EP3580216A1 - Substituted benzyl-4-aminopicolinic esters and pyrimidino-4-carboxylic esters, methods for the production thereof, and use thereof as herbicides and plant growth regulators - Google Patents

Abstract

The invention relates to benzyl carboxylic acid derivatives of benzoheterocyclyl pyridines and benzoheterocyclyl pyrimidines of general formula (I) and the use thereof as herbicides, wherein X is CH or CF, A is a benzocondensated heterocycle, R¹ is H, Hal or organic residues such as alkyl, and R² is Cl or F.

Description

 Bayer CropScience AG

Substituted benzyl-4-aminopicolinic acid esters and pyrimidine-4-carboxylic acid esters, process for their preparation and their use as herbicides and plant growth regulators Description

The invention relates to the technical field of herbicides, in particular that of herbicides for the selective control of weeds and grass weeds in crops. It is known from various documents that substituted picolinic acid derivatives and pyrimidine-4-carboxylic acid derivatives have herbicidal properties: WO 2003/011853 A1 describes poly-substituted 6-phenylpicolinic acid derivatives having herbicidal activity. WO 2009/029735 Al and WO 2010/125332 Al describe herbicidal effects for polysubstituted 2-phenyl-4-pyrimidine-carboxylic acid derivatives. Heteroaromatic-substituted picoline and pyrimidinecarboxylic acids having herbicidal properties are disclosed in WO 2009/138712 A2. Benzoheteroaromatic-substituted picoline and 4-pyrimidinecarboxylic acids are claimed as herbicides in WO 2013/014165. In

WO 2007/080382 Al and WO 2009/007751 A2 describe heteroaromatic-substituted picoline and pyrimidinecarboxylic acids having pharmacological effects. However, the compounds described there often show insufficient herbicides

Effectiveness and / or insufficient selectivity in crops.

There have been found substituted benzyl-4-aminopicolinsäureester and pyrimidine-4-carboxylic acid esters, which are particularly suitable as herbicides.

An object of the present invention is Benzylpicolinsäure- and pyrimidine-4-carboxylic acid esters of general formula (I), their N-oxides or their agrochemically acceptable salts,

A is a radical of the group consisting of Al to A20,

is halogen, CN, NO ₂ , OH, NH ₂ , (C ₁ -C ₆ ) -alkyl, (C ₁ -C ₆ ) -alkoxy, (C ₁ -C ₆ ) -haloalkyl, (C 1 -C ₆ ) -haloalkoxy, (C ₂ -C ₆₎ alkenyl, halo (C ₂ -C ₆₎ alkenyl, (C ₂ -C ₆₎ alkynyl, halo (C ₃ -C ₆₎ alkynyl, (C ₃ -C ₆₎ cycloalkyl, halo (C ₃ -C ₆₎ cycloalkyl, _(C3-C6) cycloalkyl (Ci-C ₆₎ alkyl, halo (C3-C6) - cycloalkyl- (C 1 -C ₆ ) -alkyl, (C 1 -C ₆ ) -alkylcarbonyl, (C 1 -C ₆ ) -alkylcarboxy, (C 1 -C ₆ ) -alkylamm, di (C 1 -C ₆ ) -alkylamine, (C ₁ -C ₆ ) -Alkyl-S (O) _n or (C ₁ -C ₆ ) -alkyl-S (O) ₂ NH, R ² is chlorine or fluorine,

R ³ is hydrogen,

R ⁴ is hydrogen,

R ⁵ is hydrogen, halogen, OH, NH ₂ , CN, (C ₁ -C ₃ ) -alkyl, (C ₁ -C ₃ ) -alkoxy, C ₁ -C ₃ -alkylamino or cyclopropyl,

R ⁶ is hydrogen, halogen, OH, NH ₂ , CN, (C ₁ -C ₃ ) -alkyl, (C ₁ -C ₃ ) -alkoxy, cyclopropyl or vinyl,

R ⁷ is hydrogen, halogen, (C ₁ -C ₃ ) -alkyl, (C ₁ -C ₃ ) -alkoxy, (C ₁ -C ₃ ) -alkylthio, cyclopropyl, (C ₁ -C ₃ ) -alkylamino or phenyl, R ⁸ Hydrogen, (C ₁ -C ₆ ) -alkyl, (C 1 -C ₄ ) -alkylcarbonyl, (C ₁ -C ₆ ) -alkoxycarbonyl or

 phenyl,

X is CH or CF, m is 1, 2, 3, 4 or 5, and n is 0, 1 or 2.

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

A is preferably selected from the group consisting of Al to A3, A7 to Al 5, and Al 7 to Al 8

 A1 A2 A3

 A13 A14 A15

A17 A18 selected from the group consisting of residues AI to A3 and AI 3 A is most preferably A2 or Al5.

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

R ^{1 is} preferably halogen, CN, NO ₂ , OH, NH ₂ , (C ₁ -C ₆ ) -alkyl, (C ₁ -C ₆ ) -alkoxy, (C ₁ -C ₆ ) -haloalkyl or (C ₁ -C ₆ ) -haloalkoxy , especially halogen, and most preferably fluorine. A third embodiment of the present invention comprises compounds of the general formula (I) in which

R ^{2 is} preferably chlorine. A fourth embodiment of the present invention comprises compounds of the general formula (I) in which

R ^{3 is} preferably hydrogen. A fifth embodiment of the present invention comprises compounds of the general formula (I) in which

R ^{4 is} preferably hydrogen. A sixth embodiment of the present invention comprises compounds of the general formula (I) in which

R ^{5 is} preferably hydrogen or halogen, and particularly preferably hydrogen or fluorine. A seventh embodiment of the present invention comprises compounds of the general formula (I) in which

R ^{6 is} preferably hydrogen or halogen, and particularly preferably hydrogen. An eighth embodiment of the present invention comprises compounds of the general formula (I) in which R ^{7 is} preferably hydrogen, halogen or (C 1 -C 3) -alkyl, and particularly preferably hydrogen.

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

R ^{8 is} preferably hydrogen, (C 1 -C 4) -alkyl, (C 1 -C 4) -alkylcarbonyl or (C 1 -C 4) -alkoxycarbonyl, particularly preferably hydrogen, (C 1 -C 3) -alkyl, (C 1 -C 4) -alkylcarbonyl or (C 1 -C 4) alkoxycarbonyl, and most preferably hydrogen.

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

X is preferably CH or CF.

An eleventh embodiment of the present invention comprises compounds of the general formula (I) in which m is preferably 1, 2 or 3, more preferably 1 or 2 and most preferably 1.

A twelfth embodiment of the present invention comprises compounds of the general formula (I) in which n is preferably 0 or 1, and more preferably 0.

In the context of the present invention, it is possible to combine the individual preferred, particularly preferred and very particularly preferred meanings for the substituents A, R ¹ to R ⁸ and X with one another, where the run number n is 0, 1 or 2, preferably 0 or 1, and most preferably 0, and the run number m is 1, 2, 3, 4 or 5, preferably 1, 2, or 3, more preferably 1 or 2, and most preferably 1.

That is, compounds of the general formula (I) are encompassed by the present invention in which, for example, the radical A has a preferred meaning and the substituents R ¹ to R ^{7 have} the general meaning or the substituent R ^{2 has} a preferred meaning , the substituent R ^{4 has} a particularly preferred meaning and the remaining

Substituents have a general meaning.

Three of these combinations of the above for the substituents A, R ¹ to R ⁸ and X, as well as for the running numbers n and m given definitions are exemplified below and each explicitly disclosed as further embodiments for the sake of clarity:

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

A is selected from AI to A3 and AI 3 to AI 5,

R ^{1 is} halogen, CN, NO ₂ , OH, NH ₂ , (C ₁ -C ₆ ) -alkyl, (C ₁ -C ₆ ) -alkoxy, (C ₁ -C ₆ ) -haloalkyl or (C ₁ -C ₆ ) -haloalkoxy,

R ^{2 is} chlorine,

R ^{3 is} hydrogen,

R ^{4 is} hydrogen,

 R "means hydrogen or fluorine,

R ^{6 is} hydrogen or halogen,

R ^{7 is} hydrogen, halogen or (G-C3) -alkyl,

R ^{8 is} hydrogen, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkylcarbonyl or (C 1 -C ₄ ) -alkoxycarbonyl,

X is CH or CF,

n is 0 or 1, and

m is 1, 2 or 3. A fourteenth embodiment of the present invention comprises compounds of the general formula (I) in which

A is selected from AI to A3 and AI 3 to AI 5,

R ^{1 is} halogen,

R ^{2 is} chlorine,

R ^{3 is} hydrogen,

R ^{4 is} hydrogen,

R ^{5 is} hydrogen or fluorine,

R ^{6 is} hydrogen,

R ^{7 is} hydrogen,

R ^{8 is} hydrogen, (C ₁ -C ₃ ) -alkyl, (C ₁ -C ₄ ) -alkylcarbonyl or (C 1 -C ₄ ) -alkoxycarbonyl,

X is CH or CF,

n is 0 or 1, and

m is 1, or 2. A fifteenth embodiment of the present invention comprises compounds of the general formula (I) in which

A A2 or AI 5 means

R ^{1 is} fluorine,

R ^{2 is} chlorine,

R ^{3 is} hydrogen,

R ^{4 is} hydrogen,

R ^{5 is} hydrogen or fluorine,

R ^{6 is} hydrogen,

R ^{7 is} hydrogen,

R ^{8 is} hydrogen, (C ₁ -C ₃ ) -alkyl, (C 1 -C 4) -alkylcarbonyl or (C 1 -C 4) -alkoxycarbonyl,

X is CH or CF,

n is 0 or 1, and

m means 1.

Alkylcarbonyl (alkyl-C (= O) -) means saturated, straight-chain or branched alkyl radicals which are bonded to the skeleton via -C (= O) -, such as (C 1 -C 10) -, (C 1 -C 6) - or ( Ci-C i) alkylcarbonyl. The number of C atoms refers to the alkyl radical in the alkylcarbonyl group. Alkyl is saturated, straight or branched chain hydrocarbon radicals of 1 to 10 carbon atoms, e.g. C 1 -C 6 -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1, 2 Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl.

Haloalkyl means straight-chain or branched alkyl groups having 1 to 8 carbon atoms, in which groups the hydrogen atoms may be partially or completely replaced by halogen atoms, for example C ₁ -C ₂ -haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl , Dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro, 2-difluoroethyl , 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and 1,1,1-trifluoroprop-2-yl. Alkenyl denotes unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 8

Carbon atoms and a double bond in any position, e.g. C 2 -C 6 alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, Methyl 2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl 1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3 - butenyl, 1, 1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1 Hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3 - Methyl 3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1 - Dimethyl-2-butenyl, 1, 1-dime ethyl 3 -butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-1 -butenyl, 1.3 Dimethy 1-2 -butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-1-2-butenyl, 2 , 3-Dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3 -butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl , 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl. Alkynyl means straight-chain or branched hydrocarbon radicals having 2 to 8 carbon atoms and a triple bond in any position, e.g. C 2 -C 6 -alkynyl, such as ethynyl, 1-propynyl, 2-propynyl (or propargyl), 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3 Pentynyl, 4-pentynyl, 3-methyl-1-butynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1, 1-dimethyl-2-propynyl, 1 - Ethyl 2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 3-methyl-1-pentynyl, 4-methyl-1-pentynyl, 1-methyl-2-pentynyl, 4-methyl-2-pentynyl, 1-methyl-3-pentynyl, 2-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 1, 1- Dimethy 1-2 -butynyl, 1,1-dimethyl-3-butynyl, 1, 2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1 Ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl.

Alkoxy means saturated, straight or branched alkoxy radicals of 1 to 8 carbon atoms, e.g. C 1 -C 6 -alkoxy, such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1, 1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2, 2-methylpropoxy, 1-ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1, 2

Dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy;

Haloalkoxy means straight-chain or branched alkoxy groups having 1 to 8 carbon atoms (as mentioned above), wherein in these groups some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, e.g. C 1 -C 2 -haloalkoxy such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2- Difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro, 2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and 1, 1,1-trifluoroprop-2-oxy.

Alkylthio means saturated, straight-chain or branched alkylthio radicals having 1 to 8 carbon atoms, e.g. C 1 -C 6 -alkylthio, such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2, 2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1, 2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1, 2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio and 1-ethyl-2-methylpropylthio;

Haloalkylthio means straight-chain or branched alkylthio groups having 1 to 8

Carbon atoms (as mentioned above), wherein in these groups, partially or completely, the hydrogen atoms may be replaced by halogen atoms as mentioned above, e.g. C 1 -C 2 -haloalkylthio, such as chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1-bromethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro, 2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, pentafluoroethylthio and 1, l, l trifluoroprop-2-ylthio.

Aryl is phenyl or naphthyl.

Depending on the nature of the substituents, the compounds of the formula (I) can be present in different compositions as geometric and / or optical isomers or isomer mixtures, which can optionally be separated in a customary manner. Both the pure isomers and the mixtures of isomers, their preparation and use and these containing agents are the subject of the present invention. However, in the following, for the sake of simplicity, compounds of the formula (I) will always be mentioned, although both the pure ones

Compounds as appropriate also mixtures with different proportions of isomers

Compounds are meant.

A metal ion equivalent means a metal ion with a positive charge such as Na ⁺ , K ⁺ , (Mg ²⁺ ) 1/2, (Ca ²⁺ ) i / 2, MgH ⁺ , CaH ⁺ , (Al ³⁺ ) i / 3 (Fe ²⁺ ) i / ₂ or (Fe ³⁺ ) i / ₃ .

Halogen means fluorine, chlorine, bromine and iodine.

If a group is repeatedly substituted by radicals, it is to be understood that this group is substituted by one or more identical or different radicals.

Depending on the nature of the substituents defined above, the compounds of the formula (I) have acidic or basic properties and can form salts with inorganic or organic acids or with bases or with metal ions, optionally also internal salts or adducts. If the compounds of the formula (I) bear amino, alkylamino or other basic-property-inducing groups, these compounds can be reacted with acids to form salts or are obtained directly as salts by the synthesis.

Examples of inorganic acids are hydrohalic acids such as hydrogen fluoride,

Hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid and

Nitric acid and acid salts such as NaHSC and KHSO4. Suitable organic acids are, for example, formic acid, carbonic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid,

Benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), arylsulfonic acids or -disulfonsäuren (aromatic radicals such as phenyl and naphthyl which carry one or two sulfonic acid groups), alkylphosphonic acids (phosphonic acids with straight chain or branched alkyl radicals having 1 to 20 carbon atoms), arylphosphonic acids or - diphosphonic acids (aromatic radicals such as phenyl and naphthyl which carry one or two phosphonic acid radicals), where the alkyl or aryl radicals may carry further substituents, eg p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.

The metal ions are, in particular, the ions of the elements of the second main group, in particular calcium and magnesium, the third and fourth main groups, in particular aluminum, tin and lead, and the first to eighth transition groups, in particular chromium, manganese, iron, cobalt, nickel, copper, Zinc and others into consideration. Particularly preferred are the metal ions of the elements of the fourth period. The metals can be present in the various valences that belong to them.

If the compounds of the formula (I) bear hydroxy, carboxy or other groups which induce acidic properties, these compounds can be reacted with bases to form salts.

Suitable bases are, for example, hydroxides, carbonates, bicarbonates of the alkali and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, furthermore

Ammonia, primary, secondary and tertiary amines with (Ci-C i -) - alkyl groups, mono-, di- and trialkanolamines of (Ci-C i) alkanols, choline and chlorocholine.

Depending on the nature and linkage of the substituents, the compounds of the general formula (I) can exist as stereoisomers. For example, if one or more asymmetrically substituted carbon atoms or sulfoxides are present, enantiomers and diastereomers may occur.

Stereoisomers can be prepared from the mixtures obtained in the preparation of conventional

Separation methods, for example by chromatographic separation methods obtained. Similarly, stereoisomers can be selectively prepared by using stereoselective reactions using optically active starting and / or adjuvants. The invention also relates to all stereoisomers and mixtures thereof which include but are not specifically defined by the general formula (I). In all of the formulas below, the substituents and symbols, unless otherwise defined, have the same meaning as described for formula (I).

Compounds of formula (I), for example, according to the following scheme

base-catalyzed esterification of a carboxylic acid of the formula II with a benzyl bromide of the formula III. In this scheme Het stands for the heterocycles of the groups AI to A24 fused to the phenyl ring.

The carboxylic acids of the formula (II) are known, for example, from WO2013 / 14165 A1, or can be prepared by methods known per se to the person skilled in the art. The benzyl derivatives of the formula (III) are commercially available or can be prepared by methods known to those skilled in the art. Preference is given to the compounds of the formula (I) given in Table 1 below,

with X = CY, R ² = C1, R ³ = R ⁴ = H

Table 1

Number AY PhenyH ¹ ) ™

 1-01 1 -benzothiophene-6-yl H 2-fluorophenyl

 1-02 1 -benzofuran-6-yl H 3-fluorophenyl

 1-03 1 -benzofuran-6-yl F 4-methoxyphenyl

1-04 1-benzofuran-6-yl F 4-fluorophenyl

 1-05 1 -benzofuran-5-yl H 4-fluorophenyl

 1-06 1 -benzofuran-5-yl H 2,4,5-trifluorophenyl

1-07 1 -benzothiophene-6-yl H 4-fluorophenyl

 2,4-difluoro-3-

1-08 1 -benzothiophene-6-yl H

 methoxyphenyl

1-09 1-benzothiophene-5-yl H 3-fluorophenyl

 1-10 1 -benzothiophene-6-yl H 3-fluorophenyl

 1-11 1-Benzofuran-5-yl H 3 - (trifluoromethyl) phenyl

1-12 1 -benzothiophene-6-yl H 2,4-difluorophenyl

1-13 1-Benzofuran-5-yl H 2,3,4-trifluorophenyl

1-14 1-Benzothiophene-6-yl H 4-chlorophenyl

 1-15 1 -benzofuran-6-yl F 4-chlorophenyl

 1-16 1 -benzothiophene-5-yl H 4- (trifluoromethyl) phenyl

 2,4-difluoro-3-

1-17 1 -benzofuran-5-yl H

 methoxyphenyl

1-18 1 -benzothiophene-5-yl H 2,4-difluorophenyl

1-19 1 -benzothiophene-5-yl H 4-chlorophenyl

 1-20 1 -benzofuran-5-yl H 2,4,6-trifluorophenyl

1-21 1 -benzothiophene-5-yl H 3 - (trifluoromethyl) phenyl

 2,4-difluoro-3-

1-22 1 -benzothiophene-5-yl H

methoxyphenyl Number AY PhenyH ¹ ) ™

 1-23 l -Benzofuran-6-yl H 2,3,4-trifluorophenyl

1-24 1 -benzofuran-5-yl H 2,4-difluorophenyl

1-25 1 -benzothiophene-6-yl H 2,3,4,5,6-pentafluorophenyl

1-26 1-benzofuran-6-yl H 4-fluorophenyl

1-27 1-benzofuran-6-yl H 2,4,5-trifluorophenyl

 2,4-difluoro-3-

1-28 1-benzofuran-6-yl H

 methoxyphenyl

1-29 1-benzothiophene-5-yl F 4-fluorophenyl

1-30 1-Benzofuran-6-yl H 4-chlorophenyl

1-31 1 -benzofuran-5-yl H 4-chlorophenyl

1-32 1 -benzothiophene-6-yl H 2,4,6-trifluorophenyl

7-fluoro-1-benzofuran-6

1-33H 3-chlorophenyl yi

 1-34 1 -benzofuran-5-yl F 4-fluorophenyl

1-35 1 -benzofuran-6-yl F 2,4-dimethoxyphenyl

1-36 1-Benzofuran-5-yl H 4- (trifluoromethyl) phenyl

1-37 1-Benzofuran-5-yl H 2- (trifluoromethyl) phenyl

1-38 1-Benzofuran-5-yl H 3-chlorophenyl

1-39 1, 3-Benzothiazol-6-yl H 2,4-Difluorophenyl

1-40 1 -benzothiophene-5-yl H 3-chlorophenyl

1-41 1, 3-Benzothiazol-6-yl H 3-fluorophenyl

1-42 1 -benzothiophene-6-yl F 2,4-difluorophenyl

1-43 1-Benzofuran-6-yl H 2,4-Difluorophenyl

1-44 1-Benzothiophene-6-yl H 2-chlorophenyl

1-45 1-Benzothiophene-6-yl F 4-chlorophenyl

1-46 1-Benzothiophene-6-yl H 2,3,4-trifluorophenyl

1-47 1-Benzofuran-5-yl F 4-chlorophenyl

1-48 1-Benzofuran-5-yl F 2,4-Difluorophenyl

7-fluoro-1-benzofuran-6

1-49H 4-chlorophenyl yi

 1-50 1 -benzothiophene-6-yl H 3-chlorophenyl

1-51 1-Benzofuran-6-yl F 2,4-dichlorophenyl

1-52 1 -benzofuran-5-yl F 2,4,6-trifluorophenyl

1-53 1 -benzothiophene-6-yl F 4-fluorophenyl

1-54 1-Benzofuran-6-yl H 2,3,4,5,6-pentafluorophenyl Number AY PhenyH ¹ ) ™

1-55 1-Benzothiophene-6-yl F 2,4,6-trifluorophenyl

1-56 1 -benzothiophene-5-yl F 2,4-difluorophenyl

 3,6-dichloro-2-

1-57 1 -benzofuran-5-yl H

 methoxyphenyl

6-fluoro-1-

1-58 F 4-chlorophenyl benzothiophen-5-yl

 1-59 1 -benzothiophene-5-yl F 2,4,6-trifluorophenyl

1-60 1, 3-Benzothiazol-6-yl H 3-chlorophenyl

1-61 1-Benzothiophene-6-yl H 2,3,4,5-tetrafluorophenyl

1-62 1-Benzofuran-5-yl H 2-nitrophenyl

1-63 1-Benzofuran-5-yl F 2,4-dichlorophenyl

1-64 1, 3-Benzothiazol-6-yl F 4-chlorophenyl

1-65 1 -benzothiophene-5-yl F 4-chlorophenyl

6-fluoro-1-benzofuran-5-

1-66 F 2,4-Difluorophenyl yi

 1-67 1-Benzofuran-6-yl H 2,3,4,5-tetrafluorophenyl

6-fluoro-1-benzofuran-5-

1-68 F 4-chlorophenyl yi

 1-69 1, 3-benzothiazol-6-yl H 4-chlorophenyl

1-70 1, 3-Benzothiazol-6-yl F 3-fluorophenyl

6-fluoro-1-benzofuran-5-

1-71 F 4-fluorophenyl yi

 1-72 1, 3-Benzothiazol-6-yl H 4- (trifluoromethyl) phenyl

1-73 1-benzothiophene-5-yl H 2,3,4,5-tetrafluorophenyl

1-74 1-Benzofuran-5-yl H 2,3,4,5-tetrafluorophenyl

 6-fluoro-1-

1-75 F 2,4-difluorophenyl benzothiophene-5-yl

 1-76 1-Benzothiophene-6-yl F 2,4-dichlorophenyl

 6-fluoro-1-

1-77 F 4-fluorophenyl benzothiophen-5-yl

 1-78 1, 3-Benzothiazol-6-yl H 2,4-dichlorophenyl

6-fluoro-1-benzofuran-5-

1-79 F 2,4,6-trifluorophenyl yi

 6-fluoro-1-

1-80 F 2,4-dichlorophenyl benzothiophen-5-yl Number AY PhenyH ¹ ) ™

 6-fluoro-1-benzofuran-5-

1-81 F 2,4-dichlorophenyl

 yi

 1-82 1 -benzothiophene-5-yl F 2,4-dichlorophenyl

 1-83 1, 3-Benzothiazol-6-yl F 4-fluorophenyl

 1-84 7-fluoro-1H-indol-6-yl F 3-fluorophenyl

Collections of compounds of formula (I) and / or their salts, which may be synthesized following the above reactions, may also be prepared in a parallelized manner, which may be done in a manual, partially automated or fully automated manner. It is possible, for example, to automate the reaction procedure, the work-up or the purification of the products or intermediates. Overall, this is one

Approach understood, as described for example by D. Tiebes in Combinatorial Chemistry - Synthesis, Analysis, Screening (publisher Günther Jung), Verlag Wiley 1999, on pages 1 to 34.

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

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

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

The implementation of single or several synthetic steps can be supported by the use of polymer-supported reagents / Scavanger resins. A number of experimental protocols are described in the literature, for example in ChemFiles, Vol. 1, Polymer-Supported Scavengers and Reagents for Solution Phase Synthesis (Sigma-Aldrich). In addition to the methods described herein, the preparation of compounds of formula (I) and their salts may be wholly or partially by solid phase assisted methods. For this purpose, individual intermediates or all intermediates of the synthesis or adapted for the appropriate approach synthesis are bound to a synthetic resin. Solid-phase assisted synthesis methods are well described in the literature, eg Barry A. Bunin in "The Combinatorial Index", published by Academic Press, 1998 and Combinatorial Chemistry - Synthesis, Analysis, Screening (published by Günther Jung), published by Wiley, 1999. Use from

Solid-phase assisted synthesis methods allow a number of protocols known from the literature, which in turn can be performed manually or automatically. The reactions can be carried out, for example, by means of IRORI technology in microreactors (microreactors) from Nexus Biosystems, 12140 Community Road, Poway, CA92064, USA.

Both solid and liquid phases may require the performance of one or more

Synthetic steps are supported by the use of microwave technology. In the

 Technical literature describes a number of experimental protocols, for example in Microwaves in Organic and Medicinal Chemistry (publishers C. O. Kappe and A. Stadler), published by Wiley, 2005.

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

The compounds of the formula (I) according to the invention (and / or their salts), together referred to as "compounds according to the invention", have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants which are expelled from rhizomes, rhizomes or other long-term organs, are well detected by the active ingredients. The present invention therefore also provides a method for combating

undesirable plants or for regulating the growth of plants, preferably in

Plant cultures in which one or more compounds of the invention (s) on the plants (eg harmful plants such as mono- or dicotyledonous weeds or undesirable crops), the seed (eg grains, seeds or vegetative propagules such as tubers or sprouts with buds) or the area on the plants grow (eg the acreage), are applied. The compounds according to the invention can be applied, for example, in pre-sowing (optionally also by incorporation into the soil), pre-emergence or postemergence process. In particular, be exemplary some representatives of the monocotyledonous and dicotyledonous weed flora called, which can be controlled by the compounds of the invention, without that by naming a restriction to certain species is to take place. Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata , Ishumum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.

Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis Galinsoga Galium Hibiscus Ipomoea Kochia Lamium Lepidium Lindernia Matricaria Mentha Mercurialis Mullugo Myosotis Papaver Pharbitis Plantago Polygonum Portulaca Ranunculus Raphanus Rorippa Rotala Rumex , Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.

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

When the active ingredients are applied to the green parts of the plants postemergence, growth stops after the treatment and the harmful plants remain in the growth stage existing at the time of application or die completely after a certain time, so that a weed competition harmful to the crop plants takes place very early and sustainably eliminated. Although the compounds according to the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crops of economically important crops, eg dicotyledonous crops of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, or monocotyledonous cultures of the genera Allium, Pineapple, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Seeal, Sorghum, Triticale, Triticum, Zea, especially Zea and Triticum, depending on the structure of the respective compound of the invention and its application rate only insignificantly damaged or not at all. The present compounds are suitable for these Reason very well for the selective control of undesirable plant growth in crops such as agricultural crops or ornamental plantings.

In addition, the compounds according to the invention (depending on their respective structure and the applied application rate) have excellent growth-regulatory properties in crop plants. They regulate the plant's metabolism and can thus be used to specifically influence plant constituents and facilitate harvesting, such as be used by triggering desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of undesirable vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops, since, for example, storage formation can thereby be reduced or completely prevented.

Due to their herbicidal and plant growth regulatory properties, the active compounds can also be used for controlling harmful plants in crops of known or yet to be developed genetically modified plants. The transgenic plants are usually characterized by particular advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties concern e.g. the crop in terms of quantity, quality, shelf life, composition and special ingredients. So are transgenic plants with increased starch content or altered quality of starch or those with others

Fatty acid composition of the crop known. Other particular properties may include tolerance or resistance to abiotic stressors, e.g. Heat, cold, drought, salt and ultraviolet radiation are present.

Preference is given to the use of the compounds of the formula (I) according to the invention or their salts in economically important transgenic crops of useful and ornamental plants, e.g. of cereals such as wheat, barley, rye, oats, millet, rice, manioc and maize or also crops of sugar beet, cotton, soya, rapeseed, potato, tomato, pea and other vegetables.

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

Conventional ways of producing new plants which have modified properties in comparison with previously occurring plants consist, for example, in classical methods Breeding methods and the generation of mutants. Alternatively, new plants with altered properties can be generated by means of genetic engineering methods (see, for example, EP 0221044, US Pat.

EP 0131624). In several cases, for example, genetic modifications of cultivated plants have been described for the purpose of modification in plants

 synthesized starch (eg WO 92/011376 A, WO 92/014827 A, WO 91/019806 A), transgenic crop plants which are resistant to certain glufosinate-type herbicides (cf., for example, EP 0242236 A, EP 0242246 A) or glyphosate (WO 92 / 000377 A) or the sulfonylureas (EP 0257993 A, US 5,013,659) or against combinations or mixtures of these herbicides by gene stacking resistant, such as transgenic crop plants such as corn or soybean with the

Trade name or designation Optimum ™ GAT ™ (Glyphosate ALS Tolerant), transgenic crops, for example cotton, with the ability to produce Bacillus thuringiensis toxins (Bt toxins), which make the plants resistant to certain pests (EP 0142924 A, EP 0193259 A).

transgenic crops with modified fatty acid composition (WO 91/013972 A). genetically engineered crops with new content or secondary substances, e.g. novel phytoalexins which cause increased disease resistance (EP 0309862 A, EP 0464461 A) genetically modified plants with reduced photorespiration, which have higher yields and higher stress tolerance (EP 0305398 A)

transgenic crops producing pharmaceutically or diagnostically important proteins ("molecular pharming")

 transgenic crops characterized by higher yields or better quality transgenic crops characterized by a combination of e.g. the o. g. characterize new properties ("gene stacking")

Numerous molecular biology techniques that can be used to produce novel transgenic plants with altered properties are known in principle; see, e.g. I. Potrykus and G.

Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg, or Christou, "Trends in Plant Science" 1 (1996) 423-431).

For such genetic engineering, nucleic acid molecules can be introduced into plasmids that allow mutagenesis or sequence alteration by recombination of DNA sequences. By means of standard methods, for example, base exchanges can be made, partial sequences removed or natural or synthetic sequences added. For the connection of the DNA fragments with one another adapters or linkers can be attached to the fragments, see eg Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Genes and Clones", VCH Weinheim 2nd edition 1996.

The production of plant cells having a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to obtain a cosuppression effect, or the expression of at least one appropriately engineered ribozyme which specifically cleaves transcripts of the above gene product. For this purpose, on the one hand DNA molecules can be used which comprise the entire coding sequence of a gene product including any flanking sequences, as well as DNA molecules which comprise only parts of the coding sequence, which parts have to be long enough to be present in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical.

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

The transgenic plant cells can be regenerated to whole plants by known techniques. The transgenic plants can in principle be plants of any one

Plant species, that is, both monocotyledonous and dicotyledonous plants. Thus, transgenic plants are available which have altered properties by overexpression, suppression or inhibition of homologous (= natural) genes or gene sequences or expression of heterologous (= foreign) genes or gene sequences.

Preferably, the compounds (I) according to the invention can be used in transgenic cultures which are resistant to growth substances, such as 2,4 D, dicamba or herbicides, the essential plant enzymes, for example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD) inhibit, respectively against herbicides from the group of Sulfonylureas, the glyphosate, glufosinate or Benzoylisoxazole and analogous drugs, or against any combination of these agents, resistant.

The compounds according to the invention can particularly preferably be employed in transgenic crop plants which are resistant to a combination of glyphosates and glufosinates, glyphosates and sulfonylureas or imidazolinones. Most preferably, the compounds of the invention in transgenic crops such. As corn or soybean with the trade name or the name Optimum ™ GAT ™ (Glyphosate ALS Tolerant) are used.

In the application of the active compounds according to the invention in transgenic crops, in addition to the effects observed in other crops on harmful plants, effects which are specific for the application in the respective transgenic crop often occur, for example a modified or specially extended weed spectrum which can be controlled Application rates that can be used for the application, preferably good combinability with the herbicides to which the transgenic culture is resistant, and influencing growth and yield of the transgenic crops.

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

The compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations. The invention therefore also relates to herbicidal and plant growth-regulating agents which contain the compounds according to the invention.

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

Formulation options are, for example: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as

Oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil or water based dispersions, oil miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for spreading and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.

These individual formulation types are known in principle and are described, for example, in: Winnacker-Kuchler, "Chemische Technologie", Volume 7, C. Hanser Verlag Munich, 4th ed. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY, 1973, K. Martens, "Spray Drying" Handbook, 3rd ed. 1979, G. Goodwin Ltd.

London. The necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticides Dust Diluents and Carriers", 2nd ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N.Y., C. Marsden, "Solvents Guide", 2nd Ed., Interscience, N.Y. McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J., Sisley and Wood, "Encyclopedia of

 Surface Active Agents, Chem. Pub. Co. Inc., N.Y. 1964, Schonfeldt, "Grenzflächenaktive

Äthylenoxidaddukte ", Wiss. Verlagsgesell., Stuttgart 1976, Winnacker-Küchler," Chemical

Technologie ", Volume 7, C. Hanser Verlag Munich, 4th ed. 1986. On the basis of these formulations, combinations with other pesticidally active substances, such as insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers and / or or growth regulators, for example in the form of a ready-to-use formulation or as a tank mix Suitable safeners are, for example, mefenpyr-diethyl, cyprosulfamide, isoxadifen-ethyl,

Cloquintocet-mexyl and Dichlormid.

The safeners are preferably selected from the group consisting of:

 Sl) compounds of the formula (S1),

where the symbols and indices have the following meanings: nA is a natural number from 0 to 5, preferably 0 to 3;

R _A ¹ is halogen, (C ¹ -C ₄ ) alkyl, (C 1 -C ₄ ) alkoxy, nitro or (C 1 -C ₄ ) haloalkyl; W _A is an unsubstituted or substituted divalent heterocyclic radical from the group of the unsaturated or unsaturated five-membered ring heterocycles having 1 to 3 hetero ring N and O groups, wherein at least one N atom and at most one O atom is contained in the ring, preferably a residue from the group (WA ¹ ) to (WA ⁴ ),

niA is 0 or 1;

RA is ORA, SRA or NRA RA or a saturated or unsaturated 3- to 7-membered one

 Heterocycle having at least one N atom and up to 3 heteroatoms, preferably from the group O and S, which is connected via the N atom to the carbonyl group in (S1) and unsubstituted or by radicals from the group (Ci-C i) Alkyl, (Ci-C i) alkoxy or

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

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

RA ⁴ is hydrogen, (C 1 -C 6) alkyl, (C 1 -C 6) alkoxy or substituted or unsubstituted phenyl;

RA ⁵ is H, (C 1 -C ₈ ) alkyl, (C 1 -C ₈ ) haloalkyl, (C 1 -C ₄ ) alkoxy (C 1 -C ₈ ) alkyl, cyano or COORA ⁹ , in which R _A ^{9 is} hydrogen, (C 1 -C 4) C ₈ ) alkyl, (C 1 -C ₈ ) haloalkyl, (C 1 -C ₄ ) alkoxy- (C 1 -C ₄ ) -alkyl,

(Ci-C ₆₎ hydroxyalkyl, _(C3-Ci2) -cycloalkyl or tri- _(Ci-C4) -alkyl-silyl;

RA ⁶ , RA ⁷ , RA ⁸ are identical or different hydrogen, (C 1 -C ₈ ) alkyl, (C 1 -C ₈ ) haloalkyl, (C ₃ -C 12) cycloalkyl or substituted or unsubstituted phenyl; preferably: a) compounds of the type of dichlorophenylpyrazoline-3-carboxylic acid (Sl ^a ), preferably

Compounds such as 1- (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylic acid, 1- (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5- methyl-2-pyrazoline-3-carboxylic acid ethyl ester (Sl-1) ("mefenpyr-diethyl"), and related compounds as described in WO-A-91/07874; b) dichlorophenylpyrazolecarboxylic acid derivatives (S l ^b), preferably compounds such as 1 - (2,4-dichlorophenyl) -5-methyl-pyrazole-3-carboxylic acid ethyl ester (S 1 -2)

 1 - (2,4-dichlorophenyl) -5-isopropyl-pyrazole-3-carboxylic acid ethyl ester (S 1 -3),

Ethyl 1 - (2,4-dichlorophenyl) -5- (1,1-dimethyl-ethyl) pyrazole-3-carboxylate (S 1 -4) and related compounds as described in EP-A-333 131 and EP-A A-269,806; c) derivatives of l, 5-diphenylpyrazole-3-carboxylic acid (S l ^c ), preferably compounds such

 Ethyl 1 - (2,4-dichlorophenyl) -5-phenylpyrazole-3-carboxylate (S 1 -5),

 l - (2-chlorophenyl) -5-phenylpyrazole-3-carboxylic acid methyl ester (S l -6) and related

Compounds as described, for example, in EP-A-268554; d) compounds of the type of triazolecarboxylic acids (Sl ^d ), preferably compounds such as

Fenchlorazole (ethyl ester), ie l - (2,4-dichlorophenyl) -5-trichloromethyl (lH) -l, 2,4-triazole-3-carboxylic acid ethyl ester (S l -7), and related compounds as described in EP -A-174,562 and EP-A-346,620; e) compounds of the type of 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or of 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (Sl ^e ), preferably compounds such as

 5- (2,4-dichlorobenzyl) -2-isoxazoline-3-carboxylic acid ethyl ester (S 1-8) or

 5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S 1-9) and related compounds as described in WO-A-91/08202 or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid ( S l -10) or ethyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (Sl -1 1) ("isoxadifen-ethyl")

 or n-propyl ester (S l -12) or 5- (4-fluorophenyl) -5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (Sl-13), as described in the patent application WO-A-95/07897 are described.

 S2) quinoline derivatives of the formula (S2) where the symbols and indices have the following meanings:

RB ¹ is halogen, (Ci-C ₄₎ alkyl, (Ci-C ₄₎ alkoxy, nitro or (Ci-C ₄₎ haloalkyl; ne is a natural number of 0 to 5, preferably 0 to 3; R _B ² is OR _B ³ , SR _b ³ or NR _B ³ R _B ⁴ or a saturated or unsaturated 3- to 7-membered heterocycle having at least one N atom and up to 3 heteroatoms, preferably from the group O and S, the one about the N-atom with the

Carbonyl group in (S2) and is unsubstituted or substituted by radicals from the group (Ci-C i) alkyl, (Ci-C i) alkoxy or optionally substituted phenyl, preferably a radical of the formula ORB ³ , NHRB ⁴ or N ( CH3) 2, in particular of the formula ORB ³ ;

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

RB ⁴ is hydrogen, (Ci-C6) alkyl, (Ci-Ce) alkoxy or substituted or unsubstituted phenyl;

TB is a (Ci or C2) alkanediyl chain which is unsubstituted or substituted by one or two (Ci-C i) alkyl radicals or by [(Ci-C3) alkoxy] carbonyl; preferably: a) compounds of the 8-quinolinoxyacetic acid type (S2 ^a ), preferably

 (5-Chloro-8-quinolinoxy) acetic acid (1-methylhexyl) ester ("Cloquintocet-mexyl") (S2-1), (5-chloro-8-quinolinoxy) acetic acid (1,3-dimethyl-butoxy) 1 -yl) ester (S2-2),

 (5-chloro-8-quinolinoxy) acetic acid 4-allyloxy-butyl ester (S2-3),

 (5-chloro-8-quinolinoxy) acetic acid 1 -allyloxy-prop-2-yl ester (S2-4),

 (5-chloro-8-quinolinoxy) acetic acid ethyl ester (S2-5),

 (5-chloro-8-quinolinoxy) acetic acid methyl ester (S2-6),

 Allyl (5-chloro-8-quinolinoxy) acetates (S2-7),

(5-Chloro-8-quinolinoxy) acetic acid 2- (2-propylidene-iminoxy) -l-ethyl ester (S2-8), (5-chloro-8-quinolinoxy) -acetic acid 2-oxo-prop-1-yl-ester (S2-9) and related compounds as described in EP-A-86,750, EP-A-94,349 and EP-A-191,736 or EP-A-0 492 366, as well as (5-chloro-8 -quinolinoxy) acetic acid (S2-10), their hydrates and salts, for example their lithium, sodium, potassium, calcium, magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts, such as they are described in WO-A-2002/34048; b) compounds of the type of (5-chloro-8-quinolinoxy) malonic acid (S2 ^b ), preferably

 Compounds such as diethyl (5-chloro-8-quinolinoxy) malonate,

(5-chloro-8-quinolinoxy) malonic acid diallyl ester, (5-chloro-8-quinolineoxy) malonic acid methyl ethyl ester and related compounds, as described in EP-A-0 582 198.

 S3) compounds of the formula (S3)

where the symbols and indices have the following meanings:

Rc ¹ is (Ci-C ₄₎ alkyl, (Ci-C ₄₎ haloalkyl, (C ₂ -C ₄₎ alkenyl, (C ₂ -C ₄₎ haloalkenyl, (C ₃ -C ₇₎ cycloalkyl, preferably dichloromethyl;

Rc ² , Rc ³ are identical or different hydrogen, (Ci-C ₄ ) alkyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) alkynyl, (Ci- C ₄ ) haloalkyl, (C ₂ -C ₄₎ haloalkenyl, (Ci-C ₄₎ alkylcarbamoyl _(Ci-C4) alkyl, (C ₂ - C ₄₎ Alkenylcarbamoyl- (Ci-C ₄₎ alkyl, (Ci-C ₄₎ alkoxy (Ci-C ₄ ) alkyl, dioxolanyl- (Ci-C ₄ ) alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or Rc ² and Rc ³ together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine , Piperidine, morpholine, hexahydropyrimidine or benzoxazine ring; preferably:

Active substances of the dichloroacetamide type, which are frequently used as pre-emergence safeners (soil active

Safener) are applied, such. B.

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

 "R-29148" (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer (S3-2), "R-28725" (3-dichloro-acetyl-2,2-dimethyl) 1, 3-oxazolidine) from Stauffer (S3-3),

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

 "PPG-1292" (N-allyl-N - [(1,3-dioxolan-2-yl) -methyl] -dichloroacetamide) from PPG

 Industries (S3-5),

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

 "AD-67" or "MON 4660" (3-dichloroacetyl-1-oxa-3-aza-spiro [4,5] decane) from the company

 Nitrokemia and Monsanto (S3-7),

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

 "Diclonone" (dicyclonone) or "BAS 145138" or "LAB 145138" (S3-9)

((RS) -1-dichloroacetyl-3,3,8a-trimethyl-perhydropyrrolo [1,2-a] pyrimidin-6-one) from BASF, "Furilazole" or "MON 13900" ((RS) -3-dichloroacetyl-5- (2-furyl) -2,2-dimethyloxazolidine) (S3-10); and its (R) isomer (S3-1 1).

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

wherein the symbols and indices have the following meanings:

A _D is S0 ₂ -NR _D ³ -CO or CO-NR _D ³ -S0 ₂

RD ¹ is CO-NRD ⁵ RD ⁶ or NHCO-RD ⁷ ;

RD ² is halogen, (Ci-C ₄₎ haloalkyl, (Ci-C ₄₎ haloalkoxy, nitro, (Ci-C ₄₎ alkyl, (Ci-C ₄₎ alkoxy, (Ci C ₄₎ alkylsulfonyl, (Ci- C ₄ ) alkoxycarbonyl or (C 1 -C ₄ ) alkylcarbonyl;

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

RD ⁴ is halogen, nitro, (Ci-C ₄₎ alkyl, (Ci-C ₄₎ haloalkyl, (Ci-C ₄₎ haloalkoxy, (C ₃ -C ₆₎ cycloalkyl,

Phenyl, (Ci-C ₄₎ alkoxy, cyano, (Ci-C ₄₎ alkylthio, (Ci-C ₄₎ Alkylsulfmyl, (Ci-C ₄₎ alkylsulfonyl, (Ci-C ₄₎ alkoxycarbonyl or (Ci-C ₄₎ alkylcarbonyl;

RD ⁵ is hydrogen, (C ₁ -C ₆ ) alkyl, (C ₃ -C ₆ ) cycloalkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, (C ₅ -

C6) Cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl containing VD heteroatoms from the group consisting of nitrogen, oxygen and sulfur, where the seven latter radicals are represented by VD substituents from the group halogen, (Ci-C6) alkoxy, (Ci-C6) Haloalkoxy, (Ci-C ₂ ) alkylsulfmyl, (Ci-C ₂ ) alkylsulfonyl, (C ₃ -C ₆ ) cycloalkyl, (Ci-C ₄ ) alkoxycarbonyl, (Ci-C ₄ ) alkylcarbonyl and phenyl and in the case of cyclic radicals also (C 1 -C ₄ ) alkyl and (C 1 -C ₄ ) haloalkyl;

RD ⁶ is hydrogen, (Ci-C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl or (C ₂ -C ₆ ) alkynyl, wherein the three

last-mentioned radicals are substituted by VD radicals from the group halogen, hydroxy, (Ci-C ₄₎ alkyl, (Ci-C ₄₎ alkoxy and (Ci-C ₄₎ alkylthio, or RD ⁵ and RD ⁶ together with the nitrogen atom carrying them a pyrrolidinyl or

 Form piperidinyl moiety;

RD ⁷ is hydrogen, (Ci-C ₄ ) alkylamino, di- (Ci-C ₄ ) alkylamino, (Ci-C ₆ ) alkyl, (C ₃ -C ₆ ) cycloalkyl, wherein the latter two radicals by VD substituents from the Group halogen, (Ci-C4) alkoxy, (Ci-C6) haloalkoxy and (Ci-C4) alkylthio and in the case of cyclic radicals also (Ci-C4) alkyl and (Ci-C4) haloalkyl are substituted; nD is 0, 1 or 2; niD is 1 or 2;

VD is 0, 1, 2 or 3; Of these, preference is given to compounds of the N-acylsulfonamide type, for example of the following formula (S4 ^a ), which are, for example, B. are known from WO-A-97/45016

wherein

RD ⁷ (Ci-C6) alkyl, (C3-C6) cycloalkyl, wherein the last two radicals by VD substituents selected from the group consisting of halogen, (Ci-C4) alkoxy, (Ci-C6) haloalkoxy and (Ci-C4) alkylthio and in the case of cyclic radicals also (Ci-C4) alkyl and (Ci-C4) haloalkyl are substituted;

RD ^{4 is} halogen, (C 1 -C ₄ ) alkyl, (C 1 -C ₄ ) alkoxy, CF _3; niD 1 or 2;

VD is 0, 1, 2 or 3; such as

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

eg those in which

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

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

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

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

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

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

wherein

R _D ⁸ and R _D ⁹ independently of one another are hydrogen, (C ₁ -C ₆ ) alkyl, (C 3 -C ⁹ ) cycloalkyl, (C 3 -C ₆ ) alkenyl, (C 3 -C ₆ ) alkynyl,

RD ^{4 is} halogen, (Ci-C ₄ ) alkyl, (Ci-C ₄ ) alkoxy, CF ₃ , niD 1 or 2; for example

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

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

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

N-phenylsulfonylterephthalamides of the formula (S4 ^d ) which are known, for example, from CN 101838227, O

 D 'mD

N (S4 ^d )

 H e.g. such

R _D ^{4 is} halogen, (C 1 -C ₄ ) alkyl, (C 1 -C ₄ ) alkoxy, CF _3; niD 1 or 2;

R _D ^{5 is} hydrogen, (C ₁ -C ₆ ) alkyl, (C ₃ -C ₆ ) cycloalkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, (C ₅ -C ₆ ) cycloalkenyl.

55) active ingredients from the class of hydroxyaromatic and aromatic-aliphatic

 Carboxylic acid derivatives (S5), e.g.

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

56) Agents from the class of 1,2-dihydroquinoxaline-2-ones (S6), e.g.

 1-methyl-3- (2-thienyl) -1,2-dihydroquinoxalin-2-one, 1-methyl-3- (2-thienyl) -1,2-dihydroquinoxaline-2-thione, 1- (2 -Aminoethyl) -3- (2-thienyl) -1,2-dihydroquinoxaline-2-one hydrochloride, 1- (2-methylsulfonylaminoethyl) -3- (2-thienyl) -1,2-dihydroquinoxaline 2-on, as described in WO-A-2005/112630.

Compounds of the formula (S7) as described in WO-A-1998/38856, the symbols and indices have the following meanings: RE ¹ , RE ² are each independently halogen, (Ci-C i) alkyl, (Ci-C4) alkoxy, (Ci-C4) haloalkyl,

(C 1 -C 4) alkylamino, di (C 1 -C 4) alkylamino, nitro;

A _E is Coore ³ or COSR _E ^4,

RE ³ , RE ⁴ are, independently of one another, hydrogen, (C ¹ -C ⁴ ) -alkyl, (C ² -C ⁶ ) -alkenyl,

(C ₂ -C 4) alkynyl, cyanoalkyl, (C ₁ -C 4) haloalkyl, phenyl, nitrophenyl, benzyl,

Halobenzyl, pyridinylalkyl and alkylammonium, ηε ¹ is 0 or 1, ηε ² , ηε ³ are independently 0, 1 or 2, preferably:

 diphenylmethoxy,

 Diphenylmethoxyessigsäureethylester,

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

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

wherein

nF in the case that XF = N, an integer of 0 to 4, and in the case that XF = CH, an integer of 0 to 5,

RF ¹ halogen, (C ¹ -C ₄ ) alkyl, (C 1 -C ₄ ) haloalkyl, (C 1 -C ₄ ) alkoxy, (C 1 -C ₄ ) haloalkoxy, nitro, (C 1 -C ₄ )

C4) alkylthio, (C 1 -C 4) -alkylsulfonyl, (C 1 -C 4) -alkoxycarbonyl, optionally substituted. Phenyl, optionally substituted phenoxy,

RF ^{2 is} hydrogen or (Ci-C ₄ ) alkyl,

Hydrogen, (Ci-Cg) alkyl, (C2-C4) alkenyl, (C2-C4) alkynyl, or aryl, wherein each of the aforementioned C-containing radicals unsubstituted or by one or more, preferably to substituted into three identical or different radicals from the group consisting of halogen and alkoxy; or their salts, preferably compounds wherein

nF is an integer from 0 to 2,

RF ^{1 is} halogen, (Ci-C ₄₎ alkyl, (Ci-C ₄₎ haloalkyl, (Ci-C ₄₎ alkoxy, (Ci-C ₄₎ haloalkoxy, RF ² is hydrogen or (Ci-C ₄₎ alkyl,

RF ^{3 is} hydrogen, (Ci-Cg) alkyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) alkynyl, or aryl, wherein each of the

 aforementioned C-containing radicals unsubstituted or substituted by one or more, preferably up to three identical or different radicals from the group consisting of halogen and alkoxy,

 or their salts.

S9) Agents from the class of 3- (5-tetrazolylcarbonyl) -2-quinolones (S9), e.g.

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

S 10) compounds of the formulas (S 10 ^a ) or (S 10 ^b ) as described in WO-A-2007/023719 and WO-A-2007/023764

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

RG ¹ halogen, (C ¹ -C ₄ ) alkyl, methoxy, nitro, cyano, CF ₃ , OCF ₃ , YG, ZG independently of one another O or S, no an integer from 0 to 4, (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl, (C ₃ -C ₆ ) cycloalkyl, aryl; Benzyl, halobenzyl, hydrogen or (Ci-Ce) alkyl. ) Active ingredients of the type of oxyimino compounds (Si l), which are known as seed dressings, such as. B.

 "Oxabetrinil" ((Z) -l, 3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile) (Sl 1 -1), which is known as

Seed pickling safener for millet is known against damage from metolachlor,

"Fluxofenim" (1- (4-chlorophenyl) -2,2,2-trifluoro-1-ethanone 0- (1,3-dioxolan-2-ylmethyl) -oxime) (S l 1 -2), which was used as a Seed pickling safener for millet is known against damage from metolachlor, and

"Cyometrinil" or "CGA-43089" ((Z) -cyanomethoxyimino (phenyl) acetonitrile) (Sl l -3), which is known as a seed dressing safener for millet against damage by metolachlor. ) Active substances from the class of isothiochromanones (S 12), such as. Methyl [(3-oxo-1H-2-benzothiopyran-4 (3H) -ylidene) methoxy] acetate (CAS Reg. No. 205121 -04-6) (S12-1) and related compounds of WO-A -1998 / 13361. ) One or more compounds of group (S13): "naphthalene anhydride" (1,8-naphthalenedicarboxylic anhydride) (S13-1), which is known as a seed safener for corn against damage by thiocarbamate herbicides,

"Fenclorim" (4,6-dichloro-2-phenylpyrimidine) (S 13-2), known as safener for pretilachlor in sown rice,

"Flurazole" (benzyl-2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (S 13-3), which is known as a seeder-safener for millet against damage by alachlor and metolachlor,

"CL 304415" (CAS No. 31541 -57-8)

 (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4) from American

 Cyanamide, which is known as safener for maize against damage of imidazolinones,

"MG 191" (CAS Reg. No. 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia, which is known as safener for corn,

"MG 838" (CAS Reg. No. 133993-74-5)

 (2-propenyl 1 -oxa-4-azaspiro [4.5] decane-4-carbodithioate) (S13-6) from Nitrokemia,

"Disulfone" (O-diethyl S-2-ethylthioethyl phosphorodithioate) (S 13-7), "Dietholate" (0,0-diethyl-O-phenyl phosphorothioate) (S 13-8),

"Mephenate" (4-chlorophenyl methylcarbamate) (S 13-9).

S 14) active substances which, in addition to a herbicidal activity against harmful plants, also have safener action on crops such as rice, such as, for example, rice. B.

 "Dimepiperate" or "MY 93" (S-methyl-1-phenylethyl-piperidine-1-carbothioate), which is described as

Safener for rice against damage of the herbicide Molinate is known

"Daimuron" or "SK 23" (1- (1-methyl-1-phenylethyl) -3-p-tolyl-urea) known as a safener for rice against damage by the herbicide imazosulfuron,

"Cumyluron" = "JC 940" (3- (2-chlorophenylmethyl) -1- (1-methyl-1-phenylethyl) urea, see JP-A-60087254) known as safener for rice against damage of some herbicides is

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

"CSB" (1-Bromo-4- (chloromethylsulfonyl) benzene) from Kumiai, (CAS Registry No. 54091-06-4), which is known as a safener against damage of some herbicides in rice. S 15) compounds of the formula (S15) or their tautomers

as described in WO-A-2008/131861 and WO-A-2008/131860 wherein

RH ^{1 is} a (Ci-C6) haloalkyl radical, and RH ^{2 is} hydrogen or halogen, and

R ³ , R ⁴ independently of one another denote hydrogen, (C ₁ -C 16) alkyl, (C ₂ -C 6) alkenyl or (C ₂ -C 6) alkynyl, where each of the last-mentioned 3 radicals is unsubstituted or substituted by one Hydroxy, cyano, (Ci-C i) alkoxy, (Ci-C i) haloalkoxy, (Ci-C ₄₎ alkylthio, (Ci-C ₄₎ alkylamino, di [(Ci-C ₄₎ alkyl] amino, [(Ci-C ₄₎ alkoxy] - carbonyl, [(Ci-C ₄₎ haloalkoxy] -carbonyl, (C3-C6) cycloalkyl which is unsubstituted or substituted, is phenyl which is unsubstituted or substituted, and heterocyclyl which is unsubstituted or substituted substituted, or (C3-C6) cycloalkyl, (C ₄ -C 6) Cycloalkenyl, (C ₃ -C 6) cycloalkyl fused on one side of the ring with a 4 to 6 membered saturated or unsaturated carbocyclic ring, or (C ₄ -C 6) cycloalkenyl attached to one side of the ring of 4 to 6 -membered saturated or unsaturated carbocyclic ring is fused, wherein each of the latter 4 radicals being unsubstituted or substituted by one or more radicals from the group halogen, hydroxy, cyano, (Ci-C ₄₎ alkyl, (Ci-C ₄₎ haloalkyl, (C -C ₄₎ alkoxy, (Ci-C ₄₎ haloalkoxy, (Ci-C ₄₎ alkylthio, (Ci-C ₄₎ alkylamino, di [(Ci- _C4) alkyl] amino, [(Ci-C ₄₎ Alkoxy] carbonyl, [(C 1 -C ₄ ) haloalkoxy] carbonyl,

 (C 3 -C 6) cycloalkyl which is unsubstituted or substituted, phenyl which is unsubstituted or substituted, and heterocyclyl which is unsubstituted or substituted, or denotes

RH ^{3 is} (C 1 -C ₄ ) -alkoxy, (C ₂ -C ₄ ) -alkenyloxy, (C ₂ -C 6) -alkinyloxy or (C ₂ -C ₄ ) -haloalkoxy, and RH ^{4 is} hydrogen or (C 1 -C ₄ ) -alkyl, or

RH ³ and RH ⁴ together with the directly attached N atom form a four- to eight-membered one

heterocyclic ring which, in addition to the N atom, may also contain further hetero ring atoms, preferably up to two further hetero ring atoms from the group consisting of N, O and S, and which may be unsubstituted or substituted by one or more radicals from the group consisting of halogen, cyano, nitro, C ₄ ) alkyl, (Ci-C ₄ ) haloalkyl, (Ci-C ₄ ) alkoxy, (Ci-C ₄ ) haloalkoxy and (Ci-C ₄ ) alkylthio is substituted, means.

S 16) active substances which are used primarily as herbicides, but also have safener action on crop plants, e.g.

(2,4-dichlorophenoxy) acetic acid (2,4-D),

 (4-chlorophenoxy) acetic acid,

 (R, S) -2- (4-chloro-o-tolyloxy) propionic acid (mecoprop),

 4- (2,4-dichlorophenoxy) butyric acid (2,4-DB),

 (4-chloro-o-tolyloxy) acetic acid (MCPA),

4- (4-chloro-o-tolyloxy) butyric acid, 4- (4-chlorophenoxy) butyric acid,

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

 1- (ethoxycarbonyl) ethyl 3,6-dichloro-2-methoxybenzoate (lactidichloroethyl).

Preferred safeners are: cloquintocet-mexyl, cyprosulfamide, fenchlorazole-ethyl ester, isoxadifen-ethyl, mefenpyr-diethyl, fenclorim, cumyluron, S4-1 and S4-5, particular preference is given to:

Cloquintocet-mexyl, cyprosulfamide, isoxadifen-ethyl and mefenpyr-diethyl.

Injectable powders are preparations which are uniformly dispersible in water and contain surfactants of the ionic and / or nonionic type (wetting agents, dispersants) in addition to the active ingredient except a diluent or inert substance. polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, dibutylnaphthalene-sodium sulfonate or sodium oleoylmethyltaurine. To prepare the wettable powders, the herbicidal active compounds are finely ground, for example, in customary apparatus such as hammer mills, blower mills and air-jet mills and mixed simultaneously or subsequently with the formulation auxiliaries.

Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers). Examples of emulsifiers which may be used are: alkylarylsulfonic acid calcium salts, such as

Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol ester,

Alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers,

Propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, e.g.

 Sorbitan fatty acid esters or polyoxethylenesorbitan esters such as e.g. Polyoxyethylene.

Dusts are obtained by milling the active ingredient with finely divided solids, e.g.

Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

Suspension concentrates may be water or oil based. They can be prepared, for example, by wet grinding by means of commercially available bead mills and, if appropriate, addition of surfactants, as already listed above, for example, in the other formulation types. Emulsions, for example oil-in-water emulsions (EW), can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents Solvents and optionally surfactants, such as those listed above, for example, in the other types of formulation produce.

Granules can either be prepared by atomizing the active ingredient on adsorptive, granulated inert material or by applying active substance concentrates by means of adhesives, e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils, on the surface of carriers such as sand, kaolinites or granulated inert material. Also suitable

Active ingredients in the usual manner for the production of fertilizer granules - if desired, mixed with fertilizers - granulated.

Water-dispersible granules are generally prepared by the usual methods such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material. For the preparation of plate, fluid bed, extruder and spray granules, see e.g. Procedure in

 "Spray-Drying Handbook" 3rd Ed. 1979, G. Goodwin Ltd., London, J.E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 et seq., "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57. For further details on the formulation of crop protection agents see, e.g. G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103. The agrochemical preparations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of compounds according to the invention.

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

Formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% active ingredient. In the case of water-dispersible granules, the active ingredient content depends, in part, on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used. In the case of the water-dispersible granules, the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight. In addition, the active substance formulations mentioned optionally contain the customary adhesion, wetting, dispersing, emulsifying, penetrating, preserving, antifreezing and solvent, fillers, carriers and dyes, antifoams, evaporation inhibitors and the pH and the Viscosity-influencing agent.

On the basis of these formulations, combinations with other pesticidally active substances, e.g. Insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers and / or growth regulators, e.g. in the form of a ready-made formulation or as a tank mix. As combination partners for the compounds according to the invention in mixture formulations or in the tank mix, for example, known active compounds which are based on an inhibition of, for example

Acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthetase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase,

Photosystem I, photosystem II, protoporphyrinogen oxidase, can be used, as e.g. from Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 15th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2009 and cited therein. As known herbicides or plant growth regulators which can be combined with the compounds according to the invention are e.g. the following active ingredients (the compounds are either with the "common name" according to the International Organization for Standardization (ISO) or with the chemical name or with the code number called) and always include all

Use forms such as acids, salts, esters and isomers such as stereoisomers and optical isomers. Here are an example and partly also called several application forms:

Acetochlor, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, 4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methylphenyl ) -5-fluoropyridines-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyrachloro- potassium, aminocyclopyrachloromethyl, aminopyralid, amitrole, ammonium sulfamates, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron , bensulphon-methyl, bensulide, bentazone, benzobicyclone, benzofenap, bicyclopyrone, bifenox, bilanafos, bilanafos-sodium, bispyribac, bispyribac-sodium, bromacil, bromobutide, bromofenoxime, bromoxynil, bromoxynil-butyrate, -potassium, -heptanoates and -octanoates, busoxinone, butachlor, butafenacil, butamifos, butenachlor, butraline, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chlorobromuron, chlorfenac, chlorfenac-sodium, chlorfenprop, ch lorflurenol, chlorofurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlorophthalim, chlorotoluron, chlororthal-dimethyl, chlorosulfuron, cinidon, cinidon-ethyl, cinmethylin, cinosulfuron, clacyfos, clethodim, clodinafop, clodinafop-propargyl, clomazone, clomeprop, clopyralid, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D, 2,4-D-butotyl, -butyl, - dimethylammonium, -diolamine, -ethyl, 2-ethylhexyl, -isobutyl, -isooctyl, -isopropylammonium, -potassium, -triisopropanolammonium and -trolamine, 2,4-DB, 2,4-DB-butyl, -dimethylammonium, isooctyl, - potassium and sodium, daimuron (dymron), dalapon, dazomet, n-decanol, desmedipham, detosyl-pyrazolate (DTP), dicamba, dichlobenil, 2- (2,4-dichlorobenzyl) -4,4-dimethyl-1,2 -oxazolidin-3-one, 2- (2,5-dichlorobenzyl) -4,4-dimethyl-1,2-oxazolidin-3-one, dichloroprop, dichloroprop-P, diclofop, diclofop-methyl, diclofop-P-methyl , diclosulam, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimetrasulfuron, dinitramine, dinoterb, diphenamid, diquat, diquat-dibromide, dithiopyr, diuron, DNOC, endothal, EPTC , esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethiozine, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanide, F-9600, F-5231, ie N- [2-chloro-4-fluoro-5- [4- (3-fluo rpropyl) -4,5-dihydro-5-oxo-1H-tetrazol-1-yl] -phenyl] -ethanesulfonamide, F-7967, ie 3- [7-chloro-5-fluoro-2- (trifluoromethyl) -lH benzimidazol-4-yl] -l-methyl-6- (trifluoromethyl) pyrimidine-2,4 (1H, 3H) -dione, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenquinotrione, fentrazamide, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-p-butyl,

flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazine, fluometuron, flurenol, flurenol-butyl, - dimethylammonium and -methyl, fluoroglycofen, fluoroglycofen-ethyl, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone, flurochloridone, fluroxypyr, fluroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, fosamine, glufosinate, glufosinate-ammonium, glufosinate-p-sodium, glufosinate- P-ammonium, glufosinate-P-sodium, glyphosate, glyphosate-ammonium, -isopropylammonium, -diammonium, -dimethylammonium, -potassium, -sodium and -trimesium, H-9201, ie 0- (2,4-dimethyl-6-nitrophenyl) -0-ethyl-isopropylphosphoramidothioate, halo-cy, halauxifen-methyl, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfopethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, hexazinone, HW-02, ie 1- (dimethoxyphosphoryl) ethyl- (2,4-dichlorophenoxy) acetate, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapicammonium, imazapyr, imazapyrisopropylammonium, imazaquin, imazaquinammonium, imazethapyr, imazethapyr -immonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxynil-octanoate, -potassium and sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, karbutilate, KUH-043, ie 3 - ({[5- (Difluoromethyl) -1-methyl-3- (trifluoromethyl) -1 H -pyrazol-4-yl] methyl} sulfonyl) -5,5-dimethyl-4,5-dihydro-1,2 -oxazole, ketospiradox, lactofen, lenacil, linuron, MCPA, MCPA-butotyl, -dimethylammonium, -2-ethylhexyl, - isopropylammonium, -potassium and -sodium, MCPB, MCPB-methyl, -ethyl and -sodium, mecoprop, mecoprop- sodium and -butotyl, mecoprop-P, mecoprop-P-butotyl, -dimethylammonium, -2-ethylhexyl and -potassium, mefenacet, mefluidide, mesosulfuron, mesosulfuron-methyl, mesotrione,

methabenzothiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methiopyrsulfuron, methiozoline, methyl isothiocyanate, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinate, monolinuron, monosulfuron, monosulfuron ester, MT-5950, ie N- [3-chloro -4- (1-methylethyl) phenyl] -2-methylpentanamide, NGGC-011, napropamide, NC-310, ie 4- (2,4-dichlorobenzoyl) -l-methyl-5-benzyloxypyrazole, neburon, nicosulfuron, nonanoic acid (pelargonic acid), norflurazon, oleic acid (fatty acids), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefon, oxyfluorfen, paraquat, paraquat dichloride, pebulate, pendimethalin, penoxsulam, pentachlorophenol, pentoxazone, pethoxamide, petroleum oils, phenmedipham, picloram, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisul furon, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole, pyrazolynate (pyrazolate), pyrazosulfuron, pyrazosulfuronethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalid , pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, saflufenacil , sethoxydim, siduron, simazine, simetryn, SL-261, sulcotrione, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron,, SYN-523, SYP-249, ie, 1-ethoxy-3-methyl-1-oxobut-3-ene -2-yl- 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoate, SYP-300, ie 1- [7-fluoro-3-oxo-4- (prop-2-yn-1 - yl) -3,4-dihydro-2H-l, 4-benzoxazin-6-yl] -3-propyl-2-thioxoimidazolidine-4,5-dione, 2,3,6-TBA, TCA (trifluoroacetic acid), TCA-sodium, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumetone, terbuthylazine, terbutryn, thenylchloro, thiazopyr, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, triclopyr, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazine, trifluralin, triflusulfuron, triflusulfuron-methyl, tritosulfuron, urea sulfate, vernolate, XDE-848, ZJ-0862, ie 3,4-dichloro-N- {2- [(4,6-dimethoxypyrimidin-2-yl) oxy] benzyl} aniline, and the following compounds:

Examples of plant growth regulators as possible mixing partners are:

Acibenzolar, acibenzolar-S-methyl, 5-aminolevulinic acid, ancymidol, 6-benzylaminopurine,

Brassinolide, catechin, chloroformate chloride, cloprop, cyclanilide, 3- (cycloprop-1-enyl) propionic acid, daminozide, dazomet, n-decanol, dikegulac, dikegulac-sodium, endothal, endothaldipotassium, -disodium, and mono (N, N-dimethylalkylammonium), ethephon, flumetralin, flurenol, flurenol-butyl, flurprimidol, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid (IAA), 4-indol-3-yl-butyric acid, isoprothiolane, probenazole, jasmonic acid, methyl jasmonate maleic hydrazides, mepiquat chloride, 1-methylcyclopropene, 2- (1-naphthyl) acetamide, 1 -naphthylacetic acid, 2-naphthyloxyacetic acid, nitrophenolate-mixture, 4-0x0-4 [(2-phenylethyl) amino] butyric acid, paclobutrazole , N-phenylphthalamic acid, prohexadione, prohexadione-calcium, prohydrojasmone,

Salicylic acid, strigolactone, tecnazene, thidiazuron, triacontanol, trinexapac, trinexapac-ethyl, tsitodef, uniconazole, uniconazole-P.

For use, the formulations present in commercial form are optionally diluted in a customary manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Dust-like preparations, soil or

Spreading granulates and sprayable solutions are usually no longer diluted with other inert substances before use. With the external conditions such as temperature, humidity, the type of herbicide used, u.a. varies the required application rate of the compounds of formula (I). It can vary within wide limits, e.g. between 0.001 and 1.0 kg / ha or more of active substance, but is preferably between 0.005 and 750 g / ha.

The following examples illustrate the invention in more detail. A. Chemical examples

1. Preparation of 3- (trifluoromethyl) benzyl-4-amino-6-chloro- (1-benzothiophen-5-yl) -3-chloropyridine-2-carboxylate (Example Nos. 1-21)

To a solution of 0.08 g (0.26 mmol) of 4-amino-6- (1-benzothiophene-5-yl) -3-chloropyridine-2-carboxylic acid in 10 ml of THF is added successively 0.075 ml of triethylamine and 0.094 g (0, 39mmol) 3-trifluorobenzyl bromide, and stir this reaction mixture for 12 hours at room temperature. For workup is concentrated to dryness and the crude mixture thus obtained

purified by column chromatography on silica gel (heptane / ethyl acetate 2/8). This gives 0.1 g (82%) of product as a colorless oil. IH-NMR, CDC13; 8.40 (s, 1H, benzothiophene), 7.90 (m, 2H, benzothiophene), 7.70 (s, 1H, phenyl), 7.70, 7.60 (2d, 2H, phenyl), 7.50 (t, 1H, phenyl), 7.49, 7.40 (2d, 2H,

Benzothiophene), 7.20 (s, 1H, pyridine), 5.50 (s, 2H, CH 2 -phenyl), 4.70 (bs, 2H, NH 2).

2. Preparation of 4-fluorobenzyl-4-amino-6- (1-benzothiophen-6-yl) -3-chloropyridine-2-carboxylate (Example Nos. 1-07)

 To a solution of 0.1 g (0.33 mmol) of 4-amino-6- (1-benzothiophene-6-yl) -3-chloropyridine-2-carboxylic acid in 10 ml of THF are added successively 0.09 ml of triethylamine and 0.093 g (0 , 49 mmol) 4-fluorobenzyl bromide, and this reaction mixture is stirred for 12 hours at room temperature. For workup, the mixture is evaporated to dryness and the crude mixture thus obtained by column chromatography on silica gel

(Heptane / ethyl acetate 2/8). This gives 0.09 g (66%) of product as a colorless oil. IH-NMR, CDC13; 8.50 (s, benzothiophene), 7.85 (m, 2H, benzothiophene), 7.50 (m, 3H, benzyl, benzothiophene), 7.35 (d, 1H, benzothiophene), 7.25 (s, 1H, pyridine), 7.08 (m, 2H, benzyl), 5.95 (s, 2H, OCH2), 4.70 (bs, 2H, NH2). 3. Preparation of 3-fluorobenzyl-4-amino-3-chloro-5-fluoro-6- (7-fluoro-1H-indol-6-yl) pyridine-2-carboxylate (Example Nos. 1-84)

To a solution of 0.1 g (0.31 mmol) of 4-amino-3-chloro-5-fluoro-6- (7-fluoro-1H-indol-6-yl) -pyridine-2-carboxylic acid in 11 ml of THF is added successively 0.09 ml of triethylamine and 0.088 g (0.47 mmol) of 3-fluorobenzyl bromide, heated briefly to 70 ° C and stirred this reaction mixture for 12 hours at room temperature. For working up, the mixture is evaporated to dryness and the crude mixture thus obtained is purified by column chromatography on silica gel (heptane / ethyl acetate 2/8). This gives 0.1 g (79%) of product as a colorless oil. IH-NMR, CDC13; 8.45 (bs, NH, indole), 7.50 (d, 1H, indole), 7.30 (m, 5H, indole, benzyl), 7.20 (m, 1H, benzyl), 6.60 ( m, 1H, indole), 5.40 (2H, CH 2 -benzyl), 4.90 (bs, 2H, NH 2). NMR data of selected examples

NMR peak list procedures

The 1H NMR data of selected examples are noted in terms of 1H NMR peak lists. For each signal peak, first the δ value in ppm and then the signal intensity in round brackets are listed. The δ-value signal intensity number pairs of different signal peaks are listed separated by semicolons.

The peak list of an example therefore has the form: δι (intensity ^; 82 (intensity 2);; δ; (intensity ^;; δ _η (intensity _n )

The intensity of sharp signals correlates with the height of the signals in a printed example of an NMR spectrum in cm and shows the true ratios of the signal intensities. In broad

Signals can show multiple peaks or the center of the signal and their relative intensity compared to the most intense signal in the spectrum.

To calibrate the chemical shift of 1H NMR spectra we use tetramethylsilane and / or the chemical shift of the solvent, especially in the case of spectra measured in DMSO. Therefore, the tetramethylsilane peak can occur in NMR peaks, but it does not have to.

The lists of the IH-NMR peaks are similar to the classical IH-NMR prints and thus usually contain all the peaks that are listed in a classical NMR interpretation.

In addition, like classical IH-NMR prints, they can show solvent signals, signals from stereoisomers of the target compounds, which are also the subject of the invention, and / or peaks of impurities.

When indicating compound signals in the delta range of solvents and / or water, our lists of IH NMR peaks show the usual solvent peaks, for example, peaks of DMSO in DMSO-D6 and the peak of water, which are usually average have a high intensity.

The peaks of stereoisomers of the target compounds and / or peaks of impurities usually have on average a lower intensity than the peaks of the target compounds (for example with a purity of> 90%). Such stereoisomers and / or impurities may be typical of each

Be manufacturing process. Their peaks can thus help the reproduction of our

Detect manufacturing process by "by-product fingerprints".

An expert calculating the peaks of the target compounds by known methods (MestreC, ACD simulation, but also with empirically evaluated expectancy values) can isolate the peaks of the target compounds as needed, using additional intensity filters if necessary. This isolation would be similar to peak picking in classical 1H NMR interpretation.

Further details on 1H NMR peaks can be found in Research Disclosure Database Number 564025.

Example 1-01: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,498 (6.6); 8,496 (7.0); 8,494 (6.5); 7,896 (3.2); 7,892 (3.0); 7,875 (8.2); 7,871 (8.2); 7,849 (9.0); 7,848 (9.0); 7,828 (3.4); 7.604 (1.6), 7.600 (1.7), 7.586 (3.3), 7.581 (3.3), 7.567 (1.7), 7.563 (1.8), 7.501 (12.2), 7.488 (14.5), 7.3 65 (1.1); 7.360 (1.1), 7.351 (1.4), 7.345 (8.8), 7.343 (8.2), 7.332 (7.5), 7.330 (7.1), 7.326 (2.4), 7.321 (1.5), 7.312 (1.4), 7.308 (1.4 ); 7,264 (0.6); 7,263 (0.7); 7,262 (0.8); 7,261 (1.0); 7,256 (63.5); 7,252 (0.6); 7,192 (2.9); 7,189 (3.2); 7.173 (4.9); 7.170 (5.3); 7.159 (19.8); 7.154 (2.5); 7.151 (2.4); 7.122 (2.7); 7.119 (2.4); 7.101 (2.3); 7.097 (3.6); 7.0 94 (2.5) ; 7,076 (2.1); 7,073 (2.0); 5,543 (16.0) 5,294 (8.7); 4,779 (6.3); 1,565 (1.6); 0,008 (0.8); 0,000 (28.9); -

0.008 (0.8)

Example 1-02: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8.110 (2.9), 8.107 (4.2), 8.106 (5.6), 8.104 (4.2), 8.102 (2.8), 7.833 (4.3), 7.829 (4.1), 7.812 (5.2), 7.809 (5.2), 7.678 7.742 (8.7), 7.642 (5.3), 7.641 (5.3), 7.622 (4.4), 7.621 (4.2), 7.384 (0.8), 7.382 (0.7), 7.369 (1.2), 7.366 (1.1), 7.364 (2.1); 7,349 (2.5) 7,343 (1.6); 7,329 (2.0); 7,280 (3.1) 7,278 (2.4); 7,262 (4.9); 7,260 (5.3); 7258 (53rd

5), 7.254 (1.7), 7.252 (1.1), 7.240 (1.3), 7.239 (1.4), 7.238 (1.1), 7.234 (1.7), 7.230 (1.2), 7.157 (18.4), 7.058 (1.0); 7,056 (1.0); 7,052 (0.9); 7,049 (0.9); 7,037 (1.5); 7,034 (1.7); 7,030 (1.4); 7,028 (1.5); 7,016 (0.8); 7,013 (0.8); 7.01 0 (0.8) ; 7,007 (0.8); 6,788 (5.5); 6,785 (5.7); 6,782 (5.6); 6,780 (5.3); 5,452 (16.0); 5,296 (0.8); 4,788 (4.1); 1,549 (1

0.2) 0.008 (0.7); 0,000 (22.6) - 0.008 (0.6)

Example 1-03: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,111 (1.4), 7,880 (0.6), 7,876 (1.1), 7,872 (0.6), 7,860 (0.7), 7,856 (1.3), 7,852 (0.7), 7,705 (0.6), 7,700 (2.9), 7,695 (2.9); 7,692 (0.8); 7,673 (1.8); 7,652 (1.4); 7,442 (2.4); 7,437 (1.1); 7,425 (0.8); 7,420 (2.6); 7,308 (0.7); 7,286 (0.7); 7,258 (49.5) 6,925 (3.0); 6,920 (1.0); 6,908 (1.5); 6,903 (3.0); 6,886 (0.8); 6,858 (0.5); 6,806 (1.6); 6,803 (. 1

6); 6,800 (1.6); 6,798 (1.5); 6,661 (0.6); 5,384 (6.1); 4,852 (1.4); 4,632 (0.6); 4,617 (0.6); 3,817 (16.0); 3,812 (4.7);

3,778 (2.9); 1,536 (13.4); 0008 (0.7); 0,000 (21.0) - 0.008 (0.6)

Example 1-04: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,196 (0.9); 8,115 (4.4); 7,969 (0.7); 7,949 (0.9); 7,882 (2.0); 7,878 (3.5); 7,874 (2.0); 7,861 (2.4); 7,857 (4.3); 7

.854 (2.3); 7,709 (2.3); 7,706 (8.4); 7,700 (9.6); 7,697 (2.6); 7,680 (6.4); 7,659 (4.6); 7,604 (1.0); 7,585 (1.1); 7,517

(1.0); 7,499 (3.7); 7,494 (1.6); 7,486 (3.9); 7,477 (4.2); 7,469 (1.7); 7,464 (4.1); 7,409 (1.2); 7,356 (1.0); 7,343 (1.1)

; 7,334 (1.3); 7,320 (1.3); 7,309 (0.7); 7,258 (157.8); 7,209 (1.1); 7,155 (1.0); 7,151 (1.0); 7,135 (1.0); 7,132 (1.0); 7

.105 (0.7); 7,097 (5.0); 7,092 (1.7); 7,081 (1.8); 7,076 (9.2); 7,070 (1.9); 7,067 (2.0); 7,059 (1.7); 7,054 (4.5); 7,045

(2.8); 7,039 (0.6); 7,023 (1.2); 6,994 (0.9); 6,929 (0.7); 6,915 (0.8); 6,907 (1.0); 6,893 (1.1); 6,828 (1.2); 6,826 (1.2)

; 6,822 (1.8); 6,816 (1.6); 6,814 (1.8); 6,811 (5.4); 6,808 (5.6); 6,806 (5.9); 6,803 (5.2); 6,785 (1.9); 6,763 (0.8); 5.4

08 (16.0); 5,004 (1.2); 4,872 (4.2); 4,675 (1.8); 4,661 (1.8); 4,380 (1.0); 1,623 (0.6); 1,609 (1.2); 1,594 (0.6); 1,533 (

31.0) 1,333 (0.6); 1,284 (0.8); 1,256 (0.7); 0.008 (2.3); 0,000 (67.5) - 0.008 (2.3) Example 1-05: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8.166 (5.1), 8.162 (5.2), 7.853 (3.2), 7.848 (3.1), 7.831 (3.7), 7.827 (3.6), 7.647 (6.9), 7.641 (6.9), 7.542 (4.5), 7.540 (3.1), 7.522 (2.8), 7.520 (4.0), 7.518 (2.8), 7.503 (3.8), 7.498 (1.6), 7.490 (4.0), 7.481 (4.4), 7.473 (1.7), 7.468 (4.1), 7.258 (66.9); 7,122 (16.1); 7,101 (0.6); 7,093 (5.2); 7,088 (1.6); 7,077 (1.9); 7,072 (9.7); 7,066 (1.7); 7,055 (1 .8); 7,050 (4.6) ; 6,810 (5.0); 6,807 (5.1); 6,804 (5.0); 6,802 (4.8); 5,421 (16.0); 5,296 (1.4); 4,763 (4.4); 1,551 (12.6

); 0.008 (0.8); 0,000 (25.2) - 0.008 (0.7)

 Example 1-06: 'H NMR ^ OO.O MHZ, CDC13):

δ = 8,192 (7.6); 8,189 (7.6); 7,861 (5.0); 7,857 (4.8); 7,840 (5.7); 7,835 (5.4); 7,653 (10.7); 7,648 (10.5); 7,555 (5.0)

; 7,553 (6.9); 7,551 (4.7); 7,534 (4.3); 7,532 (6.0); 7,530 (4.5); 7,527 (1.8); 7,518 (0.6); 7,510 (1.7); 7,505 (1.8); 7.5

01 (1.8); 7,488 (1.8); 7,484 (1.8); 7,479 (1.7); 7,463 (1.5); 7,268 (0.5); 7,267 (0.6); 7,266 (0.7); 7,264 (1.1); 7,264 (1

.3); 7,259 (87.5); 7,255 (0.8); 7,254 (0.6); 7,209 (0.6); 7,164 (0.5); 7,151 (27.6); 7,005 (2.2); 6,995 (0.7); 6,989 (2.3

) 6,981 (2.6); 6,964 (2.6); 6,957 (2.2); 6,941 (2.1); 6,823 (8.0); 6,821 (8.1); 6,818 (8.0); 6,815 (7.7); 5,457 (16.0); 5th

297 (11.7); 4,795 (6.5); 1,552 (9.8); 1,255 (0.6); 0.008 (1.2); 0,000 (37.8) - 0.008 (1.1)

Example 1-08: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,495 (2.5); 8,493 (2.7); 8,491 (2.6); 7,893 (1.0); 7,890 (1.0); 7,872 (3.2); 7,868 (3.3); 7,854 (3.6); 7,852 (3.5); 7,833 (1.1), 7.832 (1.0), 7.507 (4.8), 7.494 (5.6), 7.350 (2.7), 7.348 (2.7), 7.337 (2.3), 7.335 (2.2), 7.258 (26.6), 7.24 4 (0.7); 7,230 (0.7), 7,225 (0.8), 7,224 (0.8), 7,223 (0.8), 7,211 (0.8), 7,208 (1.0), 7,204 (0.8), 7,189 (0.8), 7,171 (7,6), 6,946 (1.0 ); 6,940 (1.0); 6,924 (1.0); 6,919 (1.6); 6,915 (1.1); 6,898 (0.9); 6,893 (0.9); 5,477 (4.9); 5,476 (5.1); 5th

474 (4.9); 4,791 (2.5); 4,017 (8.5); 4,014 (16.0); 4,012 (8.4); 1,559 (6.1); 0.000 (11.7)

Example 1-09: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,411 (4.8), 8,409 (4.6), 7,931 (1.7), 7,910 (7.2), 7,899 (5.0), 7,895 (4.7), 7,878 (1.2), 7,874 (1.2), 7,474 (4.9), 7,460 (7.0), 7.398 (5.4), 7.384 (3.8), 7.379 (1.2), 7.365 (1.2), 7.360 (2.4), 7.345 (2.7), 7.340 (1.8), 7.327 (1.0), 7.324 (1.6), 7.280 (2.0); 7.275 (3.9); 7.273 (4.2); 7.257 (45.7); 7.184 (14.8); 7.059 (0.9); 7.057 (1.0); 7.053 (0.9); 7.050 (0.9); 7.036 (1.7) ; 7,031 (1.6); 7,017 (0.9); 7,013 (1.0); 7,008 (0.8); 6,858 (0.7); 5,457 (16.0); 5,381 (0.8); 5,294 (12.8

); 4,797 (4.4); 1,561 (1.2); 0.008 (0.5), 0.000 (15.8)

Example 1-10: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,509 (2.8); 8,507 (4.8); 8,505 (5.3); 8,503 (5.0); 8,501 (2.7); 7,908 (2.4); 7,904 (2.3); 7,887 (6.1); 7,883 (6.1); 7,861 (6.2), 7.860 (6.3), 7.840 (2.4), 7.839 (2.3), 7.508 (8.1), 7.494 (9.4), 7.384 (1.3), 7.369 (1.2), 7.363 (3.1), 7.357 (0.5), 7.351 (5.6), 7.349 (7.2), 7.343 (2.4), 7.338 (4.1), 7.336 (4.1), 7.329 (2.0), 7.278 (3.1), 7.276 (2.6), 7.272 (1.8), 7.268 (2.0), 7.266 (2.1); 7.262 (3.4); 7.256 (37.5); 7.248 (1.4); 7.248 (1.5); 7.242 (1.7); 7.238 (1.1); 7.179 (16.4); 7 .061 (0.9); 7.058 (1.0). ; 7,055 (0.9); 7,052 (0.9); 7,040 (1.6); 7,038 (1.6); 7,033 (1.5); 7,032 (1.4); 7,019 (0.8); 7,016

(0.8); 7,013 (0.8); 7,010 (0.7); 5,458 (16.0); 5,294 (3.1); 4,797 (4.4); 1,562 (2.6); 0.008 (0.5), 0.000 (16.1)

Example 1-11: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,203 (1.0); 8,200 (1.0); 7,877 (0.6); 7,872 (0.6); 7,855 (0.8); 7,851 (0.7); 7,829 (0.7); 7,655 (1.4); 7,650 (1.4); 7,558 (0.7); 7,556 (0.9); 7,554 (0.6); 7,536 (0.9); 7,535 (1.0); 7,533 (0.6); 7,518 (0.9); 7,259 (49.0); 7,163 (4.0); 6.82 6 (1.0); 6,823 (1.0); 6,820 (1.1); 6,818 (1.0); 5,513 (3.1); 4,786 (0.8); 1,538 (16.0); 0008 (0.6); 0,000 (19.9); -

0.008 (0.6)

Example 1-12: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,497 (4.2), 8,495 (7.6), 8,493 (8.2), 8,491 (7.8), 8,489 (4.0), 7,896 (3.2), 7,892 (3.0), 7,875 (10.3), 7,871 (10.4), 7,857 (10.2 ); 7,856 (9.9); 7,836 (3.1); 7,834 (2.8); 7,597 (1.6); 7,581 (1.8); 7,576 (3.4); 7,560 (3.4); 7,555 (1.9);. 7 538 (1.8), 7.517 (0.6), 7.509 (12.5), 7.495 (14.7), 7.352 (7.5), 7.350 (7.3), 7.338 (6.3), 7.336 (6.2), 7.258 (76.0), 7.1 72 (27.0) 6,936 (1.4), 6,933 (1.3), 6,930 (1.6), 6,927 (1.6), 6,915 (2.1), 6,913 (2.2), 6,908 (2.6), 6,906 (2.8), 6,894 (1.3), 6,892 (1.3) ; 6887 (3.6); 6,881 (1.8); 6,864 (2.8); 6,862 (2.8); 6,858 (2.1); 6,856 (2.2); 6,840 (2.4); 6,834 (1.9);

5,486 (16.0); 5,296 (6.0); 4,785 (6.6); 1,553 (8.3); 0.008 (0.9) 0.000 (32.3) - 0.008 (1.0)

Example 1-13: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,166 (7.9), 8,163 (8.0), 7,852 (5.2), 7,847 (5.0), 7,830 (5.9), 7,826 (5.6), 7,651 (11,0), 7,645 (10.9), 7,548 (5.2)

; 7,546 (7.2); 7,544 (4.8); 7,526 (4.5); 7,524 (6.2); 7,522 (4.2); 7,518 (0.6); 7,341 (1.1); 7,335 (1.1); 7,327 (1.2); 7.3

21 (2.0); 7,319 (1.9); 7,313 (1.4); 7,309 (1.2); 7,303 (1.8); 7,301 (2.0); 7,295 (1.2); 7,287 (1.2); 7,281 (1.2); 7,269 (0

.6); 7,259 (86.0); 7,255 (0.6); 7,209 (0.6); 7,135 (29.3); 7,028 (1.5); 7,023 (1.5); 7,011 (1.6); 7,006 (3.2); 6,999 (1.9

); 6,995 (0.7); 6,988 (1.9); 6,982 (2.9); 6,977 (1.3); 6,965 (1.2); 6,960 (1.2); 6,814 (8.6); 6,811 (8.5); 6,808 (8.4); 6.8

06 (8.0); 5,485 (14.9); 5,484 (16.0); 5,482 (14.5); 5,297 (2.7); 4,783 (6.8); 1,554 (9.9); 0.008 (1.2); 0,000 (38.3); -

0.008 (1.0) Example 1-14: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,500 (2.6), 8,498 (4.7), 8,496 (5.0), 8,494 (4.8), 8,492 (2.4), 7,900 (2.0), 7,896 (1.9), 7,879 (6.4), 7,876 (6.5), 7,868 (0.7); 7,862 (6.2); 7,860 (6.1); 7,840 (1.9); 7,839 (1.7); 7,516 (0.5); 7,511 (8.2); 7,498 (9.7); 7,467 (0.7); 7,462

(5.4); 7,460 (4.5), 7,456 (1.8), 7,445 (2.4), 7,440 (8.4), 7,434 (1.1), 7,382 (1.6), 7,376 (10.9), 7,371 (2.9), 7,360 (2.

7355 (10.8), 7.349 (0.8), 7.341 (4.1), 7.339 (3.9), 7.265 (0.6), 7.264 (0.7), 7.263 (0.8), 7.257 (56.6), 7.253 (0.6), 7.178 (7) 16.0); 5,428 (16.0); 5,296 (4.1); 4,786 (4.0); 1,548 (1.0); 0.070 (2.3); 0.008 (0.7); 0.000 (26.3); - 0.008 (0.8) Example 1-15: ¹ H NMR (400.0 MHz, CDC13):

δ = 8,197 (0.9), 8,118 (3.9), 7,971 (0.6), 7,951 (0.8), 7,885 (1.7), 7,881 (3.1), 7,877 (1.7), 7,865 (2.1), 7,861 (3.8), 7

.857 (2.0); 7,711 (3.3); 7,708 (7.5); 7,706 (4.1); 7,703 (8.4); 7,682 (5.7); 7,663 (4.0); 7,597 (0.9); 7,576 (1.0); 7,517

(0.9); 7,450 (4.7); 7,445 (1.9); 7,434 (2.4); 7,428 (8.2); 7,407 (1.2); 7,379 (1.6); 7,374 (10.5); 7,369 (3.0); 7,358 (. 2

3); 7,352 (5.7); 7,309 (1.4); 7,258 (151.8); 7,210 (1.0); 7,148 (0.8); 7,144 (0.9); 7,128 (0.8); 7,124 (0.7); 7,079 (1.5)

; 7,075 (0.6); 7,063 (0.6); 7,058 (1.9); 6,994 (0.8); 6,876 (1.6); 6,855 (1.4); 6,832 (1.0); 6,830 (1.1); 6,827 (1.1); 6.8

23 (1.2), 6.820 (1.2), 6.818 (1.3), 6.813 (4.6), 6.811 (4.5), 6.808 (4.5), 6.805 (4.4), 5.407 (16.0), 5.297 (0.9), 5.004 (l ); 4,879 (3.7); 4,385 (0.9); 1,534 (10.0); 1,284 (0.7); 1,255 (0.7); 0.008 (1.9); 0,000 (64.5) - 0.008 (2.3)

Example 1-16: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,396 (6.0); 8,394 (5.7); 8,392 (5.4); 7,938 (2.6); 7,917 (9.1); 7,903 (6.1); 7,899 (5.8); 7,881 (1.7); 7,877 (1.7); 7,669 (2.7); 7,653 (2.6); 7,647 (13.6); 7,636 (11.5); 7,615 (2.4); 7,482 (6.3); 7,468 (8.4); 7,395 (6.3); 7,394 (6.5); 7.3 81 (4.7); 7,380 (4.7); 7,257 (58.5); 7193 (20.3); 6,875 (1.0); 5,516 (16.0); 5,444 (0.8); 5,294 (2.7); 4,802 (5.7); 1:54

8 (9.3); 1,257 (0.5); 0.071 (0.7); 0.008 (0.8); 0,000 (23.9) - 0.008 (0.7)

Example 1-17: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,086 (3.1); 7,801 (2.1); 7,797 (2.0); 7,780 (2.6); 7,777 (2.5); 7,670 (4.8); 7,664 (4.8); 7,624 (3.2); 7,604 (2.6); 7,258 (14.5); 7.242 (0.7); 7.227 (0.8); 7.223 (0.9); 7.220 (0.9); 7.208 (1.0); 7.206 (1.0); 7.201 (0.8); 7.187 (0.8); 7.13 2 (7.8); 6,943 (1.1); 6,938 (1.1); 6,921 (1.0); 6,917 (1.7); 6,912 (1.1); 6,895 (1.0); 6,890 (0.9); 6,780 (3.0); 6,777 (. 3

0); 6,774 (3.0); 6,772 (2.8); 5,470 (5.7); 5,468 (5.9); 5,467 (5.5); 5,294 (14.4); 4,792 (2.9); 4,014 (8.8); 4,012 (16.0)

; 4,009 (8.5); 0,000 (6.2)

Example 1-18: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,385 (7.0); 8,383 (6.8); 7,925 (3.2); 7,903 (10.8); 7,888 (7.0); 7,884 (6.8); 7,867 (2.0); 7,863 (2.2); 7,592 (1.6); 7,576 (1.8); 7,571 (3.4); 7,555 (3.4); 7,550 (1.9); 7,534 (1.8); 7,474 (7.7); 7,460 (10.3); 7,388 (7.6); 7,387 (7.7); 7.3 75 (5.6) 7,774 (5.5), 7,257 (75.6), 7,169 (24.4), 6,929 (1.3), 6,926 (1.3), 6,923 (1.6), 6,920 (1.6), 6,908 (2.2), 6,906 (2.2), 6,901 (2.8) 6,899 (2.9), 6,887 (1.5), 6,884 (3.3), 6,878 (2.9), 6,861 (3.0), 6,859 (3.0), 6,855 (2.1), 6,852 (2.3), 6,848 (1.1), 6,836 (2.5) ; 6,830 (2.0); 5,484 (16.0); 5,415 (0.6); 5,295 (8.2); 4,781 (6.5); 1,550 (16.9); 0.008 (0.9) 0

■ 000 (4.28) - 0008 (0.8)

Example 1-19: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8.386 (4.4), 8.383 (4.2), 8.382 (4.0), 7.930 (1.3), 7.928 (2.3), 7.926 (1.3), 7.908 (4.1), 7.907 (7.2), 7.905 (4.1), 7.890 (4.4); 7,886 (4.2); 7,869 (1.3); 7,865 (1.4); 7,476 (4.8); 7,462 (7.1); 7,457 (5.6); 7,456 (4.7); 7,452 (2.0); 7,441

(2.5), 7.435 (8.7), 7.430 (1.4), 7.391 (4.8), 7.390 (5.0), 7.377 (4.8), 7.371 (11.2), 7.366 (3.1), 7.355 (2.4), 7.350 (6.

6), 7,344 (0.8), 7,263 (0.5), 7,262 (0.6), 7,262 (0.8), 7,257 (52.0), 7,173 (15.7), 5,426 (16.0), 5,294 (7.4), 4,785 (4.0

) 1,556 (2.1); 0,008 (0.6); 0.000 (6.19) - 0008 (0.6)

Example 1-20: ¹ H-NMR (400.0 MHz, CDC13):

8.165 (7.1), 8.160 (7.1), 8.159 (6.6), 7.847 (4.6), 7.842 (4.4), 7.825 (5.2), 7.820 (5.0), 7.654 (0.7), 7.647 (0.8); 7,642 (10.0); 7,637 (9.9); 7,536 (4.8); 7,534 (6.2); 7,532 (4.7); 7,518 (1.0); 7,514 (4.1); 7,512 (5.5); 7.51 0 (4.0); 7,269 (0.6); 7,269 (0.6); 7,268 (0.7); 7,267 (0.8); 7,266 (0.9); 7,265 (1.1); 7,265 (1.4); 7,264 (1.6); 7,263 (. 2

1), 7.262 (2.8), 7.259 (115.9), 7.256 (1.7), 7.255 (1.1), 7.254 (0.8), 7.253 (0.6), 7.252 (0.5), 7.209 (0.8), 7.156 (0.5), 7.114 ( 30.2); 6,995 (0.6); 6,807 (7.8); 6,805 (7.9); 6,802 (7.8); 6,799 (7.5); 6,750 (0.6); 6,742 (1.0); 6,734 (5.3);. 6 728 (0.8), 6,716 (6.7), 6,712 (6.8), 6,700 (0.9), 6,694 (5.2), 6,691 (2.3), 6,686 (1.0), 5,489 (16.0), 5,297 (4.9), 4,755 (6.0); 4,130 (0.6); 4,112 (0.6); 3,636 (0.5); 3,476 (0.8); 2,043 (2.8); 1,551 (9.0); 1,282 (0.5); 1,276 (1.0); 1,258 (2.7)

; 1.240 (1.0), 0.938 (0.6), 0.920 (1.4), 0.902 (0.6), 0.008 (1.4), 0.000 (53.4), - 0.008 (l.4)

Example 1-22: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,373 (1.6); 8,371 (1.6); 7,913 (0.7); 7,891 (2.2); 7,874 (1.6); 7,870 (1.5); 7,849 (0.5); 7,467 (1.7); 7,454 (2.3); 7,337 (1.7), 7.364 (1.3), 7.257 (7.6), 7.214 (0.6), 7.199 (0.6), 7.195 (0.5), 7.153 (4.0), 6.936 (0.6), 6.931 (0.6), 6.914 (0.6), 6.910 (1.0); 6,905 (0.6); 6,888 (0.5); 6,883 (0.5); 5,471 (3.4); 5,293 (16.0); 4,794 (1.8); 4,009 (4.9); 4,007 (8,5); 4,004 (5.0) ; 1,256 (0.5); 0,000 (3.2) Example 1-23: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,105 (1.8), 8,103 (2.5), 8,101 (3.3), 8,100 (2.4), 8,097 (1.7), 7,819 (2.6), 7,815 (2.4), 7,799 (3.2), 7,795 (3.1), 7

.684 (5.1); 7,678 (5.0); 7,645 (3.1); 7,644 (3.1); 7,625 (2.5); 7,624 (2.4); 7,338 (0.7); 7,337 (0.7); 7,320 (0.7); 7,318

(0.7); 7,269 (0.5); 7,267 (0.7); 7,266 (0.8); 7,259 (74.4); 7,255 (0.5); 7,209 (0.5); 7,168 (11.6); 7,041 (0.5); 7,036 (0

.5); 7,024 (0.6); 7,018 (1.1); 7,012 (0.7) 7,000 (0.7); 6,995 (1.5); 6,794 (3.2); 6,791 (3.4); 6,788 (3.2); 6,786 (3.2); 5

■ 491 (5.2); 5,489 (5.7); 5,488 (5.0); 5,298 (0.6); 4,788 (2.4); 1,538 (16.0); 0008 (1.0); 0,000 (32.3) - 0.008 (0.9)

Example 1-24: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8.164 (7.2), 8.160 (7.3), 7.850 (4.5), 7.846 (4.3), 7.829 (5.1), 7.824 (4.9), 7.646 (9.8), 7.640 (9.8), 7.586 (1.7), 7.570 (1.8); 7.565 (3.5); 7.549 (3.5); 7.544 (2.3); 7.541 (4.7); 7.539 (6.5); 7.528 (1.9); 7.517 (5.8); 7.258 (75.8); 7.12 0 (21.7); 6,924 (1.3), 6,924 (1.3), 6,921 (1.6), 6,918 (1.7), 6,906 (2.2), 6,904 (2.2), 6,897 (3.0), 6,885 (1.4), 6,882 (3 .3), 6,876 (2.8 6,859 (2.9), 6,857 (2.9), 6,853 (2.1), 6,850 (2.3), 6,834 (2.5), 6,828 (2.0), 6,808 (6.9), 6,805 (7.0), 6 ■ 802 (7.0), 6,800 (6.7); 5,477 (16.0); 5,295 (2.5); 4,768 (6.3); 1,555 (18.5); 0008 (0.8); 0,000 (27.3) - 0.008 (0.8) example 1-25: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8.487 (4.4), 8.485 (8.0), 8.484 (8.6), 8.482 (8.5), 8.480 (4.4), 7.892 (2.6), 7.888 (2.3), 7.871 (10.9), 7.868 (11.3)

; 7,859 (10.9); 7858 (10.9); 7,838 (2.4); 7,837 (2.2); 7,517 (0.9); 7,513 (13.7); 7,506 (0.5); 7,499 (15.9); 7,353 (7.8)

; 7,351 (7.8); 7,339 (6.7); 7,337 (6.6); 7,267 (0.6); 7,266 (0.6); 7,266 (0.8); 7,265 (0.9); 7,264 (1.1); 7,263 (1.3); 7.2

58 (91.8); 7,255 (2.8); 7,254 (2.0); 7,253 (1.6); 7,252 (1.2); 7,252 (1.0); 7,251 (0.8); 7,250 (0.7); 7,249 (0.6); 7,248 (

0.5); 7,248 (0.5); 7,208 (0.7); 7,184 (26.0); 5,542 (9.0); 5,538 (16.0); 5,534 (9.1); 5,296 (8.1); 4,799 (6.8); 2,044 (. 1

6); 1.550 (12.3); 1,276 (0.6); 1,258 (1.5); 1,240 (0.6); 0.008 (1.3); 0.006 (0.5), 0.005 (0.6); 0,000 (40.9); -

0003 (2.0); - 0004 (0.8); - 0005 (0.6); - 0008 (1.2)

Example 1-26: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,110 (1.7), 8,108 (2.4), 8,106 (3.3), 8,105 (2.4), 8,102 (1.6), 7,821 (2.6), 7,818 (2.5), 7,801 (3.3), 7,797 (3.1), 7,681 (5.1); 7.676 (5.1); 7.642 (3.1); 7.641 (3.1); 7.622 (2.5); 7.620 (2.5); 7.518 (0.8); 7.512 (2.2); 7.507 (0.8); 7.499 (2.3); 7.496 (1.2); 7,490 (2.5); 7,482 (0.9); 7,477 (2.4); 7,269 (0.8); 7,268 (0.9); 7,266 (1.2); 7,259 (114.2); 7,255 (1 .0); 7,254 (0.7) ; 7,209 (0.6); 7,158 (11.5); 7,101 (2.9); 7,096 (0.9); 7,085 (1.0); 7,079 (5.4); 7,074 (0.9); 7,063 (0.9); 7,057 (2.6); 6,995 (0.6); 6,792 (3.4); 6,789 (3.3); 6,786 (3.4); 6,784 (3.2); 5,426 (8.6); 4,769 (2.3); 1,536 (16.0); 0.0

08 (1.4); 0000 (51.6) - 0008 (1.5)

Example 1-27: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,107 (2.3), 8,105 (3.3), 8,103 (4.2), 8,102 (3.2), 8,099 (2.0), 7,836 (3.1), 7,832 (2.9), 7,816 (3.8), 7,812 (3.6), 7,685 (6.2), 7.679 (6.1), 7.651 (4.0), 7.650 (3.8), 7.631 (3.2), 7.630 (3.1), 7.510 (0.8), 7.494 (0.8), 7.489 (0.9), 7.485 (0.9), 7.472 7,468 (0.9), 7,463 (0.8), 7,446 (0.8), 7,259 (65.7), 7,176 (13.5), 7,008 (1.0), 6,992 (1.1), 6,985 (1: 3), 6,969 (1.3) ; 6,961 (1.0); 6,944 (1.0); 6,794 (3.9); 6,792 (4.0); 6,789 (3.9); 6,786 (3.7); 5,458 (7.8); 5,298 (1.1); 4

■ 798 (3.2); 1,540 (16.0); 0008 (0.9); 0,000 (28.3) - 0.008 (0.8)

Example 1-28: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8.102 (1.6); 8,100 (2.4); 8,098 (3.0); 8,097 (2.4); 8,095 (1.5); 7,813 (2.3); 7,809 (2.2); 7,793 (2.7); 7,789 (2.7); 7

.676 (4.8); 7,670 (4.8); 7,634 (3.0); 7,633 (2.9); 7,613 (2.4); 7,612 (2.3); 7,264 (0.5); 7,259 (31.1); 7,246 (0.7); 7.23

2 (0.8); 7,228 (0.8); 7,226 (0.8); 7,225 (0.8); 7,213 (0.8); 7,210 (0.9); 7,206 (0.8); 7,192 (0.8); 7,150 (9.5); 6,947 (. 1

1); 6,942 (1.1); 6,925 (1.0); 6,920 (1.6); 6,916 (1.1); 6,899 (0.9); 6,894 (0.9); 6,786 (3.0); 6,784 (3.1); 6,781 (3.0);. 6

778 (3.0); 5,473 (5.1); 5,471 (5.2); 5,469 (5.0); 5,297 (0.7); 4,783 (2.5) 4,018 (8.7); 4,015 (16.0) 4,012 (8.6); 1552

(3.0); 0,000 (13.6)

Example 1-29: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8.397 (4.9), 7.971 (2.2), 7.950 (8.2), 7.937 (2.8), 7.933 (5.0), 7.930 (2.7), 7.912 (1.5), 7.908 (0.9), 7.518 (2.4), 7.498 (4.2); 7.494 (6.8); 7.485 (4.6); 7.480 (9.7); 7.476 (4.9); 7.468 (1.7); 7.463 (4.3); 7.414 (5.8); 7.402 (3.9); 7.259 (419.7); 7.250 (0.9); 7,102 (0.7); 7,095 (5.5); 7,090 (1.7); 7,078 (1.7); 7,073 (10.0); 7,068 (1.8); 7,057 (1.6); 7,051 (

4.8), 6.675 (2.2), 5.412 (16.0), 4.876 (4.1), 1.532 (135.8), 1.264 (0.8), 0.882 (1.6), 0.865 (0.6), 0.146 (0.6), 0.008 (5

■ l); 0.000 (171.1); - 0.008 (4.6)

Example 1-30: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,102 (3.9), 8,101 (4.9), 8,099 (3.8), 7,818 (3.6), 7,814 (3.4), 7,798 (4.4), 7,794 (4.3), 7,680 (7.9), 7.675 (7.8), 7,640 (5.0), 7.639 (4.8), 7.620 (3.9), 7.466 (0.7), 7.461 (5.2), 7.460 (4.4), 7.455 (1.9), 7.444 (2.5), 7.439 (8.3), 7.433 (1.2), 7.381 (1.7); 7,375 (10.8); 7,370 (2.8); 7,359 (2.3); 7,354 (6.0); 7,348 (0.6); 7,258 (59.4); 7153 (13.9); 6.790 (

4.78), 6.787 (5.0), 6.784 (4.9), 6.782 (4.6), 5.423 (16.0), 5.296 (11.6), 4.779 (3.9), 1.544 (8.7), 0.008 (1.0), 0.000 (28 ■ 0); -0.008 (0.7) Example 1-31: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,179 (4.6); 8,176 (4.5); 7,866 (2.8); 7,861 (2.7); 7,844 (3.1); 7,840 (3.0); 7,654 (5.6); 7,648 (5.6); 7,552 (4.0); 7,530 (3.4); 7.518 (2.0); 7.458 (5.4); 7.442 (2.3); 7.437 (8.2); 7.379 (1.6); 7.373 (9.9); 7.368 (2.7); 7.357 (2.3); 7.352 (5.8); 7.292 (0.5), 7.259 (339.7), 7.251 (1.2), 7.247 (0.5), 7.209 (0.7), 7.144 (14.7), 7.037 (0.6), 6.995 (1.9), 6.820 (4.1), 6.818 (4.5), 6.815 (4.5); 6,812 (4.3); 5,422 (16.0); 4,765 (4.0); 1,532 (55.4); 1,370 (0.8); 1,333 (1.7); 1,284 (. 2

5), 1.256 (1.3), 0.008 (4.3), 0.000 (132.2), - 0.008 (3.8)

 Example 1-32: 'H-NMR ^ OO.O MHZ, CDC13):

8,485 (7.4); 8,483 (7.0); 8,481 (3.7); 7,887 (2.9); 7,884 (2.7); 7,866 (9.1); 7,862 (9.2); 7,848 (9.4); 7,847 (9.4); 7.827 (2.9); 7.826 (2.7); 7.517 (0.5); 7.503 (13.0); 7.489 (15.1); 7.346 (7.2); 7.344 (7.1); 7.332 (6.1); 7.3.30 (6.0); 7,258 (84.1); 7,254 (0.6); 7,208 (0.6); 7,159 (21.9); 6,755 (0.6); 6,746 (1.1); 6,738 (5.3); 6,733 (0.8); 6,720 (6.6); 6,717 (6.6); (0.008; 6,704 (0.8); 6,698 (5.1); 6,691 (1.0); 5,498 (16.0); 5,296 (10.0); 4,774 (6.2); 1,555 (10.4)

1.0) 0.000 (37.4) - 0.008 (1.0)

Example 1-33: ¹ H-NMR (400.0 MHz, CDC13):

δ = 7,942 (3.2), 7,925 (3.3), 7,921 (3.7), 7,905 (3.5), 7,715 (7.7), 7,710 (7.8), 7,528 (3.9), 7,518 (5.4), 7,444 (6.2), 7,423 (5.8); 7,365 (1.9); 7,357 (2.2); 7,334 (4.8); 7,325 (7.4); 7,322 (7.2); 7,320 (4.8); 7,314 (3.0); 7,310 (4.8); 7292

(1.0), 7,290 (1.8), 7,282 (1.3), 7,259 (985.9), 7,250 (2.4), 7,237 (0.8), 7,224 (1.5), 7,209 (0.8), 6,995 (5.4), 6,837 (4 .0) ; 6,832 (4.0); 6,829 (4.3); 6,824 (3.9); 5,428 (16.0); 4,871 (1.9); 1,534 (20.7); 0.331 (0.8); 0.157 (1.2); 0146 (1.0

); 0.008 (11.2); 0.000 (368.4) - 0.008 (9.8) - 0.035 (0.8) - 0.150 (1.0)

Example 1-34: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8.173 (2.7), 8.169 (4.8), 8.166 (2.8), 7.899 (1.7), 7.895 (3.2), 7.891 (1.7), 7.878 (1.9), 7.873 (3.5), 7.869 (1.8); 7

.664 (7.1); 7,658 (7.0); 7,586 (3.3) 7,584 (4.8); 7,582 (3.5) 7,564 (3.0); 7,562 (4.2) 7,560 (3.0); 7,492 (3.9); 7486

(1.6); 7,478 (4.1); 7,477 (3.3); 7,475 (2.3); 7,473 (2.2); 7,470 (4.5); 7,462 (1.7); 7,456 (4.3); 7,449 (0.5); 7,258 (60th

4); 7,098 (0.6); 7,091 (5.3); 7,086 (1.6); 7,074 (1.8); 7,069 (9.8); 7,064 (1.8); 7,053 (1.7); 7,047 (4.7); 6,833 (5.5);. 6

831 (5.6); 6,828 (5.6); 6,825 (5.4); 5,404 (16.0); 5,295 (4.7); 4,864 (4.0); 1,547 (10.3); 0008 (0.7); 0,000 (24.2); -

0.008 (0.7)

Example 1-35: ¹ H-NMR (400.0 MHz, CDC13):

δ = 7,694 (0.6), 7,689 (0.6), 7,258 (12.0), 7,177 (1.5), 7,156 (1.5), 6,475 (2.1), 6,470 (2.2), 6,462 (1.6), 6,456 (0.7); 6,442 (1.2); 6,436 (0.9); 5,432 (1.4); 4,620 (1.8); 4,605 (1.8); 3,850 (3.4); 3,844 (14.9); 3,813 (3.7); 3,807 (16.0), 3.

780 (0.7); 3,663 (0.6); 2,118 (0.6); 1,559 (0.7); 0,000 (5.1)

Example 1-36: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,174 (5.7); 8,170 (5.7); 7,862 (3.6); 7,858 (3.4); 7,841 (4.1); 7,836 (4.0); 7,666 (2.9); 7,652 (9.4); 7,646 (16.0); 7,631 (10.2); 7,610 (2.4); 7,552 (3.6); 7,551 (5.0); 7,549 (3.4); 7,531 (3.2); 7,529 (4.3); 7,258 (42.9); 7.142 (17.1); 6 .813 (5.5 ); 6,810 (5.6); 6,807 (5.5); 6,805 (5.1); 5,509 (15.1); 5,295 (2.7); 4,791 (5.3); 2,043 (0.9); 1,558 (4.7); 1.25

7 (0.8); 0.008 (0.6); 0,000 (19.4) - 0.008 (0.6)

Example 1-37: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8.199 (8.3), 8.195 (8.2), 7.886 (5.4), 7.881 (5.2), 7.864 (6.1), 7.859 (5.8), 7.836 (3.8), 7.816 (4.4), 7.752 (0.6), 7.712 (4.0); 7.692 (4.6); 7.660 (0.7); 7.651 (11.2); 7.646 (11.2); 7.605 (2.1); 7.586 (4.2); 7.567 (2.4); 7.553 (5.1); 7.5.51 (7.3); 7,550 (5.1); 7,532 (4.4); 7,530 (6.4); 7,528 (4.5); 7,517 (0.6); 7,460 (2.5); 7,441 (4.0); 7,421 (1.6); 7,258 (9 1.3); 7,208 (0.8) ; 7,149 (28.2); 6,817 (8.3); 6,814 (8.5); 6,811 (8.3); 6,809 (8.0); 5,672 (16.0); 5,296 (4.4); 4,786 (. 7

4); 1,920 (0.5); 1,902 (0.5); 1,554 (3.6); 1,282 (0.5); 1,256 (1.3); 0.008 (1.2); 0,000 (38.2) - 0.008 (1.1)

 Example 1-38: 'H-NMR ^ OO.O MHZ, CDC13):

δ = 8.198 (4.5), 8.194 (4.6), 7.874 (2.7), 7.869 (2.6), 7.852 (3.1), 7.848 (3.0), 7.648 (5.7), 7.642 (5.7), 7.549 (7.5), 7.528 (3.4); 7,382 (0.8); 7,378 (0.9); 7,369 (2.0); 7,367 (1.9); 7,359 (1.9); 7,355 (2.0); 7,349 (0.6); 7,345 (0.7); 7,341 (0.6); 7,334 (0.6); 7,330 (0.7); 7,324 (7.4); 7,322 (6.7); 7,320 (4.7); 7,314 (2.7); 7,310 (4.4); 7,309 (4.3); 7,258 (49th

6) 7,143 (13.3), 6,819 (4.0), 6,817 (4.3), 6,814 (4.3), 6,811 (4.1), 5,432 (16.0), 5,296 (1.4), 4,779 (4.1), 1,547 (2.6)

; 1,371 (0.5); 1,333 (0.5); 1,285 (0.7); 1,282 (0.8); 1,256 (0.6); 0.008 (0.6); 0,000 (19.1) - 0.008 (0.6)

Example 1-39: ¹ H-NMR (400.0 MHz, CDC13):

δ = 9,045 (0.6), 9,039 (16.0), 8,625 (5.5), 8,621 (5.5), 8,179 (4.5), 8,178 (4.6), 8,157 (6.0), 8,156 (6.0), 8,023 (5.0); 8,018 (4.9); 8,001 (3.8); 7,997 (3.8); 7,588 (1.2); 7,572 (1.3); 7,568 (2.5); 7,551 (2.4); 7,546 (1.5); 7,530 (1.2); 7.51 8 (1.0) ; 7,259 (167.7); 7,199 (16.9); 6,995 (1.0); 6,938 (1.0); 6,935 (1.0); 6,931 (1.1); 6,929 (1.2); 6,915 (1.6); 6,908

(2.1); 6,896 (1.0), 6,892 (2.2), 6,887 (1.9), 6,870 (2.0), 6,868 (2.0), 6,861 (1.6), 6,845 (1.7), 6,839 (1.4), 5,489 (11.4) ; 5297 (1.5); 4,833 (4.1) 4,027 (0.7); 1,557 (8.4); 1,333 (2.2); 1,283 (3.0); 1,256 (2.6); 0880 (0.5), 0008 (2.0); 0th 000 (62.9) - 0008 (1.8) Example 1-40: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,414 (4.5); 8,411 (3.8); 7,937 (1.1); 7,916 (7.0); 7,910 (5.5); 7,906 (5.0); 7,889 (0.8); 7,885 (0.8); 7,552 (3.7); 7,550 (3.6); 7,548 (3.0); 7,476 (4.7); 7,462 (6.9); 7,403 (5.2); 7,389 (3.8); 7,383 (1.0); 7,379 (0.8); 7,374 (2.0); 7,372 (1.9); 7,364 (2.0), 7.360 (1.9), 7.354 (0.6), 7.350 (0.6), 7.344 (0.6), 7.336 (0.6), 7.332 (0.6), 7.326 (7.6), 7.324 (6.5), 7.322 (4.6), 7.317 (3.1); 7,313 (4.5); 7,312 (4.8); 7,257 (59.6); 7191 (12.6); 5,439 (16.0); 5,295 (3.3); 4,794 (4.0);

1,546 (4.9); 0.008 (0.7); 0,000 (22.5) - 0.008 (0.6)

Example 1-41: ¹ H-NMR (400.0 MHz, CDC13):

δ = 9,039 (15.2), 8,644 (5.2), 8,640 (5.2), 8,183 (4.4), 8,182 (4.3), 8,162 (5.8), 8,161 (5.7), 8,034 (4.8), 8,029 (4.7); 8,012 (3.6); 8,008 (3.6); 7,518 (0.6); 7,389 (1.2); 7,374 (1.3); 7,368 (3.1); 7,354 (2.4); 7,348 (2.2); 7,334 (1.8); 7.27 5 (5.0) 7.268 (2.9), 7.259 (109.3), 7.252 (2.3), 7.245 (1.9), 7.210 (16.1), 7.068 (0.9), 7.065 (1.0), 7.062 (0.9), 7.059 (0.9), 7.045 (1.7) 7.040 (1.6); 7.023 (0.8); 7.019 (0.8); 7.017 (0.7); 6.995 (0.6); 5,462 (16.0); 5,297 (2.4); 4,846 (4,3); 4,026 (0.5); 3,155 (3) 0.7); 1,559 (4.0); 1.371 (0.6); 1,334 (1.7); 1,286 (1.1); 1,282 (2.5); 1,256 (2.2); 0,008 (1.2); 0th

000 (39.4) - 0008 (1.2)

Example 1-42: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8.494 (6.8); 7.979 (2.4); 7.975 (4.3); 7.971 (2.4); 7.958 (4.1); 7.954 (7.3); 7.950 (4.2); 7.901 (8.7); 7.881 (4.9); 7

.583 (1.7); 7,567 (1.9); 7,562 (3.6); 7,547 (15.7); 7,541 (2.5); 7,534 (15.4); 7,525 (1.9); 7,517 (2.9); 7,377 (7.4); 7.3

75 (7.5); 7,364 (6.3); 7,362 (6.4); 7,259 (500.2); 7,251 (1.6); 7,208 (0.6); 6,994 (2.7); 6,935 (1.3); 6,932 (1.4); 6,929

(1.8); 6,926 (1.6); 6,912 (2.2); 6,905 (2.9); 6,888 (3.9); 6,884 (2.1); 6,863 (3.0); 6,857 (2.3); 6,841 (2.5) 6,835 (2.0)

; 5,470 (16.0); 4,881 (5.9); 1,529 (134.3); 1,306 (0.8); 1,265 (3.3); 0.899 (1.8); 0.882 (6.6); 0.864 (2.4); 0.146 (0.6);

0.008 (6.1) 0.000 (203.7) - 0.008 (5.4) - 0.150 (0.7)

Example 1-43: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,109 (1.3), 8,107 (1.9), 8,106 (2.6), 8,104 (1.9), 8,102 (1.3), 7,822 (2.0), 7,818 (2.0), 7,801 (2.5), 7,798 (2.4), 7,681 (4.0), 7,676 (4.0), 7,642 (2.4), 7,641 (2.4), 7,622 (2.0), 7,620 (1.9), 7,601 (0.5), 7,585 (0.5), 7,580 (1.0), 7,564 (1.0), 7,559 (0.6); 7,543 (0.5); 7,518 (0.5); 7,259 (91.0); 7,209 (0.6); 7,161 (9.0); 6,919 (0.6); 6,910 (0.8); 6,892 (0th

6,888 (0.9); 6,862 (0.8); 6,858 (0.6); 6,856 (0.7); 6,840 (0.7); 6,834 (0.6); 6,791 (2.6); 6. 789 (2.6); 6,786 (2.5) 6,783 (2.4); 5,483 (4.8); 5,298 (3.2) 4,773 (1.8); 1,536 (16.0) 0,008 (1.1); 0,000 (38.0); -

0.008 (1.1)

Example 1-44: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,540 (1.3); 8,538 (2.3); 8,536 (2.4); 8,534 (2.3); 8,532 (1.2); 7,932 (1.4); 7,928 (1.3); 7,911 (2.8); 7,907 (2.8); 7

.874 (2.6); 7,872 (2.6); 7,853 (1.3); 7,667 (0.9); 7,661 (0.8); 7,660 (0.9); 7,652 (0.6); 7,650 (0.6); 7,649 (0.8); 7,643

(1.0); 7,518 (0.6); 7,514 (4.0); 7,501 (4.7); 7,431 (1.1); 7,426 (0.7); 7,423 (0.6); 7,415 (1.2); 7,413 (1.1); 7,408 (1.5)

; 7,361 (2.2); 7,359 (2.2); 7,347 (1.8); 7,345 (1.8); 7,329 (0.5); 7,315 (1.8); 7,310 (1.5); 7,308 (1.7); 7,300 (4.4); 7.2

92 (1.5); 7,289 (1.3); 7,284 (1.2); 7,270 (0.6); 7,269 (0.5); 7,268 (0.5); 7,267 (0.6); 7,266 (0.9); 7,265 (1.0); 7,265 (1

.1); 7,264 (1.3); 7,263 (1.6); 7,259 (88.5); 7,256 (1.4); 7,255 (0.8); 7,254 (0.6); 7,209 (0.7); 7,205 (8.2); 6,995 (0.5);

5,589 (7.4); 5,588 (7.4); 4,791 (1.8); 2,044 (0.6); 1,538 (16.0); 1,326 (0.5); 1,258 (0.6); 0.882 (0.8); 0.008 (1.1); 0.0

00 (39.3) - 0.008 (1.0)

Example 1-45: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,494 (3.5); 8,492 (3.9); 7,978 (1.5); 7,974 (2.5); 7,969 (1.4); 7,957 (2.6); 7,952 (4.4); 7,948 (2.5); 7,903 (5.3); 7,902 (5.3), 7,882 (3.0), 7,880 (2.8), 7,547 (7.5), 7,534 (8.6), 7,457 (0.6), 7,451 (4.9), 7,450 (4.1), 7,446 (1.8), 7,435 (2.3), 7,429 (8.2) 7,424 (1.2); 7,380 (2.0); 7,377 (5.6); 7,375 (13.9) 7,369 (3.0); 7,364 (4.0); 7,362 (4.0); 7358 (second

3), 7,353 (5.9), 7,347 (0.6), 7,257 (61.5), 5,412 (16.0), 5,295 (3.4), 4,884 (3.6), 1,536 (16.5), 0.008 (0.8), 0.000 (26.

6); -0.008 (0.7)

Example 1-46: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,495 (7.0), 8,493 (7.7), 8,491 (7.4), 7,899 (2.4), 7,896 (2.2), 7,878 (8.9), 7,875 (9.1), 7,864 (10.3), 7,863 (10.3)

; 7,843 (2.6); 7,515 (13.5); 7501 (16.0); 7,357 (7.8); 7,355 (8.2); 7,347 (1.5); 7,343 (6.8); 7,342 (7.0); 7,333 (1.9); 7

(1.8) .332; 7,325 (1.3); 7,321 (1.2); 7,315 (1.8); 7,313 (1.9); 7,307 (1.2); 7,299 (1.1); 7,293 (1.2); 7,267 (0.7); 7,258

(96.6) 7,254 (0.6); 7,209 (0.7); 7,188 (20.4); 7,038 (1.4); 7,032 (1.4); 7,020 (1.4); 7,015 (3.0); 7,009 (1.8); 6,997 (1

.8); 6,994 (1.4); 6,992 (2.8); 6,986 (1.4); 6,974 (1.2); 6,969 (1.2); 5,495 (14.1); 5,493 (15.4); 5492 (13.9); 4,802 (. 6

4); 1.555 (14.8); 0.008 (1.2); 0.000 (43.6); - 0.008 (1.1)

Example 1-47: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,176 (4.3), 7,902 (2.5), 7,880 (2.6), 7,669 (7.4), 7,664 (7.3), 7,590 (4.1), 7,569 (3.6), 7,518 (3.4), 7,445 (5.5), 7,429 (2.7); 7.423 (9.7), 7.375 (2.0), 7.370 (13.4), 7.364 (3.4), 7.353 (2.9), 7.348 (7.2), 7.292 (0.7), 7.271 (2.1), 7.26 8 (2.7); 7.266 (4.2), 7.265 (4.6), 7.259 (626.6), 7.251 (2.5), 7.251 (2.2), 7.250 (1.8), 7.247 (1.2), 7.244 (0.8), 7.228 (0.7), 6.995 (3.4); 6,841 (5.1), 6,838 (5.2), 6,835 (5.1), 6,833 (5.0), 5,405 (16.0), 4,870 (4.0), 1,530 (136.4), 0.146 (0 ■ 7), 0.008 (7.4), 0.000 (239.8 ) - 0.008 (6.4); - 0150 (0.7) Example 1-48: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,178 (4.0), 8,175 (7.1), 8,171 (4.1), 7,904 (2.4), 7,899 (4.4), 7,895 (2.5), 7,882 (2.8), 7,878 (5.1), 7,874 (2.7), 7 .666 (10.3); 7,660 (10.4); 7,588 (4.9); 7,586 (7.0); 7,584 (5.0); 7,572 (1.8); 7,566 (4.4); 7,564 (6.1); 7,562 (4.4); 7.5 56 (1.8); 7,551 (3.5); 7,530 (2.1); 7,518 (2.1); 7,514 (2.0); 7,259 (349.6); 6,995 (1.9); 6,926 (1.4); 6,923 (1.4); 6,920 (1.7); 6,917 (1.8), 6,903 (2.3), 6,896 (3.2), 6,883 (3.4), 6,877 (2.9), 6,861 (3.1), 6,858 (3.1), 6,852 (2.4), 6,836 (10.5), 6,834 (8.8); 6,831 (9.4); 6,828 (8.8); 5,461 (16.0); 4,867 (5.6); 4,130 (0.8); 4,113 (0.8); 2,043 (3.6); 1

■ 598 (2.2); 1.276 (l.l); 1.258 (2.3); 1.240 (l.l); 0.008 (3.9); 0.000 (134.4); - 0.008 (4.0)

Example 1-49: ¹ H-NMR (400.0 MHz, CDC13):

δ = 7,897 (2.7); 7,881 (2.8); 7,876 (3.1); 7,860 (2.9); 7,710 (7.0); 7,705 (7.1); 7,518 (0.5); 7,446 (5.0); 7,441 (2.0); 7,428 (8.2); 7,425 (9.0); 7,419 (1.4); 7,408 (5.6); 7,373 (1.6); 7,367 (10.4); 7,362 (2.8); 7,350 (2.1); 7,346 (5.9); 7,34 0 (0.7); 7,300 (6.3), 7,296 (6.5), 7,259 (90.1), 6,995 (0.5), 6,832 (3.5), 6,826 (3.8), 6,824 (3.9), 6,818 (3.4), 5,413 (1 6.0), 5,297 (1.2) ; 4,830 (3.2); 1,561 (0.9); 1,476 (0.6); 1,432 (2.8); 1,428 (1.0); 1,255 (0.6); 0.070 (2.0); 0.008 (1.0);

0.000 (34.0); - 0.008 (l .l)

Example 1-50: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,521 (2.5); 8,519 (4.4); 8,517 (4.8); 8,515 (4.5); 8,513 (2.4); 7,916 (2.4); 7,912 (2.3); 7,895 (5.5); 7,891 (5.5); 7

.865 (5.6); 7,864 (5.6); 7,844 (2.4); 7,843 (2.2); 7,554 (1.6); 7,552 (2.9); 7,550 (3.6); 7,548 (3.6); 7,546 (2.9); 7,544

(1.6); 7,510 (7.9); 7,496 (9.4); 7,390 (0.9); 7,386 (0.9); 7,379 (2.3); 7,376 (1.8); 7,373 (1.2); 7,371 (0.8); 7,368 (2.0)

; 7,366 (1.4); 7,364 (2.0); 7,357 (0.8); 7,354 (4.8); 7,352 (4.7); 7,349 (0.7); 7,346 (0.9); 7,340 (3.9); 7,338 (4.2); 7.3

34 (0.6); 7,329 (6.4); 7,327 (8.0); 7,324 (4.0); 7,318 (3.3) 7,316 (4.2) 7,314 (6.2); 7,262 (0.6); 7,262 (0.7); 7261 (0

.9); 7,260 (1.2); 7,257 (48.2); 7,253 (0.5); 7,187 (15.1); 5440 (16.0); 5,295 (2.2); 4,795 (3.9); 1,546 (1.7); 0.071 (. 5

4); 0.008 (0.7); 0,000 (22.7) - 0.008 (0.6)

Example 1-51: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8.137 (2.1); 7.906 (1.0); 7.903 (1.7); 7.899 (1.0); 7.886 (1.2); 7.882 (2.2); 7.878 (1.2); 7.714 (4.1); 7.708 (4.4); 7 .698 (0.9); 7,690 (3.0); 7,670 (2.3); 7,588 (2.1); 7,568 (2.5); 7,560 (0.6); 7,518 (1.8); 7,453 (7.1); 7,442 (3.3); 7,437 (4.2); 7,433 (9.3); 7,405 (0.7); 7,385 (10.6); 7,380 (11.7); 7,352 (0.6); 7,310 (0.7); 7,304 (1.9); 7,298 (2.0); 7,287 (7,9); 7,282 (8.3) 7.277 (3.0), 7.273 (1.8), 7.272 (2.0), 7.266 (9.0), 7.266 (7.6), 7.265 (6.7), 7.259 (319.4), 7.253 (6.3), 7.252 (5.7), 7.252 (4.9) 7.251 (4.3), 7.250 (4.2), 7.249 (3.9), 7.248 (3.6), 7.248 (3.5), 7.247 (3.4), 7.246 (3.3), 7.2 45 (3.2), 7.244 (3.0), 7.242 (2.8 7,241 (2.8), 7,231 (7.8), 7,209 (1.5), 6,995 (1.8), 6,974 (0.9), 6,970 (1.3), 6,825 (0 .5), 6,818 (2.9), 6,815 (2.8), 6,812 (3.2); 6,810 (3.0), 5,510 (8.5), 5,136 (0.6), 4,896 (2.2), 4,766 (15.6), 4,750 (16.0), 4,723 (0.8), 2,043 (0.5), 1,888 (6.0), 1,873 (12.3) 1,857 (6.1); 1,533 (79.6); 1,505 (2.3); 1,265 (1.3); 0.899 (0.7);

0.882 (2.3); 0.864 (0.9) 0.008 (4.2) 0.000 (140.3) - 0.008 (5.0) - 0.028 (3.2) - 0.050 (0.7)

Example 1-52: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,172 (3.8); 8,169 (6.6); 8,165 (3.9); 7,897 (2.2); 7,892 (4.3); 7,888 (2.4); 7,875 (2.6); 7,871 (4.7); 7,866 (2.5); 7,674 (0.8); 7.669 (1.2); 7.666 (1.2); 7.658 (9.6); 7.652 (9.6); 7.577 (4.7); 7.575 (6.3); 7.573 (4.5); 7.555 (4.0); 7.553 (5.8); 7.551 (4.0); 7.517 (0.7); 7.458 (0.5); 7.421 (0.5); 7.258 (105.9); 6.994 (0.6); 6.852 (0.6); 6.850 (0.6); 6.847 (0.6); 6.844 (0.6) 6,829 (7.2), 6,827 (7.3), 6,823 (7.4), 6,821 (7.0), 6,750 (0.6), 6,742 (1.1), 6,734 (5.5), 6,729 (1.4), 6,726 (1.3), 6,724 (6) 6.716 (7.1), 6.712 (7.2), 6.700 (1.0), 6.694 (5.2), 6.686 (1.4), 6.678 (0.6), 6.416 (0.8), 5.474 (16.0), 5.437 (0.9), 5.296 (6.1) 15.7); 5,045 (0.9); 5,011 (0.6); 4,853 (5.4); 1,539 (19.3); 0008 (1.4); 0,000 (45.3); -

0.008 (1.2)

Example 1-53: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,488 (4.8); 7,973 (1.7); 7,969 (2.9); 7,965 (1.6); 7,952 (3.0); 7,948 (5.1); 7,944 (2.9); 7,898 (6.2); 7,877 (3.5); 7,544 (8.9); 7,530 (10.3); 7,500 (4.0); 7,494 (1.6); 7,486 (4.2); 7,478 (4.4); 7,470 (1.7); 7,464 (4.3); 7,374 (5.2); 7.37 2 (5.1); 7,360 (4.5), 7,358 (4.4), 7,257 (56.1), 7,105 (0.6), 7,098 (5.4), 7,092 (1.6), 7,081 (1.8), 7,076 (10,0), 7,070 (1.8), 7,059 (1.6); 7,054 (4.8); 5,413 (16.0) 5,294 (5.2); 4,877 (4.2) 1,541 (3.3) 0,008 (0.7); 0,000 (24.3); -

0.008 (0.7)

Example 1-54: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,092 (2.0); 8,090 (2.9); 8,089 (3.7); 8,087 (2.8); 8,085 (1.9); 7,813 (2.8); 7,810 (2.6); 7,793 (3.5); 7,789 (3.4); 7,681 (5.5); 7,676 (5.5); 7,641 (3.6); 7,640 (3.5); 7,620 (2.9); 7,259 (72.1); 7,164 (12.2); 6,790 (3.5); 6,787 (3.5); 6.7 84 (3.4); 6,782 (3.3); 5,537 (4.1); 5,533 (7.1); 5,530 (3.9); 4,787 (3.0); 1,537 (16.0); 0008 (1.0); 0,000 (31.9); -

0.008 (0.9)

Example 1-55: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8.484 (5.8), 8.483 (5.2), 7.970 (2.2), 7.965 (3.6), 7.961 (2.1), 7.949 (3.6), 7.944 (6.3), 7.940 (3.6), 7.890 (7.3), 7.889 (7.4), 7,869 (4.3), 7,868 (4.2), 7,539 (11.4), 7,525 (13.2), 7,517 (0.6), 7,368 (6.4), 7,366 (6.4), 7,354 (5.5), 7.3 52 (5.5); 7,258 (109.2), 6,994 (0.6), 6,747 (1.0), 6,740 (4.9), 6,734 (0.8), 6,721 (6.2), 6,718 (6.2), 6,705 (0.8), 6,700 (4.8), 6,692 (1.0); 5,482 (14.4); 5,296 (16.0); 4,867 (5.1); 1,537 (32.2); 0008 (1.3); 0,000 (43.5) - 0.008 (1.2) Example 1-56: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,400 (6.7), 7,971 (3.0), 7,949 (11.7), 7,948 (6.9), 7,939 (4.1), 7,935 (7.2), 7,931 (3.7), 7,914 (2.0), and 7,578 (1.7); 7,561 (1.8); 7,557 (3.5); 7,541 (3.4); 7,535 (1.9); 7,518 (4.1); 7,493 (8.0); 7,479 (11.3); 7,414 (8.1); 7,400 (5.8); 7.3 82 (0.6) ; 7,342 (0.5); 7,259 (581.0); 7,228 (0.6); 7,210 (0.6); 6,995 (3.3); 6,925 (1.4); 6,922 (1.7); 6,919 (1.6); 6,905

(2.2); 6,899 (3.0), 6,885 (3.6), 6,878 (3.0), 6,860 (3.0), 6,854 (2.2), 6,838 (2.6), 6,832 (2.1), 5,468 (16.0), 4,878 (5.

8), 1.532 (172.4), 0.146 (0.6), 0.008 (7.2), 0.000 (237.4), - 0.008 (6.6), - 0.150 (0.7)

Example 1-57: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8.147 (2.3), 8.143 (2.3), 7.837 (1.2), 7.832 (1.2), 7.815 (1.4), 7.811 (1.4), 7.643 (2.6), 7.637 (2.6), 7.525 (1.9), 7.504 (1.6); 7,355 (2.4); 7,334 (3.0); 7,259 (31.3); 7,176 (2.9); 7,155 (2.3); 7,117 (5.5); 6,799 (2.0); 6,793 (2.0); 5.62

7 (9.2); 5,297 (4.9); 4,748 (2.5); 3,995 (16.0); 1,546 (4.3); 0,000 (9.9)

 Example 1-58: 'H-NMR ^ OO.O MHZ, CDC13):

δ = 8,027 (5.0); 8,011 (5.0); 7,660 (3.7); 7,635 (3.6); 7,505 (0.5); 7,437 (6.4); 7,423 (11.4); 7,421 (5.1); 7,417 (2.1); 7,406 (2.5), 7,401 (9.2), 7,395 (1.5), 7,360 (2.3), 7,357 (5.7), 7,355 (13.9), 7,349 (3.4), 7,344 (3.6), 7,342 (3.6), 7.3 38 (2.4) ; 7,333 (6.0); 7,327 (0.7); 7,266 (0.7); 7,265 (0.7); 7,258 (73.8); 5393 (16.0); 5,296 (4.3); 4,911 (3.8); 1,539

(22.9) 1,257 (0.6); 0.008 (0.9) 0.000 (30.6) - 0.008 (0.8)

Example 1-59: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,397 (6.1); 8,395 (6.4); 7,961 (2.5); 7,940 (11.1); 7,938 (6.6); 7,931 (4.2); 7,928 (7.0); 7,924 (3.7); 7,910 (0.9); 7,906 (1.6), 7,903 (0.9), 7,517 (1.4), 7,485 (7.4), 7,471 (10.7), 7,410 (7.5), 7,408 (7.9), 7,396 (5.3), 7,395 (5.4), 7.2 58 (243.0) ; 6,994 (1.3); 6,753 (0.6); 6,745 (1.1); 6,737 (5.4); 6,718 (6.8); 6,715 (6.9); 6,702 (0.9); 6,697 (5.3); 6,689

(l, l); 6,681 (0.5); 5,480 (16.0); 4,865 (5.6); 1,534 (96.9); 0.008 (3.0); 0.000 (97.0); - 0.008 (2.6)

Example 1-60: ¹ H-NMR (400.0 MHz, CDC13):

δ = 9,044 (11.9), 8,659 (3.7), 8,657 (4.1), 8,654 (4.0), 8,653 (3.9), 8,189 (3.4), 8,188 (3.5), 8,168 (4.5), 8,166 (4.6); 8,040 (3.9); 8,035 (3.9); 8,018 (3.0); 8,014 (3.0); 7,560 (1.3); 7,556 (3.0); 7,554 (2.8); 7,552 (2.5); 7,518 (1.1); 7.38 8 (0.7) ; 7,384 (0.7); 7,379 (0.5); 7,377 (1.0); 7,375 (1.6); 7,372 (1.6); 7,365 (1.8); 7,361 (1.8); 7,354 (0.7); 7,353 (0th

9), 7,351 (0.7), 7,346 (0.6), 7,341 (0.6), 7,336 (6.9), 7,334 (5.9), 7,332 (4.1), 7,326 (2.3), 7,323 (3.7), 7,321 (3.4), 7. 275 (0.5), 7.274 (0.5), 7.273 (0.6), 7.272 (0.6), 7.271 (0.7), 7.271 (0.8), 7.270 (0.9), 7.269 (1.0), 7.268 (1.2), 7.267 (1.3); 7,267 (1.5); 7,266 (1.8); 7,265 (2.1); 7,264 (2.7); 7,263 (3.6); 7,259 (199.4); 7,255 (3.2); 7,254 (2.1); 7,254 (. 1

4,253 (1.0), 7,252 (0.8), 7,251 (0.6), 7,250 (0.6), 7,234 (0.6), 7,230 (10.8), 7,226 (0.6), 6,995 (1.1), 5,447 (13.6), 4,888 (4) 2.0); 4,148 (1.1); 4,130 (3.4); 4,113 (3.4); 4,095 (1.1); 2,050 (0.6); 2,043 (16.0); 1,598 (0.6); 1,283 (0.7) -1. 276 (5.2); 1,258 (10.5); 1,241 (4.9); 0,008 (2.2); 0,006 (0.6); 0000 (81.2) - 0005 (1.0); - 0006 (0.8); - 0007 (0.7); -

0.008 (2.3)

Example 1-61: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,512 (1.5), 8,510 (2.7), 8,508 (2.9), 8,506 (2.7), 8,504 (1.4), 7,920 (1.1), 7,916 (1.0), 7,899 (3.6), 7,895 (3.7), 7,881 (3.5); 7,880 (3.5); 7,860 (1.0); 7,859 (1.0); 7,525 (4.8); 7,518 (0.6); 7,511 (5.6); 7,366 (2.7); 7,364 (2.6); 7,353

(2.3), 7.351 (2.2), 7.324 (0.5), 7.320 (0.6), 7.305 (0.5), 7.299 (0.6), 7.259 (83.1), 7.255 (0.7), 7.220 (9.6), 7.209 (0.

5); 5,488 (4.3); 5,487 (5.2); 5,485 (4.3); 4,823 (2.1); 1,543 (16.0); 0.008 (1.1); 0.004 (0.5); 0.002 (1.4); 0.000 (34.9)

; -0.008 (1.0)

Example 1-62: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8.226 (5.5), 8.222 (5.7), 8.196 (3.2), 8.193 (3.4), 8.175 (3.4), 8.172 (3.5), 7.961 (2.7), 7.942 (3.2), 7.916 (3.2), 7 .911 (3.2), 7.894 (3.6), 7.889 (3.6), 7.711 (1.8), 7.692 (3.4), 7.673 (2.4), 7.665 (6.8), 7.660 (6.5), 7.574 (5.0), 7.552 (4.0), 7.531 (1.9), 7.518 (3.5), 7.492 (1.4), 7.259 (521.2), 7.223 (0.9), 7.191 (15.3), 6.995 (2.8), 6.836 (5.1), 6.832 (4.8), 6.830 (4.8), 5.901 (16.0) 5,523 (1.0); 5,298 (1.9); 4,806 (5.2); 1,530 (124.6); 1,332 (0.8); 1,284 (1.2); 1,256 (1

■ 0), 0145 (0.7); 0,008 (6.5); 0000 (189.9) - 0,008 (5.8); - 0150 (0.7)

Example 1-63: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,199 (2.4), 8,195 (4.1), 8,192 (2.4), 7,926 (1.5), 7,922 (2.7), 7,918 (1.5), 7,905 (1.6), 7,900 (3.0), 7,896 (1.6), 7,671 (6.1); 7.666 (6.1); 7.597 (3.0); 7.595 (4.1); 7.593 (3.1); 7.576 (2.8); 7.573 (5.6); 7.572 (6.6); 7.551 (4.5); 7.517 (0.5); 7.440 (5.3), 7.435 (5.6), 7.290 (3.7), 7.284 (3.6), 7.269 (3.6), 7.264 (4.1), 7.258 (97.8), 7.252 (0.6), 6.994 (0, 5), 6.842 (4.9) 6.840 (5.0); 6.837 (4.9); 6.834 (4.8); 5.507 (16.0); 4.884 (3.6); 1.533 (21.7); 0.008 (1.3); 0.000 (44.2); - 0.008 (l.l) Example 1-64: ¹ H-NMR (400.0 MHz, CDC13):

δ = 9,071 (14.0), 9,036 (1.8), 8,585 (4.5), 8,242 (0.7), 8,237 (0.7), 8,231 (0.8), 8,222 (4.3), 8,201 (5.9), 8,200 (5.8); 8.132 (2.3), 8.127 (4.4), 8.123 (2.3), 8.110 (1.5), 8.106 (2.8), 8.101 (1.4), 7.833 (0.6), 7.828 (0.6), 7.807 (0.5), 7.51 8 (0.9) 7,447 (4.8), 7,442 (1.8), 7,431 (2.3), 7,426 (8.6), 7,420 (1.3), 7,382 (1.7), 7,376 (11.0), 7,371 (3.0), 7,360 (2 .2), 7,355 (7) 7.349 (0.9), 7.345 (1.7), 7.339 (0.8), 7.329 (1.4), 7.323 (7.3), 7.319 (1.9), 7.310 (5.4), 7.304 (1.0), 7.294 (0.6); 7,288 (1.5); 7,259 (160.5); 6,995 (0.9); 5,414 (16.0); 4,925 (3.7); 4,676 (6.1); 3,016 (1.3); 1,552 (2.7) -1.

370 (0.8); 1,286 (1.2); 1,255 (0.8); 0,008 (1.8); 0000 (59.7) - 0008 (1.6)

Example 1-65: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,399 (4.1); 7,974 (2.2); 7,954 (4.0); 7,953 (7.3); 7,951 (4.1); 7,940 (2.4); 7,936 (4.2); 7,932 (2.3); 7,919 (0.6); 7,914 (1.2), 7.911 (0.7), 7.517 (1.5), 7.496 (4.7), 7.482 (6.7), 7.449 (5.1), 7.444 (1.9), 7.432 (2.5), 7.427 (8.7), 7.422 (1.5), 7.418 (5.0); 7.417 (5.1); 7.405 (3.5); 7.403 (3.5); 7.377 (1.7); 7.372 (11.2); 7.366 (3.0); 7.355 (2.3); 7.350 (6..1); 7.344 (0.7) ; 7,259 (274.2); 6,995 (1.5); 5,411 (16.0); 4,882 (3.6); 2,043 (1.4); 1,531 (81.3); 1,276 (0.5); 1,258 (. 1

0); 0008 (3.4); 0000 (113.4) - 0,008 (3.0)

Example 1-66: ¹ H-NMR (400.0 MHz, CDC13):

δ = 7,797 (8.8); 7,780 (8.7); 7,653 (11.8); 7,647 (11.9); 7,543 (1.7); 7,527 (1.9); 7,522 (3.5); 7,518 (1.0); 7,506 (3.5)

; 7,501 (2.1); 7,485 (1.9); 7,319 (5.3); 7,318 (5.4); 7,295 (5.2); 7,294 (5.3); 7,293 (5.5); 7,267 (0.9); 7,266 (1.0); 7.2

59 (110.0); 6,995 (0.6); 6,910 (1.4); 6,908 (1.4); 6,904 (1.8); 6,901 (1.8); 6,889 (2.1); 6,887 (2.3); 6,881 (3.3) 6,869

(3.4); 6,863 (2.6); 6,860 (2.1); 6,848 (3.0); 6,846 (3.0); 6,842 (2.0); 6,839 (2.3); 6,823 (2.7); 6,817 (2.2); 6,799 (8.1)

; 6,797 (8.3); 6,794 (8.3); 6,791 (8.0); 5,447 (16.0); 5,296 (2.0); 4,896 (5.9); 1,543 (22.2); 1,257 (0.6); 0.008 (1.4) 0

■ 000 (44.2) - 0008 (1.2)

Example 1-67: ¹ H-NMR (400.0 MHz, CDC13):

8,108 (1.8), 8,103 (1.3), 8,101 (1.0), 7,838 (1.5), 7,834 (1.4), 7,817 (1.8), 7,814 (1.8), 7,690 (2.8), 7,684 (2.8), 7,658 (1.7), 7,657 (1.7), 7,638 (1.4), 7,636 (1.4), 7,259 (76.5), 7,255 (0.5), 7,192 (6.8), 6.79 9 (1.9); 6,797 (1.9); 6,794 (1.9); 6,791 (1.8); 5,482 (2.6); 5,480 (3.2); 5,478 (2.7); 4,810 (1.3); 1,533 (16.0); 0008 (1

■ 1); 0.004 (0.6); 0.002 (1.5); 0.000 (33.4); - 0.003 (1.4); - 0.008 (1.0)

Example 1-68: ¹ H-NMR (400.0 MHz, CDC13):

δ = 7,797 (5.3); 7,779 (5.3); 7,657 (7.1); 7,651 (7.2); 7,518 (1.0); 7,427 (0.7); 7,421 (4.9); 7,420 (4.0); 7,416 (1.8); 7,405 (2.4); 7,400 (9.0); 7,394 (1.5); 7,361 (1.9); 7,355 (11.6); 7,350 (3.0); 7,339 (2.2); 7,334 (5.6); 7,324 (3.3); 7,32 2 (3.3); 7,299 (3.2); 7,298 (3.4); 7,259 (179.7); 6,995 (1.0); 6,804 (4.9); 6,802 (5.0); 6,798 (5.0); 6,796 (4.9); 5,390 (

16.0) 4,898 (3.6); 1,535 (43.9) 1,255 (0.6); 0,008 (2.1); 0000 (70.1) - 0008 (2.0)

Example 1-69: ¹ H-NMR (400.0 MHz, CDC13):

δ = 9,040 (10.6), 8,622 (3.4), 8,621 (3.6), 8,618 (3.6), 8,616 (3.4), 8,179 (3.1), 8,178 (3.1), 8,158 (4.1), 8,156 (4.1); 8,022 (3.5); 8,017 (3.4); 8,000 (2.7); 7,996 (2.7); 7,459 (3.9); 7,458 (3.2); 7,454 (1.4); 7,443 (1.8); 7,438 (6.3); 7.43 2 (1.0) 7,375 (1.2), 7,379 (8.0), 7,374 (2.2), 7,362 (1.9), 7,357 (4.8), 7,352 (0.8), 7,259 (78.8), 7,254 (0.5), 7,199 (1: 2,0), 5,431 (11.8 ); 5,297 (16.0); 4,839 (2.8); 1,427 (0.5); 1,422 (0.8); 1.371 (1.3); 1,333 (8.5); 1,286 (2.7); 1,282 (12

■ 0); 1,256 (6.4); 1,232 (0.8); 0.880 (1.4); 0.862 (0.6); 0.008 (0.9) 0.000 (32.7) - 0.008 (1.0)

Example 1-70: ¹ H-NMR (400.0 MHz, CDC13):

δ = 9,073 (13.3), 8,606 (4.7), 8,229 (3.7), 8,228 (3.6), 8,207 (6.1), 8,206 (6.1), 8,149 (2.5), 8,145 (4.6), 8,141 (2.4); 8,128 (1.5), 8,123 (2.7), 8,119 (1.4), 7,518 (1.7), 7,387 (1.2), 7,372 (1.8), 7,367 (3.1), 7,352 (2.5), 7,346 (2.0), 7.33 3 (1.8) 7.292 (0.7), 7.259 (316.7), 7.247 (3.8), 7.232 (1.5), 7.227 (1.6), 7.225 (1.4), 7.066 (1.0), 7.062 (1.0), 7.045 (1.8), 7.040 (1.5) ; 7,024 (0.9); 7,020 (0.8); 6,995 (1.7); 5,446 (16.0); 4,934 (4.0); 1,536 (65.6); 1,333 (1.0); 1,284 (. 1

6) 1,256 (1.8); 0,008 (3.8); 0000 (123.8) - 0,008 (3.4)

 Example 1-71: 'H NMR ^ OO.O MHZ, CDC13):

7,747 (6.1), 7,654 (8.2), 7,648 (8.3), 7,471 (4.0), 7,466 (1.6), 7,458 (4.3), 7,455 (2.2), 7,449 (4.6), 7,442 (1.8), 7.436 (4.4), 7.429 (0.5), 7.320 (3.7), 7.319 (3.8), 7.296 (3.8), 7.294 (3.8), 7.268 (0.5), 7.266 (0.8), 7.258 (86.2), 7.086 (0.7); 7,078 (5.5); 7,073 (1.7); 7,069 (0.6); 7,062 (1.8); 7,056 (10,0); 7,051 (1.8); 7,040 (1.6); 7,035 (4,8); 7,027 (0.5) ; 6,799 (5.7); 6,796 (5.8); 6,793 (5.8); 6,791 (5.7); 5,391 (16.0); 5,296 (1.4); 4,894 (4.1); 1,543 (18.2

); 1,256 (0.6); 0.008 (1.0); 0,000 (34.6) - 0.008 (0.9)

Example 1-72: ¹ H-NMR (400.0 MHz, CDC13):

δ = 9,045 (16.0), 8,635 (5.2), 8,634 (5.8), 8,631 (5.6), 8,629 (5.4), 8,190 (4.8), 8,189 (4.9), 8,169 (6.3), 8,168 (6.3); 8,037 (5.4), 8,033 (5.3), 8,016 (4.2), 8,011 (4.1), 7,676 (2.8), 7,655 (9.8), 7,638 (8.6), 7,617 (2.5), 7,518 (1.2), 7.25 9 (205.7) 7.250 (0.5), 7.220 (18.6), 6.995 (1.2), 5.521 (13.5), 4.850 (4.5), 4.027 (0.8), 3.227 (1.0), 1.548 (21.2), 1.3.33 (3.3), 1.283 (4.6 ) 1,257 (3.6); 0,880 (0.8); 0,008 (2.4); 0000 (83.2) - 0008 (2.4) Example 1-73: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8.417 (5.1); 8.414 (4.9); 7.952 (1.7); 7.950 (3.2); 7.948 (1.7); 7.930 (4.6); 7.929 (8.3); 7.927 (4.6); 7.906 (5.0); 7

.902 (4.6); 7,885 (1.8); 7,881 (1.9); 7,518 (1.0); 7,492 (5.3); 7,478 (7.5); 7,413 (5.5); 7,411 (5.6); 7,399 (4.0); 7,398

(3.9); 7,359 (0.7); 7,354 (0.7); 7,341 (1.4); 7,335 (1.3); 7,326 (1.0); 7,319 (0.9); 7,313 (1.2); 7,309 (0.8); 7,300 (0.8)

; 7,294 (0.8); 7,273 (0.6); 7,272 (0.6); 7,271 (0.6); 7,270 (0.7); 7,270 (0.8); 7,269 (0.9); 7,268 (1.0); 7,267 (1.2); 7.2

66 (1.3); 7,266 (1.5); 7,265 (1.8); 7,264 (2.3); 7,263 (3.2); 7,259 (172.2); 7,254 (2.2); 7,253 (1.6); 7,252 (1.2); 7,252

(1.0); 7,251 (0.8); 7,250 (0.6); 7,249 (0.5); 7,222 (21.1); 7,209 (1.1); 6,995 (1.0); 5,489 (8.8); 5,487 (10.8); 5.485 (9

■ 4); 5,298 (0.6); 4,819 (4.5); 1,537 (16.0) 1,258 (0.5), 0008 (2.0); 0000 (75.0) - 0008 (2.2)

Example 1-74: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,394 (2.2); 8,377 (1.0); 8,373 (1.0); 8,348 (2.8); 8,345 (2.6); 7,946 (0.8); 7,925 (3.2); 7,906 (2.2); 7,904 (3.7); 7,902 (2.1), 7.886 (0.9), 7.882 (0.9), 7.864 (0.6), 7.857 (2.3), 7.854 (2.2), 7.836 (1.2), 7.832 (1.2), 7.518 (0.7), 7.480 (3.9), 7.467 (5.5); 7,405 (1.4); 7,404 (1.4); 7,398 (3.0); 7,397 (3.0); 7,392 (1.0); 7,390 (1.0); 7,385 (2.1); 7,383 (2.1); 7,259 (119.0); 7,237 (0.7), 7.223 (0.8), 7.216 (0.9), 7.209 (0.8), 7.201 (0.9), 7.197 (0.8), 7.182 (0.8), 7.123 (3.0), 7.044 (6.5), 6.995 (0.9) 6,961 (0.5), 6,953 (0.9), 6,939 (2.0), 6,934 (1.6), 6,920 (1.1), 6,916 (2.2), 6,912 (2.8), 6,908 (1.2), 6,891 (2.7), 6,886 (2.1) 6,869 (0.6); 6,864 (0.7); 5,472 (5.1); 5,429 (0.6); 5,414 (1.2); 5,398 (0.6); 4,588 (2.8); 4,573 (2.6); 4,029 (8.6); 4,027 (12.4) ; 4,024 (8.2); 4,012 (8.6); 4,010 (16.0); 4,007 (8.5); 1,545 (3.4); 1,255 (1.0) 0

.008 (1.4); 0.000 (51.0); - 0.008 (l .4)

Example 1-75: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,029 (8.2); 8,013 (8.2); 7,732 (0.6); 7,730 (0.6); 7,657 (6.0); 7,632 (6.0); 7,545 (1.8); 7,529 (1.9); 7,525 (3.7); 7

.517 (1.0); 7,509 (3.6); 7,504 (2.9); 7,488 (2.0); 7,435 (10.5); 7421 (14.8); 7,356 (7.6); 7,354 (7.9); 7,342 (5.5); 7.3

40 (5.5); 7,269 (0.7); 7,269 (0.7); 7,268 (0.7); 7,267 (0.7); 7,265 (1.3); 7,264 (1.5); 7,258 (132.2); 7,251 (0.5); 6,994

(0.7); 6,911 (1.5); 6,908 (1.5); 6,904 (1.8); 6,902 (1.9); 6,890 (2.2); 6,888 (2.3); 6,883 (3.0); 6,881 (3.5) 6,870 (3.3)

; 6,863 (2.5) 6,860 (2.2); 6,848 (3.0); 6,846 (3.2) 6,842 (2.1); 6,840 (2.4); 6,824 (2.5) 6,818 (2.0); 5,451 (16.0); 5th

4,907 (6.3);; 1,540 (36.8); 1,258 (0.7); 0.008 (1.4); 0,000 (53.5); 296 (1.5) - 0.008 (1.5)

Example 1-76: ¹ H-NMR (400.0 MHz, CDC13):

8,518 (3.5), 8,517 (3.9), 8,001 (1.6), 7,996 (2.8), 7,992 (1.6), 7,979 (2.5), 7,975 (4.5), 7,971 (2.5), 7,912 (5.2), 7.910 (5.2), 7.890 (3.2), 7.889 (3.1), 7.588 (3.9), 7.567 (4.5), 7.553 (7.9), 7.540 (9.2), 7.517 (0.7), 7.445 (5.4), 7.440 (5.8); 7,383 (4.5); 7,381 (4.5); 7,369 (3.8); 7,368 (3.8); 7,302 (3.6); 7,297 (3.4); 7,281 (3.2); 7,276 (3.1)

; 7,258 (123.4); 6,994 (0.7); 5,515 (16.0); 4,900 (3.8); 1,531 (35.1); 0.008 (1.7) 0.000 (52.5) - 0.008 (1.4)

Example 1-77: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,027 (5.4); 8,011 (5.4); 7,658 (4.0); 7,634 (4.0); 7,517 (0.7); 7,505 (0.6); 7,503 (0.6); 7,492 (0.6); 7,481 (0.5); 7,474 (3.8), 7,469 (1.7), 7,461 (4.0), 7,458 (2.4), 7,455 (2.2), 7,452 (4.5), 7,444 (1.7), 7,439 (4.6), 7,436 (7.8), 7,422 (9.7), 7,355 (5.2), 7,353 (5.4), 7,341 (3.8), 7,340 (3.8), 7,266 (0.8), 7,258 (87.9), 7,086 (0.6), 7,079 (5.3), 7,074 (1, 7), 7,062 (1.7) ; 7,057 (9.7); 7,052 (1.8); 7,041 (1.5); 7,035 (4.6); 5,396 (16.0); 5,296 (2.8); 4,904 (4.4); 1,538 (25.2)

; 1,258 (0.6); 0.008 (1.2); 0,000 (36.6) - 0.008 (1.0)

Example 1-78: ¹ H-NMR (400.0 MHz, CDC13):

δ = 9,051 (15.7); 9,039 (1.8); 8,648 (4.8); 8,647 (5.2); 8,644 (5.1); 8,643 (4.9); 8,586 (0.6); 8,401 (1.0); 8,194 (4.9);

8,193 (4.6); 8,173 (6.5); 8,171 (6.0); 8,045 (5.0); 8,040 (4.9); 8,023 (4.0); 8,019 (4.1); 8,003 (0.6); 7,998 (0.6); 7:59

0 (4.1); 7,569 (4.7); 7,520 (3.1); 7,453 (5.8); 7,448 (6.2); 7,312 (0.7); 7,307 (3.9); 7,302 (3.5); 7,286 (3.7); 7,281 (. 3

7); 7,270 (3.4); 7,262 (553.5); 7,255 (2.3); 7,254 (1.9); 7,253 (1.4); 7,252 (0.9); 7,252 (0.9); 7,251 (0.9); 7,250 (0.8)

; 7,249 (0.7); 7,248 (0.6); 7,248 (0.6); 7,247 (0.6); 7,234 (0.6); 7,225 (17.8); 7,212 (1.1); 7,136 (1.9); 6,998 (3.0); 5th

537 (16.0); 5,302 (2.0); 4,849 (4.2); 1,551 (125.9); 1,333 (2.6); 1,284 (3.8); 1,255 (2.0); 0.882 (0.7); 0.146 (0.6); 0.0

08 (6.5); 0.000 (207.3) - 0.006 (1.5) - 0.007 (1.3) - 0.008 (5.5) - 0.150 (0.6)

Example 1-79: ¹ H-NMR (400.0 MHz, CDC13):

δ = 7,798 (8.3), 7,780 (8.2), 7,648 (11.1), 7,642 (11.2), 7,518 (0.7), 7,309 (5.2), 7,308 (5.1), 7,285 (4.9), 7,283 (5.2), 7,270 (0.6 7,268 (0.7), 7,259 (116.9), 6,995 (0.6), 6,796 (7.8), 6,794 (8.0), 6,791 (7.9), 6,788 (7.7), 6,739 (0.6), 6,731 (1.1), 6,723 (5.5); 6,717 (1.0); 6,705 (6.8); 6,702 (6.9); 6,689 (0.8); 6,683 (5.2); 6,676 (1.1); 5,462 (16.0); 5.29

7 (4.8); 4,882 (5.6); 2,042 (0.6); 1,541 (36.3); 1,258 (0.9); 0.008 (1.4); 0,000 (46.7) - 0.008 (1.3)

 Example 1-80: 'H NMR ^ OO.O MHZ, CDC13):

δ = 8,045 (4.9); 8,028 (4.9); 7,669 (3.8); 7,645 (3.7); 7,535 (4.2); 7,518 (6.2); 7,514 (5.2); 7,445 (6.5); 7,431 (10.1); 7,424 (6.6), 7,378 (1.0), 7,364 (4.8), 7,352 (3.6), 7,309 (1.3), 7,274 (5.9), 7,269 (7.4), 7,259 (1013.5), 7,249 (4.5), 6 .995 (5.4 5,499 (16.0), 4,923 (4.1), 1,530 (299.2), 0.146 (1.3), 0.008 (12.5), 0.000 (401.7), - 0.008 (10.7), - 0.150 (1.2) Example 1-81: ¹ H-NMR (400.0 MHz, CDC13):

δ = 7,811 (5.5); 7,794 (5.4); 7,661 (7.4); 7,655 (7.5); 7,529 (4.0); 7,518 (2.7); 7,509 (4.7); 7,428 (6.1); 7,423 (6.5); 7,330 (3.4), 7.307 (3.4), 7.305 (3.4), 7.274 (4.9), 7.269 (5.9), 7.259 (480.7), 7.248 (3.6), 6.995 (2.5), 6.809 (5.1), 6.8.07 (5.2); 6,804 (5.2); 6,801 (5.2); 5,495 (16.0); 4,911 (3.8); 1,532 (126.2); 1,258 (0.6); 0.146 (0.5), 0.008 (5.8); 0:00

0 (185.6) - 0.008 (4.8) - 0.150 (0.6)

Example 1-82: ¹ H-NMR (400.0 MHz, CDC13):

δ = 8,423 (4.0); 8,421 (4.2); 7,982 (0.9); 7,961 (7.2); 7,959 (6.9); 7,955 (5.6); 7,952 (3.0); 7,934 (0.7); 7,580 (4.0); 7,559 (4.6); 7.517 (1.0); 7.500 (5.2); 7.486 (7.3); 7.443 (5.9); 7.438 (6.2); 7.420 (5.6); 7.407 (3.8); 7.293 (3.7); 7.287 (3.6); 7.272 (3.7); 7,266 (4.0); 7,258 (185.5); 7,250 (0.8); 7,249 (0.6); 6,994 (1.0); 5,513 (16.0); 4,898 (3.8); 1,532 (

59.6) 0,008 (2.3); 0000 (74.0) - 0008 (2.1)

Example 1-83: ¹ H-NMR (400.0 MHz, CDC13):

δ = 9,071 (14.2), 8,584 (4.8), 8,221 (4.0), 8,220 (4.0), 8,200 (6.4), 8,198 (6.3), 8,131 (2.6), 8,126 (4.8), 8,122 (2.5); 8,109 (1.7), 8,105 (3.1), 8,100 (1.6), 7,518 (1.8), 7,498 (3.6), 7,493 (1.5), 7,485 (3.8), 7,476 (4.2), 7,468 (1.6), 7.46 3 (4.0) 7,258 (318.6), 7,108 (0.5), 7,100 (4.9), 7,095 (1.5), 7,084 (1.7), 7,079 (9.1), 7,074 (1.6), 7,062 (1.4), 7,057 (4.3), 6,995 (1.8) 5,498 (16.0), 5,298 (1.4), 4,917 (4.2), 1,536 (33.0), 1,370 (0.8), 1,333 (1.0), 1,284 (1.7), 1,256 (1, 7), 0.008 (3.8), 0.000 ( 120.5) - 0,008 (3.3)

B. Formulation Examples 1. Dusts

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

2. Dispersible powder

A wettable powder readily dispersible in water is obtained by mixing 25 parts by weight of a compound of the general formula (I), 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of oleoylmethyltaurine sodium as a wetting and dispersing agent, and grinded in a pin mill. 3. Dispersion concentrate

 A dispersion concentrate readily dispersible in water is obtained by reacting 20 parts by weight of a compound of the general formula (I), 6 parts by weight of alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71% by weight. Parts of paraffinic mineral oil (boiling range, for example, about 255 to about 277 ° C) mixed and ground in a ball mill to a fineness of less than 5 microns.

4. Emulsifiable concentrate

An emulsifiable concentrate is obtained from 15 parts by weight of a compound of general formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier. 5. Water-dispersible granules

 A water-dispersible granule is obtained by

75 parts by weight of a compound of general formula (I),

 lignosulfonic acid calcium,

 sodium lauryl sulfate,

 Polyvinyl alcohol and

 kaolin

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

A water-dispersible granule is also obtained by

25 parts by weight of a compound of general formula (I),

5 "2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium,

 2 "oleoylmethyl tauric acid sodium,

 1 "polyvinyl alcohol,

 17 "calcium carbonate and

 50 "water

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

C. Biological examples

1. Herbicidal action against harmful plants in the pre-emergence

Seeds of monocotyledonous or dicotyledonous weed or crop plants are laid out in sandy loam in wood fiber pots and covered with soil. The compounds of the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then applied to the surface of the cover soil as an aqueous suspension or emulsion having a water application rate of 600 to 800 l / ha with the addition of 0.2% wetting agent applied. After the treatment, the pots are placed in the greenhouse and kept under good growth conditions for the test plants. The visual assessment of the damage to the test plants takes place after a trial period of

3 weeks compared to untreated controls (herbicidal activity in% (%)): 100%

Effect = plants have died, 0% effect = like control plants). Numerous compounds according to the invention at an application rate of 0.32 kg or less per hectare showed an at least 80% action against a large number of harmful plants. At the same time, compounds according to the invention leave gramineous crops such as barley, wheat, rye, millet, maize or rice in the pre-emergence process practically undamaged even at high doses of active ingredient. In addition, some substances also protect dicotyledonous crops such as soya, cotton, rapeseed, sugar beet or potatoes. _{Some of the} compounds according to the invention show high selectivity and are therefore suitable in the pre-emergence process for controlling undesirable plants _ECHC Gwuchs in agricultural crops. The following tables show by way of example the herbicidal action of the compounds according to the invention in the pre-emergence, wherein the

_SET V _I

herbicidal activity is given in percent.

AMA _RE Table 2: Herbicidal action in advance V _I O _TR run (PE)

A _BUTH

A _L OM _Y

 Herbicidal activity against [%]

_P O _LC O

 Example dosage

 No. [g / ha]

 1-09 320 100 90 90 60 70 20 90

 1-03 320 90 40 100 90 80 20 50

 1-07 320 100 90 100 50 80 90 100

 1-05 320 90 90 90 50 50 30 90

 1-06 320 100 90 100 60 20 80 100

 1-16 320 100 80 80 30 80 30 70

 1-04 320 90 70 100 40 90 40 50

 1-01 320 100 90 100 70 80 60 100

 1-08 320 100 90 100 20 0 60 100

 1-02 320 100 90 100 70 30 80 100

 1-13 320 90 100 100 30 30 80 100

 1-36 320 90 90 100 0 90 50 90

 1-20 320 100 100 100 40 50 70 100

 1-10 320 100 90 100 40 30 70 0

 1-12 320 100 90 100 20 20 70 100

1-18 320 100 70 100 20 40 30 10 Table 3: Pre-emergence herbicidal action (PE)

_EC H _C G

AMA _RE

Table 4: Pre-emergence herbicidal action (PE)

Herbicidal action

 versus [%]

Example dosage

 No. [g / ha]

 1-40 320 10 80

 1-33 320 20 90

 1-28 320 90 100

1-48 320 10 90

 1-45 320 40 100

1-37 320 90 100

1-17 320 90 100

1-50 320 70 80

 1-34 320 50 100

1-27 320 60 100

1-56 320 30 80

 1-59 320 30 80

1-41 320 90 50 Herbicidal action

 versus [%]

Example dosage

 No. [g / ha]

 1-53 320 70 100

 1-24 320 60 90

1-23 320 9 ^EC H ^C G0 100

 1-51 320 20 70

 1-35 320 40 100

1-55 320 40 1 AMA ^RE 00

 1-44 320 60 90

 1-46 320 60 100

 1-26 320 70 100

 1-43 320 0 100

 1-54 320 0 80

2. Herbicidal action against harmful plants in postemergence

 Seeds of monocotyledonous or dicotyledonous crops are laid out in sandy loam soil in wood fiber pots, covered with soil and grown in the greenhouse under good growth conditions. 2 to 3 weeks after sowing, the test plants are treated in the single leaf stage. The compounds of the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then sprayed onto the green parts of plants as an aqueous suspension or emulsion having a water application rate of 600 to 800 l / ha with addition of 0.2% wetting agent , After about 3 weeks life of the test plants in the greenhouse under optimal growth conditions, the effect of the preparations is scored visually in comparison to untreated controls (herbicidal action in percent (%)): 100% action = plants are dead, 0% effect = like control plants) , Numerous compounds according to the invention at an application rate of 0.08 kg or less per hectare showed an at least 80% action against a large number of harmful plants. At the same time, compounds of the invention allow gramineous crops such as barley, wheat, rye, millet, corn or rice

Post-emergence even with high doses of active ingredient undamaged. In addition, some substances also protect dicotyledonous crops such as soya, cotton, rapeseed, sugar beet or potatoes. Some of the compounds according to the invention show a high selectivity and are therefore suitable postemergence for combating undesired plant growth in agricultural crops. The following tables show, by way of example, the herbicidal action of the compounds according to the invention in postemergence, the herbicidal activity being given in percent. Table 5: Post-emergence herbicidal action (PO)

Herbicidal activity against [%]

A _RE AM

Table 6: Post-emergence herbicidal action (PO)

Herbicidal action

 versus [%]

 ÜJ IE

 Example dosing> Έ

 LU

 No. [g / ha] OY O

 <

 1-33 320 80 100 90 90

 1-49 320 80 100 90 90

1-38 320 90 100 100 100

Table 7: Post-emergence herbicidal action (PO)

Herbicidal action

 versus [%]

 UJ DZ

 Example dosing u> 1- <1-

 Z>

No. [g / ha] u UJ O

 UJ l / l <<

 1-69 320 90 80 100 90

 1-60 320 90 80 80 90

1-43 320 80 90 100 90 Herbicidal action

 versus [%]

Example dosage u> <

 No. [g / ha] u

 <<

 1-50 320 90 40 100 90

 1-17 320 90 100 100 90

1-54 320 80 A _RE AM 80 100 80

Table 8: Post-emergence herbicidal action (PO)

 Table 9: Post-emergence herbicidal action (PO)

Herbicidal action

 versus [%]

Example dosage

 No. [g / ha] <

 1-61 320 90 80

 1-46 320 100 90

 1-58 320 100 90

 1-51 320 90 80

 1-63 320 80 80

 1-32 320 100 90

 1-68 320 80 80

 1-62 320 40 100

 1-71 320 80 40

Claims

Claims:

1. Compounds of the formula (I)

 their N-oxides or their agrochemically acceptable salts, in which

A is a radical of the group consisting of Al to A20,

 A5 A6 A7 A8

A9 A10 A1 1 A12

 A13 A14 A15 A16

A1 7 A1 8 A19 A20 R ¹ halogen, CN, NO ₂ , OH, NH ₂ , (C ₁ -C ₆ ) -alkyl, (C ₁ -C ₆ ) -alkoxy, (C ₁ -C ₆ ) -haloalkyl, C ₆ ) - haloalkoxy, (C ₂ -C ₆ ) -alkenyl, halogeno (C ₂ -C ₆ ) -alkenyl, (C ₂ -C ₆ ) -alkynyl, halogeno (C ₃ -C ₆ ) -alkynyl, (C ₃ -C ₆₎ cycloalkyl, halo (C ₃ -C ₆₎ cycloalkyl, _(C3-C6) cycloalkyl (Ci-C ₆₎ alkyl, halo (C3-C6) -cycloalkyl (C 1 -C ₆ ) -alkyl, (C 1 -C ₆ ) -alkylcarbonyl, (C 1 -C ₆ ) -alkylcarboxy, (C 1 -C ₆ ) -alkylamm, di (C 1 -C ₆ ) -alkylamine, (C ₁ -C ₆ ) -alkyl -S (0) _n or (Ci-C ₆ ) -alkyl-S (0) ₂ NH means,

R ^{2 is} chlorine or fluorine,

R is hydrogen, R ^{4 is} hydrogen,

R ⁵ is hydrogen, halogen, OH, NH ₂ , CN, (C ₁ -C ₃ ) -alkyl, (C ₁ -C ₃ ) -alkoxy, C ₁ -C ₃ -alkylamino or cyclopropyl, R ⁶ is hydrogen, halogen, OH, NH ₂ , CN, (C ₁ -C ₃ ) -alkyl, (C ₁ -C ₃ ) -alkoxy, cyclopropyl or vinyl,

R ⁷ is hydrogen, halogen, (C ₁ -C ₃ ) -alkyl, (C ₁ -C ₃ ) -alkoxy, (C ₁ -C ₃ ) -alkylthio, cyclopropyl, (C ₁ -C ₃ ) -alkylamino or phenyl,

R ⁸ is hydrogen, (C 1 -C 6) -alkyl, (C 1 -C 10) -alkylcarbonyl, (C 1 -C 6) -alkoxycarbonyl or

phenyl, X is CH or CF, m is 1, 2, 3, 4 or 5, and n is 0, 1 or 2.

2. Compounds of formula (I) according to claim 1, in which A is a radical from the group consisting of Al to A3, A7 to A15 and A17 to A18.

 A1 A2 A3

A9 A10 A1 1 A12

 A13 A14 A15

 A17 A18

3. Compounds of formula (I) according to claim 1 or 2, in which R ^{1 is} halogen, CN, NO ₂ , OH, NH ₂ , (C ₁ -C ₆ ) -alkyl, (C ₁ -C ₆ ) -alkoxy, (Ci -C ₆ ) haloalkyl or (Ci-C ₆ ) haloalkoxy.

4. Compounds of formula (I) according to one of the preceding claims, in which R ^{2 is} chlorine

 means.

5. Compounds of formula (I) according to one of the preceding claims, in which R ³ and R ^{4 are} hydrogen.

6. Compounds of formula (I) according to one of the preceding claims, in which R ^{5 is} hydrogen or halogen.

7. Compounds of formula (I) according to one of the preceding claims, in which R ^{6 is} hydrogen or halogen.

8. Compounds of formula (I) according to one of the preceding claims, in which R ⁷

 Is hydrogen, halogen or (C 1 -C 3) -alkyl.

9. Compounds of formula (I) according to one of the preceding claims, in which R ⁸

 Hydrogen, (Ci-C i) alkyl, (Ci-C i) alkylcarbonyl or (Ci-C i) alkoxycarbonyl means.

10. Compounds of formula (I) according to one of the preceding claims, in which n is 0 or 1 and m is 1, 2, or 3.

11. A herbicidal composition, characterized by a herbicidally effective content of at least one compound of the formula (I) according to one of claims 1 to 10.

12. A herbicidal composition according to claim 11 in admixture with formulation auxiliaries.

13. A herbicidal composition according to claims 11 or 12 containing at least one other

 Pesticides effective substances from the group insecticides, acaricides, herbicides, fungicides, safeners and growth regulators.

14. A herbicidal composition according to claim 11 or 12 containing a safener.

15. A herbicidal composition according to claim 14 containing a further herbicide.

16. A method for controlling undesirable plants, characterized in that an effective amount of at least one compound of formula (I) according to any one of claims 1 to 10 or a herbicidal composition according to any one of claims 11 to 15 on the plants or on the place of unwanted plant growth applied.

17. Use of compounds of formula (I) according to any one of claims 1 to 10 or a herbicidal composition according to any one of claims 11 to 15 for controlling undesirable plants.

18. Use according to claim 17, characterized in that the compounds of formula (I) are used for controlling undesirable plants in crops of crops.

19. Use according to claim 18, characterized in that the crops transgenic

 Are crops.