378681).

The new substituted benzoic acids of the general formula (III) are also obtained if halogen (alkyl) benzoic acids of the general formula (V)

in which
n, A, R ³ and R ^{4 have} the meaning given above and
X represents halogen (in particular fluorine, chlorine or bromine),
with compounds of the general formula (VI),

in which
Z has the meaning given above,
optionally in the presence of a reaction auxiliary, such as. B. triethylamine or potassium carbonate, and optionally in the presence of a diluent, such as. B. acetone, acetonitrile, N, N-dimethyl-formamide or N, N-dimethyl-acetamide, at temperatures between 50 ° C and 200 ° C (see. The preparation examples).

Instead of the halogen (alkyl) benzoic acids of the general formula (V) can analogous to the methodology described above, corresponding nitriles, amides and Esters - especially the methyl esters or the ethyl esters - with compounds of all general formula (VI) are implemented. By subsequent hydrolysis after usual methods, for example by reaction with aqueous ethanolic Potash lye, can then receive the corresponding substituted benzoic acids become.

The halogen (alkyl) benzoic acids of the formula (V) - or Corresponding nitriles or esters - are known and / or can be per se known processes can be prepared (cf. EP-A-90369, EP-A-93488, EP-A-399732, EP-A-480641, EP-A-609798, EP-A-763524, DE-A-2126720, WO-A-93/03722, WO-A-97/38977, US-A-3978127, US-A-4837333).

The compounds of the general formula (VI) required as precursors are known and / or can be produced by methods known per se.  

The process according to the invention for the preparation of the new substituted benzoyl Cyclohexanediones of the general formula (I) is using a De hydrating agent performed. The usual bindings occur here chemicals suitable for water.

Examples include dicyclohexylcarbodiimide and carbonyl-bis-imidazole called.

Dicyclohexylcarbodiimide is a particularly suitable dehydrating agent called.

The process according to the invention for the preparation of the new substituted benzoyl Cyclohexanediones of the general formula (I) is optionally used carried out a reaction aid.

Examples include sodium cyanide, potassium cyanide, acetone cyanohydrin, Called 2-cyano-2- (trimethylsilyloxy) propane and trimethylsilylcyanide.

Trimethylsilyl cyanide is another particularly suitable reaction auxiliary called.

The process according to the invention for the preparation of the new substituted benzoyl Cyclohexanediones of the general formula (I) is optionally used another reaction aid. As a further reaction aid basic organic are generally used for the process according to the invention Nitrogen compounds such as trimethylamine, triethylamine, tripropyl amine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclohexylamine, di cyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethyl-aniline, N, N-dimethyl benzylamine, pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 3,4-dimethyl and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethyl-ami no-pyridine, N-methylpiperidine, 1,4-diazabicyclo [2,2,2] -oetane (DABCO),  1,5-diazabicyclo [4,3,0] non-5-ene (DBN), or 1,8-diazabicyclo [5,4,0] -undec-7-ene (DBU) into consideration.

Coming as a diluent for carrying out the process according to the invention inert organic solvents. These include in particular special aliphatic, alicyclic or aromatic, optionally halogenated Hydrocarbons, such as gasoline, benzene, toluene, xylene, chlorobenzene, Dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetra chloromethane or 1,2-dichloroethane; Ethers, such as diethyl ether, diisopropyl ether, Dioxane, tetrahydrofuran, ethylene glycol dimethyl or diethyl ether; Ketones like Acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or butyronitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide.

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

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

To carry out the process according to the invention, the starting materials in generally used in approximately equimolar amounts. However, it is also possible Lich to use one of the components in a larger excess. The order settlement is generally in a suitable diluent in the presence performed a dehydrating agent and the reaction mixture is in all  agitated several hours at the required temperature. The on work is carried out according to customary methods (cf. games).

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

The active compounds according to the invention can, for. B. ver in the following plants be applied:

Dicotyledon 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.

Dicotyledon cultures of the genera

Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersieon, Arachis, Brassiea, 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, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.  

Monocot cultures of the genera

Oryza, Zea, Triticum, Hordeum, Avena, Secale, sorghum, panicum, saccharum, pineapple, asparagus, allium.

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

Depending on the concentration, the compounds are suitable for the total weed control z. B. on industrial and track systems and on paths and squares with and without tree cover. Likewise, the connections to weed beds fighting in permanent crops, e.g. B. forest, ornamental wood, fruit, wine, citrus, nut, Banana, coffee, tea, gum, oil palm, cocoa, berry fruit and hops plants, on ornamental and sports turf and pastures and for selective weeds fighting in annual crops.

The compounds of formula (I) according to the invention are particularly suitable for selective control of monocotyledon and dicotyledon weeds in monocotyledons Cultures both pre-emergence and post-emergence.

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

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients with extenders, i.e. liquid solvents and / or solid carriers gerstoffe, optionally using surfactants, so Emulsifiers and / or dispersants and / or foaming agents.  

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

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

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

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

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

The active compounds according to the invention can be used as such or in their formulations also used in a mixture with known herbicides for weed control find, where ready formulations or tank mixes are possible.

Known herbicides are suitable for the mixtures, for example Acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), Ametryne, Amidochlor, Amidosulfuron, Anilofos, Asulam, Atrazine, Azafenidin, Azimsulfuron, benazolin (-ethyl), benfuresate, bensulfuron (-methyl), bentazone, Benzofenap, Benzoylprop (-ethyl), Bialaphos, Bifenox, Bispyribae (-sodium), Bromo butides, bromofenoxim, bromoxynil, butachlor, butroxydim, butylates, cafenstrole, Caloxydim, carbetamides, carfentrazone (-ethyl), chloromethoxyfen, chloramben, Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, Chlorsulfuron, Chlortoluron, Cini don (-ethyl), cinmethylin, cinosulfuron, clethodim, clodinafop (-propargyl), Clomazone, Clomeprop, Clopyralid, Clopyrasulfuron (-methyl), Cloransulam (-me thyl), cumyluron, cyanazines, cybutryne, cycloates, cyclosulfamuron, cycloxy dim, cyhalofop (-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, dialates, dicamba, Diclofop (-methyl), diclosulam, diethatyl (-ethyl), difenzoquat, diflufenican, diflu fenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, Dimexyflam, Dinitramine, Diphenamid, Diquat, Dithiopyr, Diuron, Dymron, Epo prodan, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron (-methyl), Ethofumesate, Ethoxyfen, ethoxysulfuron, etobenzanide, fenoxaprop (-P-ethyl), flamprop (-iso propyl), flamprop (-isopropyl L), flamprop (-methyl), flazasulfuron, fluazifop (-P-bu  tyl), fluazolates, flucarbazones, flufenacet, flumetsulam, flumiclorae (-pentyl), Flumioxazin, Flumipropyn, Flumetsulam, Fluometuron, Fluorochloridone, Fluoro glycofen (-ethyl), flupoxam, flupropacil, flurpyrsulfuron (-methyl, -sodium), Flurenol (-butyl), Fluridone, Fluroxypyr (-meptyl), Flurprimidol, Flurtamone, Flu thiacet (-methyl), fluthiamide, fomesafen, glufosinate (-aminonium), glyphosate (-iso propylammonium), halosafen, haloxyfop (-ethoxyethyl), haloxyfop (-P-methyl), Hexazinones, imazamethabenz (-methyl), imazamethapyr, imazamox, imazapic, Imazapyr, Imazaquin, Imazethapyr, Imazosulfuron, Iodosulfuron, Ioxynil, Iso propalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, Lactofen, Lenacil, Linuron, MCPA, MCPP, Mefenacet, Mesotrione, Metamitron, Metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-) metola chlorine, metosulam, metoxuron, metribuzin, metsulfüron (-methyl), molinate, mono linuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orben carb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxazielomefone, oxyfluorfen, Paraquat, pelargonic acid, pendimethalin, pentoxazone, pheninedipham, piperophos, Pretilachlor, Primisulfuron (-methyl), Procarbazone, Prometryn, Propachlor, Propanil, Propaquizafop, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen (-ethyl), Pyrazolates, pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxime, pyributi carb, pyridate, pyriminobac (methyl), pyrithiobac (sodium), quinchlorac, quin merac, quinoclamine, quizalofop (-P-ethyl), quizalofop (-P-tefuryl), rimsulfuron, Sethoxydim, Simazine, Simetryn, Sulcotrione, Sulfentrazone, Sulfometuron- (me thyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthyl azine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulf uron (-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallates, triasulfuron, tri benuron (methyl), trielopyr, tridiphane, trifluralin and triflusulfuron.

Also a mixture with other known active ingredients, such as fungicides, insects ziden, acaricides, nematicides, bird repellants, plant nutrients and soil structure improvers are possible.  

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

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

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

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

Manufacturing examples

example 1

1.2 g (3.48 mmol) of 5-ethoxy-4-methyl-2- (2-carboxy-5-trifluoromethyl-benzyl) -2,4-di hydro-3H-1,2,4-triazol-3-one are suspended in 30 ml of acetonitrile and mixed with 0.39 g (3.48 mmol) of 1,3-cyclohexanedione and 0.76 g (3.7 mmol) of dicyclohexylcarbo diimide (DCC) at room temperature (approx. 20 ° C). The reaction mixture is stirred overnight (approx. 15 hours) at room temperature and then with 1.0 ml (7.0 mmol) Triethylamine and 0.10 ml (1.39 mmol) of trimethylsilyl cyanide were added. After 3 Hours at room temperature with 100 ml of 5% aqueous sodium carbonate Solution stirred, the dicyclohexylurea which separates and the alkaline aqueous phase extracted several times with ethyl acetate. Then the watery one Phase adjusted to pH 2 with 35% hydrochloric acid and several times with methylene chloride extracted. The methylene chloride phases are dried over sodium sulfate and constricted.  

0.8 g (52% of theory) of 5-ethoxy-4-methyl-2- [2- (2,6-dioxo-cyclohexyl carbonyl) -5-trifluoromethyl-benzyl] -2,4-dihydro-3H-1 are obtained , 2,4-triazol-3-one as an amorphous residue.
logP (determined at pH = 2): 2.70.

Example 2

To a suspension of 2.15 g (6.5 mmol) of 2- (4-carboxy-3-chlorophenyl) -4-me thyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 0.83 g (7.2 mmol) 1,3-cyclo hexanedione and 40 ml of acetonitrile becomes a solution of 1.5 g (7.2 mmol) of dicyclo hexylcarbodiimide in 40 ml of acetonitrile and the reaction mixture is 16 Stirred at 20 ° C for hours. Then 1.3 g (13 mmol) of triethylamine and 0.26 g (2.6 mmol) Trimethylsilylcyanid added and the reaction mixture is white Stirred at 20 ° C for 4 hours. Then with 180 ml of 2% aqueous soda solution stirred and vacuumed. The mother liquor is extracted with ethyl acetate. Then the aqueous phase is acidified with 2N hydrochloric acid and with methylene chloride extracted. The organic phase is dried and concentrated in a water jet vacuum  and digested with diethyl ether / petroleum ether. The crystalline product is isolated by suction.

1.6 g (59% of theory) of 2- [4- (2,6-dioxocyclohexylcarbonyl) -3-chlorophenyl] -4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1,2 are obtained , 4-triazol-3-one with melting point 182 ° C.
logP (determined at pH = 2): 3.13.

Analogous to preparation examples 1 and 2 and in accordance with the general Description of the manufacturing processes according to the invention can for example also the compounds listed in Tables 1 and 2 below Formula (I) - or the formulas (IA-3), (IB-2), (IC-2) or (ID) - are prepared.  

Table 1

Examples of the compounds of the formulas (IA-3), (IB-2), (IC-2)

Table 2

Examples of the compounds of the formula (ID)

The logP values given in Tables 1 and 2 were determined according to EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a phase reversal column (C 18). Temperature: 43 ° C.  

• (a) Eluents for determination in the acidic range: 0.1% aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with ^a) .
• (b) eluents for determination in the neutral range: 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with ^b) .

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

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

Starting materials of formula (III)

Example (III-1)

4.5 g (15 mmol) of 2- (3-chloro-4-cyano-phenyl) -4-methyl-5-trifluoromethyl-2,4-dihy dro-3H-1,2,4-triazol-3-one are taken up in 80 ml of 60% sulfuric acid and the Mixture is heated under reflux for 6 hours. After cooling to room temperature The crystalline product is isolated by suction.

4.5 g (91% of theory) of 2- (3-carboxy-4-chlorophenyl) -4-methyl-5-tri are obtained fluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one, melting point 223 ° C.

Example (III-2)

2 g (4.9 mmol) of 5-bromo-4-methyl-2- (2-ethoxycarbonyl-5-trifluoromethyl-benzyl) -2,4-di hydro-3H-1,2,4-triazol-3-one (see Example IV-I) are dissolved in 30 ml of 10% ethano dissolved potassium hydroxide solution and heated under reflux for 2 hours. The reaction mixture is concentrated in a water jet vacuum, taken up in 20 ml of water and mixed with ver acidified with thinner hydrochloric acid. The precipitated solid is filtered and dried.  

1.2 g (71% of theory) of 5-ethoxy-4-methyl-2- (2-carboxy-5-trifluoromethyl-benzyl) -2,4-dihydro-3H-1,2,4-triazole are obtained -3-one as a solid product.
logP: 2.18 ^a) .

Example (III-3)

13.4 g (35 mmol) of 4-methyl-5-trifluoromethyl-2- (2,6-dichloro-3-methoxycarbonyl benzyl) -2,4-dihydro-3H-1,2,4-triazol-3-one are placed in 60 ml of 1,4-dioxane and a solution of 1.54 g (38.5 mmol) of sodium hydroxide in 20 ml of water is added Room temperature slowly metered in. The reaction mixture is at 150 minutes Stirred 60 ° C and then concentrated in a water jet vacuum. The residue is dissolved in 100 ml of water and by adding conc. Hydrochloric acid the pH Solution value set to 1. The product obtained in crystalline form is isolated by suction.

11.7 g (90% of theory) of 4-methyl-5-trifluoromethyl-2- (2,6-dichloro-3-car) are obtained boxy-benzyl) -2,4-dihydro-3H-1,2,4-triazol-3-one, melting point 207 ° C.

Analogous to Examples (III-1) to (III-3), for example, those in the Compounds of the general formula (III) listed in Table 2 below getting produced.

Table 2

Examples of the compounds of the formula (III)

The logP values given in Table 2 were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromato graphy) on a phase inversion column (C 18). Temperature: 43 ° C.

• (a) Eluents for determination in the acidic range: 0.1% aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with ^a) .
• (b) eluents for determination in the neutral range: 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with ^b) .

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

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

Starting materials of formula (IV)

Example (IV-1)

step 1

10 g (49 mmol) of 2-methyl-4-trifluoromethyl-benzoic acid are dissolved in 150 ml of ethanol dissolved and with 1 ml of conc. Sulfuric acid added. After heating for 24 hours The solution is refluxed, taken up in methylene chloride and washed with ge saturated aqueous sodium bicarbonate solution extracted. The methylene The chloride phase is dried over sodium sulfate and in a water jet vacuum constricted.

9 g (80% of theory) of ethyl 2-methyl-4-trifluoromethylbenzoate are obtained as an amorphous residue.  

Level 2

9 g (39 mmol) of ethyl 2-methyl-4-trifluoromethylbenzoate are dissolved in 200 ml Tetrachloromethane dissolved and with 7 g (39 mmol) of N-bromosuccinimide and 0.1 g of Di benzoyl peroxide added. After heating under reflux for 6 hours, this is abge Different succinimide filtered off and the filtrate was concentrated in a water jet vacuum.

12 g of an amorphous residue are obtained which, in addition to 2-bromomethyl-4-trifluoro methyl benzoic acid ethyl ester still 17% 2,2-dibromomethyl-4-trifluoromethyl-ben ethyl zoate and 12% ethyl 2-methyl-4-trifluoromethyl benzoate ent holds.

level 3

4 g of ethyl 2-bromomethyl-4-trifluoromethyl-benzoate (approx. 70%) and 2.28 g (12.8 mmol) 5-bromo-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one are dissolved in 150 ml Acetonitrile dissolved, mixed with 5.3 g (38.4 mmol) of potassium carbonate and vigorously heated to reflux with stirring for 2 hours. The reaction mixture is in water recorded and extracted several times with methylene chloride. The collected Methylene chloride phases are dried over sodium sulfate, in a water jet concentrated in vacuo and chromatographed.  

2 g (38% of theory) of 5-bromo-4-methyl-2- (2-ethoxycarbonyl-5-trifluoromethyl-benzyl) -2,4-dihydro-3H-1,2,4-triazole-3 are obtained -on as an amorphous product. ¹ H NMR (CDCl ₃ , δ): 5.46 ppm.

Example (IV-2)

6.7 g (40 mmol) of 4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one who submitted in 150 ml of acetonitrile and ver with 11 g (80 mmol) of potassium carbonate stirs. After heating the mixture to 50 ° C, a solution of 13.1 g (44 mmol) methyl 3-bromomethyl-2,4-dichloro-benzoate in 20 ml acetonitrile added dropwise with stirring and the reaction mixture is 15 Heated to reflux for hours. Then in the water jet concentrated in vacuo, the residue taken up in methylene chloride, with IN salt acid washed, dried with sodium sulfate and filtered. The filtrate is under concentrated under reduced pressure, the residue digested with petroleum ether and the crystalline product isolated by suction.

14.9 g (97% of theory) of 4-methyl-5-trifluoromethyl-2- (2,6-dichloro-3-me) are obtained thoxycarbonyl-benzyl) -2,4-dihydro-3H-1,2,4-triazol-3-one from the melting point 109 ° C.

Analogous to Examples (IV-1) and (IV-2), for example, those in the Compounds of the general formula (IVa) listed in Table 3 below getting produced.  

Table 3

Examples of the compounds of the formula (IV)

The logP values given in Table 3 were determined in accordance with EEC Directive 79/831 Annex V.A8 through HPLC (High Performance Liquid Chromato graphy) on a phase inversion column (C 18). Temperature: 43 ° C.

• (a) Eluents for determination in the acidic range: 0.1% aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with ^a) .
• (b) eluents for determination in the neutral range: 0.01 molar aqueous phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with ^b) .

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

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

Examples of use Example A Pre-emergence test

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

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

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

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

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

In this test, for example, the compounds according to Preparation Example I show and 10 with partially good tolerance to crops, such as. B. corn, strong action against weeds.  

Example B Post emergence test

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

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

Test plants with a height of 5-15 cm are sprayed with the active substance preparation have so that the desired amounts of active ingredient per unit area be applied. The concentration of the spray liquor is chosen so that in 1000 l of water / ha the desired amounts of active ingredient are applied. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.

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

In this test, for example, the compounds according to the preparation example show 10 and 15 with good tolerance to crops, such as. B. Corn, strong against weeds.

Claims (11)

1. Substituted benzoylcyclohexanediones of the general formula (I),
in which
m represents the numbers 0, 1, 2 or 3,
n represents the numbers 0, 1, 2 or 3,
A represents a single bond or alkanediyl (alkylene),
R ^{1 represents} hydrogen or represents optionally substituted alkyl or alkoxycarbonyl,
R ^{2 stands} for optionally substituted alkyl, or together with R ^{1 stands} for alkanediyl (alkylene), in which case m stands for 1 and
R ¹ and R ^{2 are} on the same carbon atom ("geminal") or on two adjacent carbon atoms ("vicinal"),
R ^{3 represents} hydrogen, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or represents optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino or dialkylaminosulfonyl,
R ^{4 represents} nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or represents optionally substituted alkyl, alkoxy, alkylthio, alkyl sulfinyl, alkylsulfonyl, alkylamino, dialkylamino or dialkyl aminosulfonyl, and
Z represents an optionally substituted 4- to 12-membered, saturated or unsaturated, monocyclic or bicyclic, heterocyclic grouping which has 1 to 4 heteroatoms (up to 4 nitrogen atoms and optionally - alternatively or additively - an oxygen atom or a sulfur atom, or contains an SO group or an SO _{2 group} ), and which additionally contains one to three oxo groups (C = O) and / or thioxo groups (C = S) as constituents of the heterocycle,
including all possible tautomeric forms of the compounds of the general formula (I) and the possible salts of the compounds of the general formula (I). 2. Substituted benzoylcyclohexanediones according to claim 1, characterized in that
m represents the numbers 0, 1 or 2,
n represents the numbers 0, 1 or 2,
A represents a single bond or alkanediyl (alkylene) having 1 to 4 carbon atoms,
R ¹ for hydrogen, for optionally substituted by halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl or C ₁ -C ₄ alkylsulfonyl substituted alkyl having 1 to 6 carbon atoms or for Alkoxy carbonyl having up to 6 carbon atoms,
R ^{2 stands} for optionally halogen-substituted alkyl with 1 to 6 carbon atoms, or together with R ^{1 stands} for alkanediyl (alkylene) with 2 to 5 carbon atoms, in which case m stands for 1 and R ¹ and R ² on the same carbon atom ( "geminal") or on two adjacent carbon atoms ("vicinal"),
R ³ for hydrogen, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, for each optionally by halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl or C ₁ - C ₄ -alkylsulfonyl-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkyl sulfonyl each having up to 4 carbon atoms in the alkyl groups, or represents alkylamino, dialkylamino or dialkylaminosulfonyl each having up to 4 carbon atoms in the alkyl groups,
R ⁴ for nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, for each optionally halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl thio, C ₁ -C ₄ alkylsulfinyl or C ₁ -C _4- alkylsulfonyl substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having up to 4 carbon atoms in the alkyl groups, or represents alkylamino, dialkylamino or dialkylaminosulfonyl each having up to 4 carbon atoms in the alkyl groups, and
Z represents one of the heterocyclic groupings below
in which the bond shown in dashed lines is a single bond or a double bond,
Q represents oxygen or sulfur,
R ⁵ for hydrogen, hydroxy, mercapto, cyano, halogen, each for optionally by halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl or C ₁ -C ₄ -Alkylsulfonyl-substituted alkyl, alkylcarbonyl, alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl each having up to 6 carbon atoms in the alkyl groups, each optionally substituted by halogen-substituted alkylamino or di alkylamino each having up to 6 carbon atoms in the alkyl groups, each optionally halogen-substituted alkenyl, alkynyl, alkenyloxy, alkenylthio or alkenylamino, each with up to 6 carbon atoms in the alkenyl or alkynyl groups, for cycloalkyl, cycloalkylalkyl, cycloalkyloxy, cycloalkylthio or cycloalkylamino, each with 3 to 6 carbon atoms each, optionally substituted by halogen Cycloalkyl groups and optionally up to 4 carbon atoms in the alkyl part, or for each optionally by Halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy substituted phenyl, phenyloxy, phenyl thio, phenylamino, benzyl, benzyloxy, benzylthio or benzylamino, and
R ⁶ for hydrogen, hydroxyl, amino, alkylidene amino with up to 4 carbon atoms, for alkyl, alkoxy, alkylamino, dialkylamino or alkanoylamino, each optionally substituted by halogen or C ₁ -C ₄ alkoxy, each having up to 6 carbon atoms in the alkyl groups, for each optionally substituted by halogen-substituted alkenyl, alkynyl or alkenyloxy, each having up to 6 carbon atoms in the alkenyl or alkynyl groups, for each optionally substituted by halogen, cycloalkyl, cycloalkylalkyl or cycloalkylamino, each having 3 to 6 carbon atoms in the cycloalkyl groups and optionally up to 3 Carbon atoms in the alkyl part, or for phenyl or benzyl optionally substituted by halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, or together with a neighboring radical R ⁵ or R ⁶ for optionally by halogen or C ₁ -C ₄ alkyl-substituted alkanediyl having 3 to 5 carbon atoms, or - for the case l that two adjacent radicals R ⁵ and R ⁵ are located on a double bond - together with the adjacent radical R ⁵ also stands for a benzo grouping. 3. Substituted benzoylcyclohexanediones according to claim 1, characterized in that
m represents the numbers 0, 1 or 2,
n represents the numbers 0, 1 or 2,
A represents a single bond, methylene, ethylidene (ethane-1,1-diyl) or dimethylene (ethane-1,2-diyl),
R ^{1 represents} hydrogen, each optionally by fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, or represents methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl,
R ² for methyl, ethyl, n- or i-propyl, or together with R ¹ for methylene, ethane-1,1-diyl (ethylidene, -CH (CH ₃ ) -), ethane-1,2-diyl (Di methylene, -CH ₂ CH ₂ -), propane-1,3-diyl (trimethylene, -CH ₂ CH ₂ CH ₂ -), butane-1,4-diyl (tetramethylene, -CH ₂ CH ₂ CH ₂ CH ₂ - ) or pentane-1,5-diyl (pentamethylene, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -), in which case m stands for 1 and R ¹ and R ² on the same carbon atom ("geminal") or are at two adjacent carbon atoms ("vicinal"),
R ³ for hydrogen, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, each optionally with fluorine and / or chlorine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i -Propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each optionally with fluorine and / or chlorine, methoxy, ethoxy, n - or i-propoxy substituted methoxy, ethoxy, n- or i-propoxy, for each methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methyl optionally substituted by fluorine and / or chlorine sulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, or represents methyl amino, ethylamino, n- or i-propylamino, dimethylamino, diethyl amino, dimethylaminosulfonyl or diethylaminosulfonyl,
R ⁴ for nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, for each optionally by fluorine and / or chlorine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio , Methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, for each optionally by fluorine and / or chlorine, methoxy, ethoxy, n- or i-propoxy substituted methoxy, ethoxy, n- or i-propoxy, for each methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methyl sulfonyl optionally substituted by fluorine and / or chlorine , Ethylsulfonyl, n- or i-propylsulfonyl, or represents methyl amino, ethylamino, n- or i-propylamino, dimethylamino, diethyl amino, dimethylaminosulfonyl or diethylaminosulfonyl, and
Z represents one of the heterocyclic groupings below
in which the bond shown in dashed lines is a single bond or a double bond,
Q represents oxygen or sulfur,
R ⁵ for hydrogen, hydroxy, mercapto, cyano, fluorine, chlorine, bromine, iodine, for each optionally by fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy , Methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl substituted methyl , Ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio , n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, for methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, di-n-propylamino or di-i-propylamino, for ethenyl, propenyl optionally substituted by fluorine and / or chlorine, Butenenyl, ethynyl, propynyl, butynyl, propenyloxy, butenyloxy , Propenylthio, butenylthio, propenylamino or butenylamino, for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropyloxy, cyclobutyloxy, cyclohexylthio, cyclohexyloxy, cyclohexylthio, cyclohexylthio, cyclohexylthio Cyclopentylthio, Cyclo hexylthio, Cyclopropylamino, Cyclobutylamino, Cyclopentyl amino or Cyclohexylamino, or for each optionally by fluorine, chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy , n- or i-propoxy substituted phenyl, phenyloxy, phenylthio, phenylamino, benzyl, benzyloxy, benzylthio or benzylamino, and
R ⁶ for hydrogen, hydroxy, amino, for each methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, methoxy, ethoxy, n which is optionally substituted by fluorine and / or chlorine, methoxy or ethoxy - or i-propoxy, methylamino, ethyl amino or dimethylamino, for each optionally substituted by fluorine and / or chlorine, ethenyl, propenyl, ethynyl, propynyl or propenyloxy, for each optionally substituted by fluorine and / or chlorine, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , Cyclopropylmethyl, Cyclobutyl methyl, Cyclopentylmethyl, Cyclohexylmethyl, or for each optionally by fluorine, chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy-substituted phenyl or benzyl, or together with an adjacent radical R ⁵ or R ⁶ each represents propane-1,3-diyl (trimethylene) or butane-1,4-diyl (optionally substituted by methyl and / or ethyl) ( Tetra methylene), or - in the event that two adjacent radicals R ⁵ and R ⁵ are located on a double bond - together with the neighboring radical R ⁵ also stands for a benzo grouping. 4. Substituted benzoylcyclohexanediones according to claim 1, characterized by the general formula (IA),
in which
m represents the numbers 0, 1 or 2,
n represents the numbers 0, 1 or 2,
A represents a single bond or methylene,
Q represents oxygen or sulfur,
R ^{1 represents} hydrogen, methyl, ethyl, n- or i-propyl,
R ^{2 represents} methyl,
R ³ for hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinyl methyl, methylsulfonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or dimethylaminosulfonyl,
R ^{4 represents} nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, methylsulfonyl, ethylsulfonyl ,
R ^{5 is} methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methyl sulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, or stands for cyclopropyl, and
R ^{6 represents} methyl, ethyl, methoxy, ethoxy or cycloproypyl. 5. Substituted benzoylcyclohexanediones according to claim 1, characterized by the general formula (IB),
in which
m represents the numbers 0, 1 or 2,
n represents the numbers 0, 1 or 2,
A represents a single bond or methylene,
Q represents oxygen or sulfur,
R ^{1 represents} hydrogen, methyl, ethyl, n- or i-propyl,
R ^{2 represents} methyl,
R ³ for hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinyl methyl, methylsulfonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or dimethylaminosulfonyl,
R ^{4 represents} nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, methylsulfonyl, ethylsulfonyl ,
R ^{5 is} methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methyl sulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, or stands for cyclopropyl, and
R ^{6 represents} methyl, ethyl, methoxy, ethoxy or cycloproypyl. 6. Substituted benzoylcyclohexanediones according to claim 1, characterized by the general formula (IC),
in which
m represents the numbers 0, 1 or 2,
n represents the numbers 0, 1 or 2,
A represents a single bond or methylene,
Q represents oxygen or sulfur,
R ^{1 represents} hydrogen, methyl, ethyl, n- or i-propyl,
R ^{2 represents} methyl,
R ³ for hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinyl methyl, methylsulfonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or dimethylaminosulfonyl,
R ^{4 represents} nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, methylsulfonyl, ethylsulfonyl ,
R ^{5 is} methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methyl sulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, or stands for cyclopropyl, and
R ^{6 represents} methyl, ethyl, methoxy, ethoxy or cycloproypyl. 7. Substituted benzoylcyclohexanediones according to one of claims 1 to 6, characterized in that the salts are the sodium, potassium, magnesium, calcium, ammonium, C ₁ -C ₄ alkyl-ammonium, di - (C ₁ -C ₄ -alkyl) -ammonium-, tri- (C ₁ -C ₄ -alkyl) -ammonium-, tetra- (C ₁ -C ₄ -alkyl) -ammonium, tri- (C ₁ - C ₄ alkyl) sulfonium, C ₅ or C ₆ cyclo alkyl ammonium and di (C ₁ -C ₂ alkyl) benzyl ammonium salts. 8. A process for the preparation of substituted benzoylcyclohexanediones according to any one of claims 1 to 6, characterized in that 1,3-cyclohexanedione or its derivatives of the general formula (II),
in which
m, R ¹ and R ^{2 have} the meaning given in one of claims 1 to 6,
with substituted benzoic acids of the general formula (III),
in which
n, A, R ³ , R ⁴ and Z have the meaning given in one of claims 1 to 6,
in the presence of a dehydrating agent, if appropriate in the presence of one or more reaction auxiliaries and if appropriate in the presence of a diluent,
and, if appropriate, subsequently carrying out the compounds of the formula (I) thus obtained within the scope of the definition of the substituent in a customary manner, electrophilic or nucleophilic or oxidation or reduction reactions, or converting the compounds of the formula (I) into salts in the customary manner. 9. Substituted benzoic acids of the general formula (III),
in which
n, A, R ³ , R ⁴ and Z have the meaning given in one of claims 1 to 6,
except for the compounds 2- (5-carboxy-2,4-dichlorophenyl) -4-difluoro methyl-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one and 2- (5-carboxy-2,4-di chlorophenyl) -4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazol-3-one. 10. Use of at least one substituted benzoylcyclohexanedione according to one of claims 1 to 6 for combating undesirable Plants. 11. Herbicidal agents, characterized by the content of at least one substituted benzoylcyclohexanedione according to any one of claims 1 to 6 and usual extenders.