KR20010053474A - Substituted benzoylcyclohexandiones - Google Patents

Abstract

The present invention relates to novel substituted benzoylcyclohexanediones of the general formula (I), their preparation and their use as herbicides:

Where

m, n, A, R ¹ , R ² , R ³ , R ⁴ and Z are each as defined in the specification.

Description

Substituted benzoylcyclohexandiones

The present invention relates to novel substituted benzoylcyclohexanediones, their preparation and their use as herbicides.

It is already known that certain substituted benzoylcyclohexanediones have herbicidal properties (see 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 activity of these compounds is not satisfactory in all respects.

Accordingly, the present invention provides novel substituted benzoylcyclohexanediones of general formula (I), including all possible tautomers and possible salts of compounds of general formula (I):

Where

m represents a number of 0, 1, 2 or 3,

n represents a number of 0, 1, 2 or 3,

A represents a single bond or an alkanediyl (alkylene),

R ¹ represents hydrogen or, in each case, optionally substituted alkyl or alkoxycarbonyl,

R ² represents optionally substituted alkyl or, together with R ¹ , represents alkanediyl (alkylene), in which case m represents ¹ and R ¹ and R ² represent the same carbon atom (“geminal) ") Or two adjacent carbon atoms (" vicinal ")

R ³ represents hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl or halogen, in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkyl Amino or dialkylaminosulfonyl;

R ⁴ represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl or halogen, in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino or Dialkylaminosulfonyl,

Z is 1 to 4 heteroatoms (up to 4 nitrogen atoms, and optionally or optionally one oxygen atom or one sulfur atom, or one SO group or one SO ₂ group) and further hetero 4- to 12-membered containing 1 to 3 oxo groups (C═O) and / or thioxo groups (C═S) as members of a cycle and optionally substituted, saturated or unsaturated, monocyclic or bicyclic (membered) represents a heterocyclic group.

In the definition, hydrocarbon chains such as alkyl or alkanediyl, including those bonded with heteroatoms as in alkoxy, are in each case straight or branched chains.

In addition to the compounds of general formula (I) above, corresponding tautomers which may be present, in each case exemplarily shown below, are also possible:

Preferred substituents of the radicals represented by the above general formula are described below:

m preferably represents a number of 0, 1 or 2,

n preferably represents a number of 0, 1 or 2,

A preferably represents a single bond or an alkanediyl (alkylene) having 1 to 4 carbon atoms,

R ¹ preferably represents hydrogen or optionally 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 alkoxycarbonyl having 6 or less carbon atoms,

R ² preferably denotes alkyl having 1 to 6 carbon atoms optionally substituted with halogen, or together with R ¹ represents alkanediyl (alkylene) having 2 to 5 carbon atoms, in which case m represents 1 , R ¹ and R ² are located on the same carbon atom ("minal") or two adjacent carbon atoms ("visinal"),

R ³ preferably represents hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl or halogen, or in each case has up to 4 carbon atoms in the alkyl group and in each case optionally 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 or in each case an alkylamino, dialkylamino or dialkylaminosulfonyl having up to 4 carbon atoms in the alkyl group,

R ⁴ preferably represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl or halogen, or in each case has up to 4 carbon atoms in the alkyl group and optionally in each case 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 Fonyl, or in each case alkylamino, dialkylamino or dialkylaminosulfonyl having up to 4 carbon atoms in the alkyl group,

Z represents one of the following heterocyclic groups:

From here,

The dotted bond represents in each case a single bond or a double bond,

Q represents oxygen or sulfur,

R ⁵ represents hydrogen, hydroxyl, mercapto, cyano or halogen, in each case up to 6 carbon atoms in the alkyl group and in each case optionally cyano-, 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, Denotes alkylsulfinyl or alkylsulfonyl, denotes propadienylthio, in each case up to 6 carbon atoms in the alkyl group and in each case optionally represents halogen-substituted alkylamino or dialkylamino In each case represent an alkenyl or alkynyl group having up to 6 carbon atoms and in each case optionally represent a halogen-substituted alkenyl, alkynyl, alkenyloxy, alkenylthio or alkenylamino, or in each case Or 3 to 6 carbon atoms in the cycloalkyl group And in each case optionally have a halogen-substituted cycloalkyl, cycloalkyloxy, cycloalkylthio, cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylalkylthio or cycloalkylalkyl Amino, or in each case optionally halogen-, C ₁ -C ₄ -alkyl- or C ₁ -C ₄ -alkoxy-substituted phenyl, phenyloxy, phenylthio, phenylamino, benzyl, benzyloxy, benzylthio or represent a benzylamino, or pyrrolidino, piperidino or morpholino the display or, together with two adjacent radicals R ⁵ and the radical R ⁵ R adjacent to the case ⁵ is located on a double bond, and also represents a benzo group,

R ⁶ represents hydrogen, hydroxyl, amino or alkylideneamino having up to 4 carbon atoms, or in each case has up to 6 carbon atoms in the alkyl group and in each case optionally halogen- or C ₁ -C _4- Alkenyl which represents an alkoxy-substituted alkyl, alkoxy, alkylamino, dialkylamino or alkanoylamino or in each case has up to 6 carbon atoms in the alkenyl or alkynyl group, and in each case an optionally halogen-substituted, Cycloalkyl, cycloalkylalkyl or alkynyl or alkenyloxy, or in each case having from 3 to 6 carbon atoms in the cycloalkyl group and optionally up to 3 carbon atoms in the alkyl moiety; Cycloalkylimino, or in each case optionally represents halogen-, C ₁ -C ₄ -alkyl- or C ₁ -C ₄ -alkoxy-substituted phenyl or benzyl, Together with the adjacent radicals R ⁵ or R ⁶ , optionally represents a halogen- or C ₁ -C ₄ -alkyl-substituted alkanediyl having 3 to 5 carbon atoms,

Individual radicals R ⁵ and R ⁶ may have the same or different meanings in connection with the above definition when two or more of them are bonded to the same heterocyclic group.

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, or in each case optionally 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, or n-, i- or s-butyl, or methoxycarbonyl, ethoxycarbonyl, or n- or i-propoxycarbonyl,

R ² particularly preferably represents methyl, ethyl, or n- or i-propyl, or together with R ¹ , 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 represents ¹ and R ¹ and R ² is located on the same carbon atom (“mineral”) or on two adjacent carbon atoms (“bisinal)”

R ³ particularly preferably represents hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine or iodine, in each case optionally 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, or n-, i-, s- or t-butyl, or in each case optionally fluorine- and / or chlorine-, methoxy-, ethoxy-, or n- or i-propoxy-substituted methoxy, ethoxy, or n- or i-propoxy, or in each case optionally fluorine- and / or chlor-substituted methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, or n- or i-propylsulfonyl, or methylamino, It represents the amino, n- or i- propylamino, dimethylamino, diethylamino, dimethylamino sulfonyl, or diethylamino-sulfonyl,

R ⁴ particularly preferably represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine or bromine, in each case optionally 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, or n-, i-, s- or t-butyl, or in each case optionally fluorine- and / or chlorine-, methoxy-, ethoxy-, or n- or i Methylthio, ethylthio, n- or i-propylthio, which represents, or in each case optionally fluorine- and / or chlorine-substituted, propoxy-substituted methoxy, ethoxy, or n- or i-propoxy , Methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, or n- or i-propylsulfonyl, methylamino, ethylamino, n- or Represents an i- propylamino, dimethylamino, diethylamino, dimethylamino sulfonyl, or diethylamino-sulfonyl,

Z is particularly preferably A heterocyclic group of

R ⁵ particularly preferably represents hydrogen, hydroxyl, mercapto, cyano, fluorine, chlorine, bromine or iodine, or in each case optionally 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-butyl Thio-, methylsulfinyl-, ethylsulfinyl-, n- or i-propylsulfinyl-, methylsulfonyl-, ethylsulfonyl-, or 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, Or n- or i-propylsulfonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-part Ethenyl, propenyl, butenyl, ethynyl, which represents amino, dimethylamino, diethylamino, di-n-propylamino or di-i-propylamino, or in each case optionally fluorine- and / or chlor-substituted , Propynyl, butynyl, propenyloxy, butenyloxy, propenylthio, butenylthio, propenylamino or butenylamino, in each case optionally fluorine- and / or chlorine-substituted cyclopropyl, Cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino, Cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclo Lofilmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopropylmethylthio, cyclobutylmethylthio, cyclopentylmethylthio, cyclohexylmethylthio, cyclopropylmethylamino, cyclobutylmethylamino, cyclo Pentylmethylamino or cyclohexylmethylamino, or in each case optionally fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, Methoxy-, ethoxy-, or n- or i-propoxy-substituted phenyl, phenyloxy, phenylthio, phenylamino, benzyl, benzyloxy, benzylthio or benzylamino, or two adjacent radicals R ⁵ And together with the adjacent radicals R ⁵ when R ⁵ is located in a double bond, also represent a benzo group,

R ⁶ particularly preferably represents hydrogen, hydroxyl or amino, in each case optionally fluorine- and / or chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n -ethenyl which represents i- or s-butyl, methoxy, ethoxy, n- or i-propoxy, methylamino, ethylamino or dimethylamino, optionally in each case fluorine- and / or chlorine-substituted , Propenyl, ethynyl, propynyl or propenyloxy, or in each case optionally fluorine- and / or chlorine-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, Cyclopentylmethyl or cyclohexylmethyl, or in each case optionally fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, methy Oxy-, ethoxy-, or n- or i-propoxy-substituted phenyl or Indicate the quality or, together with the adjacent radical R ⁵ or R ^6, in each case optionally methyl-and / or ethyl-substituted propane-1,3-diyl (trimethylene), butane-1,4-diyl (tetramethylene ) Or pentane-1,5-diyl (pentamethylene),

Individual radicals R ⁵ and R ⁶ may have the same or different meanings in connection with the above definition when two or more of them are bonded to the same heterocyclic group.

A very particularly preferably represents a single bond or methylene,

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

R ² very particularly preferably represents methyl,

R ³ is very particularly preferably hydrogen, nitro, cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, Methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminosulfonyl,

R ⁴ is very particularly preferably nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, Methoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminosulfonyl,

R ⁵ is very particularly preferably hydrogen, hydroxyl, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, tri Fluoromethyl, 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, chlorodifluoroethoxy, fluorodichloro Ethoxy, methylthio, ethylthio, n- or i-propylthio, fluoroethylthio, chloroethylthio, difluoro Ethylthio, dichloroethylthio, chlorofluoroethylthio, chlorodifluoroethylthio, fluorodichloroethylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl , n- or i-propylsulfonyl, dimethylamino, propenylthio, butenylthio, propynylthio, butynylthio, cyclopropyl, cyclopropylmethyl, cyclopropylmethoxy, phenyl or phenoxy,

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

A most preferably represents methylene.

The invention preferably comprises m, n, A, R ¹ , R ² , R ³ , R ⁴ and Z, respectively, of sodium, potassium, magnesium, calcium, ammonium, of the compounds of general formula (I) 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.

Preference is given to compounds of the formula (I) which comprise according to the invention a combination of the meanings mentioned as preferred above.

Particular preference is given to compounds of the formula (I) which comprise according to the invention a combination of the meanings mentioned as particularly preferred above.

Very particular preference is given to compounds of the formula (I) which comprise according to the invention a combination of the meanings mentioned above as very particularly preferred.

Of particular interest in the present invention are compounds of the general formulas (IA), (IB) and (IC):

Where

m represents a number of 0, 1 or 2,

n represents a number of 0, 1 or 2,

A particularly preferably represents a single bond or methylene,

Q represents oxygen or sulfur,

R ¹ represents hydrogen, methyl, ethyl, or n- or i-propyl,

R ² represents methyl,

R ³ is hydrogen, nitro, cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy Difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminosulfonyl,

R ⁴ is nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, difluorome Methoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminosulfonyl,

R ⁵ is hydrogen, hydroxyl, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloro Chloromethyl, 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, fluorine Loethoxy, chloroethoxy, difluoroethoxy, dichloroethoxy, trifluoroethoxy, trichloroethoxy, chlorofluoroethoxy, chlorodifluoroethoxy, fluorodichloroethoxy, methylthio , Ethylthio, n- or i-propylthio, fluoroethylthio, chloroethylthio, difluoroethylthio, dichloroethyl O, chlorofluoroethylthio, chlorodifluoroethylthio, fluorodichloroethylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i Propylsulfonyl, dimethylamino, propenylthio, butenylthio, propynylthio, butynylthio, cyclopropyl, cyclopropylmethyl, cyclopropylmethoxy, phenyl or phenoxy,

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

Of particular importance here are compounds of general formula (IA) wherein A is methylene.

The general or preferred radical definitions mentioned above apply to the final product of general formula (I) and also correspondingly to the starting materials or intermediates necessary in each case for preparation. These radical definitions may be combined with one another as desired, ie including combinations between given preferred ranges.

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

Group 1

Wherein R ³ , (R ⁴ ) _n , R ⁵ and R ⁶ each have the meaning shown, for example, in the table below:

Group 2

Wherein R ³ , (R ⁴ ) _n , R ⁵ and R ⁶ each have the meaning shown, for example, in the table below:

Group 3

Wherein R ³ , (R ⁴ ) _n , R ⁵ and R ⁶ each have the meaning given to group 1, for example.

Group 4

Wherein R ³ , (R ⁴ ) _n , R ⁵ and R ⁶ each have the meaning given to group 1, for example.

Newly substituted benzoylcyclohexanediones of formula (I) have useful potent and selective herbicidal activity.

Newly substituted benzoylcyclohexanediones of general formula (I) may be prepared by reacting 1,3-cyclohexanedione or a derivative thereof of the general formula (II) in the presence of a dehydrating agent, optionally in the presence and in the case of one or more reaction Accordingly reacted with substituted benzoic acid of formula (III) in the presence of diluent,

Optionally, electrophilic, nucleophilic, oxidation or reduction reactions are carried out in a conventional manner with respect to the compound of general formula (I) obtained by the above method, or the compound of general formula (I) Obtained by conversion to its salt by conventional methods:

Where

m, R ¹ , R ² , n, A, R ³ , R ⁴ and Z are each as defined above.

Compounds of formula (I) may be prepared by conventional methods, for example nucleophilic substitution (eg R ⁵ : Cl → OC ₂ H ₅ , SCH ₃ ), or oxidation (eg: R ⁵ : CH ₂ SCH ₃ → CH ₂ S (O) CH ₃ ) can be converted to other compounds of formula (I) according to the above definition.

In principle, the compounds of general formula (I) can also be synthesized by the process shown below:

Optionally 1,3-cyclohexanedione of formula (II) in the presence of a reaction aid such as triethylamine (and optionally also zinc chloride) and optionally a diluent such as methylene chloride or The derivatives thereof are reacted with the reactive derivatives of the substituted benzoic acids of the general formula (III), in particular having the corresponding carbonyl chloride, carboxylic anhydride, carboxylic acid cyanide, methyl carboxylate or ethyl carboxylate:

In the above formula, Y is CN, Cl, for example.

In the reactions indicated above to prepare compounds of general formula (I), O-benzoylation also occurs in addition to the desired C-benzoylation in cyclohexanedione (see Scheme below) (see Synthesis 1978, 925-927; Tetrahedron). Lett. 37 (1996), 1007-1009, WO-A-91 / 05469). However, the O-benzoyl compound formed in the above process isomerized to the corresponding C-benzoyl compound of general formula (I) under the reaction conditions according to the present invention.

For example, 1,3-cyclohexanedione and 2- (3-carboxy-5-fluorobenzyl) -5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4- When triazol-3-one is used as the starting material, the reaction process of the process according to the invention can be represented by the following scheme:

Formula (II) provides a general definition of cyclohexanedione used as starting material in the process according to the invention for the preparation of compounds of formula (I). In formula (II), m, R ¹ and R ² are each preferably, particularly preferred or preferred for m, R ¹ and R ² with respect to the description of the compounds of formula (I) according to the invention And very particularly preferred.

Starting materials of formula (II) are known and / or can be prepared by known methods per se.

Formula (III) provides a general definition of substituted benzoic acid which is further used as starting material in the process according to the invention for the preparation of compounds of formula (I). In general formula (III), n, A, R ³ , R ⁴ and Z are each preferably n, A, R ³ , R ⁴ and Z in connection with the description of the compounds of general formula (I) according to the invention. Has the meanings mentioned above as being preferred, particularly preferred, very particularly preferred, or most preferred.

2- (5-carboxy-2,4-dichloro-phenyl) -4-difluoromethyl-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one-aka 2,4-Dichloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl) -benzoic acid (CAS -Reg.-No. 90208-77-8) and 2- (5-carboxy-2,4-dichloro-phenyl) -4,5-dimethyl-2,4-dihydro-3H-1,2,4- Triazol-3-one-aka 2,4-dichloro-5- (4,5-dihydro-3,4-dimethyl-5-oxo-1H-1,2,4-triazol-1-yl)- Starting materials of the general formula (III), except for benzoic acid (CAS-Reg.-No. 90208-76-7), have not yet been described in the literature. 2- (5-carboxy-2,4-dichloro-phenyl) -4-difluoromethyl-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one and 2 -(5-carboxy-2,4-dichloro-phenyl) -4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazol-3-one (cf. JP-A-58225070 -Chem. Abstracts 100: 209881, JP-A-02015069-Compounds of formula (III), except Chem. Abstracts 113: 23929), are novel substances and are also subject to the patent of the present application.

Newly substituted benzoic acids of the general formula (III) are obtained by reacting a benzoic acid derivative of the general formula (IV) with water at a temperature of 50 to 120 ° C., optionally in the presence of a hydrolysis aid, for example sulfuric acid ( Reference: Manufacturing Examples):

Where

n, A, R ³ , R ⁴ and Z are each as defined above,

Y represents cyano, carbamoyl, halogenocarbamoyl or alkoxycarbonyl.

The benzoic acid derivatives of the general formula (IV) required as precursors are known and / or can be prepared by themselves known methods (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).

Newly substituted benzoic acids of the general formula (III) also contain halogeno (alkyl) benzoic acids of the general formula (V), optionally in the presence of reaction aids such as triethylamine or potassium carbonate and optionally diluents Obtained by reacting with a compound of the general formula (VI) at a temperature of 50 to 200 ° C., for example in the presence of acetone, acetonitrile, NN-dimethyl-formamide or NN-dimethyl-acetamide (see Preparation Preparative Yes):

Where

n, A, R ³ , R ⁴ and Z are each as defined above,

X represents halogen (especially fluorine, chlorine or bromine).

Instead of halogeno (alkyl) benzoic acid of formula (V) it is also possible to react nitriles, amides and esters, in particular methyl esters or ethyl esters, which are analogously similar to the above process, with compounds of formula (VI). The corresponding substituted benzoic acid can then be obtained by hydrolysis according to conventional methods, for example by reaction with an aqueous-ethanol potassium hydroxide solution.

Halogeno (alkyl) benzoic acids or the corresponding nitriles or esters of the general formula (V) required as precursors are known and / or themselves can be prepared by known methods (see EP-A-90369, EP-). A-93488, EP-A-399732, EP-A-480641, EP-A-609798, EP-A-763254, DE-A-2126720, WO-A-93 / 03722, WO-A-97 / 38977, US-A-3978127, US-A-4837333).

Compounds of formula (VI) which are additionally required as precursors are known and / or can be prepared by known methods per se.

The process according to the invention for preparing the new substituted benzoylcyclohexanedione of general formula (I) is carried out using a dehydrating agent. Suitable dehydrating agents are those conventional chemicals suitable for bonding with water.

Examples of these are dicyclohexylcarbodiimide and carbonyl-bis-imidazole.

Further suitable dehydrating agents are dicyclohexylcarbodiimide.

The process according to the invention for preparing new substituted benzoylcyclohexanediones of general formula (I) is optionally carried out using reaction aids.

Examples thereof include sodium cyanide, potassium cyanide, acetone or cyanohydrin, 2-cyano-2- (trimethylsilyloxy) -propane and trimethylsilyl cyanide.

Particularly suitable reaction aids are trimethylsilyl cyanide.

The process according to the invention for preparing new substituted benzoylcyclohexanediones of general formula (I) is optionally carried out using further reaction aids. Further reaction aids suitable for the process according to the invention are generally for example trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclohexylamine, Dicyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethyl-aniline, N, N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4- Dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo- [2,2,2] -octane (DABCO), 1,5-diazabicyclo- [4,3,0] -non-5-ene (DBN) or 1, Basic organic nitrogen compounds such as 8-diazabicyclo- [5,4,0] -undec-7-ene (DBU).

Suitable diluents for carrying out the process according to the invention are especially inert organic solvents. These include especially optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons such as benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane or 1, 2-dichloroethane; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether or ethylene glycol diethyl ether; Ketones such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile, or butyronitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethylsulfoxide.

In carrying out the process according to the invention, the reaction temperature can vary within a significant range. In general, the process is carried out at temperatures of 0 to 150 ° C, preferably 10 to 120 ° C.

The process according to the invention is generally carried out at atmospheric pressure. However, it is also possible to carry out the process according to the invention at elevated or reduced pressure, generally from 0.1 to 10 bar.

When carrying out the process according to the invention, the starting materials are generally used in approximately equimolar amounts. However, one of the components can be used in large excess. In general, the reaction is carried out in a suitable diluent in the presence of a dehydrating agent and the reaction mixture is usually stirred for several hours at the required temperature. Post-treatment is carried out in a conventional manner (see Preparation Examples).

The active compounds according to the invention can be used as defoliants, desiccants, haul killers and in particular herbicides. Weeds, in the broadest sense, mean all plants that grow in unwanted places. Whether the substance according to the invention acts as a total or selective herbicide depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in connection with the following plants:

Dicotyledonous weeds in the following genus: Sinapis, Lepidium, Gallium, Stellaria, Matricaria, Anthemis, Galinsoga, Kenopho Chenopodium, Urtica, Senesio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Poly Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala , Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papa Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.

Dicotyledonous crops of the following genus: Gossypium, Glycine, Beta, Doaucus, Phaseolus, Pisum, Solanum, Linum , Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis And Cucurbita.

Monocotyledonous weeds in the following genus: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Ele Eleusin, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Sinodon Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Iscamum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledonous crops of the following genus: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum ), Saccharum, Ananas, Asparagus and Allium.

However, the use of the active compounds according to the invention is not limited at all in the above, but also extends to other plants in the same way.

The compounds according to the invention are suitable for the total control of weeds, depending on the concentration, for example on industrial zones and railroads, and on sidewalks and plazas, with or without trees. Likewise, the compounds according to the invention are for example plantations, ornamental water plantations, orchards, vineyards, citrus fields, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, palm plantations, cocoa plantations, soft fruit plantations and It can be used to control weeds in perennial crops growing on hop fields, grass, race track grass and pasture, and to selectively control weeds in annual crops.

The active compounds of formula (I) according to the invention are suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous crops by both pre- and post-germination methods.

Active compounds include solutions, emulsions, hydrating powders, suspensions, powders, powders, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with the active compounds, and microcapsules in polymeric materials. It may be converted to a conventional formulation.

These formulations are prepared by known methods, for example by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, optionally using surfactants, ie emulsifiers and / or dispersants and / or foam-forming agents. .

If the extender used is water, for example an organic solvent can also be used as an auxiliary solvent. Suitable liquid solvents include mainly aromatic compounds such as xylene, toluene or alkylnaphthalene, chlorinated aromatic and chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, cyclohexane or paraffins, for example petroleum fractions, mineral oils and vegetable oils. Strong polar solvents such as aliphatic hydrocarbons, alcohols such as butanol or glycol and ethers and esters thereof, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, dimethylformamide and dimethyl sulfoxide and also water .

Suitable solid carriers are, for example, ammonium salts and ground natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly dispersed silica, alumina and silicates. Suitable granular solid carriers are, for example, pulverized and classified natural rocks such as calcite, marble, pumice, calcite and dolomite, and synthetic granules of inorganic and organic powders, and organic such as sawdust, coconut husk, corncobs and tobacco stems. Granules of matter. Suitable emulsifiers and / or foam-forming agents are for example nonionic and anionic emulsifiers, for example polyoxyethylene fatty alcohol ethers such as polyoxyethylene fatty acid esters, alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, Aryl sulfonates and protein hydrolysates. Suitable dispersants are for example lignin-sulfite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latex, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipids such as cephalin and lecithin, and synthetic phospholipids Can be used. Other possible additives are mineral and vegetable oils.

Colorants such as inorganic pigments such as iron oxide, titanium oxide and prussian blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes and salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc Micronutrients can be used.

The formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight of active compound.

In the case of weed control, the active compounds according to the invention can be used on their own or in admixture with known herbicides in the form of their preparations, finished formulations or tank mixes are possible.

Possible components in the mixture are known herbicides such as acetochlor, acifluorfen (-sodium), acloniphene, alachlor, alkoxydim (-sodium), amethrin, amidochlor, amidosulfuron, anil Lofos, asulam, atrazine, azaphenidine, azimsulfuron, benazolin (-ethyl), benfurate, bensulfuron (-methyl), bentazone, benzophene, benzoylprop (-ethyl), viala Phos, biphenox, bispyribac (-sodium), bromobutide, bromophenoxime, bromoxynil, butachlor, butoxyldim, butyrate, carfenstrol, caloxydim, carbetamid, carpent Lazone (-ethyl), Chlomethoxyphene, Chlorambene, Chloridazone, Chlorimuron (-ethyl), Chlornitropen, Chlorsulfuron, Chlortoluron, Cinidon (-ethyl), Cynmethyline, Cino Sulfuron, Cletodim, Clodinafof (-propargyl), Clomazone, Clomeprop, Clopyralide, Clopyrasulfuron (-Me ), Chloransullam (-methyl), cumyluron, cyanazine, cybutrin, cycloate, cyclosulfamuron, cyanoxydim, sihalofop (-butyl), 2,4-D, 2, 4-DB, 2,4-DP, Desmedipham, diallate, dicamba, diclofo (-methyl), diclosullam, dietatyl (-ethyl), dipfencuart, diflufenican, diflufen Zofir, Dimefuron, Dimepiperate, Dimethachlor, Dimethamethine, Dimethenamide, Dimexlam, Dinitramine, Diphenamide, Diquat, Dithiopyr, Diuron, Dimron, Epoprodan , EPTC, esprocarb, etafluralin, etamethsulfuron (-methyl), etofumesate, ethoxyphene, ethoxysulfuron, etobenzanide, phenoxaprop (-P-ethyl), flamprop (-Isopropyl), flamprop (-isopropyl-L), flamprop (-methyl), plazasulfuron, fluazipof (-P-butyl), fluazolate, flucarbazone, flufenacet , Flumetol , Flumiclolac (-pentyl), flumioxazine, flumipropine, flumetsulam, fluoromethuron, fluorocloridone, fluoroglycopene (-ethyl), flupoxam, flupropacyl, flupyr Sulfuron (-methyl, -sodium), flurenol (-butyl), flulidone, fluoroxypyr (-methl), fluprimidol, flutamone, fluthiacet (-methyl), flutiamide , Pomesafen, glufosinate (-ammonium), glyphosate (-isopropylammonium), halosafen, halooxyphosph (-ethoxyethyl), halooxyphosph (P-methyl), hexazinone, imazametha Mercedes-benz (-methyl), imazamethafir, imazamox, imazapic, imazaphyr, imazaquin, imazetapyr, imazasulfuron, iodosulfuron, oxynyl, isoprophalin, isoproturon, isou Ron, isoxaben, isoxachlortol, isoxaplutol, isoxapyrupif, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, mesotrione, meso Tamitron, metazachlor, metabenzthiazuron, methopenzuron, methopromurone, (alpha-) metolachlor, methotsalam, methoxuron, metribuzin, metsulfuron (-methyl), molinate , Monolinuron, naproanilide, naproproamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzaline, oxadiargyl, oxadione, oxasulfuron, oxazilomepon, oxy Fluorophene, paraquat, pelagonate, pendimethalin, pentoxazone, phenmedipham, piperophosph, pretilachlor, primisulfuron (-methyl), procarbazone, promethrin, profachlor, Propanyl, propaquizapov, propisochlor, propizamide, prosulfocarb, prosulfuron, pyraflufen (-ethyl), pyrazolate, pyrazosulfuron (-ethyl), pyrazoxifen, Pyribenzoxime, pyributicab, pyridate, pyriminobac-(-methyl), pyrithiobac (-sodium), quinclolac, quinmerak, Noclamine, quizolopop (-P-ethyl), quizolopop (-P-tefuryl), rimsulfuron, cetoxydim, simazine, cymetrine, sulforion, sulfentrazone, sulfomethuron (-Methyl), sulfosate, sulfosulfuron, tebutam, tebutiuuron, tepraloxydim, tebutylrazine, terbutrin, tenylchlor, thiafluamide, thiazopyr, thiadiazimin, thifensulfuron (-Methyl), thiobencarb, thiocarbasil, tralcoxysid, trialate, triasulfuron, tribenuron (-methyl), triclopyr, tridiphane, trituraline and triplelusulfuron.

Mixtures with other known active compounds are also possible, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and soil remediators.

The active compounds can be used on their own, in the form of their preparations, or in the forms of use prepared from them by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The active compounds are used in conventional manner, for example by watering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied before or after germination of plants. They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a relatively wide range. This depends essentially on the nature of the desired effect. Generally the amount used is 1 to 10 kg, preferably 5 to 5 kg of active compound per hectare of soil surface.

Examples of the preparation and use of the active compounds according to the invention can be seen from the following examples.

Manufacturing Example:

Example 1

1.2 g of 5-ethoxy-4-methyl-2- (2-carboxy-5-trifluoromethyl-benzyl) -2,4-dihydro-3H-1,2,4-triazol-3-one ( 3.48 mmol) was 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 dicyclohexylcarbodiimide (DCC) at room temperature (about 20 ° C.). It was. The reaction mixture was stirred at room temperature overnight (about 15 hours) and then mixed with 1.0 mL (7.0 mmol) triethylamine and 0.10 mL (1.39 mmol) trimethylsilyl cyanide. After 3 h at rt, the mixture was mixed with 100 mL of 5% aqueous sodium carbonate solution, the dicyclohexylurea was separated by suction filtration, and the alkaline aqueous phase was extracted repeatedly with ethyl acetate. The pH of the aqueous phase was then adjusted to 2 with 35% hydrochloric acid and extracted repeatedly with methylene chloride. The methylene chloride phase was dried over sodium sulphate and then concentrated.

5-ethoxy-4-methyl-2- [2- (2,6-dioxo-cyclohexyl-carbonyl) -5-trifluoromethyl-benzyl] -2,4-dihydro-3H-1, 0.8 g (52% of theory) of 2,4-triazol-3-one were obtained as an amorphous residue.

logP (measured at pH = 2): 2.70.

Example 2

A solution of 1.5 g (7.2 mmol) of dicyclohexylcarbodiimide in 40 ml of acetonitrile was added with 2- (4-carboxy-3-chloro-phenyl) -4-methyl-5-trifluoromethyl-2,4-di 2.15 g (6.5 mmol) of hydro-3H-1,2,4-triazol-3-one, 0.83 g (7.2 mmol) of 1,3-cyclohexanedione and 40 ml of acetonitrile were added to the suspension and the reaction mixture was added. Stir at 20 ° C for 16 h. After addition of 1.3 g (13 mmol) of triethylamine and 0.26 g (2.6 mmol) of trimethylsilyl cyanide, the reaction mixture was further stirred at 20 ° C. for 4 hours. The mixture was then stirred with 180 ml of a 2% aqueous sodium carbonate solution and then suction filtered. The mother liquor was extracted with ethyl acetate. The aqueous phase was then acidified with 2N hydrochloric acid and extracted with methylene chloride. The organic phase was dried and concentrated under a water pump vacuum and then degraded with diethyl ether / petroleum ether. The resulting crystalline product was isolated by filtration.

2- [4- (2,6-dioxocyclohexylcarbonyl) -3-chlorophenyl] -4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1 having a melting point of 182 ° C; 1.6 g (59% of theory) of 2,4-triazol-3-one were obtained.

logP (measured at pH = 2): 3.13.

General formula (I)-or general formula (IA-3), (IB-2) described in the following Tables 1 and 2 according to the general description of the methods of preparation examples 1 and 2 and the preparation method according to the invention, for example. ), (IC-2) or (ID)-may also be prepared.

Table 1: Examples of Compounds of Formulas (IA-3), (IB-2) and (IC-2)

Table 2: Examples of Compounds of Formula (D)

Starting material of general formula (III)

Example (III-1)

4.5 g of 2- (3-chloro-4-cyano-phenyl) -4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one ( 15 mmol) was dissolved in 80 ml of 60% sulfuric acid and the mixture was heated at reflux for 6 hours. After cooling to room temperature, the resulting crystalline product was isolated by suction filtration.

2- (3-carboxy-4-chloro-phenyl) -4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-one having a melting point of 223 ° C. 4.5 g (91% of theory) were obtained.

Example (III-2)

5-bromo-4-methyl-2- (2-ethoxycarbonyl-5-trifluoromethyl-benzyl) -2,4-dihydro-3H-1,2,4-triazol-3-one (Example IV-1) 2 g (4.9 mmol) were dissolved in 30 mL of 10% ethanol potassium hydroxide solution and heated at reflux for 2 hours. The reaction mixture was concentrated under a water pump vacuum, then dissolved in 20 ml of water and acidified with dilute hydrochloric acid. The precipitated solid was filtered off and dried.

1.2 g of 5-ethoxy-4-methyl-2- (2-carboxy-5-trifluoromethyl-benzyl) -2,4-dihydro-3H-1,2,4-triazol-3-one ( 71% of theory) were obtained as a solid product.

Example (III-3)

4-methyl-5-trifluoromethyl-2- (2,6-dichloro-3-methoxycarbonylbenzyl) -2,4-hydro-3H-1,2,4-triazol-3-one 13.4 g (35 mmol) was first introduced into 60 mL of 1,4-dioxane, and a solution of 1.54 g (38.5 mmol) of sodium hydroxide in 20 mL of water was slowly added by weighing at room temperature. The reaction mixture was stirred at 60 ° C. for 150 minutes and then concentrated under water pump vacuum. The residue was dissolved in 100 mL of water and the pH of the solution was adjusted to 1 by addition of concentrated hydrochloric acid. The resulting crystalline product was isolated by suction filtration.

4-methyl-5-trifluoromethyl-2- (2,6-dichloro-3-carboxy-benzyl) -2,4-dihydro-3H-1,2,4-triazole-3 having a melting point of 207 ° C. 11.7 g (90% of theory) of -on were obtained.

By the methods of Examples (III-1) and (III-3), for example, it is also possible to produce compounds of the general formula (III) shown in Table 3 below.

Table 3: Examples of Compounds of Formula (III)

Starting Material of Example (IV)

Example (IV-1)

Step 1

10 g (49 mmol) of 2-methyl-4-trifluoromethyl-benzoic acid were dissolved in 150 ml of ethanol and mixed with 1 ml of concentrated sulfuric acid. The solution was heated at reflux for 24 h, then concentrated and the residue was dissolved in methylene chloride and then extracted with saturated aqueous sodium bicarbonate solution. The methylene chloride phase was dried over sodium sulphate and concentrated under a water pump vacuum.

9 g (80% of theory) of ethyl 2-methyl-4-trifluoromethyl-benzoate were obtained as an amorphous residue.

Step 2

9 g (39 mmol) ethyl 2-methyl-4-trifluoromethyl-benzoate are dissolved in 200 mL tetrachloromethane, 7 g (39 mmol) N-bromo-succinimide and 0.1 dibenzoyl peroxide mixed with g. The mixture was heated at reflux for 6 hours, after which the precipitated succinimide was filtered off and the filtrate was concentrated under a water pump vacuum.

17% ethyl 2,2-dibromomethyl-4-trifluoromethyl-benzoate and ethyl 2-methyl-4-trifluoromethyl in addition to ethyl 2-bromomethyl-4-trifluoromethyl-benzoate 12 g of an amorphous residue containing 12% of benzoate was obtained.

Step 3

4 g of ethyl 2-bromomethyl-4-trifluoromethyl-benzoate (about 70% pure) and 5-bromo-4-methyl-2,4-dihydro-3H-1,2,4-tria 2.28 g (12.8 mmol) of sol-3-one was dissolved in 150 mL of acetonitrile, mixed with 5.3 g (38.4 mmol) of potassium carbonate, and heated at reflux for 2 hours with vigorous stirring. The reaction mixture was dissolved in water and extracted repeatedly with methylene chloride. The methylene chloride phases were combined and dried over sodium sulphate, concentrated in a water pump vacuum and then chromatographed.

5-bromo-4-methyl-2- (2-ethoxycarbonyl-5-trifluoromethyl-benzyl) -2,4-dihydro-3H-1,2,4-triazol-3-one 2 g (38% of theory) were obtained 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 are first introduced into 150 ml of acetonitrile, followed by potassium carbonate. Mix with 11 g (80 mmol). The mixture was heated to 50 ° C. and then a solution of 13.1 g (44 mmol) of methyl 3-bromomethyl-2,4-dichloro-benzoate in 20 ml of acetonitrile was added dropwise with stirring, and the reaction mixture was stirred for 15 hours. Heated under reflux. The mixture was then concentrated under water pump vacuum, then the residue was dissolved in methylene chloride, washed with 1N hydrochloric acid, dried over sodium sulfate and filtered. The filtrate was concentrated under reduced pressure, the residue was digested with petroleum ether and the crystalline product was isolated by smoking filtration.

4-methyl-5-trifluoromethyl-2- (2,6-dichloro-3-methoxycarbonyl-benzyl) -2,4-dihydro-3H-1,2,4-tria having a melting point of 109 ° C 14.9 g (97% of theory) of sol-3-one were obtained.

By the methods of Examples (IV-1) and (IV-2), it is also possible to produce compounds of the general formula (IVa), for example, as described in Table 4 below.

Table 4: Examples of Compounds of Formula (IV)

The logP values given in the table were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (high performance liquid chromatography) using a reversed phase column (C 18). Temperature: 43 ° C.

(a) Mobile phase for determination in acidic range: 0.1% aqueous phosphoric acid, acetonitrile; 10% acetonitrile → linear gradient with 90% acetonitrile-the corresponding data are indicated in the table as ^a) .

(b) mobile phase for measurement in the neutral range: 0.01 molar aqueous phosphate buffer, acetonitrile; Linear gradient with 10% acetonitrile to 90% acetonitrile-the corresponding data are indicated in the table as ^b) .

Calibration was performed using unbranched alkan-2-ones (3-16 carbon atoms) with known logP values (measured logP values as retention times by linear interpolation over two consecutive alkanones).

UV spectra of 200-400 nm were used to determine the lambda-max value as the maximum of the chromatographic signal.

Example of use:

Example A

Germination test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

A suitable formulation of the active compound is prepared by mixing 1 part by weight of the active compound with the solvent in the amounts mentioned above, adding the aforementioned amount of emulsifier and then diluting the concentrate with water to the desired concentration.

Seeds of the test plants were sown on top soil. After about 24 hours, the soil was sprayed with the active compound formulation to apply a specific amount of the desired active compound per unit area. The concentration of the spray solution was chosen such that a specific amount of the active compound of interest was applied to 1000 l / ha of water.

After 3 weeks, the degree of damage of the plants was recorded as percent damage compared to the development of the untreated control.

The figures represent the following:

0% = no effect (same as untreated control)

100% = Complete Exam

In this test, for example, the compounds of Preparation Examples 1 and 10 showed very potent activity against weeds, some of them tolerant to crops such as, for example, corn.

Table A: Pre-germination Test / Greenhouse

Example B

Post Germination Test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

A suitable formulation of the active compound is prepared by mixing 1 part by weight of the active compound with the solvent in the amounts mentioned above, adding the aforementioned amount of emulsifier and then diluting the concentrate with water to the desired concentration.

Test plants of 5 to 15 cm in height were sprayed with the active compound preparation to apply a specific amount of the desired active compound per unit area. The concentration of the spray solution was chosen such that a specific amount of the active compound of interest was applied to 1000 l / ha of water.

After 3 weeks, the degree of damage of the plants was recorded as percent damage compared to the development of the untreated control.

The figures represent the following:

0% = no effect (same as untreated control)

100% = Complete Exam

In this test, for example, the compounds of Preparation Examples 10 and 15 showed very potent activity against weeds, some of them tolerant to crops such as, for example, corn.

Table B: Post Germination Tests / Greenhouses

Claims (11)

Substituted benzoylcyclohexanediones of formula (I), including all possible tautomers and possible salts of compounds of formula (I): Where m represents a number of 0, 1, 2 or 3, n represents a number of 0, 1, 2 or 3, A represents a single bond or an alkanediyl (alkylene), R ¹ represents hydrogen or, in each case, optionally substituted alkyl or alkoxycarbonyl, R ² represents optionally substituted alkyl or, together with R ¹ , represents alkanediyl (alkylene), in which case m represents ¹ and R ¹ and R ² represent the same carbon atom (“geminal) ") Or two adjacent carbon atoms (" vicinal ") R ³ represents hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl or halogen, in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkyl Amino or dialkylaminosulfonyl; R ⁴ represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl or halogen, in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino or Dialkylaminosulfonyl, Z is 1 to 4 heteroatoms (up to 4 nitrogen atoms, and optionally or optionally one oxygen atom or one sulfur atom, or one SO group or one SO ₂ group) and further hetero 4- to 12-membered containing 1 to 3 oxo groups (C═O) and / or thioxo groups (C═S) as members of a cycle and optionally substituted, saturated or unsaturated, monocyclic or bicyclic (membered) represents a heterocyclic group. The method of claim 1, m represents a number of 0, 1 or 2, n represents a number of 0, 1 or 2, A represents a single bond or alkanediyl (alkylene) having 1 to 4 carbon atoms, R ¹ represents hydrogen or optionally halogen-, C ₁ -C ₄ -alkoxy-, C ₁ -C ₄ -alkylthio-, C ₁ -C ₄ -alkylsulfinyl- or C ₁ -C ₄ -alkylsul Phenyl-substituted alkyl having 1 to 6 carbon atoms, or alkoxycarbonyl having 6 or less carbon atoms, R ² represents optionally halogen-substituted alkyl having 1 to 6 carbon atoms or, together with R ¹ , represents alkanediyl (alkylene) having 2 to 5 carbon atoms, in which case m represents 1 and R ¹ And R ² is located on the same carbon atom (“mineral”) or two adjacent carbon atoms (“bisinal)” R ³ represents hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl or halogen, in each case up to 4 carbon atoms in the alkyl group and in each case optionally 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 Or in each case an alkylamino, dialkylamino or dialkylaminosulfonyl having up to 4 carbon atoms in the alkyl group, R ⁴ represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl or halogen, or in each case has up to 4 carbon atoms in the alkyl group and in each case optionally 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 Or in each case alkylamino, dialkylamino or dialkylaminosulfonyl having up to 4 carbon atoms in the alkyl group, Z represents one of the following heterocyclic groups: From here, The dotted bond represents in each case a single bond or a double bond, Q represents oxygen or sulfur, R ⁵ represents hydrogen, hydroxyl, mercapto, cyano or halogen, in each case up to 6 carbon atoms in the alkyl group and in each case optionally 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, in each case up to 6 carbon atoms in the alkyl group and optionally in each case halogen-substituted alkylamino or dialkylamino, or in each case 6 in the alkenyl or alkynyl group And in each case optionally represent a halogen-substituted alkenyl, alkynyl, alkenyloxy, alkenylthio or alkenylamino, or in each case from 3 to 6 carbon atoms and optionally alkyl 4 or less carbon atoms in the site It said optionally halogen in each case represent a substituted cycloalkyl, cycloalkylalkyl, cycloalkyloxy, cyclo alkylthio, or cycloalkyl, amino, or halogen, optionally in each case, C ₁ -C ₄ - alkyl- or C ₁ - C ₄ -alkoxy-substituted phenyl, phenyloxy, phenylthio, phenylamino, benzyl, benzyloxy, benzylthio or benzylamino, R ⁶ represents hydrogen, hydroxyl, amino or alkylideneamino having up to 4 carbon atoms, or in each case has up to 6 carbon atoms in the alkyl group and in each case optionally halogen- or C ₁ -C _4- Alkenyl which represents an alkoxy-substituted alkyl, alkoxy, alkylamino, dialkylamino or alkanoylamino or in each case has up to 6 carbon atoms in the alkenyl or alkynyl group, and in each case an optionally halogen-substituted, Cycloalkyl, cycloalkylalkyl or alkynyl or alkenyloxy, or in each case having from 3 to 6 carbon atoms in the cycloalkyl group and optionally up to 3 carbon atoms in the alkyl moiety; Cycloalkylamino, or in each case optionally represents halogen-, C ₁ -C ₄ -alkyl- or C ₁ -C ₄ -alkoxy-substituted phenyl or benzyl, Together with the adjacent radicals R ⁵ or R ⁶ , optionally represents a halogen- or C ₁ -C ₄ -alkyl-substituted alkanediyl of 3 to 5 carbon atoms, or two adjacent radicals R ⁵ and R ⁵ are attached to a double bond Substituted benzoylcyclohexanedione, characterized in that together with the adjacent radical R ⁵ when positioned, also represents a benzo group. The method of claim 1, m represents a number of 0, 1 or 2, n represents a number of 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 or, in each case, optionally 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, or n-, i- or s-butyl, or methoxycarbonyl, ethoxycarbonyl, or n- or i-propoxycarbonyl; R ² represents methyl, ethyl, or n- or i-propyl, or together with R ¹ , 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 represents ¹ and R ¹ and R ² are the same Is located on a carbon atom ("minal") or on two adjacent carbon atoms ("visinals") R ³ represents hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine or bromine, or in each case optionally 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, or n-, i-, s- or t-butyl, or in each case optionally fluorine- and / or chlorine-, methoxy-, ethoxy-, or n- or i-pro Methylthio, ethylthio, n- or i-propylthio, methyl, which represents, or in each case optionally fluorine- and / or chlorine-substituted, oxy-substituted methoxy, ethoxy, or n- or i-propoxy Sulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, or n- or i-propylsulfonyl, or methylamino, ethylamino, n- or i-propyla Denotes a furnace, dimethylamino, diethylamino, dimethylamino sulfonyl, or diethylamino-sulfonyl, R ⁴ represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine or bromine or in each case optionally 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, or n-, i-, s- or t-butyl, or in each case optionally fluorine- and / or chlorine-, methoxy-, ethoxy-, or n- or i-propoxy- Methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, which represents substituted methoxy, ethoxy, or n- or i-propoxy, or in each case optionally fluorine- and / or chlorine-substituted , Ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, or n- or i-propylsulfonyl, methylamino, ethylamino, n- or i-propylamino, Denotes a methylamino, diethylamino, dimethylamino sulfonyl, or diethylamino-sulfonyl, Z represents one of the following heterocyclic groups: From here, The dotted bond represents in each case a single bond or a double bond, Q represents oxygen or sulfur, R ⁵ represents hydrogen, hydroxyl, mercapto, cyano, fluorine, chlorine, bromine or iodine, or in each case optionally 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-, methyl Sulfinyl-, ethylsulfinyl-, n- or i-propylsulfinyl-, methylsulfonyl-, ethylsulfonyl-, or 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, or n- or i-propylsulfonyl or methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethyla Ethenyl, propenyl, butenyl, ethynyl, propynyl, which represents, or in each case, optionally fluorine- and / or chlorine-substituted , Butynyl, propenyloxy, butenyloxy, propenylthio, butenylthio, propenylamino or butenylamino, in each case optionally fluorine- and / or chlorine-substituted cyclopropyl, cyclobutyl, Cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio , Cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino or cyclohexylamino, or in each case Fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, methoxy-, ethoxy-, or n- or i-pro Foxoxy-substituted phenyl, phenyloxy, phenylthio, phenylamino, benzyl, benzyloxy, benzylthio or benzylamino, R ⁶ represents hydrogen, hydroxyl or amino, or in each case optionally fluorine- and / or chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- Or eth-butyl, methoxy, ethoxy, n- or i-propoxy, methylamino, ethylamino or dimethylamino, in each case optionally fluorine- and / or chlor-substituted ethenyl, propenyl, Cyclotin, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, or, in each case, which represents ethynyl, propynyl or propenyloxy or is optionally substituted with fluorine- and / or chlorine- Cyclohexylmethyl, or in each case optionally fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, methoxy-, Oxy-, or n- or i-propoxy-substituted phenyl or benzyl, or Adjacent radical R ⁵ or R ⁶ together with, in each case optionally methyl-and / or ethyl-substituted propane-1,3-diyl, or represents a (trimethylene) or butane-1,4-diyl (tetramethylene), Substituted benzoylcyclohexanedione, characterized in that together with adjacent radicals R ⁵ when two adjacent radicals R ⁵ and R ⁵ are located in a double bond, also represents a benzo group. The substituted benzoylcyclohexanedione according to claim 1, characterized by the following general formula (IA): Where m represents a number of 0, 1 or 2, n represents a number of 0, 1 or 2, A represents a single bond or methylene, Q represents oxygen or sulfur, R ¹ represents hydrogen, methyl, ethyl, or n- or i-propyl, R ² represents methyl, R ³ is hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, di Fluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminosulfonyl, R ⁴ is nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, difluorome Methoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminosulfonyl, 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, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl or cyclopropyl, R ⁶ represents methyl, ethyl, methoxy, ethoxy or cyclopropyl. The substituted benzoylcyclohexanedione of claim 1, characterized by the following general formula (IB): Where m represents a number of 0, 1 or 2, n represents a number of 0, 1 or 2, A represents a single bond or methylene, Q represents oxygen or sulfur, R ¹ represents hydrogen, methyl, ethyl, or n- or i-propyl, R ² represents methyl, R ³ is hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, di Fluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminosulfonyl, R ⁴ is nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, difluorome Methoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminosulfonyl, 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, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl or cyclopropyl, R ⁶ represents methyl, ethyl, methoxy, ethoxy or cyclopropyl. The substituted benzoylcyclohexanedione of claim 1, characterized by the following general formula (IC): Where m represents a number of 0, 1 or 2, n represents a number of 0, 1 or 2, A represents a single bond or methylene, Q represents oxygen or sulfur, R ¹ represents hydrogen, methyl, ethyl, or n- or i-propyl, R ² represents methyl, R ³ is hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, di Fluoromethoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminosulfonyl, R ⁴ is nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methylthiomethyl, methylsulfinylmethyl, methylsulfonylmethyl, methoxy, ethoxy, difluorome Methoxy, trifluoromethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or dimethylaminosulfonyl, 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, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl or cyclopropyl, R ⁶ represents methyl, ethyl, methoxy, ethoxy or cyclopropyl. The salt according to claim 1, wherein the salt is 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 Substituted benzoylcyclohexanedione characterized by alkyl-ammonium and di- (C ₁ -C ₂ -alkyl) -benzyl-ammonium salts. Substituted 1,3-cyclohexanedione of the general formula (II) below or derivatives thereof in the presence of a dehydrating agent, optionally in the presence of one or more reaction aids and optionally in the presence of a diluent React with benzoic acid, Optionally, electrophilic, nucleophilic, oxidation or reduction reactions are carried out in a conventional manner with respect to the compound of general formula (I) obtained by the above method, or the compound of general formula (I) Process for preparing a substituted benzoylcyclohexanedione according to any one of claims 1 to 6, characterized in that it is converted to its salt by conventional methods: Where m, R ¹ , R ² , n, A, R ³ , R ⁴ and Z are as defined in any one of claims 1 to 6, respectively. Substituted benzoic acid of formula (III) Where n, A, R ³ , R ⁴ and Z are each as defined in any one of claims 1 to 6, Provided that, among these compounds, 2- (5-carboxy-2,4-dichloro-phenyl) -4-difluoromethyl-5-methyl-2,4-dihydro-3H-1,2,4-triazole- 3-ones and 2- (5-carboxy-2,4-dichloro-phenyl) -4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazol-3-one are excluded . Use of at least one substituted benzoylcyclohexanedione according to any one of claims 1 to 6 for controlling unwanted plants. A herbicide composition characterized by containing at least one substituted benzoylcyclohexanedione according to any one of claims 1 to 6 and a conventional bulking agent.