EP2294058A1 - 2-(benzylsulfonyl)-oxazole derivatives, chiral 2- (benzylsulfinyl) -oxazole derivatives and 2-(benzylsulfanyl)-oxazole derivatives, methods for the production thereof, and use thereof as herbicides and plant growth regulators - Google Patents

2-(benzylsulfonyl)-oxazole derivatives, chiral 2- (benzylsulfinyl) -oxazole derivatives and 2-(benzylsulfanyl)-oxazole derivatives, methods for the production thereof, and use thereof as herbicides and plant growth regulators

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Publication number
EP2294058A1
EP2294058A1 EP09735369A EP09735369A EP2294058A1 EP 2294058 A1 EP2294058 A1 EP 2294058A1 EP 09735369 A EP09735369 A EP 09735369A EP 09735369 A EP09735369 A EP 09735369A EP 2294058 A1 EP2294058 A1 EP 2294058A1
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Prior art keywords
alkyl
crc
alkoxy
cycloalkyl
general formula
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EP09735369A
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German (de)
French (fr)
Inventor
Christopher Hugh ROSINGER
Dieter Feucht
Dirk Schmutzler
Isolde Haeuser-Hahn
Jan Dittgen
Adriana Martelletti
Hansjörg Dietrich
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Bayer CropScience AG
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Bayer CropScience AG
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Priority to EP09735369A priority Critical patent/EP2294058A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/46—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • This invention relates to specific compounds selected from the group of 2- (benzylsulfonyl) -oxazole derivatives, chiral 2- (benzylsulfinyl) -oxazole derivatives and 2- (benzylsulfanyl) -oxazole derivatives, and to specific processes for their preparation.
  • Another object of the present invention is the use of these compounds as herbicides, in particular as herbicides for the selective control of harmful plants in crops.
  • the present invention relates to their use as plant growth regulators alone or in combination with safeners and / or in admixture with other herbicides, their use for plant control in specific crops or as crop protection regulators.
  • WO 2004/013112 A describes herbicidally active oxazole derivatives which have a thioether group at the 2-position of the oxazole ring, which in turn comprises a fluoroalkene unit.
  • DE 102 54 876 A describes 2- (fluoalkenylthio) -oxazole compounds and their use as herbicides.
  • EP 0 435 794 A describes 1-heterocyclylsulfonyl-2-phenyl-2-propenes and their use as herbicides.
  • Pesticidal properties of 2-trifluorobutene-thio-oxazole derivatives are e.g. described in WO 2001/066529 A, WO 99/52874 A and WO 95/024403 A.
  • WO 02/62770 A and WO 2006/123088 there are some 2 - [(1 H -pyrazol-4-ylmethyl) -sulfinyl] and 2 - [(1 H-pyrazol-4-ylmethyl) sulfonyl] derivatives which carry a suitable substituted (1 H-pyrazol-4-ylmethyl) group as a substituent on the 2-sulfonyl or 2-sulfinyl group.
  • a process for their preparation is also described in the abovementioned publications.
  • the present invention therefore relates to compounds of the general formula (I) and their agrochemically compatible salts
  • Alkylsulfonyloxy (C 1 -C 6 -alkylsulfonyl) C 1 -C 6 -alkyl, (C 1 -C 6 ) - Alkylthio (C r C6) alkoxy - alkylsulfinyl (C r C6) alkyl, d CRCE-CeJ-alkylthio ⁇ ⁇ alkyl and (C r C6);
  • R 9 and R 10 are selected from the group consisting of hydrogen, (C 1 -C 6 -alkyl, (C 3 -C 6 ) -cycloalkyl, (C 1 -C 6 ) -haloalkyl, or where R 9 and R 10 together form a (dC 6 ) alkylene group which may contain an oxygen or sulfur atom or one or two amino or (dC 6 ) alkylamino groups, the substituents R 3 to R 7 , respectively independently, are selected from the group consisting of
  • radicals previously defined for R 3 to R 7 may optionally be cyclically linked with each other, provided that they are o / t ⁇ o-permanent; and or
  • radicals R 1 to R 2 may be mono- or polysubstituted and independently of one another by radicals which are selected from the group consisting of halogen and (C 1 -C 6 ) -
  • the compounds defined above comprise, on the aryl radical, at least one radical from R 3 to R 7 , which is not hydrogen; that is, the aryl radical in addition to the radical - (CH 2 JS (O) n - comprises at least one further substituent, which is not hydrogen or such compounds does not include the inventive definition of the compounds of general formula (I) are in which the aryl ring is unsubstituted.
  • the substituents are preferably selected from the group consisting of (C 1 -Ce) - alkyl, (C 1 -Ce) -HaIOaIkVl, (C 1 -Ce ) -alkoxy, nitro, cyano, (C r C 3) cycloalkyl, (C 1 -C 6) - haloalkoxy, (CrC 6) alkylthio, (CrC 6) alkylcarbonyl, (C r C6) alkoxycarbonyl, or Halogen, wherein these radicals of the second substituent level may optionally be cyclically linked to each other, provided that they are ortho-constantly.
  • a first embodiment of the present invention comprises compounds of the general formula (I) in which
  • R 1 is preferably selected from the group consisting of
  • Cycloalkylthio (C 1 -C 4) alkylsulfinyl, (C 3 -C 6) cycloalkyl, sulfinyl, (CrC 4) alkylsulfonyl, (C 3 -C 6) cycloalkylsulfonyl, (C 1 -C 4 ) -alkylsulfonyloxy, (C 3 -C 6 ) -cycloalkylsulfonyloxy, (C 2 -C 3 ) -alkenyl, (C 2 -C 3 ) -alkynyl, (C 2 -C 3 ) -alkenyloxy, ( C 2 - C 3) alkynyloxy, -NHCO- (C 1 -C 3) alkyl, -NHCO 2 - (C 1 -C 3) - alkyl, -NHCONH- (C r C 3) alkyl, -NH
  • R 1 is particularly preferably selected from the group consisting of H, F, Cl,
  • R 1 is very particularly preferably selected from the group consisting of H, F, Cl,
  • a second embodiment of the present invention comprises compounds of the general formula (I) in which
  • R 2 is preferably selected from the group consisting of hydrogen, halogen, nitro, cyano, carboxyl, (C 1 -Ce) - alkyl, (C 3 -C 6) -cycloalkyl, (C 3 -C 6) cycloalkoxy, (C 1 -C 6 ) -alkoxy, (C 1 -C 6 -alkylcarbonyl, (C 3 -C 6 ) -cycloalkylcarbonyl, (C 1 -C 6 -alkoxycarbonyl, (C 3 -C 6 ) -cycloalkoxycarbonyl, mono - ((C 1 -C 4 ) - alkyl) aminocarbonyl, di - ((C 1 -C 4) alkyl) - aminocarbonyl, mono - ((CrC 4) alkyl) aminosulfonyl, di ((CrC ⁇ -alkyO-aminosulfonyl, (C
  • R 2 is more preferably selected from the group consisting of H, F, Cl, Br, I, Me, Et, NO 2 , C (O) OEt, CHF 2 and CF 3 ;
  • R is more preferably selected from the group consisting of H, F, Cl, Br and I.
  • a third embodiment of the present invention comprises compounds of the general formula (I) in which
  • R 3 is preferably selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C (O) OH, (C 1 -C 4 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (Ci-C 4) -haloalkyl, (C 1 - C 4) alkoxy, (CrC 4) -haloalkoxy, (C 1 -C 4 J-AIkOXy- (C 1 -C 2) - alkyl, (CrC 3) alkylcarbonyl, (CrC 3) alkylcarbonyloxy, (C- ⁇ -C 4) alkoxycarbonyl, (C 3 -C 6) cycloalkoxycarbonyl, (C 3 -C 6) cycloalkyl (C r C 2) alkoxy, (C 3 -C 6 ) -cycloalkoxy, (C 1 -C 4 ) -alkoxy
  • R is more preferably selected from the group consisting of H, F, Cl,
  • R 3 is very particularly preferably selected from the group consisting of H, F, Cl, Br, Me, CHF 2 , CF 3 , OMe, OCHF 2 , OCF 3 , OCH 2 CF 3 , I and OEt.
  • a fourth embodiment of the present invention comprises compounds of the general formula (I) in which
  • R 4 is preferably selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C (O) OH, (C 1 -C -J) -alkyl, (C 3 -C 6) -cycloalkyl, (dC 4) -haloalkyl, (C 1 - C 4) alkoxy, (C r C 4) -haloalkoxy, (C 1 -C 4 J-AIkOXy- (Ci-C 2) - alkyl, (dC ⁇ alkylcarbonyl, (dC ⁇ alkylcarbonyloxy, (CrC 4) alkoxycarbonyl, (C 3 -C 6) cycloalkoxycarbonyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 2 ) -alkoxy > (C 3 -C 6 ) -cycloalkoxy, (C 1 -C 4 ) -al
  • R 4 is particularly preferably selected from the group consisting of H, F, Cl,
  • R 4 is very particularly preferably selected from the group consisting of H, F, Cl, Me, CF 3 and OMe.
  • a fifth embodiment of the present invention comprises compounds of the general formula (I) in which
  • R 5 is preferably selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C (O) OH, (C r C4) alkyl, (C 3 -C 6) -cycloalkyl, (dC 4) -haloalkyl, (C 1 - C 4) alkoxy, (Ci-C 4) haloalkoxy, (C 1 -C 4- alkoxy- (C 1 -C 2 ) -alkyl, (C 1 -C 3 ) -alkylcarbonyl, (C 1 -C 4 ) -alkoxycarbonyl, (C 3 -C 6 ) -cycloalkoxycarbonyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 2 ) -alkoxy, (C 3 -C 6 ) -cycloalkoxy, (CrC 4) alkoxycarbonyl (Ci-C 2) alk
  • R 5 is particularly preferably selected from the group consisting of H, F, Cl,
  • R 5 is very particularly preferably selected from the group consisting of H, F, Cl, Br, CF 3 and Me.
  • a sixth embodiment of the present invention comprises compounds of the general formula (I) in which
  • R 6 is preferably selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C (O) OH, (dC 4) -alkyl, (C 3 -C 6) -cycloalkyl, (Ci-C 4) -haloalkyl, (C 1 - C 4) alkoxy, (Ci-C 4) haloalkoxy, (C 1 -CO -Alkoxy (C 1 -C 2 ) -alkyl, (C 1 -C 3 ) -alkylcarbonyl, (C 1 -C 4 -alkylcarbonyloxy, (C 1 -C 4 ) -alkoxycarbonyl, (C 3 -C 6 ) -cycloalkoxycarbonyl, (C 3 -C 6 ) Cycloalkyl- (C 1 -C 2) -alkoxy, (C 3 -C 6 ) -cycloalkoxy, (C 3
  • R 9 and R 10 independently of one another, are selected from the group consisting of hydrogen, (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (C 1 -C 6 ) -haloalkyl, or wherein R 9 and
  • R 10 together form a (Ci-C fi ) -alkylene group which may contain an oxygen or sulfur atom or one or two amino or (dC 6 ) alkylamino groups;
  • R 6 is more preferably selected from the group consisting of H, F, Cl,
  • R 6 is very particularly preferably selected from the group consisting of H, F, Cl, Me, CF 3 and OMe.
  • a seventh embodiment of the present invention comprises compounds of the general formula (I) in which
  • R 7 is preferably selected from the group consisting of water Substance, hydroxy, halogen, cyano, nitro, amino, C (O) OH, (d-OO-alkyl, (C 3 -C 6 ) -cycloalkyl, (dC ⁇ -haloalkyl, (C 1 -C 4 ) -alkoxy , (C r C 4) -haloalkoxy, (C 1 -C 4 J-AIkOXy- (C 1 -C 2) - alkyl, (CrC 3) -alkylcarbonyl, (CrC ⁇ -alkylcarbonyloxy, (C 1 -C 4) Alkoxycarbonyl, (C 3 -C 6 ) cycloalkoxycarbonyl,
  • R 7 is particularly preferably selected from the group consisting of H, F, Cl,
  • OCH 2 CH CH 2 and OCH 2 C ⁇ CH
  • R 7 is very particularly preferably selected from the group consisting of H, F, Cl, Me, CF 3 , OCHF 2 , OCF 3 and OMe.
  • radicals R 3 to R 7 on the aryl ring as defined in these embodiments of the present invention may be used in any combination with those described in US Pat Present invention as preferred, particularly preferred and most preferably defined meanings of the substituents R 1 and R 2 are combined on Oxazolring.
  • the compound of the general formula (I) also includes compounds which are quaternized by a) protonation, b) alkylation or c) oxidation on a nitrogen atom.
  • the compounds of general formula (I) may optionally be prepared by addition of a suitable inorganic or organic acid such as HCl, HBr, H 2 SO 4 or HNO 3 , but also oxalic acid or sulfonic acids to a basic group such as amino or alkylamino form.
  • Suitable substituents which are present in deprotonated form such as, for example, sulfonic acids or carboxylic acids, can form internal salts with groups which can themselves be protonated, such as amino groups. Salts can also be formed by replacing the hydrogen with a suitable cation in the agrochemical field with suitable substituents, such as, for example, sulfonic acids or carboxylic acids.
  • salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or else ammonium salts, salts with organic amines or quaternary ammonium salts with cations of the formula [NRR'R "R '"] + , where R to R "1 each independently represent an organic radical, in particular alkyl, aryl, arylalkyl or alkylaryl.
  • these radicals are the lower carbon skeletons, eg having 1 to 6 C atoms, in particular 1 to 4 C atoms, or unsaturated groups having 2 to 6 C atoms, in particular 2 to 4 C atoms , prefers.
  • Alkyl radicals also in the compound meanings such as alkoxy, haloalkyl, etc., mean, for example, methyl; ethyl; n- or i-propyl; n-, i-, t- or 2-butyl; Pentyls, such as n-pentyl; Hexyls such as n-hexyl, i-hexyl and 1, 3-dimethylbutyl; Heptyls such as n-heptyl, 1-methylhexy and 1, 4-dimethylpentyl; Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; wherein at least one double bond or triple bond, preferably a double bond or triple bond, is contained in the rest.
  • Alkenyl is, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-ene-1 -yl, 1-methylbut-3-en-1-yl and 1-methyl-but-2-en-1-yl;
  • Alkynyl includes, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl and 1-methyl-but-3-yn-1-yl.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • substituted by one or more radicals means one or more identical or different radicals.
  • first substituent level may, if not already expressis verbis defined and if they contain hydrocarbon-containing moieties, optionally further substituted there ("second level of substitution"), for example by one of the substituents, as for the first Substituentbene is defined.
  • second level of substitution may be further substituted there.
  • substituent levels are possible.
  • substituted radical includes only one or two substituent levels.
  • radicals with C atoms those having 1 to 6 C atoms, preferably 1 to 4 C atoms, in particular 1 or 2 C atoms, are preferred.
  • Preferred are usually Substituents from the group halogen, for example fluorine and chlorine, (Ci-C 4 ) alkyl, preferably methyl or ethyl, (Ci-C 4 ) haloalkyl, preferably trifluoromethyl, (C r C 4 ) alkoxy, preferably methoxy or ethoxy , (CrC4) haloalkoxy, nitro and cyano.
  • halogen for example fluorine and chlorine
  • (Ci-C 4 ) alkyl preferably methyl or ethyl
  • (Ci-C 4 ) haloalkyl preferably trifluoromethyl
  • C r C 4 ) alkoxy preferably methoxy or ethoxy
  • CrC4 haloalkoxy
  • the invention also relates to all stereoisomers which are encompassed by formula (I) and mixtures thereof.
  • the present invention also provides methods for the preparation of the compounds of general formula (I) and / or salts thereof.
  • compounds of the formula (I) according to the invention can be prepared by various analogously known methods, which are not exhaustively described below:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given in formula (I) above, oxidized with one equivalent of an oxidizing agent to the optically active sulfoxides (III), for the n the number 1 means, or two
  • the sulfones (IV) can also be obtained from the optically active sulfoxides (III), with one equivalent of an oxidizing agent oxidizing to the sulfones (IV).
  • the oxidizing agents which can be used for this reaction are not subject to any special provisions and may contain oxidizing agents which are capable of oxidizing corresponding sulfur compounds into sulfoxide compounds.
  • the reaction can be carried out in halogenated hydrocarbons, for example dichloromethane, 1,2-dichloroethane, an alcohol, such as methanol, or in dimethylformamide, acetonitrile, water or acetic acid or in a mixture of the abovementioned solvents.
  • enantioselective synthesis of chiral sulfoxides of the formula (III) in optically enriched or pure form can be carried out starting from thio compounds of the formula (II) by methods as described, for example, in Chem. Rev., 103 (2003) 3651-3705, or US Pat literature cited therein, and Adv. Synth. Catal., 347 (2005) 19-31, or literature cited therein.
  • the absolute configuration of the product depends in each case on the structure of the optically active catalyst.
  • this sulfur atom can have both an (R) and an (S) configuration.
  • the present invention covers compounds of the general formula (III) having both (S) and (R) -configuration, that is to say that the present invention covers the compounds of the general formula (III) in which the relevant sulfur atom ( 1) an (R) configuration; or (2) an (S) configuration having.
  • the present invention includes compounds of the general formula (IM) which are racemic, i. in which the compounds of general formula (IM) with (S) configuration (compounds of general formula (IM-S)) compared to the (R) configuration (compounds of general formula (Ml-R)) as 1: 1 Mixture (50% stereochemical purity) are present.
  • compounds of the general formula (III) with (S) -configuration in comparison with the (R) -configuration (compounds of the general formula (III-R) ) having a stereochemical purity of generally over 50% to 100%, preferably 60 to 100%, in particular 80 to 100%, very particularly 90 to 100%, especially 95 to 100%, preferred, wherein the respective (S) compound with an enantioselectivity of in each case more than 50% ee, preferably 60 to 100% ee, in particular 80 to 100% ee, very particularly 90 to 100% ee, most preferably 95 to 100% ee, based on the total content of (S) Compound present, preferably present.
  • compounds of the general formula (III) having (R) -configuration in comparison with the (S) -configuration (compounds of the general formula (III-R) ) having a stereochemical purity of generally over 50% to 100%, preferably 60 to 100%, in particular 80 to 100%, very particularly 90 to 100%, especially 95 to 100%, preferred, wherein the respective (R) compound with an enantioselectivity of in each case more than 50% ee, preferably 60 to 100% ee, in particular 80 to 100% ee, very particularly 90 to 100% ee, most preferably 95 to 100% ee, based on the total content of (S) Compound present, preferably present.
  • the present invention also relates to compounds of general formula (III) in which the stereochemical configuration at the marked (*) sulfur atom (S) having a stereochemical purity of 60 to 100% (S), preferably 80 to 100% (S ), in particular 90 to 100% (S), very particularly 95 to 100% (S).
  • Racemic mixtures for example of optically active sulfoxides of the general formula (III), can be separated by known processes.
  • Such racemate resolution methods are described in handbooks of stereochemistry, for example in Basic Organic Stereochemistry (Eds .: Eliel, Ernest L, Wilen, Samuel H, Doyle, Michael P, 2001, John Wiley & Sons) and Stereochemistry of Organic Compounds (Eds .: Eliel, Ernest L .: Wilen, Samuel H., Mander, Lewis N, 1994, John Wiley & Sons), for example, the adduct formation with an optically active auxiliary reagent, the separation of the diastereomeric adducts in the corresponding diastereomers, for example by crystallization, chromatographic methods, especially column chromatography and high pressure liquid chromatography, distillation, optionally under reduced pressure, extraction and other methods and subsequent cleavage of the diastereomers in the enantiomers
  • processes such as crystallization diastereo
  • optically active acid for example, camphorsulfonic acid, camphoric acid, Bromcamphersulfonklare, quinic acid, tartaric acid, dibenzoyltartaric acid and other analogous acids into consideration; quinine, cinchonine, quinidine, brucine, 1-phenylethylamine and other analogous bases are suitable as optically active bases.
  • the crystallizations are then usually carried out in aqueous or aqueous-organic solvents, the diastereomer with the lower solubility optionally failing initially after inoculation.
  • the one enantiomer of the compound of formula (III) is then released from the precipitated salt or the other from the crystals by acidification or with base.
  • racemates can be separated chromatographically with chiral stationary phases. Enantiomer separations of this type can be carried out from mg to the 100 kg range with preparative HPLC systems in single or continuous operation.
  • R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given in formula (I) above and Lg is a leaving group, in the presence of a suitable alkali metal or alkaline earth metal base, for example potassium carbonate or sodium hydride, or an organic base such as For example, preferably 1, 8-diazabicyclo (5.4.0) undec-7-ene (DBU), in a suitable solvent, for example dimethylformamide, tetrahydrofuran, ethanol, or preferably acetonitrile, in a temperature range between 0 0 C and 100 ° C, and optionally reacted under an inert gas atmosphere, eg nitrogen.
  • a suitable alkali metal or alkaline earth metal base for example potassium carbonate or sodium hydride
  • organic base such as For example, preferably 1, 8-diazabicyclo (5.4.0) undec-7-ene (DBU)
  • a suitable solvent for example dimethylformamide, tetrahydrofuran
  • leaving groups Lg chlorine, bromine, iodine or sulfonate groups, such as methane trifluoromethane, ethane, benzene or toluenesulfonate are preferred.
  • benzyl derivatives of the general formula (VI) used in process b.) are known to the person skilled in the art or are commercially available or can be prepared by processes known to the person skilled in the art [see, for example: a) WO 01/12613 A, b) WO 02/062770 A, c) WO 03/000686 A, d) WO 2006/024820 A].
  • R 1 , R 2 have the meanings given above according to formula (I) and Lg 'is a leaving group, which may function as leaving groups inter alia fluorine, chlorine, bromine, iodine, sulfide, sulfoxide or sulfonate groups, with a benzyl Imidothiocarbamate salt of general formula (VIII)
  • Lg represents a leaving group, carried out in a one-pot process in the presence of an aqueous alkali or alkaline earth metal base.
  • oxazole derivatives of the general formula (VII) used in process c.) are known to the person skilled in the art or are commercially available or can be prepared by processes known to the person skilled in the art [e.g. as described in "Science of Synthesis”, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed E. Schaumann and DE 26 25 229 A].
  • imidothiocarbamate salts isothiuronium salts
  • the preparation of the imidothiocarbamate salts (VIII) by reaction of a benzylating agent of the general formula (VI) with thiourea is carried out by known methods (such as the method described in DD 152557 A), preferably by reaction with an equimolar amount of thiourea and optionally in the presence of alkali iodide, eg sodium iodide,
  • Potassium iodide in an inert solvent such as lower alcohols, such as methanol, ethanol or isopropanol; Hydrocarbons, such as Benzene or toluene; halogenated hydrocarbons, such as dichloromethane or chloroform; or ether derivatives, such as methyl tert-butyl ether, tetrahydrofuran or dioxane at temperatures between 0 to 150 0 C, preferably between 20 to 100 0 C.
  • an inert solvent such as lower alcohols, such as methanol, ethanol or isopropanol
  • Hydrocarbons such as Benzene or toluene
  • halogenated hydrocarbons such as dichloromethane or chloroform
  • ether derivatives such as methyl tert-butyl ether, tetrahydrofuran or dioxane at temperatures between 0 to 150 0 C, preferably between 20 to 100 0 C.
  • an inert solvent such as tetrahydrofuran, diethyl ether, acetonitrile.
  • Suitable phase transfer catalysts are quaternary ammonium or phosphonium salts and also crown ethers, cryptands or polyethylene glycols. Examples of such catalysts can be found e.g. in W.P. Weber, G.W. Gokel; Phase Transfer Catalysis in Organic Synthesis, Springer-Verlag, Berlin 1977 or E.V. Dehmlow, S.S. Dehmlow, Phase Transfer Catalysis, Second Ed. Verlag Chemie, Weinheim 1983.
  • the reactants and the catalyst at temperatures of 20 to 100 0 C are stirred vigorously under a protective gas atmosphere.
  • the intermediately formed under the reaction conditions Mercaptan allallggeemmeeiinnenn FFoorrmmeell ((IIXX)), wwooririnn RR 33 ,, RR 44 ,, RR 55 ,, RR 66 ,, RR 77 have the meaning given above according to the general formula (I) above,
  • D R2 have the meanings given above according to formula (I) and Lg ' a leaving group, where as leaving groups, inter alia, chlorine, bromine or methylsulfonyl groups can act, with a benzyl imidothiocarbamate salt (isothiuronium salt) of the general formula (VIII)
  • Lg is a leaving group, in a one-pot process in the presence of an alkali metal or alkaline earth metal carbonate base and a solvent such as an alcohol , respectively.
  • the imidothiocarbamate salts (isothiuronium salts) of the general formula (VIII) be in the process of the invention generally without further purification steps with vigorous stirring with a slight excess of the oxazole derivatives of the general formula (VII) and with a slight excess of a carbonate base, for example potassium carbonate, sodium carbonate or potassium bicarbonate, or a hydroxide, for example potassium hydroxide, or an alkoxide, eg sodium alkoxide, in alcohol, eg ethanol, ethers, eg 1, 4-dioxane, tetrahydrofuran; a polar solvent such as water, dimethylformamide; or a mixture of these solvents in a temperature range between 20 and 200 ° C., preferably between 50 and 150 ° C., optionally under an inert gas atmosphere, for example nitrogen, or in a microwave apparatus.
  • a carbonate base for example potassium carbonate, sodium carbonate or potassium bicarbonate
  • imidothiocarbamate salts (isothiuronium salts) of the general formula (VIII) can also be reacted further in situ, without isolation.
  • oxazole derivatives of the general formula (VII) used in process d.) are known to the person skilled in the art or are commercially available or can be prepared by processes known to the person skilled in the art [see, for example, US Pat. Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann].
  • R 1 , R 2 have the meanings given above in accordance with formula (I) and Lg ' denotes a leaving group, where as leaving groups inter alia fluorine, chlorine, bromine or sulfonate groups can function, with a benzyl mercaptan of the general formula (IX )
  • R 3 , R 4 , R 5 , R 6 , R 7 have the meaning given above according to the general formula (I) above, in the presence of an alkali or alkaline earth metal base, for example potassium carbonate or sodium hydride, or organic base, for example 1, 8-diazabicyclo (5.4.0) undec-7-ene (DBU) 1 optionally in a solvent, for example dimethylformamide, tetrahydrofuran, ethanol, or preferably acetonitrile, in a temperature range between 0 and 100 ° C, and optionally under an inert gas - Atmosphere, such as nitrogen, take place.
  • an alkali or alkaline earth metal base for example potassium carbonate or sodium hydride
  • organic base for example 1, 8-diazabicyclo (5.4.0) undec-7-ene (DBU) 1
  • DBU 1, 8-diazabicyclo
  • DBU 1, 8-diazabicyclo
  • acetonitrile in a temperature
  • oxazole derivatives of the general formula (VII) used in process e.) are known to the person skilled in the art or are commercially available or can be prepared by processes known to the person skilled in the art [see, for example, US Pat. Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann].
  • the mercaptans of the general formula (IX) used in process e.) are known to the person skilled in the art (see, for example, WO 2004/013106 A) or can be prepared in analogy to processes known to the person skilled in the art for producing mercaptan.
  • halogenating agent such as chlorine, bromine, iodine or halo-succinimide, such as N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS), N-iodosuccinimide (NIS), or for nitro with a nitrating agent, such.
  • a halogenating agent e.g. Halogen, such as chlorine, bromine, iodine or halo-succinimide, such as N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS), N-iodosuccinimide (NIS), or for nitro with a nitrating agent, such.
  • Nitrating acid prepared from sulfuric acid and nitric acid, and treated in suitable solvents, such as chlorinated hydrocarbons, e.g. Carbon tetrachloride, dichloromethane, 1, 2-dichloroethane, or dimethylform
  • R 12 Lg ' an alkylating agent R 12 Lg '
  • R 2 has the meanings given in formula (I) above
  • R 12 is preferably (C 1 -C 6 ) -alkyl which is unsubstituted or is substituted by one or more identical or different radicals from the group halogen, particularly preferably methyl or ethyl
  • Lg ' denotes a leaving group, where as leaving groups, inter alia, chlorine, bromine or methylsulfonyl groups can act, with a strong base and a Alkylating agent R 1 Lg ' , wherein R 1 have the meanings given above according to formula (I), according to the scheme
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given above according to formula (I) and Lg or Lg 'is a leaving group
  • said leaving groups include fluorine, chlorine , Bromine, iodine or sulfonate groups such as methane trifluoromethane, ethane, phenyl or toluenesulfonate can act.
  • lithium diisopropylamide LDA
  • lithium tetramethylpiperidine LTMP
  • lithium hexamethyldisilazane LHMDS
  • LDA lithium diisopropylamide
  • LTMP lithium tetramethylpiperidine
  • LHMDS lithium hexamethyldisilazane
  • Hexamethylphosphoramide can be used as co-solvent, for example.
  • Suitable solvents are inert solvents such as hydrocarbons, such as hexane, heptane, cyclohexane, aromatic hydrocarbons such as benzene, ethers, such as diethyl ether, methyl tert-butyl ether (MTBE), tetrahydrofuran and dioxane, preferably tetrahydrofuran.
  • the aforementioned solvents can also be used as mixtures.
  • the compounds of the formula (XI) and the base or the alkylating agent R 1 Lg ' are preferably used in 0.9-1.5 mol of the latter per mole of the former.
  • the reaction is preferably carried out in a temperature range between -90 0 C and the boiling point of the solvent.
  • the reaction time is not limited, the reactions are generally completed after 1 to 24 hours.
  • R 1 is fluorine
  • reagents for electrophilic fluorination for example 1-chloromethyl-4-fluoro-1,4-diazabicyclo- [2,2,2] octane-bis-tetrafluoroborate TEDA-BF4, SelectFluor TM), N-fluorobenzenesulfonic acid imide (NFBS or NFSi), N-fluoro-o-benzenedisulfonimide (NFOBS), 1-fluoro-4-hydroxy-1,4-diazoniabicyclo [2.2.2] octane bis (tetrafluoroborate) (NFTh, AccuFluor TM) and others as described in "Modern Fluoroorganic Chemistry", 2004, Wiley-VCH Verlag, Ed. P. Kirsch.
  • the 2-mercaptooxazole derivatives or corresponding salts of the 2-mercaptooxazole derivatives of the general formula (V) used in process g.) are known to the person skilled in the art, or are commercially available or can be prepared by processes known to those skilled in the art, for example as described in Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann.
  • Oxazole derivatives (XI) can be deprotonated regioselectively in the 5-position, analogously to processes known to those skilled in the art.
  • Analogous reactions using an alkyl base such as butyllithium have been described in the literature, eg in Boger, DL et al; J. Med. Chem. (2007) 50 (33), 1058-1068 and Molinski, TF et al; J. Org. Chem. (1998) 63, 551-555, and with terf-butyllithium and a copper salt in Marino, JP; Nguyen, N. Tel Lett. (2003) 44, 7395-7398 and literature cited therein.
  • the oxazole derivatives of general formula (XI) used in process g.) Can be prepared, for example, according to process b.) By reaction of a 2-mercaptooxazole derivative of general formula (V) with an alkylating agent R 12 Lg ' or after Those skilled in the art [see, eg, Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann], or are commercially available.
  • the compounds of the formula (XIII) mentioned in process g.) Can be prepared from the compounds of the formula (XII) by oxidation according to the above process a) or by processes known to the person skilled in the art.
  • the compounds of the general formula (XIII), in turn, can be prepared by the above processes c.) Or d.) With benzyl imidothiocarbamate salts (VIII) or with benzyl mercaptans of the formula (IX) according to the above process e.)
  • R 1 , R 2 , R 3 , R 4 , R 5 have the meanings given above according to formula (I).
  • benzyl disulfides of the general formula (XV) are reacted with a diazotization agent and a 2-aminooxazole derivative of the general formula (XIV) in a suitable solvent to form compounds! (M) reacted.
  • Suitable solvents are inert solvents to the reaction, e.g. Hydrocarbons, such as hexane, heptane, cyclohexane; aromatic hydrocarbons, such as benzene, chlorobenzene, toluene, xylene; halogenated hydrocarbons, e.g. Dichloromethane, dichloroethane, chloroform and carbon tetrachloride; Esters, e.g. Ethyl acetate and methyl acetate; Ethers, e.g. Diethyl ether, methyl tert-butyl ether, dioxane; Nitriles, e.g.
  • Hydrocarbons such as hexane, heptane, cyclohexane
  • aromatic hydrocarbons such as benzene, chlorobenzene, toluene, xylene
  • halogenated hydrocarbons e.g. Dichloromethane, dich
  • Alcohols e.g. Methanol, ethanol, isopropyl alcohol
  • Amides e.g. N, N-dimethylformamide and sulfoxides, e.g. Dimethyl sulfoxide.
  • the diazotization reagent may be, for example, a nitrite ester such as isoamyl nitrite or a nitrite salt such as sodium nitrite.
  • the molar ratios can be chosen freely, equimolar amounts of the heteroarylalkyl disulfides and the diazotization agents are preferred.
  • the reaction is carried out at a temperature between -20 0 C and the boiling point of the chosen solvent and is generally completely completed after a time of 0.1 to 40 hours.
  • the diazotization of a 2-aminooxazole derivative of the general formula (XIV) is described, for example, in Hodgetts, KJ; Kershaw, MT Org. Lett. (2002), 4 (17), 2905-2907.
  • oxazole derivatives of the general formula (XIV) used in process h) are known to the person skilled in the art or are commercially available, or can be prepared by processes known to the person skilled in the art [see, for example, US Pat. Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann.
  • benzyl disulfides of the general formula (XV) can be prepared by methods known to those skilled in the art, e.g. in Gladysz, J.A., Wong, V.K., Jick, B.S. Tetrahedron (1979) 35, 2329.
  • leaving groups Lg are halogens, e.g. Chlorine, bromine, iodine, or alkyl or aryl-sulfonyl groups, such as methyl, ethyl, phenyl or TolylsulfonyL or haloalkylsulfonyl group, such as trifluoromethyl, or nitro preferred, but especially chlorine and methylsulfonyl are preferred.
  • halogens e.g. Chlorine, bromine, iodine, or alkyl or aryl-sulfonyl groups, such as methyl, ethyl, phenyl or TolylsulfonyL or haloalkylsulfonyl group, such as trifluoromethyl, or nitro preferred, but especially chlorine and methylsulfonyl are preferred.
  • leaving groups Lg ' are halogens, for example chlorine, bromine, iodine, or alkyl or arylsulfonyl groups, such as methyl, ethyl, phenyl or tolylsulfonyl, or a haloalkylsulfonyl group, such as trifluoromethyl, or nitro preferred, but especially Chlorine and methylsulfonyl are preferred.
  • halogens for example chlorine, bromine, iodine, or alkyl or arylsulfonyl groups, such as methyl, ethyl, phenyl or tolylsulfonyl, or a haloalkylsulfonyl group, such as trifluoromethyl, or nitro preferred, but especially Chlorine and methylsulfonyl are preferred.
  • group R 12 preference is given to (C 1 -C 6) -alkyl, which is unsubstituted or optionally substituted by one or more, identical or different radicals from the group halogen, more preferably methyl or ethyl.
  • this sulfur atom can have both an (R) and an (S) configuration.
  • the present invention encompasses compounds of the general formula (III) with both (S) and (R) -configuration, ie that the present invention covers the compounds of the general formula (I), in which the relevant sulfur atom
  • the present invention includes compounds of general formula (III) which are racemic, i. in which the compounds of general formula (IM) having (S) configuration (compounds of general formula (Ml-S)) compared to the (R) configuration (compounds of general formula (Ml-R)) as 1: 1 Mixture (50% stereochemical purity) are present.
  • compounds of the general formula (III) with (S) -configuration in comparison with the (R) -configuration (compounds of the general formula (III-R) ) having a stereochemical purity of generally over 50% up to 100%, preferably 60 to 100%, in particular 80 to 100%, very particularly 90 to 100%, especially 95 to 100%, preferred, where the particular (S) compound having an enantioselectivity of more than 50% ee, preferably 60 to 100% ee, in particular 80 to 100% ee, very particularly 90 to 100% ee, most preferably 95 to 100% ee, based on the total content of the relevant (S) compound present, is preferably present.
  • compounds of the general formula (III) having (R) -configuration in comparison with the (S) -configuration (compounds of the general formula (III-R) ) having a stereochemical purity of generally over 50% to 100%, preferably 60 to 100%, in particular 80 to 100%, very particularly 90 to 100%, especially 95 to 100%, preferred, wherein the respective (R) compound with an enantioselectivity of in each case more than 50% ee, preferably 60 to 100% ee, in particular 80 to 100% ee, very particularly 90 to 100% ee, most preferably 95 to 100% ee, based on the total content of (S) Compound present, preferably present.
  • the present invention also relates to compounds of the general formula (III) in which the stereochemical configuration at the (S) sulfur atom (S) with a stereochemical purity of 60 to 100% (S), preferably 80 to 100% (S. ), in particular 90 to 100% (S), very particularly 95 to 100% (S).
  • the compounds of the general formula (III) may contain further chiral centers as the S atom ( * ) marked with an asterisk ( * ) and correspondingly exist as stereoisomers.
  • the possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers, Z and E isomers, are all encompassed by the formula (IM). For example, if one or more alkenyl groups are present, then
  • Diastereomers (Z and E isomers) occur. For example, if one or more asymmetric carbon atoms are present, then enantiomers and Diastereomers occur.
  • Stereoisomers can be obtained from the mixtures obtained in the preparation by customary separation methods, for example by chromatographic separation methods. Similarly, stereoisomers can be selectively prepared by using stereoselective reactions using optically active sources and / or adjuvants. The invention thus also relates to all stereoisomers which comprises the general formula (III), but are not specified with their specific stereoform and their mixtures.
  • diastereomers (Z and E isomers) can occur.
  • enantiomers and diastereomers may occur.
  • Corresponding stereoisomers can be obtained from the mixtures obtained in the preparation by customary separation methods, for example by chromatographic separation methods. Similarly, stereoisomers can be selectively prepared by using stereoselective reactions using optically active sources and / or adjuvants. The invention thus also relates to all stereoisomers which are encompassed by the general formula (I) but are not specified with their specific stereoform and their mixtures.
  • inert solvents denoted in the preceding process variants are meant in each case solvents which are inert under the respective reaction conditions, but need not be inert under any reaction conditions.
  • Hydrohalic acids such as hydrochloric acid or hydrobromic acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- or bifunctional carboxylic acids and hydroxycarboxylic acids such as acetic acid, maleic acid, amber acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid or lactic acid, as well as sulfonic acids such as p-toluenesulfonic acid or 1, 5-naphthalenedisulfonic acid.
  • the acid addition compounds of the formula (I) can be prepared in a simple manner by the usual salt formation methods, for example by dissolving a compound of the formula (I) in a suitable organic solvent such as methanol, acetone, methylene chloride or benzene and adding the acid at temperatures of 0 to 100 0 C are obtained and in a known manner, for example by filtration, isolated and optionally purified by washing with an inert organic solvent.
  • a suitable organic solvent such as methanol, acetone, methylene chloride or benzene
  • the base addition salts of the compounds of the formula (I) are preferably prepared in inert polar solvents such as, for example, water, methanol or acetone at temperatures of 0 to 100 ° C.
  • Suitable bases for the preparation of the salts according to the invention are, for example, alkali metal carbonates, such as potassium carbonate, alkali metal and alkaline earth metal hydroxides, for example NaOH or KOH, alkali metal and alkaline earth metal hydrides, for example NaH, alkali metal and alkaline earth metal alkoxides, for example sodium methoxide or potassium tert-butoxide.
  • 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 understood to mean a procedure as described, for example, by D. Tiebes in Combinatorial Chemistry - Synthesis, Analysis, Screening (publisher Günther Jung), Verlag Wiley 1999, on pages 1 to 34.
  • a number of commercially available devices can be used, for example Calypyso 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 from Perkin Elmar, Waltham, Massachusetts 02451, USA.
  • Calypyso reaction blocks Calypyso reaction blocks
  • reaction stations from Radleys, Shirehill, Saffron Waiden, Essex, CB 11 3AZ, England
  • MultiPROBE Automated Workstations from Perkin Elmar, Waltham, Massachusetts 02451, USA.
  • chromatography apparatuses are 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 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 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, for example, the crop in terms of quantity, quality, shelf life, composition and special ingredients.
  • transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known.
  • Other special properties may include tolerance or resistance to abiotic stressors such as heat, cold, drought, salt and ultraviolet radiation.
  • cereals such as wheat, barley, rye, oats, millet, rice, manioc and maize or also cultures of sugar beet , Cotton, soy, rapeseed, potato, tomato, pea and other vegetables.
  • 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.
  • transgenic crops which are resistant to certain glufosinate-type herbicides (cf., for example, EP 0 242 236 A, EP 0 242 246 A) or glyphosate (WO 92/000377 A) or the sulfonylureas (EP 0 257 993 A, US Pat. No. 5,013,659) or combinations or mixtures of these herbicides are "gene stacking" resistant, such as transgenic crops such as corn or soybean with the
  • Optimum TM GAT TM Glyphosate ALS Tolerant
  • transgenic crops for example cotton, capable of producing Bacillus thuringiensis toxins (Bt toxins) which render the plants resistant to certain pests (EP 0 142 924 A, EP 0 193259 A); Transgenic crop plants with modified fatty acid composition (WO 91/013972 A); genetically modified crops with new content or secondary substances, for example new phytoalexins, which cause increased disease resistance (EP 0 309 862 A, EP 0 464 461 A); genetically modified plants with reduced photorespiration, which have higher yields and higher stress tolerance (EP 0 305 398 A); transgenic crops that produce pharmaceutically or diagnostically important proteins ("molecular pharming"), transgenic crops that are characterized by higher yields or better quality, - transgenic crops that are characterized by a combination of the above-mentioned new properties (“gene stacking”) ,
  • nucleic acid molecules can be introduced into plasmids that allow mutagenesis or sequence alteration by recombination of DNA sequences.
  • Base exchanges are 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 e.g. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., CoId Spring Harbor Laboratory Press, CoId 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 for the purpose of achieving a co-suppression effect or the expression of at least one appropriately designed one Ribozyme which specifically cleaves transcripts of the above-mentioned gene product.
  • DNA molecules may be used which comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules which comprise only parts of the coding sequence, which parts must be long enough to be present in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical.
  • the synthesized protein may be located in any compartment of the plant cell.
  • the coding region is linked to DNA sequences which ensure localization in a particular compartment.
  • sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad., U.S.A. 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106).
  • the expression of the nucleic acid molecules can also take place in the organelles of the plant cells.
  • the transgenic plant cells can be regenerated to whole plants by known techniques.
  • the transgenic plants may, in principle, be plants of any plant species, that is, both monocotyledonous and dicotyledonous plants.
  • the compounds (I) according to the invention can be used in transgenic cultures which are resistant to growth substances, such as Dicamba or against herbicides which inhibit essential plant enzymes, eg acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD), respectively against herbicides from the group of sulfonylureas, glyphosates, glufosinates or benzoylisoxazoles and analogues or against Any combinations of these agents are resistant.
  • Dicamba acetolactate synthases
  • EPSP synthases eg acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD)
  • ALS acetolactate synthases
  • GS glutamine synthases
  • HPPD hydroxyphenylpyruvate dioxygenases
  • the compounds according to the invention can particularly preferably be used 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 TM GAT TM (Glyphosate ALS Tolerant) are used.
  • 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 provides herbicides and plant growth-regulating agents which contain the compounds according to the invention.
  • the compounds of the general formula (I) can be formulated in various ways, depending on which biological and / or chemical-physical parameters are predetermined.
  • Possible formulation options are, for example: wettable powder (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions , Suspension concentrates (SC), oil or water based dispersions, oil miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for litter and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
  • WP wettable powder
  • SP water-soluble powders
  • EC emulsifiable concentrates
  • EW emulsions
  • SC Suspension concentrates
  • SC oil or water based dispersions
  • Injection powders are preparations which are uniformly dispersible in water and, in addition to the active ingredient, also contain ionic and / or nonionic surfactants (wetting agent, dispersant) in addition to a diluent or inert substance, eg.
  • the herbicidal active compounds are finely ground, for example, in customary apparatus such as hammer mills, blower mills and air-jet mills and mixed simultaneously or subsequently with the formulation auxiliaries.
  • Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent z.
  • organic solvent z B. butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers).
  • emulsifiers which can be used are: alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide / ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as, for example, B. Sorbitanfett Text- ester or Polyoxethylenensorbitanester such. B. Polyoxyethylensorbitanfett Text- ester.
  • alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate
  • nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide / ethylene oxide condensation products, alkyl polyethers,
  • Dusts are obtained by grinding the active ingredient with finely divided solids, eg. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • Suspension concentrates may be water or oil based. You can, for example, by wet grinding using commercially available bead mills and optionally added surfactants, such as. B. are already listed above in the other formulation types, are produced.
  • Emulsions eg. As oil-in-water emulsions (EW) can be, for example, by means of stirring, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as. B. are listed above in the other types of formulation produced.
  • EW oil-in-water emulsions
  • Granules can be prepared either by spraying the active ingredient on adsorptive, granulated inert material or by applying active substance concentrates by means of adhesives, for.
  • adhesives for.
  • polyvinyl alcohol polyacrylic acid sodium or mineral oils, on the surface of carriers such as sand, kaolinites or granulated inert material. It is also possible to granulate suitable active ingredients in the manner customary for the production of fertilizer granules, if desired mixed with fertilizers.
  • Water-dispersible granules are generally prepared by the usual methods such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
  • the agrochemical preparations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of active compound of the formula (I).
  • the active ingredient concentration z. B. about 10 to 90 wt .-%, the remainder to 100 wt .-% consists of conventional formulation components.
  • the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%.
  • Dusty formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% of active ingredient.
  • the active ingredient content depends, in part, on whether the active compound is liquid or solid and which granulating aids, fillers and the like are present. be used.
  • the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the active substance formulations mentioned optionally contain the customary adhesion, wetting, dispersing, emulsifying, penetrating, preserving, antifreezing and solvent-based agents, fillers, carriers and colorants, defoamers, evaporation inhibitors and the pH value and Viscosity-influencing agent.
  • the compounds of the general formula (I) or salts thereof can be used as such or in the form of their preparations (formulations) with other pesticidal substances, such.
  • pesticidal substances such as insecticides, acaricides, nematicides, herbicides, fungicides, safeners, fertilizers and / or growth regulators are used, z. B. as a ready-made formulation or as tank mixes.
  • combination partners for the compounds of general formula (I) according to the invention in mixture formulations or in tank mix are known active compounds which are based on 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 for example from Weed Research 26 (1986) 441 445 or "The Pesticide Manual", 14th edition, The British Crop Protection Council and the Royal Soc.
  • herbicides or plant growth regulators which can be combined with the compounds according to the invention are the following active substances (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 and always include all forms of use such as acids, salts, esters and isomers such as stereoisomers and optical isomers.
  • ISO International Organization for Standardization
  • isomers such as stereoisomers and optical isomers.
  • Acetochlor acibenzolar, acibenzolar-S-methyl, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, aminocyclopyrachlor, aminopyralid, amitrole, ammonium sulfamate, ancymidol, anilofos, asulam, Atrazine.
  • Methylisothiocyanate metobenzuron, metobenzuron, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinates, monalides, monocarbamides, monocarbamide dihydrogen sulfate, monolinuron, monosulfuron, monuron, MT 128, MT-5950, d , H. N- [3-chloro-4- (1-methylethyl) phenyl] -2-methylpentanamide, NGGC-011, naproanilides, napropamide, naptalam, NC-310, i.
  • CDEC compact disc sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosate (glyphosate trimesium), sulfosulfuron, SYN-523, SYP-249, SYP-298, SYP-300, tebutam, Tebuthiuron, tecnazenes, tefuryltriones, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumetone, terbuthylazine, terbutryn, TH-547, thenylchloro, thiafluamides, thiazafluron, thiazopyr, thidiazimine, thidiazuron, thiencarbazones, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, Thiobencarb, ti
  • inventive compounds of general formula (I) are of particular interest, which are the compounds of general formula (I) or their combinations with other herbicides or pesticides and safeners.
  • the safeners which are used in an antidote effective content, reduce the phytotoxic side effects of the herbicides / pesticides used, eg. B.
  • cereals wheat, barley, rye, corn, rice, millet
  • sugar beet sugar cane
  • rapeseed cotton and soybeans, preferably cereals.
  • the following groups of compounds are suitable, for example, as safeners for the compounds (I), alone or in combinations thereof with other pesticides:
  • ⁇ A is a natural number from 0 to 5, preferably 0 to 3;
  • RA 1 is halogen, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, nitro or (C 1 -C 4 ) haloalkyl;
  • W A is an unsubstituted or substituted divalent heterocyclic radical from the group of the unsaturated or unsaturated five-membered ring heterocycles having 1 to 3 hetero ring atoms from the group N and O, wherein at least one N atom and at most one O atom is contained in the ring, preferably a radical from the group (W A 1 ) to (W A 4 ),
  • RA 2 is ORA 3 , SRA 3 or NRA 3 RA 4 or a saturated or unsaturated 3- to 7-membered heterocycle having at least one N atom and up to 3 heteroatoms, preferably from the group O and S, via the N atom is connected to the carbonyl group in (S1) and is unsubstituted or substituted by radicals from the group (dC-OAlkyl, (CrC 4 ) AIkOXy or optionally substituted phenyl, preferably a radical of the formula OR A 3 , NHRA 4 or N (CH 3 ) 2 , in particular the formula OR A 3 ;
  • RA 3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having in total 1 to 18 carbon atoms;
  • R A 4 is hydrogen, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkoxy or substituted or unsubstituted phenyl;
  • R A 5 is H, (Ci-C 8 ) alkyl, (dC 8 ) haloalkyl, (C 1 -C 4 ) alkoxy (Ci-C 8 ) alkyl, cyano or COORA 9 , wherein R A 9 is hydrogen, (dC 8 ) alkyl, (d-C ⁇ JHaloalkyl, (C 1 - C 4) alkoxy (Ci-C 4) alkyl, (CrC 6) hydroxyalkyl, (C3-Ci2) -cycloalkyl or tri- (d-C4) -alkyl -silyl is;
  • RA 6 , RA 7 , RA 8 are identical or different hydrogen, (Ci-C 8 ) alkyl ; (Ci-C 8) alkyl halo-, (C 3 -C 2) cycloalkyl or substituted or unsubstituted phenyl;
  • EP-A-333,131 and EP-A-269,806 are described; c) derivatives of 1, 5-diphenylpyrazole-3-carboxylic acid (S1 C), preferably comparison compounds such as ethyl 1- (2,4-dichlorophenyl) -5-phenylpyrazole-3-carboxylate (S1-5), 1- (2-chlorophenyl) -5-phenylpyrazole-3-carboxylic acid methyl ester (S 1-6) and related Compounds as described, for example, in EP-A-268554; d) compounds of the type of the triazolecarboxylic acids (S1 d ), preferably compounds such as fenchlorazole (ethyl ester), ie 1- (2,4-dichlorophenyl) -5-trichloromethyl- (1 H) -1, 2,4-triazole-3 ethyl carboxylic acid ester (S1-7), and related compounds as described in EP-A-174
  • R 8 1 is halogen, (C 1 -C 4 ) AIKyI, (C 1 -C 4 ) alkoxy, nitro or (C r C 4 ) haloalkyl;
  • n B is a natural number from 0 to 5, preferably 0 to 3;
  • R 8 2 is OR B 3 , SR B 3 or NR 8 3 RB 4 or a saturated or unsaturated 3- to 7-membered heterocycle having at least one N atom and up to 3 heteroatoms, preferably from the group O and S, which is connected via the N atom with the carbonyl group in (S2) and unsubstituted or by radicals from the group (Ci-C 4 ) alkyl, (CrC 4 ) alkoxy or optionally substituted phenyl is substituted, preferably a radical of the formula OR B 3 , NHR 8 4 or N (CH 3 ) 2 , in particular of the formula OR B 3 ;
  • RB 3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having a total of 1 to 18 C atoms;
  • RB 4 is hydrogen, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkoxy or substituted or unsubstituted phenyl;
  • T 5 is a (C 1 or C 2 ) alkanediyl chain which is unsubstituted or substituted by one or two (C 1 -C 4 ) alkyl radicals or by [(C 1 -C 3 ) alkoxy] carbonyl;
  • Rc 1 is (C 1 -C 4) AIRyI, (Ci-C 4) haloalkyl, (C 2 -C 4) alkenyl, (C 2 -C 4) haloalkenyl,
  • Benoxacor (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4), "PPG-1292" (N-Allyl-N-KI.S-dioxolane-cyano-methyn-dichloroacetamide) from PPG Industries (S3-5),
  • TI-35 (1-dichloroacetyl-azepane) from TRI-Chemical RT (S3-8), "diclonone” (dicyclonone) or "BAS145138” or “LAB145138” (S3-9) (3-dichloroacetyl-2, 5,5-trimethyl-1,3-diazabicyclo [4.3.0] nonane) from BASF,
  • X 0 is CH or N;
  • RD 1 is CO-NRD 5 RD 6 or NHCO-RD 7 ;
  • R 0 2 is halogen, (Ci-C 4) haloalkyl, (C r C4) haloalkoxy, nitro, (dC 4) alkyl, (C 1 -C 4) -alkoxy, (Ci-C 4) alkylsulfonyl, (CrC 4 ) Alkoxycarbonyl or (C 1 -C 4) alkylcarbonyl;
  • R 0 3 is hydrogen, (C r C 4 ) alkyl, (C 2 -C 4 ) alkenyl or (C 2 -C 4 ) alkynyl; R 0 4 is halogen, nitro, (C r C 4 ) alkyl, (Ci-C 4 ) haloalkyl, (C 1 -C 4 ) haloalkoxy, (C 3 -C 6 ) cycloalkyl, phenyl, (C 1 -C 4 ) AIkOXy, cyano, (CrC 4 ) alkylthio,
  • 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 -C 6 ) cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl containing V D heteroatoms from the group nitrogen, oxygen and sulfur, wherein the seven latter radicals by v D substituents from the group halogen, (CrC 6 ) alkoxy , (CrC 6) haloalkoxy, (dC 2) alkylsulfinyl, (dC 2) alkylsulfonyl, (C
  • C 4 alkylcarbonyl and phenyl and in the case of cyclic radicals also (C 1 -C 4 ) alkyl and (dC-OHaloalkyl substituted;
  • RD 6 is hydrogen, (dC 6 ) alkyl, (C 2 -C 6 ) alkenyl or (C 2 -C 6) -alkynyl, where the three last-mentioned radicals are substituted by VD radicals from the group halogen, hydroxy, (Ci-C 4) AIlCyI 1 (Ci-C 4) alkoxy and (C r C 4) alkylthio, or
  • RD 7 is hydrogen, (dC ⁇ alkylamino, DKD ⁇ alkylamino, (C r C6) alkyl,
  • Substituents from the group halogen, (CrC 4 ) AIkOXy, (CrC ⁇ JHaloalkoxy and (C r C 4 ) alkylthio and in the case of cyclic radicals are also (CrC 4 ) alkyl and (CrC 4 ) haloalkyl substituted;
  • R D 4 is halogen, (C r C 4 ) alkyl, (C 1 -C 4 ) alkoxy, CF 3 ; limit 1 or 2;
  • V 0 is 0, 1, 2 or 3;
  • Acylsulfamoylbenzoeklareamide for example, the following formula (S4 b ), for example, are known from WO-A-99/16744,
  • R 0 R 8 and D 9 are independently hydrogen, (CrC 8) alkyl, (C 3 -C 8) cycloalkyl, (C 3 -C 6) alkenyl, (C 3 -C 6) alkynyl, R D ITID 4 is halogen, (Ci-C 4) alkyl, (C 1 -C 4) -alkoxy, CF 3 1 or 2;
  • R E 1 , RE 2 are each independently halogen, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy,
  • RE 4 are independently hydrogen, (Ci-C 4) alkyl, (C 2 - C 6) alkenyl, (C 2 -C 4) AI kinyl, cyanoalkyl, (CrC 4) haloalkyl, phenyl,
  • n E 1 is 0 or 1 ⁇ IE 2
  • n E 3 are independently 0, 1 or 2
  • RF 1 is halogen, (C r C4) alkyl, (C r C 4) haloalkyl, (Ci-C 4) alkoxy, (CrC 4) haloalkoxy, nitro, (C r C4) alkylthio, (C r C 4) Alkylsulfonyl, (dC 4 ) alkoxycarbonyl, optionally substituted. Phenyl, optionally substituted phenoxy, RF 2 hydrogen or (C r C 4 ) alkyl
  • RF 3 is hydrogen, (C 1 -C 8 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, or aryl, wherein each of the aforementioned C-containing radicals is unsubstituted or substituted by one or more, preferably up to three the same or different radicals from the group consisting of halogen and alkoxy is substituted, mean, or their salts,
  • ⁇ F is an integer from 0 to 2
  • R G 1 is halogen, (C r C 4 ) alkyl, methoxy, nitro, cyano, CF 3 , OCF 3
  • nc is an integer from 0 to 4, RG 2 (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 3 -C 6 ) cycloalkyl, aryl; Benzyl, halobenzyl, RG 3 is hydrogen or (C r C 6 ) alkyl.
  • Oxabetrinil ((Z) -1, 3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile) (S11-1), which is known as a seed dressing safener for millet against damage by metolachlor,
  • Fluorofenim (1- (4-chlorophenyl) -2,2,2-trifluoro-1-ethanone-O- (1,3-dioxolan-2-ylmethyl) oxime) (S11-2) which was used as seed dressing Safener for millet is known against damage from metolachlor, and
  • Isothiochromanone (S12) class agents e.g. Methy! - [(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.
  • Naphthalene anhydride (1,8-naphthalenedicarboxylic anhydride) (S13-1), which is known as
  • Seed pickling safener for maize known for damage from thiocarbamate herbicides
  • Imidazolinones are known "MG 191” (CAS Reg. No. 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia, which is known as safener for corn, " MG-838 "(CAS Reg. No. 133993-74-5)
  • Some of the safeners are already known as herbicides and therefore, in addition to the herbicidal effect on harmful plants, also have a protective effect on the crop plants.
  • the weight ratio of herbicide (mixture) to safener generally depends on the application rate of herbicide and the effectiveness of the particular safener and can vary within wide limits, for example in the range from 200: 1 to 1: 200, preferably 100: 1 to 1: 100, in particular 20: 1 to 1:20.
  • the safeners can be formulated analogously to the compounds of the formula (I) or mixtures thereof with further herbicides / pesticides and provided and used as finished formulation or tank mixture with the herbicides.
  • the formulations present in commercial form are optionally diluted in the usual way, for.
  • emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Dust-like preparations, ground or scattered granules and sprayable solutions are usually no longer diluted with other inert substances before use.
  • the type of herbicide used u.a. varies the required application rate of the compounds of general formula (I). It can vary within wide limits, eg. B. between 0.001 and 10.0 kg / ha or more active substance, but it is preferably between 0.005 and 5 kg / ha.
  • 1, 3-oxazol-2 (3H) -thione (0.500 g, 5 mmol, prepared according to WO 03/006442 A) is initially charged in 15 ml of acetonitrile. With ice bath cooling, 1,8-diazabicyclo (5.4.0) undec-7-ene (DBU, 0.81 ml, 5 mmol) is added dropwise. It is stirred for 10 minutes at 25 0 C. A solution of 2- (bromomethyl) -1, 4-dimethylbenzene (0.984 g, 5 mmol) dissolved in acetonitrile is added dropwise. The mixture is stirred for a further 4 hours at 25 0 C and allowed to stand overnight.
  • DBU 1,8-diazabicyclo
  • reaction mixture is added to water and extracted twice with dichloromethane, then washed with water and finally with saturated NaCl solution.
  • the combined organic phases are dried over magnesium sulfate, filtered off and concentrated.
  • the crude product is purified by chromatography (heptane: ethyl acetate, gradient 10: 0 to 8: 2). This gives 0.78 g of product (68.3% of theory).
  • 1, 3-oxazol-2 (3H) -thione (0.500 g, 5 mmol, prepared according to WO 03/006442 A) is initially charged in 10 ml of acetonitrile. With ice-bath cooling, 1,8-diazabicyclo (5.4.0) undec-7-ene (DBU, 0.812 ml, 5 mmol) is added dropwise. It is stirred for 10 minutes at 25 0 C. A solution of 2- (bromomethyl) -1,3-dichlorobenzene (1.186 g, 5 mmol) dissolved in acetonitrile is added dropwise. The mixture is stirred for a further 5 hours at 25 0 C and allowed to stand overnight.
  • DBU 1,8-diazabicyclo
  • reaction mixture is water and extracted twice with dichloromethane, then washed with water and finally with saturated NaCl solution.
  • the combined organic phases are dried over magnesium sulfate, filtered off and concentrated.
  • the crude product is purified by chromatography (heptane: ethyl acetate, gradient 10: 0 to 7: 3). This gives 0.66 g of product (48.7% of theory).
  • 1, 3-oxazol-2 (3H) -thione (0.500 g, 5 mmol, prepared according to WO 03/006442 A) is initially charged in 10 ml of acetonitrile. With ice-bath cooling, 1,8-diazabicyclo (5.4.0) undec-7-ene (DBU, 0.812 ml, 5 mmol) is added dropwise. It is stirred for 10 minutes at 25 0 C. A solution of 2- (bromomethyl) -1,3-difluorobenzene (1.024 g, 5 mmol) dissolved in acetonitrile is added dropwise. The mixture is stirred for a further 5 hours at 25 0 C and allowed to stand overnight.
  • reaction mixture is added to water and extracted twice with dichloromethane, then washed with water and finally with saturated NaCl solution.
  • the combined organic phases are dried over magnesium sulfate, filtered off and concentrated.
  • the crude product is purified by chromatography (heptane: ethyl acetate, gradient 10: 0 to 8: 2). This gives 0.69 g of product (58.3% of theory).
  • Portionwise 3- chloroperbenzoic acid (5.100 g, 23 mmol, 77% strength) is added to the thus obtained ducks dichloromethane solution under stirring and ice-cooling, stirred for a further 6 hours at 25 0 C and allowed to stand overnight.
  • the reaction mixture is washed twice with 2 molar sodium hydroxide solution, then with water and finally with saturated NaCl solution.
  • the combined organic phases are dried over magnesium sulfate, filtered off and concentrated. 0.820 g of product (50.7% of theory) are obtained.
  • 2,3,6-Trichlorobenzylbromide (0.267 g, 1 mmol) is presented in ethanol (10 ml). Thiourea (0.074 g, 1 mmol) is added and the mixture is refluxed for 2 hours. The solution is then cooled to 25 ° C. and 2- (methylsulfonyl) -1,3-oxazole (0.130 mg, 1 mmol) is added, followed by potassium carbonate (0.183 g, 1 mmol). The mixture is refluxed for 6 hours erhizt. For workup, the reaction solution is added to water and extracted with dichloromethane. The combined organic phases are dried and concentrated. This gives 0.063 g of product (23% of theory).
  • Retention times (R t, in minutes) and Enatiomerensch (ee) of chiral compounds were determined by analytical chiral HPLC [Chiralcel ® OD column (250 x 4.6 mm, particle size 5 .mu.m), temperature 25 0 C, flow 1 ml / min, hexane / 2-propanol 90:10 v / v].
  • Racemates or enantiomeric mixtures were separated by preparative chiral HPLC into the respective enantiomeric [Chiralcel ® OD column (250 x 5 mm, particle size 10 .mu.m), temperature 25 C C, flow 0.6 ml / min, hexane / 2-propanol 90:10 v / v].
  • a dust is obtained by mixing 10 parts by weight of a compound of formula (I) and / or salts thereof and 90 parts by weight of talc as an inert material and comminuted in a hammer mill.
  • a wettable powder readily dispersible in water is obtained by reacting 25 parts by weight of a compound of the formula (I) and / or its salts, 64 parts by weight of kaolin-containing quartz as inert material, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of oleoylmethyl tauric acid sodium as a wetting and dispersing agent and grinding in a pin mill.
  • a dispersion concentrate readily dispersible in water is obtained by reacting 20 parts by weight of a compound of the formula (I) and / or salts thereof with 6 parts by weight of alkylphenol polyglycol ether ( ⁇ Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO ) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to about 277 C) and milled in a ball mill to a fineness of less than 5 microns.
  • An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I) and / or salts thereof, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.
  • a water-dispersible granule is also obtained by reacting 25 parts by weight of a compound of formula (I) and / or salts thereof, 5 parts by weight of 2,2'-dinaphthylmethane 6,6'-disulfonic acid sodium 2 parts by weight of sodium oleoylmethyltaurate, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water homogenized on a colloid mill and pre-crushed, then grinded on a bead mill and the resulting suspension in a spray tower by means of a Einstoffdüse atomized and dried.
  • the present invention therefore also provides a method for controlling undesirable plants or for regulating the growth of plants, preferably in plant crops, wherein one or more compounds of the invention are applied to the plants (eg harmful plants such as monocotyledonous or dicotyledonous weeds or undesired crop plants), the seeds (eg grains, seeds or vegetative propagules such as tubers or sprout parts with buds) or the area on which the plants grow (eg the acreage) are applied.
  • the compounds of the invention may be e.g. in pre-sowing (possibly also by incorporation into the soil), pre-emergence or Nachauflaufmaschinene.
  • some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned, which can be controlled by the compounds according to the invention, without the intention of limiting them to certain species.
  • 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.
  • 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 very well suited for the selective control of undesired ones Plant growth in crops such as agricultural crops or ornamental plantings
  • 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.
  • the active compounds can also be used to control harmful plants in crops of genetically engineered or conventional mutagenized plants.
  • the transgenic plants are usually characterized by particular advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
  • Other special properties relate to z. B. the crop in terms of quantity, quality, shelf life, composition and special ingredients.
  • transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known.
  • transgenic cultures Preferred with respect to transgenic cultures is the use of the compounds of the invention in economically important transgenic crops of useful and ornamental plants, eg. As cereals such as wheat, barley, rye, oats, millet, rice and corn or even crops of sugar beet, cotton, soybeans, rapeseed, potato, tomato, Pea and other vegetables.
  • cereals such as wheat, barley, rye, oats, millet, rice and corn or even crops of sugar beet, cotton, soybeans, rapeseed, potato, tomato, Pea and other vegetables.
  • the compounds of the invention as herbicides in
  • Crop crops are used, which compared to the phytotoxic
  • 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 according to the invention formulated in the form of wettable powders (WP) are then applied to the surface of the cover soil as an aqueous suspension having a water application rate of 600 l / ha, with the addition of 0.2% wetting agent.
  • compounds of the invention have a good herbicidal pre-emergence activity against a broad spectrum of grass weeds and weeds.
  • compounds Nos. 11, 14, 131, 44, 65, 66, 203, 2517 and other compounds of Tables 1-3 have very good herbicidal activity against harmful plants such as Echinochloa crus galli, Lolium multiflorum, Veronica persica and Alopecurus myosuroides Pre-emergence method at an application rate of 0.32 kg and less active substance per hectare.
  • compounds according to the invention leave dicotyledonous crops, such as rape seed pre-emergence, undamaged even at high doses of active ingredient.
  • some substances also protect graminaceous crops such as wheat and corn.
  • Some of the compounds according to the invention show a high selectivity and are therefore suitable in the pre-emergence process for controlling undesired plant growth in agricultural crops.
  • compounds according to the invention have a good herbicidal postemergence activity against some weeds or weeds.
  • the compounds Nos. 44, 65, 131, 203, 2517 and other compounds from Tables 1-3 have very good herbicidal activity against harmful plants such as Echinochloa crus galli and Lolium multiflorum postemergence at an application rate of 0.32 kg and less active ingredient per hectares.
  • compounds according to the invention leave dicotyledonous crops, such as rapeseed, undamaged even after high doses of active ingredient.
  • some substances also protect graminaceous crops such as wheat and corn.
  • 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.

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Abstract

The invention relates to 2-(benzylsulfonyl)-oxazole derivatives, chiral 2-(benzylsulfinyl)-oxazole derivatives and 2-(benzylsulfanyl)-oxazole derivatives of general formula (I) and the salts thereof, wherein the individual radicals and indexes have the meaning indicated in the description. Also described are methods for the production thereof as well as the use of said compounds as herbicides and plant growth regulators, in particular as herbicides for selectively controlling weeds in plant crops.

Description

2-(Benzylsulfonyl)-Oxazol-Derivate, chirale 2-(Benzylsulfinyl)-Oxazol-Derivate 2- (Benzylsulfanyl)-Oxazol-Derivate, Verfahren zu deren Herstellung sowie deren Verwendung als Herbizide und Pflanzenwachstumsregulatoren 2- (Benzylsulfonyl) -oxazole derivatives, chiral 2- (benzylsulfinyl) -oxazole derivatives 2- (benzylsulfanyl) -oxazole derivatives, processes for their preparation and their use as herbicides and plant growth regulators
Beschreibungdescription
Diese Erfindung betrifft spezielle Verbindungen, ausgewählt aus der Gruppe der 2- (Benzylsulfonyl)-Oxazol-Derivate, chiralen 2-(Benzylsulfinyl)-Oxazol-Derivate und 2- (Benzylsulfanyl)-Oxazol-Derivate, sowie spezielle Verfahren zu deren Herstellung. Weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung dieser Verbindungen als Herbizide, insbesondere als Herbizide zur selektiven Bekämpfung von Schadpflanzen in Nutzpflanzenkulturen. Ferner betrifft die vorliegende Erfindung deren Verwendung als Pflanzenwachstumsregulatoren allein oder in Kombination mit Safenern und/oder in Mischung mit anderen Herbiziden, deren Anwendung zur Pflanzenbekämpfung in speziellen Pflanzenkulturen oder als Pflanzenschutzregulatoren.This invention relates to specific compounds selected from the group of 2- (benzylsulfonyl) -oxazole derivatives, chiral 2- (benzylsulfinyl) -oxazole derivatives and 2- (benzylsulfanyl) -oxazole derivatives, and to specific processes for their preparation. Another object of the present invention is the use of these compounds as herbicides, in particular as herbicides for the selective control of harmful plants in crops. Furthermore, the present invention relates to their use as plant growth regulators alone or in combination with safeners and / or in admixture with other herbicides, their use for plant control in specific crops or as crop protection regulators.
Aus verschiedenen Schriften ist bereits bekannt, dass bestimmte Oxazol-Derivate herbizide Eigenschaften besitzen.It is already known from various publications that certain oxazole derivatives have herbicidal properties.
So beschreibt die WO 2004/013112 A herbizid wirksame Oxazol-Derivate, welche an der 2-Position des Oxazol-Ringes eine Thioethergruppe aufweisen, die wiederum eine Fluoroalken-Einheit umfasst.Thus, WO 2004/013112 A describes herbicidally active oxazole derivatives which have a thioether group at the 2-position of the oxazole ring, which in turn comprises a fluoroalkene unit.
Die US 4,022,607 beschreibt 2-(Alkylsulfinyl)-Oxazol-Derivate, deren Herstellung, sowie deren Verwendung als Herbizide.No. 4,022,607 describes 2- (alkylsulfinyl) -oxazole derivatives, their preparation, and their use as herbicides.
Die DE 102 54 876 A beschreibt 2-(Fluoralkenylthio)-oxazolverbindungen und ihre Verwendung als Herbizide. EP 0 435 794 A beschreibt 1-Heterocyclylsulfonyl-2-phenyl-2-propene und ihre Verwendung als Herbizide.DE 102 54 876 A describes 2- (fluoalkenylthio) -oxazole compounds and their use as herbicides. EP 0 435 794 A describes 1-heterocyclylsulfonyl-2-phenyl-2-propenes and their use as herbicides.
Schädlingsbekämpfende Eigenschaften von 2-Trifluorbutenthio-Oxazol-Derivate sind z.B. beschrieben in WO 2001/066529 A, WO 99/52874 A und WO 95/024403 A.Pesticidal properties of 2-trifluorobutene-thio-oxazole derivatives are e.g. described in WO 2001/066529 A, WO 99/52874 A and WO 95/024403 A.
Des weiteren sind auch 2-[(1 H-Pyrazol-4-ylmethyl)-sulfinyl] und 2-[(1H-Pyrazol-4- ylmethyl)-sulfonyl]-Derivate beschrieben, die herbizide Eigenschaften besitzen. So sind in wo 2007/071900 A, WO 02/62770 A und WO 2006/123088 einige 2-[(1 H- Pyrazol-4-ylmethyl)-sulfinyl] und 2-[(1 H-Pyrazol-4-ylmethyl)-sulfonyl]-Derivate beschrieben, die eine geeignete substituierte (1 H-Pyrazol-4-ylmethyl)-Gruppe als Substituent an der 2-Sulfonyl-bzw 2-Sulfinyl-Gruppe tragen. Ein Verfahren zu deren Herstellung ist ebenfalls in den obengenannten Schriften beschrieben.Furthermore, 2 - [(1H-pyrazol-4-ylmethyl) -sulfinyl] and 2 - [(1H-pyrazol-4-ylmethyl) -sulfonyl] derivatives which have herbicidal properties are also described. For example, in 2007/071900 A, WO 02/62770 A and WO 2006/123088 there are some 2 - [(1 H -pyrazol-4-ylmethyl) -sulfinyl] and 2 - [(1 H-pyrazol-4-ylmethyl) sulfonyl] derivatives which carry a suitable substituted (1 H-pyrazol-4-ylmethyl) group as a substituent on the 2-sulfonyl or 2-sulfinyl group. A process for their preparation is also described in the abovementioned publications.
Des weiteren sind auch 2-(Arylmethyl-sulfonyl)-substituierte-Derivate beschrieben, die herbizide Eigenschaften besitzen. So sind in JP 2003/096059 A und WO 01/112613 A und US 3,960,542 einige 2-(Arylmethyl-sulfonyl)-Derivate beschrieben, die eine geeignete substituierte Phenylmethyl-Gruppe als Substituent an der 2- Sulfonyl-Gruppe tragen. Ein Verfahren zu deren Herstellung ist ebenfalls in den obengenannten Schriften beschrieben.Furthermore, 2- (arylmethyl-sulfonyl) -substituted derivatives which have herbicidal properties are also described. Thus, JP 2003/096059 A and WO 01/112613 A and US Pat. No. 3,960,542 describe some 2- (arylmethylsulfonyl) derivatives which carry a suitable substituted phenylmethyl group as substituent on the 2-sulfonyl group. A process for their preparation is also described in the abovementioned publications.
Die gemäß den oben benannten Schriften bereits bekannten Wirkstoffe weisen bei ihrer Anwendung als Herbizid jedoch Nachteile auf, sei es, (a) dass sie keine oder aber eine nur unzureichende herbizide Wirkung gegen Schadpflanzen, (b) ein zu geringes Spektrum der Schadpflanzen, das mit einem Wirkstoff bekämpft werden kann, oder (c) eine zu geringe Selektivität in Nutzpflanzenkulturen besitzen.However, the already known in the above-mentioned publications agents have disadvantages in their application as a herbicide, whether (a) that they have no or only insufficient herbicidal activity against harmful plants, (b) too low a spectrum of harmful plants, with an active ingredient can be controlled, or (c) have too low selectivity in crops.
Es ist deshalb wünschenswert, alternative chemische Wirkstoffe bereitzustellen, die gegebenenfalls mit weiteren Vorteilen als Herbizide oder Pflanzenwachstumsregulatoren eingesetzt werden können. Aus dem Gebiet der Medizin sind Benzodioxazolderivate bekannt, die zur Behandlung von Leberkrankheiten geeignet sind JP 620 39 583 A.It is therefore desirable to provide alternative chemical agents which may optionally be used with further advantages as herbicides or plant growth regulators. From the field of medicine Benzodioxazolderivate are known which are suitable for the treatment of liver diseases JP 620 39 583 A.
Erfindungsgemäß wurden nun 2-(Benzylsulfonyl)-Oxazol-Derivate, 2- (Benzylsulfanyl)-Oxazol-Derivate und chirale 2-(Benzylsulfinyl)-Oxazol-Derivate gefunden, welche Vorteile gegenüber den vorbeschriebenen Verbindungen aufweisen.According to the invention, 2- (benzylsulfonyl) -oxazole derivatives, 2- (benzylsulfanyl) -oxazole derivatives and chiral 2- (benzylsulfinyl) -oxazole derivatives have now been found which have advantages over the compounds described above.
Gegenstand der vorliegenden Erfindung sind daher Verbindungen der allgemeinen Formel (I) und deren agrochemisch verträglichen SalzeThe present invention therefore relates to compounds of the general formula (I) and their agrochemically compatible salts
worin wherein
n gleich 0, 1 , 2 entspricht; die Substituenten R1 und R2, jeweils unabhängig voneinander, ausgewählt sind aus der Gruppe, bestehend ausn equals 0, 1, 2; the substituents R 1 and R 2 , each independently, are selected from the group consisting of
Wasserstoff, Halogen, Nitro, Cyano, Formyl, -C(O)OH, Hydroxy, undHydrogen, halogen, nitro, cyano, formyl, -C (O) OH, hydroxy, and
Amino;amino;
(Ci-C6)-Alkyl, (Ci-C6)-Alkylcarbonyl, (Ci-C6)-Alkylcarbonyl-(d-C4)- alkyl und (CrC^-Alkylcarbonyloxy;(C 1 -C 6 ) -alkyl, (C 1 -C 6 ) -alkylcarbonyl, (C 1 -C 6 ) -alkylcarbonyl (C 1 -C 4 ) -alkyl and (C 1 -C 4 -alkylcarbonyloxy;
(d-C6)-Alkoxy, (CrC6)-Alkoxycarbonyl, (Ci-C6)-Alkoxycarbonyl-(Cr (dC 6) alkoxy, (C r C6) alkoxycarbonyl, (Ci-C 6) alkoxycarbonyl (C r
C6)-alkyl, (CrC6)-Alkoxy-(Ci-C6)-alkyl, (C1-Ce)-AIkOXy-(C1-C6)^IkOXy und (C1-C6)-AIkoxycarbony1-(Ci-C6)-aIkoxy;C 6) alkyl, (CrC 6) alkoxy- (Ci-C 6) alkyl, (C 1 -Ce) -AIkOXy- (C 1 -C 6) ^ IkOXy and (C 1 -C 6) -AIkoxycarbony1 - (C 1 -C 6 ) -alkoxy;
(C2-C6)-Alkenyl, (C2-C6)-Alkenyloxy, (C2-C6)-Alkinyl und (C2-C6)-(C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyl and (C 2 -C 6 ) -
Alkinyloxy;alkynyloxy;
(CrC6)-Alkylthio, (CrC6)-Alkylsulfinyl, (CrC6)-Alkylsulfonyl, (C1-C6)-(CrC 6) alkylthio, (C r C6) alkylsulfinyl, (C r C6) alkylsulfonyl, (C 1 -C 6) -
Alkylsulfonyloxy, (CrCeJ-Alkylsulfonyl^CrCβJ-alkyl, (C1-C6)- Alkylsulfinyl-(CrC6)-alkyl, d-CeJ-Alkylthio^CrCe^alkyl und (CrC6)- Alkylthio-(CrC6)-alkoxy;Alkylsulfonyloxy, (C 1 -C 6 -alkylsulfonyl) C 1 -C 6 -alkyl, (C 1 -C 6 ) - Alkylthio (C r C6) alkoxy - alkylsulfinyl (C r C6) alkyl, d CRCE-CeJ-alkylthio ^ ^ alkyl and (C r C6);
Mono-((d-C6)-alkyl)-amino, Di-((Ci-C6)-alkyl)-amino, N-((d-C6)- Alkanoyl)-amino, Aminocarbonyl-(Ci-C6)-alkyl, Mono-((CrC6)-alkyl)- aminocarbonyl, Di-((CrC6)-alkyl)-aminocarbonyl, Mono-((Ci-C6)-alkyl)- aminosulfonyl und Di-((Ci-C6)-alkyl)-aminosulfonyl; (C3-C8)-Cycloalkyl, (C3-C8)-Cycloalkoxy, (C3-C8)-Cycloalkyl-(d-C6)- alkyl, (C3-C8)-Cycloalkyl-(d-C6)-alkoxy, (C3-C8)-Cycloalkylcarbonyl und (C3-C8)-Cycloalkoxycarbonyl; (C3-C8)-Cycloalkenyl, (C3-C8)-Cycloalkenyloxy, (C3-C8)-Cycloalkylthio,Mono - ((dC 6) alkyl) amino, di - ((Ci-C 6) alkyl) amino, N - ((dC 6) - alkanoyl) -amino, aminocarbonyl (Ci-C 6) - alkyl, mono ((C 1 -C 6 ) alkyl) aminocarbonyl, di (C 1 -C 6 ) alkyl) aminocarbonyl, mono (C 1 -C 6 ) alkyl) aminosulfonyl, and di (C 1 -C 4) 6 ) -alkyl) -aminosulfonyl; (C 3 -C 8 ) -cycloalkyl, (C 3 -C 8 ) -cycloalkoxy, (C 3 -C 8 ) -cycloalkyl- (dC 6 ) -alkyl, (C 3 -C 8 ) -cycloalkyl- (dC 6 ) -alkoxy, (C 3 -C 8 ) -cycloalkylcarbonyl and (C 3 -C 8 ) -cycloalkoxycarbonyl; (C 3 -C 8 ) -cycloalkenyl, (C 3 -C 8 ) -cycloalkenyloxy, (C 3 -C 8 ) -cycloalkylthio,
(C3-C8)-Cycloalkylsulfinyl, (C3-C8)-Cycloalkylsulfonyl und (C3-C8)- Cycloalkylsulfonyloxy;(C 3 -C 8 ) -cycloalkylsulfinyl, (C 3 -C 8 ) -cycloalkylsulfonyl and (C 3 -C 8 ) -cycloalkylsulfonyloxy;
Cyano-(Ci-Ce)-alkoxy und Cyano-(Ci-Ce)-alkyl; -CONH-SO2-(CrC6)-Alkyl, -NHCHO, -NHCO-(CrC6)-Alkyl, -NHCO2- (d-C6)-Alkyl, -NHCONH-(CrC6)-Alkyl, -NHSO2-(C1-C6)-Alkyl,Cyano (Ci-Ce) alkoxy and cyano (Ci-Ce) alkyl; -CONH-SO 2 - (CrC 6) alkyl, -NHCHO, -NHCO (C r C6) alkyl, -NHCO 2 - (dC 6) alkyl, -NHCONH- (C r C6) alkyl , -NHSO 2 - (C 1 -C 6 ) -alkyl,
-OCONH-(C1-Ce)-AIkVl, (Ci-CeVAlkylaminosulfonyKd-CoValky!, Di- (d-CeJ-alkylaminosulfonyl-Cd-Cshalkyl, -C(O)NHR9, -C(O)NR9R10, wobei R9 und R10, jeweils unabhängig voneinander, ausgewählt werden aus der Gruppe, bestehend aus Wasserstoff, (d-CεJ-Alkyl, (C3-C6)-Cycloalkyl, (d-C6)-Haloalkyl, oder wo R9 und R10 zusammen eine (d-C6)-Alkylen-Gruppe bilden, die ein Sauerstoff-, oder Schwefel-Atom oder ein oder zwei Amino oder (d-C6)-Alkylamino- Gruppen enthalten kann, die Substituenten R3 bis R7, jeweils unabhängig voneinander, ausgewählt sind aus der Gruppe, bestehend aus-OCONH- (C 1 -Ce) -AlkVl, (Ci-CeValkylaminosulfonyKd-CoValky !, di- (d-CeJ-alkylaminosulfonyl-Cd-Cshalkyl, -C (O) NHR 9 , -C (O) NR 9 R 10 wherein R 9 and R 10 , each independently, are selected from the group consisting of hydrogen, (C 1 -C 6 -alkyl, (C 3 -C 6 ) -cycloalkyl, (C 1 -C 6 ) -haloalkyl, or where R 9 and R 10 together form a (dC 6 ) alkylene group which may contain an oxygen or sulfur atom or one or two amino or (dC 6 ) alkylamino groups, the substituents R 3 to R 7 , respectively independently, are selected from the group consisting of
Wasserstoff, Halogen, Hydroxy, Cyano, Nitro, Amino, C(O)OH und Formyl;Hydrogen, halogen, hydroxy, cyano, nitro, amino, C (O) OH and formyl;
(d-C6)-Alkyl, (d-C6)-Halogenalkyl, (d-C6)-Alkylcarbonyl, (d- C6)-Haloalkylcarbonyl, (d-C^-Alkylcarbonyloxy, (d-C6)-Halogen- alkylcarbonyloxy, (d-C6)-Alkylcarbonyl-(d-C4)-alkyl, (CrC6)-Ha- loalkylcarbonyl-(Ci-C4)-alkyl, (CrC6)-Alkylcarbonyl-(Ci-C4)-ha- loalkyl und (CrCeJ-HaloalkylcarbonyKCi^J-haloalkyl; (CrC6)-Alkoxy, (d-C6)-Halogenalkoxy, (Ci-C6)-Alkoxycarbonyl, (CrC6)-Haloalkoxycarbonyl, (Ci-C6)-Alkoxycarbonyl-(Ci-C6)-alkyl, (Ci-C6)-Haloalkoxycarbonyl-(Ci-C6)-alkyl, (CrC6)-Alkoxycarbonyl- (Ci-C6)-halogenalkyl und (d-Ce)-Halogenalkoxycarbonyl-(CrC6)- halogenalkyl;(dC 6) alkyl, (dC 6) haloalkyl, (dC 6) alkylcarbonyl, (dC 6) haloalkylcarbonyl, (dC ^ alkylcarbonyloxy, (d-C6) alkylcarbonyloxy-halo, (dC 6) alkylcarbonyl (dC 4) alkyl, (C r C6) -Ha- loalkylcarbonyl- (Ci-C 4) alkyl, (CrC 6) alkylcarbonyl (Ci-C 4) -ha- loalkyl, and (CrCeJ -HaloalkylcarbonyKCi ^ J-haloalkyl; (CrC 6) alkoxy, (dC 6) haloalkoxy, (Ci-C 6) -alkoxycarbonyl, (CrC 6) -Haloalkoxycarbonyl, (Ci-C 6) alkoxycarbonyl (Ci-C 6) alkyl, (C -C 6) -Haloalkoxycarbonyl- (Ci-C 6) alkyl, (CrC 6) alkoxycarbonyl (Ci-C 6) -haloalkyl and (d-Ce) -Halogenalkoxycarbonyl- (CrC 6) - haloalkyl;
(C2-C6)-Alkenyl, (C2-C6)-Halogenalkenyl, (C2-C6)-Alkenylcarbonyl, (C2-C6)-Haloalkenylcarbonyl, (C2-C6)-Alkenyloxy, (C2-C6)-Halo- alkenyloxy, (C2-C6)-Alkenyloxycarbonyl und (C2-C6)-Haloalkenyl- oxycarbonyl; (C2-Ce)-Al kinyl, (C2-C6)-Halogenalkinyl, (C2-C6)-Alkinylcarbonyl,(C 2 -C 6 ) alkenyl, (C 2 -C 6 ) -haloalkenyl, (C 2 -C 6 ) -alkenylcarbonyl, (C 2 -C 6 ) -haloalkenylcarbonyl, (C 2 -C 6 ) -alkenyloxy, (C 2 -C 6 ) -haloalkenyloxy, (C 2 -C 6 ) -alkenyloxycarbonyl and (C 2 -C 6 ) -haloalkenyl-oxycarbonyl; (C2 -Ce) -Al kinyl, (C 2 -C 6) -haloalkynyl, (C 2 -C 6) alkynylcarbonyl,
(C2-C6)-Haloalkinylcarbonyl, (C2-C6)-Alkinyloxy, (C2-C6)-Haloalki- nyloxy, (C2-C6)-Alkinyloxycarbonyl und (C2-C6)-Halogenalkinyloxy- carbonyl; (d-C6)-Alkylthiocarbonyl, (d-CeJ-Haloalkylthiocarbonyl, (C1-C6)- Alkylthiocarbonyloxy und (d-C6)-Haloalkylthiocarbonyloxy;(C 2 -C 6 ) -haloalkynylcarbonyl, (C 2 -C 6 ) -alkynyloxy, (C 2 -C 6 ) -haloalkynyloxy, (C 2 -C 6 ) -alkynyloxycarbonyl and (C 2 -C 6 ) - Haloalkynyloxycarbonyl; (dC 6 ) alkylthiocarbonyl, (d-CeJ-haloalkylthiocarbonyl, (C 1 -C 6 ) -alkylthiocarbonyloxy and (dC 6 ) -haloalkylthiocarbonyloxy;
(Ci-C6)-Alkylthio-(CrC6)-alkoxy, (CrC-sKALkyJthio^CrCeJ-alkylcar- bonyl und (C-i-C6)-Alkylthio-(Ci-C6)-alkylcarbonyloxy; (d-C6)-Alkylsulfonyl, (d-C6)-Alkylthio, (CrC6)-Alkylsulfinyl, (C1- C6)-Haloalkylsulfonyl, (d-C6)-Halogenalkylthio, (d-C6)-Halogen- alkylsulfinyl, (d-C6)-Alkylsulfonyl-(Ci-C6)-alkyl, (d-C6)-Alkylthio-(CiC 6) alkylthio (C r C6) alkoxy, (CrC ^ CrCeJ-alkylcarboxylic sKALkyJthio carbonyl and (CiC 6) alkylthio (CiC 6) alkylcarbonyloxy; (dC 6) - alkylsulfonyl, (dC 6) alkylthio, (C r C6) alkylsulfinyl, (C 1 - C 6) haloalkylsulfonyl, (dC 6) haloalkylthio, (dC 6) halo-alkylsulfinyl, (dC 6) alkylsulfonyl (C 1 -C 6 ) -alkyl, (C 1 -C 6 ) -alkylthio
(d-C6)-alkyl, (d-CeJ-Alkylsulfinyl^d-CeJ-alkyl, (Ci-C6)- Haloalkylsulfonyl-(d-C6)-alkyl, (d-C^-Haloalkylthio^d-CeJ-alkyl, (d-CeJ-Haloalkylsulfinyl^d-CeJ-alkyl^d-CeJ-Alkylsulfonyl^d- C6)-haloalkyl, (d-CeJ-Alkylthio^Ci-CeJ-haloalkyl, (C1-C6)- Alkylsulfinyl-(d-C6)-haloalkyl, (d-C6)-Haloalkylsulfonyl-(d-C6)- haloalkyl, (CrCeJ-Haloalkylthio^CrCeJ-haloalkyl, (C1-Ce)-Ha- loalkylsulfinyl-(d-C6)-haloalkyl, (d-C6)-Alkylsulfonyloxy und (C1- C6)-Halogenalkylsulfonyloxy; Mono-((C1-C6)-alkyl)-amino, Mono-((C1-C6)-haloalkyl)-amino, Di- ((CrCeJ-alkyO-amino, Di-((C1-C6)-haloalkyl)-amino, ((CrC6)-Alkyl-(dC 6) alkyl, (d-CeJ-alkylsulfinyl ^ d-CeJ-alkyl, (Ci-C 6) - Haloalkylsulfonyl- (dC 6) alkyl, (dC ^ haloalkylthio ^ d-CeJ-alkyl, (d -CeJ-haloalkylsulfinyl ^ d-CeJ-alkyl ^ d-CeJ-alkylsulfonyl ^ d- C 6 ) -haloalkyl, (d-CeJ-alkylthio ^ Ci-CeJ-haloalkyl, (C 1 -C 6 ) -alkylsulfinyl- (dC 6) -haloalkyl, (dC 6) -Haloalkylsulfonyl- (dC 6) - haloalkyl, (CrCeJ-haloalkylthio ^ CrCeJ-haloalkyl, (C 1 -Ce) -Ha- loalkylsulfinyl- (dC 6) -haloalkyl, (dC 6) -alkylsulfonyloxy and (C 1 - C 6) -Halogenalkylsulfonyloxy; mono - ((C 1 -C 6) alkyl) amino, mono - ((C 1 -C 6) haloalkyl) amino, di ((CrCeJ -alkyO-amino, di - ((C 1 -C 6) haloalkyl) amino, ((C r C6) alkyl
(CrC6)-haloalkyl)-amino, N-((C1-C6)-Alkanoyl)-amino, N-((d-C6)- Haloalkanoyl)-amino, Aminocarbonyl-(Ci-C6)-alkyl, MOnO-(C1-C6)- AlkylaminocarbonyKCrCβJ-alkyl, Di-(CrC6)-Alkylaminocarbonyl- (Ci-C6)-alkyl und Mono-((Ci-C6)-alkyl)-aminocarbonyl; (Ci-Cβ)-Alkoxy-(Ci-C6)-alkyl, (Ci-C6)-Alkoxy-(CrCβ)-alkoxy, (C1- C6)-Alkoxycarbonyl-(CrC6)-alkoxy, - (C3-C8)-Cycloalkyl, (C3-C8)-Cycloalkoxy, (C3-C8)-Cycloalkyl-(Ci-(C r C6) haloalkyl) amino, N - ((C 1 -C 6) alkanoyl) amino, N - ((dC 6) - haloalkanoyl) amino, aminocarbonyl (Ci-C 6) - alkyl, MOnO- (C 1 -C 6 ) - AlkylaminocarbonyKCrCβJ-alkyl, di- (CrC 6 ) -alkylaminocarbonyl- (Ci-C 6 ) -alkyl and mono - ((Ci-C 6 ) -alkyl) -aminocarbonyl; (Ci-Cβ) alkoxy (Ci-C 6) alkyl, (Ci-C 6) alkoxy (CrCβ) alkoxy, (C 1 - C 6) alkoxycarbonyl (CrC 6) alkoxy, - (C 3 -C 8 ) -cycloalkyl, (C 3 -C 8 ) -cycloalkoxy, (C 3 -C 8 ) -cycloalkyl- (C 3 -C 8 ) -cycloalkoxy,
C6)-alkyl, (Ca-CβJ-CycloalkyKd-CβJ-haloalkyl, (C3-C8)-Cycloalkyl- (CrC6)-alkoxy, (C3-C8)-Cycloalkyl-(CrC6)-haloalkoxy, (C3-C8)- Cycloalkylcarbonyl, (C3-C8)-Cycloalkoxycarbonyl, (C3-Cs)-Cy- cloalkyl-(CrC6)-alkylcarbonyl, (Cs-CβJ-CycloalkyKd-CeJ-halo- alkylcarbonyl, (C3-C8)-Cycloalkyl-(CrC6)-alkoxycarbonyl, (C3-C8)-C 6 ) -alkyl, (Ca-CβJ -cycloalkyKd-CβJ-haloalkyl, (C 3 -C 8 ) -cycloalkyl- (C r C 6 ) -alkoxy, (C 3 -C 8 ) -cycloalkyl- (CrC 6 ) haloalkoxy, (C 3 -C 8) - cycloalkylcarbonyl, (C 3 -C 8) -cycloalkoxycarbonyl, (C 3 -Cs) -Cy- cloalkyl- (CrC 6) alkylcarbonyl, (Cs-CβJ-CycloalkyKd-CeJ- halo- alkylcarbonyl, (C 3 -C 8) cycloalkyl (C r C6) -alkoxycarbonyl, (C 3 -C 8) -
Cycloalkyl-(CrC6)-haloalkoxycarbonyl, (C3-C8)-Cycloalkylcarbo- nyloxy, (C3-C8)-Cycloalkoxycarbonyloxy, (C3-C8)-Cycloalkyl-(Ci- C6)-alkylcarbonyloxy, (C3-C8)-Cycloalkyl-(Ci-C6)-halogen- alkylcarbonyloxy, (C3-C8)-Cycloalkyl-(Ci-C6)-alkoxycarbonyloxy und (C3-C8)-Cycloalkyl-(CrC6)-haloalkoxycarbonyloxy;Cycloalkyl- (C 1 -C 6 ) -haloalkoxycarbonyl, (C 3 -C 8 ) -cycloalkylcarbonyloxy, (C 3 -C 8 ) -cycloalkoxycarbonyloxy, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 6 ) -alkylcarbonyloxy, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 6 ) -halogenalkylcarbonyloxy, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 6 ) -alkoxycarbonyloxy and (C 3 -C 8 ) -cycloalkyl- (CrC 6 ) haloalkoxycarbonyloxy;
(C3-Gs)-Cyc!oa!keny!, (C3-C8)-Cycloalkenyloxy, (C3-C3)-Cyc!oa!ke- nyl-(CrC6)-alkyl, (C3-C8)-Cycloalkenyl-(Ci-C6)-halogenalkyl, (C3- C8)-Cycloalkenyl-(Ci-C6)-alkoxy, (C3-C8)-Cycloalkenyl-(Ci-C6)- halogenalkoxy, (C3-C8)-Cycloalkenylcarbonyl, (C3-C8)-Cycloal- kenyloxycarbonyl, (C3-C8)-Cycloalkenyl-(Ci-C6)-alkylcarbonyl, (C3-(C 3 -G s ) -Cyc! O! Keny !, (C 3 -C 8 ) -cycloalkenyloxy, (C 3 -C 3 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, (C 3 -C 8) cycloalkenyl (Ci-C 6) -haloalkyl, (C 3 - C 8) cycloalkenyl (Ci-C 6) alkoxy, (C 3 -C 8) cycloalkenyl (C 6 ) - halogenoalkoxy, (C 3 -C 8 ) -cycloalkenylcarbonyl, (C 3 -C 8 ) -cycloalkenyloxycarbonyl, (C 3 -C 8 ) -cycloalkenyl- (C 1 -C 6 ) -alkylcarbonyl, (C 3 -
C8)-Cycloalkenyl-(Ci-C6)-halogenalkylcarbonyl, (C3-C8)-Cyclo- alkenyl-(CrC6)-alkoxycarbonyl, (C3-C8)-Cycloalkenyl-(Ci-C6)-ha- loalkoxycarbonyl, (C3-C8)-Cycloalkenylcarbonyloxy, (C3-C8)-Cyclo- a I kenyloxyca rbo nyloxy , (C3-C8)-Cycloa I kenyl-(C1 -C6)-a I kylca r- bonyloxy, (C3-C8)-Cycloalkenyl-(Ci-C6)-halogenalkylcarbonyloxy,C 8) cycloalkenyl (Ci-C6) haloalkylcarbonyl, (C 3 -C 8) cyclo- alkenyl (CrC 6) -alkoxycarbonyl, (C 3 -C 8) cycloalkenyl (Ci-C 6) -ha-loalkoxycarbonyl, (C 3 -C 8 ) -cycloalkenylcarbonyloxy, (C 3 -C 8 ) -cycloalkhenyloxycarboxylloxy, (C 3 -C 8 ) -cycloalkenyl- (C 1 -C 6 ) -a I kylca r bonyloxy, (C 3 -C 8 ) -cycloalkenyl- (C 1 -C 6 ) -haloalkylcarbonyloxy,
(C3-C8)-Cycloalkenyl-(Ci-C6)-alkoxycarbonyloxy und (C3-Ca)-Cy- cloalkenyl-(Ci-C6)-haloalkoxycarbonyloxy; (C3-C8)-Cycloalkylthio, (C3-C8)-Alkenylthio, (C3-C8)-Cycloalkenyl- thio und (C3-C6)-Alkinylthio; - Hydroxy-(Ci-C6)-alkyl, Hydroxy^d-CeJ-alkoxy, Cyano-(Ci-C6)- alkoxy und Cyano-(Ci-Ce)-alkyl; 3-Oxetanyloxy-, -C(O)NHR9 oder -C(O)NR9R10, wobei R9 und R10, jeweils unabhängig voneinander, ausgewählt werden aus der Gruppe, bestehend aus Wasserstoff, (d-C6)-Alkyl, (C3-C6)-Cycloalkyl, (Cr CβJ-Haloalkyl, oder wo R9 und R10 zusammen eine (C-i-Cβ)- Alkylen-Gruppe bilden, die ein Sauerstoff-, oder Schwefel-Atom oder ein oder zwei Amino oder (CrC6)-Alkylamino-Gruppen enthalten kann, wobei(C 3 -C 8 ) -cycloalkenyl- (C 1 -C 6 ) -alkoxycarbonyloxy and (C 3 -Ca) -cycloalkenyl- (C 1 -C 6 ) -haloalkoxycarbonyloxy; (C 3 -C 8 ) -cycloalkylthio, (C 3 -C 8 ) -alkenylthio, (C 3 -C 8 ) -cycloalkenylthio and (C 3 -C 6 ) -alkynylthio; Hydroxy (C 1 -C 6 ) -alkyl, hydroxy, C 1 -C 6 -alkoxy, cyano- (C 1 -C 6 ) -alkoxy and cyano- (C 1 -C 6 ) -alkyl; 3-Oxetanyloxy-, -C (O) NHR 9 or -C (O) NR 9 R 10 , wherein R 9 and R 10 are each independently selected from the group consisting of hydrogen, (C 1 -C 6 ) alkyl, (C 3 -) C 6 ) -cycloalkyl, (C r CβJ-haloalkyl or where R 9 and R 10 together form a (Ci-Cβ) - alkylene group which is an oxygen or sulfur atom or one or two amino or (CrC 6 ) -alkylamino groups may contain, wherein
(1 ) die zuvor für R3 bis R7 definierten Reste gegebenenfalls untereinander zyklisch verknüpft sein können, unter der Voraussetzung, dass sie o/tΛo-ständig sind; und/oder(1) the radicals previously defined for R 3 to R 7 may optionally be cyclically linked with each other, provided that they are o / tΛo-permanent; and or
(2) zwei ortho-ständige Substituenten zusammen eine (CrC6)- Alkylengruppe bilden, die ein oder mehrere Sauerstoff- und/oder Schwefelatome enthalten können, wobei die (C-i-CβJ-Alkylengruppe durch Halogen einfach oder mehrfach substituiert sein kann und die jeweilgen Halogensubstituenten gleich oder verschieden sein können; und/oder(2) two ortho-substituents together form a (CrC 6 ) - alkylene group which may contain one or more oxygen and / or sulfur atoms, wherein the (Ci-CβJ-alkylene group may be monosubstituted or polysubstituted by halogen and the respective Halogen substituents may be the same or different, and / or
(3) die zuvor genannten Reste R1 bis R2 einfach oder mehrfach und unabhängig voneinander durch Reste substituiert sein können, welche ausgewählt sind aus der Gruppe, bestehend aus Halogen und (CrC6)-(3) the abovementioned radicals R 1 to R 2 may be mono- or polysubstituted and independently of one another by radicals which are selected from the group consisting of halogen and (C 1 -C 6 ) -
Alkyl; undalkyl; and
(4) mindestens ein Rest, ausgewählt aus der Gruppe der Reste R3 bis R7 ungleich Wasserstoff ist,(4) at least one radical selected from the group of radicals R 3 to R 7 is not hydrogen,
wobei die Verbindung 2-[(1 ,3-Benzodioxol-5-ylmethyl)sulfanyl]-4-methyl-1 ,3-oxazol ausgenommen ist.wherein the compound 2 - [(1, 3-benzodioxol-5-ylmethyl) sulfanyl] -4-methyl-1,3-oxazole is excluded.
Die zuvor definierten Verbindungen umfassen an dem Arylrest zumindest einen Rest von R3 bis R7, welcher ungleich Wasserstoff ist; das heißt, dass der Arylrest neben dem Rest -(CH2J-S(O)n- mindestens einen weiteren Substituenten umfasst, welcher ungleich Wasserstoff ist bzw. solche Verbindungen nicht von der erfindungsgemäßen Definition der Verbindungen der allgemeinen Formel (I) umfasst sind, in welchen der Arylring unsubstitiert ist.The compounds defined above comprise, on the aryl radical, at least one radical from R 3 to R 7 , which is not hydrogen; that is, the aryl radical in addition to the radical - (CH 2 JS (O) n - comprises at least one further substituent, which is not hydrogen or such compounds does not include the inventive definition of the compounds of general formula (I) are in which the aryl ring is unsubstituted.
Darüber hinaus sind insbesondere solche Verbindungen nicht von der erfindungsgemäßen Definition der Verbindungen der allgemeinen Formel (I) umfasst, in welchen R1 und/oder R2 am Oxazolring die Bedeutung (C6)-Aryl aufweist.In addition, in particular, such compounds are not encompassed by the definition according to the invention of the compounds of the general formula (I) in which R 1 and / or R 2 on the oxazole ring has the meaning (C 6 ) -aryl.
Wenn die Reste R1 bis R7, insbesondere Cycloalkyl, substituiert sind, so sind die Substituenten vorzugsweise ausgewählt aus der Gruppe, bestehend aus (C1-Ce)- Alkyl, (C1-Ce)-HaIOaIkVl, (C1-Ce)-AIkOXy, Nitro, Cyano, (CrC3)-Cycloalkyl, (C1-C6)- Haloalkoxy, (CrC6)-Alkylthio, (CrC6)-Alkylcarbonyl, (CrC6)-Alkoxycarbonyl oder Halogen, wobei diese Reste der zweiten Substituentenebene gegebenenfalls untereinander zyklisch verknüpft sein können, unter der Voraussetzung, dass sie ortho-ständig sind.When the radicals R 1 to R 7 , in particular cycloalkyl, are substituted, the substituents are preferably selected from the group consisting of (C 1 -Ce) - alkyl, (C 1 -Ce) -HaIOaIkVl, (C 1 -Ce ) -alkoxy, nitro, cyano, (C r C 3) cycloalkyl, (C 1 -C 6) - haloalkoxy, (CrC 6) alkylthio, (CrC 6) alkylcarbonyl, (C r C6) alkoxycarbonyl, or Halogen, wherein these radicals of the second substituent level may optionally be cyclically linked to each other, provided that they are ortho-constantly.
Die Überschneidung mit der Offenbarung der auf dem Gebiet der Medizin liegenden Schrift JP 620 39 583 A wurde durch einen Disclaimer, der die Verbindung 2-[(1 ,3- Benzodioxol-5-ylmethyl)sulfanyl]-4-methyl-1 ,3-oxazol vom Schutzumfang ausnimmt, berücksichtigt.The overlap with the disclosure in the field of medicine JP 620 39 583 A has been made by a disclaimer which describes the compound 2 - [(1,3-benzodioxol-5-ylmethyl) sulfanyl] -4-methyl-1,3 -oxazole excludes the scope of protection, taken into account.
Eine erste Ausführungsform der vorliegenden Erfindung umfasst Verbindungen der allgemeinen Formel (I), in denenA first embodiment of the present invention comprises compounds of the general formula (I) in which
R1 bevorzugt ausgewählt ist aus der Gruppe, bestehend ausR 1 is preferably selected from the group consisting of
Wasserstoff, Halogen, Nitro, Cyano, Carboxyl, (C1-C6)- Alkyl, (C3-C6)-Cycloalkyl, (C3-C6)-Cycloalkoxy, (C1-C6)-Hydrogen, halogen, nitro, cyano, carboxyl, (C 1 -C 6) - alkyl, (C 3 -C 6) -cycloalkyl, (C 3 -C 6) cycloalkoxy, (C 1 -C 6) -
Alkoxy, (CrCe)-Alkylcarbonyl, (C3-C6)-Cycloalkylcarbonyl, (d-CeJ-Alkoxycarbonyl, (C3-Ce)-Cycloalkoxycarbonyl, Mono-((CrC4)-alkyl)-aminocarbonyl, Di-((CrC4)-alkyl)- aminocarbonyl, Mono-((CrC4)-alkyl)-aminosulfonyl, Di- ((CrC^O-alkyO-aminosulfonyl, (CrC4)-Alkylthio, (C3-C6)-Alkoxy, (CRCE) alkylcarbonyl, (C 3 -C 6) cycloalkylcarbonyl, (d-CeJ-alkoxy, (C3 -Ce) -cycloalkoxycarbonyl, mono - ((CrC 4) alkyl) aminocarbonyl, di- ( (C r C4) alkyl) - aminocarbonyl, mono - ((CrC 4) alkyl) aminosulfonyl, di ((CrC ^ O-alkyO-aminosulfonyl, (CrC 4) alkylthio, (C 3 -C 6 ) -
Cycloalkylthio, (C1-C4)-Alkylsulfinyl, (C3-C6)-Cycloalkyl- sulfinyl, (CrC4)-Alkylsulfonyl, (C3-C6)-Cycloalkylsulfonyl, (Ci-C4)-Alkylsulfonyloxy, (C3-C6)-Cycloalkylsulfonyloxy, (C2-C3)-Alkenyl, (C2-C3)-Alkinyl, (C2-C3)-Alkenyloxy, (C2- C3)-Alkinyloxy, -NHCO-(C1-C3)-Alkyl, -NHCO2-(C1-C3)- Alkyl, -NHCONH-(CrC3)-Alkyl, -NHSO2-(C1-C3)-Alkyl, - OCONH-(d-C3)-Alkyl, -CONHR9, -CONR9R10, wobei R9 und R10 unabhängig voneinander ausgewählt sind aus der Gruppe, bestehend aus Wasserstoff, (C-ι-C6)-Alkyl, (C3-C6)-Cycloalkyl und (CrC6)-Haloalkyl; und wobei der Rest R1 einfach oder mehrfach durch Reste substituiert sein kann, welche ausgewählt sind aus der Gruppe, bestehend aus Halogen und (Ci-Cβ)-Alkyl;Cycloalkylthio, (C 1 -C 4) alkylsulfinyl, (C 3 -C 6) cycloalkyl, sulfinyl, (CrC 4) alkylsulfonyl, (C 3 -C 6) cycloalkylsulfonyl, (C 1 -C 4 ) -alkylsulfonyloxy, (C 3 -C 6 ) -cycloalkylsulfonyloxy, (C 2 -C 3 ) -alkenyl, (C 2 -C 3 ) -alkynyl, (C 2 -C 3 ) -alkenyloxy, ( C 2 - C 3) alkynyloxy, -NHCO- (C 1 -C 3) alkyl, -NHCO 2 - (C 1 -C 3) - alkyl, -NHCONH- (C r C 3) alkyl, -NHSO 2 - (C 1 -C 3 ) -alkyl, -OCONH- (dC 3 ) -alkyl, -CONHR 9 , -CONR 9 R 10 , wherein R 9 and R 10 are independently selected from the group consisting of hydrogen, (C-ι-C6) alkyl, (C 3 -C 6) cycloalkyl and (C r C 6) -haloalkyl; and wherein the radical R 1 may be monosubstituted or polysubstituted by radicals selected from the group consisting of halogen and (C 1 -C 6) -alkyl;
R1 besonders bevorzugt ausgewählt wird aus der Gruppe, bestehend aus H, F, Cl,R 1 is particularly preferably selected from the group consisting of H, F, Cl,
Br, I, Me, Et, NO2, C(O)OEt, CHF2 und CF3; undBr, I, Me, Et, NO 2 , C (O) OEt, CHF 2 and CF 3 ; and
R1 ganz besonders bevorzugt ausgewählt wird aus der Gruppe, bestehend aus H, F, Cl,R 1 is very particularly preferably selected from the group consisting of H, F, Cl,
Br, I, Me, und NO2.Br, I, Me, and NO 2 .
Eine zweite Ausführungsform der vorliegenden Erfindung umfasst Verbindungen der allgemeinen Formel (I), in denenA second embodiment of the present invention comprises compounds of the general formula (I) in which
R2 bevorzugt ausgewählt ist aus der Gruppe, bestehend aus Wasserstoff, Halogen, Nitro, Cyano, Carboxyl, (C1-Ce)- Alkyl, (C3-C6)-Cycloalkyl, (C3-C6)-Cycloalkoxy, (C1-C6)- Alkoxy, (CrCβJ-Alkylcarbonyl, (C3-C6)-Cycloalkylcarbonyl, (CrCβJ-Alkoxycarbonyl, (C3-C6)-Cycloalkoxycarbonyl, Mono-((Ci-C4)-alkyl)-aminocarbonyl, Di-((C1-C4)-alkyl)- aminocarbonyl, Mono-((CrC4)-alkyl)-aminosulfonyl, Di- ((C-rC^-alkyO-aminosulfonyl, (CrC4)-Alkylthio, (C3-C6)- Cycloalkylthio, (CrC4)-Alkylsulfinyl, (C3-C6)-Cycloalkyl- sulfinyl, (d-CO-Alkylsulfonyl, (C3-C6)-Cycloalkylsulfonyl, (Ci-C4)-Alkylsulfonyloxy, (C3-C6)-Cycloalkylsulfonyloxy, (C2-C3)-Alkenyl, (C2-C3)-Alkinyl, (C2-C3)-Alkenyloxy, (C2- C3)-Alkinyloxy, -NHCO-(CrC3)-Alkyl, -NHCO2-(C1-C3)- Alkyl, -NHCONH-(CrC3)-Alkyl, -NHSO2-(CrC3)-Alkyl, - OCON H-(C1 -C3)-Alkyl, -CONHR9, -CONR9R10, wobei R9 und R10 unabhängig voneinander ausgewählt sind aus der Gruppe, bestehend aus Wasserstoff, (C-i -Ce)-AIkVl, (C3-C6)-Cycloalkyl und (d-CeJ-Haloalkyl; und wobei der Rest R2 einfach oder mehrfach durch Reste substituiert sein kann, welche ausgewählt sind aus der Gruppe, bestehend aus Halogen und (Ci-Cβ)-Alkyl;R 2 is preferably selected from the group consisting of hydrogen, halogen, nitro, cyano, carboxyl, (C 1 -Ce) - alkyl, (C 3 -C 6) -cycloalkyl, (C 3 -C 6) cycloalkoxy, (C 1 -C 6 ) -alkoxy, (C 1 -C 6 -alkylcarbonyl, (C 3 -C 6 ) -cycloalkylcarbonyl, (C 1 -C 6 -alkoxycarbonyl, (C 3 -C 6 ) -cycloalkoxycarbonyl, mono - ((C 1 -C 4 ) - alkyl) aminocarbonyl, di - ((C 1 -C 4) alkyl) - aminocarbonyl, mono - ((CrC 4) alkyl) aminosulfonyl, di ((CrC ^ -alkyO-aminosulfonyl, (C r C 4) -alkylthio, (C 3 -C 6) - cycloalkylthio, (C r C4) alkylsulfinyl, (C 3 -C 6) cycloalkyl, sulfinyl, (d-CO-alkylsulfonyl, (C 3 -C 6 ) cycloalkylsulfonyl, (C 1 -C 4 ) -alkylsulfonyloxy, (C 3 -C 6 ) -cycloalkylsulfonyloxy, (C 2 -C 3 ) -alkenyl, (C 2 -C 3 ) -alkynyl, (C 2 -C 3 ) -alkenyloxy, ( C 2 - C 3) alkynyloxy, -NHCO- (-C 3) alkyl, -NHCO 2 - (C 1 -C 3) - alkyl, -NHCONH- (C r C 3) alkyl, -NHSO 2 - ( C r C 3) alkyl, - OCON H- (C 1 -C 3) alkyl, -CONHR 9, -CONR 9 R 10 wherein R 9 and R 10 are independently selected from the group consisting of hydrogen, (Ci-Ce) -AlkVl, (C 3 -C 6 ) -cycloalkyl and (d-CeJ-haloalkyl; and wherein the radical R 2 may be monosubstituted or polysubstituted by radicals which are selected from the group consisting of halogen and (C 1 -C 6) -alkyl;
R2 besonders bevorzugt ausgewählt wird aus der Gruppe, bestehend aus H, F, Cl, Br, I, Me, Et, NO2, C(O)OEt, CHF2 und CF3; undR 2 is more preferably selected from the group consisting of H, F, Cl, Br, I, Me, Et, NO 2 , C (O) OEt, CHF 2 and CF 3 ; and
R ganz besonders bevorzugt ausgewählt wird aus der Gruppe, bestehend aus H, F, Cl, Br und I.R is more preferably selected from the group consisting of H, F, Cl, Br and I.
Eine dritte Ausführungsform der vorliegenden Erfindung umfasst Verbindungen der allgemeinen Formel (I), in denenA third embodiment of the present invention comprises compounds of the general formula (I) in which
R3 bevorzugt ausgewählt ist aus der Gruppe, bestehend aus Wasserstoff, Hydroxy, Halogen, Cyano, Nitro, Amino, C(O)OH, (C-ι-C4)-Alkyl, (C3-C6)-Cycloalkyl, (Ci-C4)-Haloalkyl, (C1- C4)-Alkoxy, (CrC4)-Haloalkoxy, (C1-C4J-AIkOXy-(C1-C2)- alkyl, (CrC3)-Alkylcarbonyl, (CrC3)-Alkylcarbonyloxy, (C-ι-C4)-Alkoxycarbonyl, (C3-C6)-Cycloalkoxycarbonyl, (C3-C6)-Cycloalkyl-(CrC2)-alkoxy, (C3-C6)-Cycloalkoxy, (C1-C4)-Alkoxycarbonyl-(C1-C2)-alkoxy, (C3-C4)-Alkenyl- oxy, (C3-C4)-Alkinyloxy, (CrC^-Alkylthio, (CrC4)-Haloal- kylthio, (C1-C4)-Alkylsulfinyl, (d^-Haloalkylsulfinyl, (C1- C4)-Alkylsulfonyl, (CrC4)-Haloalkylsulfonyl, (C1-C4J-AI- kylsulfonyloxy, Di-(CrC4)-Alkylamino, (C3-C4)- Alkenyloxycarbonyl, (C2-C4)-Alkinyloxycarbonyl, Formyl, (C2-C4)-Alkenyl, (C2-C4)-Alkinyl, -C(O)NR9R10, wobei R9 und R10, unabhängig voneinander, ausgewählt sind aus der Gruppe, bestehend aus Wasserstoff, (Ci-C6)-Alkyl, (C3-C6)-Cycloalkyl, (CrC6)-Haloalkyl, oder worin R9 und R10 zusammen eine (Ci-CβJ-Alkylen-Gruppe bilden, die ein Sauerstoff- oder Schwefel-Atom oder ein oder zwei Amino- oder (C-i-CβJ-Alkylamino-Gruppen enthalten kann;R 3 is preferably selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C (O) OH, (C 1 -C 4 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (Ci-C 4) -haloalkyl, (C 1 - C 4) alkoxy, (CrC 4) -haloalkoxy, (C 1 -C 4 J-AIkOXy- (C 1 -C 2) - alkyl, (CrC 3) alkylcarbonyl, (CrC 3) alkylcarbonyloxy, (C-ι-C 4) alkoxycarbonyl, (C 3 -C 6) cycloalkoxycarbonyl, (C 3 -C 6) cycloalkyl (C r C 2) alkoxy, (C 3 -C 6 ) -cycloalkoxy, (C 1 -C 4 ) -alkoxycarbonyl- (C 1 -C 2 ) -alkoxy, (C 3 -C 4 ) -alkenyl-oxy, (C 3 -C 4 ) - alkynyloxy, (CrC ^ alkylthio, (C r C4) -Haloal- alkylthio, (C 1 -C 4) alkylsulfinyl, (d ^ haloalkylsulfinyl, (C 1 - C 4) alkylsulfonyl, (CrC 4) haloalkylsulfonyl, (C 1 -C 4 J-AI kylsulfonyloxy, di- (CrC 4) alkylamino, (C 3 -C 4) - alkenyloxycarbonyl, (C 2 -C 4 ) -Alkinyloxycarbonyl, formyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, -C (O) NR 9 R 10 , wherein R 9 and R 10 , independently of one another, are selected from group consisting of hydrogen, (Ci-C 6) -alkyl, (C 3 -C 6) -cycloalkyl, (C r C6) haloalkyl, or wherein R 9 and R 10 together form a (Ci-CβJ alkylene Form a group which may contain an oxygen or sulfur atom or one or two amino or (Ci-CβJ-alkylamino groups;
R besonders bevorzugt ausgewählt ist aus der Gruppe, bestehend aus H, F, Cl,R is more preferably selected from the group consisting of H, F, Cl,
Br, I1 CN, OH, NH2, NO2, Me, Et, Ph, CHF2, CF3, OMe, OEt, OPr, OiPr, OBu, OcPen, OcHex, OCHF2, OCF3, OCH2CF3, C(O)OH, C(O)OMe, C(O)OEt, C(O)OPr,Br, I 1 CN, OH, NH 2 , NO 2 , Me, Et, Ph, CHF 2 , CF 3 , OMe, OEt, OPr, OiPr, OBu, OcPen, OcHex, OCHF 2 , OCF 3 , OCH 2 CF 3 , C (O) OH, C (O) OMe, C (O) OEt, C (O) OPr,
C(O)OiPr, C(O)OBu, C(O)OiBu, C(O)OsBu, C(O)OcPen, C(O)OCH2CH=CH2, C(O)OCH2C=CH, C(O)OCH2Ph, CH2OMe, CH2OEt, CH2OBu, OCH2CPr, OCH2CH=CH2, OCH2C=CH, OCH2Ph, OCH2C(O)OMe, OCH2C(O)OEt, OCH2CH2C(O)OMe, OCH2CH2C(O)OEt, OC(O)Me,C (O) OiPr, C (O) OBu, C (O) OiBu, C (O) OsBu, C (O) OcPen, C (O) OCH 2 CH = CH 2 , C (O) OCH 2 C = CH , C (O) OCH 2 Ph, CH 2 OMe, CH 2 OEt, CH 2 OBu, OCH 2 CPr, OCH 2 CH = CH 2 , OCH 2 C = CH, OCH 2 Ph, OCH 2 C (O) OMe, OCH 2 C (O) OEt, OCH 2 CH 2 C (O) OMe, OCH 2 CH 2 C (O) OEt, OC (O) Me,
OSO2Me, S(O)Me, SCF3, S(O)CF3 und S(O)2CF3;OSO 2 Me, S (O) Me, SCF 3 , S (O) CF 3 and S (O) 2 CF 3 ;
R3 ganz besonders bevorzugt ausgewählt ist aus der Gruppe, bestehend aus H, F, Cl, Br, Me, CHF2, CF3, OMe, OCHF2, OCF3, OCH2CF3, I und OEt.R 3 is very particularly preferably selected from the group consisting of H, F, Cl, Br, Me, CHF 2 , CF 3 , OMe, OCHF 2 , OCF 3 , OCH 2 CF 3 , I and OEt.
Eine vierte Ausführungsform der vorliegenden Erfindung umfasst Verbindungen der allgemeinen Formel (I), in denenA fourth embodiment of the present invention comprises compounds of the general formula (I) in which
R4 bevorzugt ausgewählt ist aus der Gruppe, bestehend aus Wasserstoff, Hydroxy, Halogen, Cyano, Nitro, Amino, C(O)OH, (C1-C-J)-AIkYl, (C3-C6)-Cycloalkyl, (d-C4)-Haloalkyl, (C1- C4)-Alkoxy, (CrC4)-Haloalkoxy, (C1-C4J-AIkOXy-(Ci-C2)- alkyl, (d-C^-Alkylcarbonyl, (d-C^-Alkylcarbonyloxy, (CrC4)-Alkoxycarbonyl, (C3-C6)-Cycloalkoxycarbonyl, (C3-C6)-Cycloalkyl-(C1-C2)-alkoxy> (C3-C6)-Cycloalkoxy, (C1-C4)-Alkoxycarbonyl-(C1-C2)-alkoxy, (C3-C4)-Alkenyl- oxy, (C3-C4)-Alkinyloxy, (C1-C4)-Alkylthio, (CrC4)-Haloal- kylthio, (CrC4)-Alkylsulfinyl, (d-C4)-Haloalkylsulfinyl, (C1- C4)-Alkylsulfonyl, (CrC4)-Haloalkylsulfonyl, (CrC4)-AI- kylsulfonyloxy, Di-(CrC4)-Alkylamino, (C3-C4)- Alkenyloxycarbonyl, (C2-C4)-Alkinyloxycarbonyl, Formyl, (C2-C4)-Alkenyl, (C2-C4)-Alkinyl, -C(O)NR9R10, wobei R9 und R10, unabhängig voneinander, ausgewählt sind aus der Gruppe, bestehend aus Wasserstoff, (CrC6)-Alkyl, (C3-C6)-Cycloalkyl, (d-CeVHaloalkyl, oder worin R9 und R10 zusammen eine (C-j-CεKALkylen-Gruppe bilden, die ein Sauerstoff- oder Schwefel-Atom oder ein oder zwei Amino- oder (Ci-C6)-Alkylamino-Gruppen enthalten kann;R 4 is preferably selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C (O) OH, (C 1 -C -J) -alkyl, (C 3 -C 6) -cycloalkyl, (dC 4) -haloalkyl, (C 1 - C 4) alkoxy, (C r C 4) -haloalkoxy, (C 1 -C 4 J-AIkOXy- (Ci-C 2) - alkyl, (dC ^ alkylcarbonyl, (dC ^ alkylcarbonyloxy, (CrC 4) alkoxycarbonyl, (C 3 -C 6) cycloalkoxycarbonyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 2 ) -alkoxy > (C 3 -C 6 ) -cycloalkoxy, (C 1 -C 4 ) -alkoxycarbonyl- (C 1 -C 2 ) -alkoxy, (C 3 -C 4) -alkenyl oxy, (C 3 -C 4) alkynyloxy, (C 1 -C 4) alkylthio, (C r C4) -Haloal- alkylthio, (C r C4) alkylsulfinyl, (dC 4 ) haloalkylsulfinyl, (C 1 - C 4) alkylsulfonyl, (CrC 4) haloalkylsulfonyl, (CrC 4) -AI- kylsulfonyloxy, di- (CrC 4) alkylamino, (C 3 -C 4) - alkenyloxycarbonyl, ( C 2 -C 4 ) alkynyloxycarbonyl, formyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, -C (O) NR 9 R 10 , wherein R 9 and R 10 are independently are selected from the group consisting of hydrogen, (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (C 1 -C 4 -haloalkyl, or in which R 9 and R 10 together form a (C 1 -C 6 -alkylene group, the one saue or may contain one or two amino or (Ci-C 6 ) alkylamino groups;
R4 besonders bevorzugt ausgewählt ist aus der Gruppe, bestehend aus H, F, Cl,R 4 is particularly preferably selected from the group consisting of H, F, Cl,
Br, OH, NO2, Me, iPr, CHF2, CF3, OMe, OEt, OPr, OiPr, OBu, OCHF2, OCF3, OCH2CF3, C(O)OH und C(O)OMe;Br, OH, NO 2 , Me, iPr, CHF 2 , CF 3 , OMe, OEt, OPr, OiPr, OBu, OCHF 2 , OCF 3 , OCH 2 CF 3 , C (O) OH and C (O) OMe;
R4 ganz besonders bevorzugt ausgewählt ist aus der Gruppe, bestehend aus H, F, Cl, Me, CF3 und OMe.R 4 is very particularly preferably selected from the group consisting of H, F, Cl, Me, CF 3 and OMe.
Eine fünfte Ausführungsform der vorliegenden Erfindung umfasst Verbindungen der allgemeinen Formel (I), in denenA fifth embodiment of the present invention comprises compounds of the general formula (I) in which
R5 bevorzugt ausgewählt ist aus der Gruppe, bestehend aus Wasserstoff, Hydroxy, Halogen, Cyano, Nitro, Amino, C(O)OH, (CrC4)-Alkyl, (C3-C6)-Cycloalkyl, (d-C4)-Haloalkyl, (C1- C4)-Alkoxy, (Ci-C4)-Haloalkoxy, (C1-C4^AIkOXy-(C1-C2)- alkyl, (Ci-C3)-Alkylcarbonyl, (Ci-C4)-Alkoxycarbonyl, (C3-C6)-Cycloalkoxycarbonyl, (C3-C6)-Cycloalkyl-(Ci-C2)-alkoxy, (C3-C6)-Cycloalkoxy, (CrC4)-Alkoxycarbonyl-(Ci-C2)-alkoxy, (C3-C4)-Alkenyl- oxy, (C3-C4)-Alkinyloxy, (Ci-C4)-Alkylthio, (CrC4)-Haloal- kylthio, (d-C^-Alkylsulfinyl, (CrC4)-Haloalkylsulfinyl, (C1- C4)-Alkylsulfonyl, (CrC4)-Haloalkylsulfonyl, (CrC4)-AI- kylsulfonyloxy, Di-(CrC4)-Alkylamino, (C3-C4)- Alkenyloxycarbonyl, (C2-C4)-Alkinyloxycarbonyl, Formyl, (C2-C4)-Alkenyl, (C2-C4)-Alkinyl, -C(O)NR9R10, wobei R9 und R10, unabhängig voneinander, ausgewählt sind aus der Gruppe, bestehend aus Wasserstoff, (C-ι-C6)-Alkyl, (C3-C6)-Cycloalkyl, (CrC6)-Haloalkyl, oder worin R9 und R10 zusammen eine (Ci-CeJ-Alkylen-Gruppe bilden, die ein Sauerstoff- oder Schwefel-Atom oder ein oder zwei Amino- oder (CrC-eJ-Alkylamino-Gruppen enthalten kann;R 5 is preferably selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C (O) OH, (C r C4) alkyl, (C 3 -C 6) -cycloalkyl, (dC 4) -haloalkyl, (C 1 - C 4) alkoxy, (Ci-C 4) haloalkoxy, (C 1 -C 4- alkoxy- (C 1 -C 2 ) -alkyl, (C 1 -C 3 ) -alkylcarbonyl, (C 1 -C 4 ) -alkoxycarbonyl, (C 3 -C 6 ) -cycloalkoxycarbonyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 2 ) -alkoxy, (C 3 -C 6 ) -cycloalkoxy, (CrC 4) alkoxycarbonyl (Ci-C 2) alkoxy, (C 3 -C 4) -alkenyl oxy, (C 3 -C 4) alkynyloxy, (Ci-C 4) alkylthio, (C r C 4 ) -Haloal- alkylthio, (dC ^ alkylsulfinyl, (cr C4) haloalkylsulfinyl, (C 1 - C 4) alkylsulfonyl, (CrC 4) kylsulfonyloxy haloalkylsulfonyl, (C r C4) -AI-, Di - (C 1 -C 4 ) -alkylamino, (C 3 -C 4 ) -alkenyloxycarbonyl, (C 2 -C 4 ) -alkynyloxycarbonyl, formyl, (C 2 -C 4 ) -alkenyl, (C 2 -C 4 ) -alkynyl, -C (O) NR 9 R 10, wherein R 9, and R 10, are independently selected from the group consisting of hydrogen, (C-ι-C6) alkyl, (C 3 -C 6) -cycloalkyl , (C 1 -C 6 ) -haloalkyl, or wherein R 9 and R 10 together form a (C 1 -C 6 ) -alkylene group which has one oxygen or sulfur atom or one or two amino or (C 1 -C 6 -alkylamino groups may contain;
R5 besonders bevorzugt ausgewählt ist aus der Gruppe, bestehend aus H, F, Cl,R 5 is particularly preferably selected from the group consisting of H, F, Cl,
Br, OH, Me, CF3, OMe, OCHF2, OCF3, OCH2CF3, C(O)OMe und C(O)OEt; undBr, OH, Me, CF 3 , OMe, OCHF 2 , OCF 3 , OCH 2 CF 3 , C (O) OMe and C (O) OEt; and
R5 ganz besonders bevorzugt ausgewählt ist aus der Gruppe, bestehend aus H, F, Cl, Br, CF3 und Me.R 5 is very particularly preferably selected from the group consisting of H, F, Cl, Br, CF 3 and Me.
Eine sechste Ausführungsform der vorliegenden Erfindung umfasst Verbindungen der allgemeinen Formel (I), in denenA sixth embodiment of the present invention comprises compounds of the general formula (I) in which
R6 bevorzugt ausgewählt ist aus der Gruppe, bestehend aus Wasserstoff, Hydroxy, Halogen, Cyano, Nitro, Amino, C(O)OH, (d-C4)-Alkyl, (C3-C6)-Cycloalkyl, (Ci-C4)-Haloalkyl, (C1- C4)-Alkoxy, (Ci-C4)-Haloalkoxy, (C1-C-O-AIkOXy-(C1-C2)- alkyl, (CrC3)-Alkylcarbonyl, (d-C^-Alkylcarbonyloxy, (CrC4)-Alkoxycarbonyl, (C3-C6)-Cycloalkoxycarbonyl, (C3-C6)-Cycloalkyl-(CrC2)-alkoxy, (C3-C6)-Cycloalkoxy,R 6 is preferably selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C (O) OH, (dC 4) -alkyl, (C 3 -C 6) -cycloalkyl, (Ci-C 4) -haloalkyl, (C 1 - C 4) alkoxy, (Ci-C 4) haloalkoxy, (C 1 -CO -Alkoxy (C 1 -C 2 ) -alkyl, (C 1 -C 3 ) -alkylcarbonyl, (C 1 -C 4 -alkylcarbonyloxy, (C 1 -C 4 ) -alkoxycarbonyl, (C 3 -C 6 ) -cycloalkoxycarbonyl, (C 3 -C 6 ) Cycloalkyl- (C 1 -C 2) -alkoxy, (C 3 -C 6 ) -cycloalkoxy,
(Ci-C4)-Alkoxycarbonyl-(C1-C2)-alkoxy, (C3-C4)-Alkenyl- oxy, (C3-C4)-Alkinyloxy, (d-C4)-Alkylthio, (d-C4)-Haloal- kylthio, (d-C4)-Alkylsulfinyl, (CrC4)-Haloalkylsulfinyl, (C1- C4)-Alkylsulfonyl, (d-C4)-Haloalkylsulfonyl, (d-C4)-AI- kylsulfonyloxy, Di-(d-C4)-Alkylamino, (C3-C4)-(C 1 -C 4 ) -alkoxycarbonyl- (C 1 -C 2 ) -alkoxy, (C 3 -C 4 ) -alkenyl-oxy, (C 3 -C 4 ) -alkynyloxy, (C 1 -C 4 ) -alkylthio, (dC 4) -Haloal- alkylthio, (dC 4) alkylsulfinyl, (C r C4) haloalkylsulfinyl, (C 1 - C 4) alkylsulfonyl, (dC 4) haloalkylsulfonyl, (dC 4) -AI- kylsulfonyloxy, Di - (dC 4) alkylamino, (C 3 -C 4) -
Alkenyloxycarbonyl, (C2-C4)-Alkinyloxycarbonyl, Formyl, (C2-C4)-Alkenyl, (C2-C4)-Alkinyl, -C(O)NR9R10, wobei R9 und R10, unabhängig voneinander, ausgewählt sind aus der Gruppe, bestehend aus Wasserstoff, (d-CβJ-Alkyl, (C3-C6)-Cycloalkyl, (d-C6)-Haloalkyl, oder worin R9 undAlkenyloxycarbonyl, (C 2 -C 4 ) alkynyloxycarbonyl, formyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, -C (O) NR 9 R 10 , wherein R 9 and R 10 , independently of one another, are selected from the group consisting of hydrogen, (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (C 1 -C 6 ) -haloalkyl, or wherein R 9 and
R10 zusammen eine (Ci-Cfi)-Alkylen-Gruppe bilden, die ein Sauerstoff- oder Schwefel-Atom oder ein oder zwei Amino- oder (d-C6)-Alkylamino-Gruppen enthalten kann;R 10 together form a (Ci-C fi ) -alkylene group which may contain an oxygen or sulfur atom or one or two amino or (dC 6 ) alkylamino groups;
R6 besonders bevorzugt ausgewählt ist aus der Gruppe, bestehend aus H, F, Cl,R 6 is more preferably selected from the group consisting of H, F, Cl,
Br, NO2, Me, iPr, OMe, OEt1 OPr, OiPr, OBu, OCHF2, CF3, OCF3, OCH2CF3, OCH2CH=CH2 und OCH2C≡CH; undBr, NO 2 , Me, iPr, OMe, OEt 1 OPr, OiPr, OBu, OCHF 2 , CF 3 , OCF 3 , OCH 2 CF 3 , OCH 2 CH = CH 2 and OCH 2 C≡CH; and
R6 ganz besonders bevorzugt ausgewählt ist aus der Gruppe, bestehend aus H, F, Cl, Me, CF3 und OMe.R 6 is very particularly preferably selected from the group consisting of H, F, Cl, Me, CF 3 and OMe.
Eine siebte Ausführungsform der vorliegenden Erfindung umfasst Verbindungen der allgemeinen Formel (I), in denenA seventh embodiment of the present invention comprises compounds of the general formula (I) in which
R7 bevorzugt ausgewählt ist aus der Gruppe, bestehend aus Wasser- stoff, Hydroxy, Halogen, Cyano, Nitro, Amino, C(O)OH, (d-OO-Alkyl, (C3-C6)-Cycloalkyl, (d-C^-Haloalkyl, (C1- C4)-Alkoxy, (CrC4)-Haloalkoxy, (C1-C4J-AIkOXy-(C1-C2)- alkyl, (CrC3)-Alkylcarbonyl, (CrC^-Alkylcarbonyloxy, (C1-C4)-Alkoxycarbonyl, (C3-C6)-Cycloalkoxycarbonyl,R 7 is preferably selected from the group consisting of water Substance, hydroxy, halogen, cyano, nitro, amino, C (O) OH, (d-OO-alkyl, (C 3 -C 6 ) -cycloalkyl, (dC ^ -haloalkyl, (C 1 -C 4 ) -alkoxy , (C r C 4) -haloalkoxy, (C 1 -C 4 J-AIkOXy- (C 1 -C 2) - alkyl, (CrC 3) -alkylcarbonyl, (CrC ^ -alkylcarbonyloxy, (C 1 -C 4) Alkoxycarbonyl, (C 3 -C 6 ) cycloalkoxycarbonyl,
(C3-C6)-Cycloalkyl-(C1-C2)-alkoxy) (C3-C6)-Cycloalkoxy, (C1-C4)-Alkoxycarbonyl-(C1-C2)-alkoxy, (C3-C4)-Alkenyl- oxy, (C3-C4)-Alkinyloxy, (CrC4)-Alkylthio, (Ci-C4)-Haloal- kylthio, (CrC4)-Alkylsulfinyl, (CrC^-Haloalkylsulfinyl, (C1- C4)-Alkylsulfonyl, (d^-Haloalkylsulfonyl, (C1-C4J-AI- kylsulfonyloxy, Di-(C1-C4)-Alkylamino, (C3-C4)- Alkenyloxycarbonyl, (C2-C4)-Alkinyloxycarbonyl, Formyl, (C2-C4)-Alkenyl, (C2-C4)-Alkinyl, -C(O)NR9R10, wobei R9 und R10, unabhängig voneinander, ausgewählt sind aus der Gruppe, bestehend aus Wasserstoff, (CrC6)-Alkyl,(C 3 -C 6 ) -cycloalkyl- (C 1 -C 2 ) -alkoxy ) (C 3 -C 6 ) -cycloalkoxy, (C 1 -C 4 ) -alkoxycarbonyl- (C 1 -C 2) -alkoxy, ( C 3 -C 4) -alkenyl oxy, (C 3 -C 4) alkynyloxy, (CrC 4) alkylthio, (Ci-C 4) -Haloal- alkylthio, (C r C4) alkylsulfinyl, (CrC ^ haloalkylsulfinyl, (C 1 - C 4) alkylsulfonyl, (d ^ haloalkylsulfonyl, (C 1 -C 4 J-AI kylsulfonyloxy, di- (C 1 -C 4) alkylamino, (C 3 -C 4 ) - alkenyloxycarbonyl, (C 2 -C 4 ) -alkynyloxycarbonyl, formyl, (C 2 -C 4 ) -alkenyl, (C 2 -C 4 ) -alkynyl, -C (O) NR 9 R 10 , wherein R 9 and R 10 , independently of one another, are selected from the group consisting of hydrogen, (C 1 -C 6 ) -alkyl,
(C3-C6)-Cycloalkyl, (C1-Ce)-HaIOaIkVl, oder worin R9 und R10 zusammen eine (C-i-CβJ-Alkylen-Gruppe bilden, die ein Sauerstoff- oder Schwefel-Atom oder ein oder zwei Amino- oder (C-i-CβJ-Alkylamino-Gruppen enthalten kann;(C 3 -C 6 ) -cycloalkyl, (C 1 -Ce) -HaIOaIkVl, or wherein R 9 and R 10 together form a (Ci-CβJ-alkylene group which is an oxygen or sulfur atom or one or two Amino or (Ci-CβJ-alkylamino groups may contain;
R7 besonders bevorzugt ausgewählt ist aus der Gruppe, bestehend aus H, F, Cl,R 7 is particularly preferably selected from the group consisting of H, F, Cl,
Br, OH, NO2, NMe2, NEt2, Me, Et, CHF2, CF3, OMe, OEt, OPr, OiPr, OBu, OiBu, OCHF2, OCF3, OCH2CF3, C(O)OH, C(O)OMe, C(O)OEt, C(O)OPr, C(O)OiPr, C(O)OBu, C(O)OiBu, C(O)OsBu, C(O)OCH2Ph,Br, OH, NO 2 , NMe 2 , NEt 2 , Me, Et, CHF 2 , CF 3 , OMe, OEt, OPr, OiPr, OBu, OiBu, OCHF 2 , OCF 3 , OCH 2 CF 3 , C (O) OH, C (O) OMe, C (O) OEt, C (O) OPr, C (O) OiPr, C (O) OBu, C (O) OiBu, C (O) OsBu, C (O) OCH 2 Ph,
OCH2CH=CH2 und OCH2C≡CH; undOCH 2 CH = CH 2 and OCH 2 C≡CH; and
R7 ganz besonders bevorzugt ausgewählt ist aus der Gruppe, bestehend aus H, F, Cl, Me, CF3, OCHF2, OCF3 und OMe.R 7 is very particularly preferably selected from the group consisting of H, F, Cl, Me, CF 3 , OCHF 2 , OCF 3 and OMe.
Vor allem aus den Gründen der höheren herbizide Wirkung, besseren Selektivität und/oder besseren Herstellbarkeit sind erfindungsgemäße Verbindungen der genannten Formel (I) oder deren Salze von besonderem Interesse, worin einzelne Reste eine der bereits genannten oder im folgenden genannten bevorzugten Bedeutungen haben, oder insbesondere solche, worin eine oder mehrere der bereits genannten oder im folgenden genannten bevorzugten Bedeutungen kombiniert auftreten.Especially for the reasons of higher herbicidal activity, better selectivity and / or better manufacturability are compounds of the formula (I) according to the invention or salts thereof of particular interest, in which individual radicals have one of the meanings already mentioned or mentioned below, or in particular those in which one or more of those already mentioned or hereinafter mentioned preferred meanings occur in combination.
Die oben angeführten allgemeinen oder in Vorzugsbereichen angeführten Restedefinitionen gelten sowohl für die Endprodukte der Formel (I) als auch entsprechend für die jeweils zur Herstellung benötigten Ausgangs- undThe general or preferred radical definitions given above are valid both for the end products of the formula (I) and correspondingly for the starting and in each case required for the preparation
Zwischenprodukte. Diese Restedefinitionen können untereinander, als auch zwischen den angegebenen bevorzugten Bereichen beliebig kombiniert werden.Intermediates. These remainder definitions can be combined as desired among themselves as well as between the specified preferred ranges.
Die Kombinationsmöglichkeiten der verschiedenen Substituenten der allgemeinen Formel (I) sind so zu verstehen, dass die allgemeinen Grundsätze des Aufbaus chemischer Verbindungen zu beachten sind. d.h. die Formel (I) nicht Verbindungen umfasst, von denen der Fachmann weiß, dass sie chemisch nicht möglich sind.The possible combinations of the various substituents of the general formula (I) are to be understood in such a way that the general principles of the construction of chemical compounds are to be observed. i.e. the formula (I) does not include compounds which the person skilled in the art knows are chemically impossible.
Im Rahmen dieser ersten bis siebten Ausführungsformen der vorliegenden Erfindung ist es möglich, die einzelnen bevorzugten, besonders bevorzugten und ganz besonders bevorzugten Bedeutungen für die Substituenten R1 bis R7 beliebig miteinander zu kombinieren. Das heißt, dass Verbindungen der allgemeinen Formel (I) von der vorliegenden Erfindung umfasst sind, in welchen beispielsweise der Substituent R1 eine bevorzugte Bedeutung aufweist und die Substituenten R4 bis R7 die allgemeine Bedeutung aufweisen oder aber beispielsweise der Substituent R1 eine bevorzugte Bedeutung aufweist, der Substituent R2 eine besonders bevorzugte Bedeutung, der Substituent R3 eine ganz besondere Bedeutung und die Substituenten R4 und R7 die allgemeine Bedeutung aufweisen.In the context of these first to seventh embodiments of the present invention, it is possible to arbitrarily combine the individual preferred, particularly preferred and most preferred meanings for the substituents R 1 to R 7 . That is, compounds of the general formula (I) are encompassed by the present invention in which, for example, the substituent R 1 has a preferred meaning and the substituents R 4 to R 7 have the general meaning or, for example, the substituent R 1 is a preferred one Meaning, the substituent R 2 has a particularly preferred meaning, the substituent R 3 has a very special meaning and the substituents R 4 and R 7 have the general meaning.
Die in diesen Ausführungsformen der vorliegenden Erfindung definierten bevorzugten, besonders bevorzugten und ganz besonders bevorzugten Definition für die Reste R3 bis R7 am Arylring können in beliebiger Kombination mit den in der vorliegenden Erfindung als bevorzugt, besonders bevorzugt und ganz besonders bevorzugt definierten Bedeutungen der Substituenten R1 und R2 am Oxazolring kombiniert werden.The preferred, particularly preferred and most particularly preferred definition of the radicals R 3 to R 7 on the aryl ring as defined in these embodiments of the present invention may be used in any combination with those described in US Pat Present invention as preferred, particularly preferred and most preferably defined meanings of the substituents R 1 and R 2 are combined on Oxazolring.
Im Rahmen der vorliegenden Erfindung sind von der Verbindung der allgemeinen Formel (I) auch Verbindungen umfasst, die durch a) Protonierung, b) Alkylierung oder c) Oxidation an einem Stickstoffatom quaterniert sind.In the context of the present invention, the compound of the general formula (I) also includes compounds which are quaternized by a) protonation, b) alkylation or c) oxidation on a nitrogen atom.
Die Verbindungen der allgemeinen Formel (I) können gegebenenfalls durch Anlagerung einer geeigneten anorganischen oder organischen Säure, wie beispielsweise HCl, HBr, H2SO4 oder HNO3, aber auch Oxalsäure oder Sulfonsäuren an eine basische Gruppe, wie z.B. Amino oder Alkylamino, Salze bilden. Geeignete Substituenten, die in deprotonierter Form, wie z.B. Sulfonsäuren oder Carbonsäuren, vorliegen, können innere Salze mit ihrerseits protonierbaren Gruppen, wie Aminogruppen bilden. Salze können ebenfalls dadurch gebildet werden, dass bei geeigneten Substituenten, wie z.B. Sulfonsäuren oder Carbonsäuren, der Wasserstoff durch ein im agrochemischen Bereich geeignetes Kation ersetzt wird. Diese Salze sind beispielsweise Metallsalze, insbesondere Alkalimetallsalze oder Erdalkalimetallsalze, insbesondere Natrium- und Kaliumsalze, oder auch Ammoniumsalze, Salze mit organischen Aminen oder quartäre (quatemäre) Ammoniumsalze mit Kationen der Formel [NRR'R"R'"]+, worin R bis R"1 jeweils unabhängig einen organischen Rest, insbesondere Alkyl, Aryl, Arylalkyl oder Alkylaryl darstellen.The compounds of general formula (I) may optionally be prepared by addition of a suitable inorganic or organic acid such as HCl, HBr, H 2 SO 4 or HNO 3 , but also oxalic acid or sulfonic acids to a basic group such as amino or alkylamino form. Suitable substituents which are present in deprotonated form, such as, for example, sulfonic acids or carboxylic acids, can form internal salts with groups which can themselves be protonated, such as amino groups. Salts can also be formed by replacing the hydrogen with a suitable cation in the agrochemical field with suitable substituents, such as, for example, sulfonic acids or carboxylic acids. These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or else ammonium salts, salts with organic amines or quaternary ammonium salts with cations of the formula [NRR'R "R '"] + , where R to R "1 each independently represent an organic radical, in particular alkyl, aryl, arylalkyl or alkylaryl.
In der allgemeinen Formel (I) und allen übrigen Formeln in der vorliegenden Erfindung können die Reste Alkyl, Alkoxy, Haloalkyl, Haloalkoxy, Alkylamino, Alkylthio, Haloalkylthio, Alkylsulfinyl, Alkylsulfonyl, Haloalkylsulfinyl und Haloalkylsulfonyl, sowie die entsprechenden ungesättigten und/oder substituierten Reste im Kohlenstoffgerüst jeweils geradkettig oder verzweigt sein. Wenn nicht speziell angegeben, sind bei diesen Resten die niederen Kohlenstoffgerüste, z.B. mit 1 bis 6 C-Atomen, insbesondere 1 bis 4 C-Atomen, bzw. bei ungesättigten Gruppen mit 2 bis 6 C-Atomen, insbesondere 2 bis 4 C-Atomen, bevorzugt. Alkylreste, auch in den zusammengesetzten Bedeutungen wie Alkoxy, Haloalkyl usw., bedeuten z.B. Methyl; Ethyl; n- oder i-Propyl; n-, i-, t- oder 2-Butyl; Pentyle, wie n-Pentyl; Hexyle, wie n-Hexyl, i-Hexyl und 1 ,3-Dimethylbutyl; Heptyle, wie n-Heptyl, 1 -Methylhexy und 1 ,4-Dimethylpentyl; Alkenyl- und Alkinylreste haben die Bedeutung der den Alkylresten entsprechenden möglichen ungesättigten Reste; wobei mindestens eine Doppelbindung bzw. Dreifachbindung, vorzugsweise eine Doppelbindung bzw. Dreifachbindung, im Rest enthalten ist. Alkenyl bedeutet z.B. Vinyl, AIIyI, 1- Methylprop-2-en-i-yl, 2-Methyl-prop-2-en-1-yl, But-2-en-1-yl, But-3-en-1-yl, 1- Methyl-but-3-en-1-yl und 1-Methyl-but-2-en-1-yl; Alkinyl bedeutet z.B. Ethinyl, Propargyl, But-2-in-1-yl, But-3-in-1-yl und 1-Methyl-but-3-in-1-yl.In general formula (I) and all other formulas in the present invention, the radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino, alkylthio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylsulfinyl and haloalkylsulfonyl, as well as the corresponding unsaturated and / or substituted radicals in the Carbon skeleton in each case be straight-chain or branched. Unless specifically stated, these radicals are the lower carbon skeletons, eg having 1 to 6 C atoms, in particular 1 to 4 C atoms, or unsaturated groups having 2 to 6 C atoms, in particular 2 to 4 C atoms , prefers. Alkyl radicals, also in the compound meanings such as alkoxy, haloalkyl, etc., mean, for example, methyl; ethyl; n- or i-propyl; n-, i-, t- or 2-butyl; Pentyls, such as n-pentyl; Hexyls such as n-hexyl, i-hexyl and 1, 3-dimethylbutyl; Heptyls such as n-heptyl, 1-methylhexy and 1, 4-dimethylpentyl; Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; wherein at least one double bond or triple bond, preferably a double bond or triple bond, is contained in the rest. Alkenyl is, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-ene-1 -yl, 1-methylbut-3-en-1-yl and 1-methyl-but-2-en-1-yl; Alkynyl includes, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl and 1-methyl-but-3-yn-1-yl.
Halogen bedeutet Fluor, Chlor, Brom oder lod. Haloalkyl, -alkenyl und -alkinyl bedeuten durch Halogen, vorzugsweise durch Fluor, Chlor oder Brom, insbesondere durch Fluor und/oder Chlor, teilweise oder vollständig substituiertes Alkyl, Alkenyl bzw. Alkinyl, z.B. Monohaloalkyl (= Monohalogenalkyl), Perhaloalkyl, CF3, CHF2, CH2F, CF3CF2, CH2FCHCI, CCI3, CHCI2, CH2CH2CI; Haloalkoxy ist z=B. OCF3, OCHF2, OCH2F, CF3CF2O, OCH2CF3 und OCH2CH2CI; entsprechendes gilt für Haloalkenyl und andere durch Halogen substituierte Reste.Halogen is fluorine, chlorine, bromine or iodine. Haloalkyl, alkenyl and alkynyl are halogen, preferably fluorine, chlorine or bromine, in particular by fluorine and / or chlorine, partially or completely substituted alkyl, alkenyl or alkynyl, for example monohaloalkyl (= monohaloalkyl), perhaloalkyl, CF 3 , CHF 2 , CH 2 F, CF 3 CF 2 , CH 2 FCHCl, CCI 3 , CHCl 2 , CH 2 CH 2 Cl; Haloalkoxy is z = B. OCF 3 , OCHF 2 , OCH 2 F, CF 3 CF 2 O, OCH 2 CF 3 and OCH 2 CH 2 Cl; the same applies to haloalkenyl and other halogen-substituted radicals.
Mit der Definition „mit einem oder mehreren Resten substituiert ist" sind, wenn nicht anders definiert, ein oder mehrere gleiche oder verschiedene Reste gemeint.Unless defined otherwise, the definition "substituted by one or more radicals" means one or more identical or different radicals.
Die beispielhaft genannten Substituenten ("erste Substituentenebene") können, soweit dieses nicht bereits expressis verbis definiert wurde und sofern sie kohlenwasserstoffhaltige Anteile enthalten, dort gegebenenfalls weiter substituiert sein ("zweite Substitutentenebene"), beispielsweise durch einen der Substituenten, wie er für die erste Substituentenebene definiert ist. Entsprechende weitere Substituentenebenen sind möglich. Vorzugsweise werden vom Begriff "substituierter Rest" nur ein oder zwei Substitutentenebenen umfasst.The substituents exemplified ("first substituent level") may, if not already expressis verbis defined and if they contain hydrocarbon-containing moieties, optionally further substituted there ("second level of substitution"), for example by one of the substituents, as for the first Substituentbene is defined. Corresponding further substituent levels are possible. Preferably, the term "substituted radical" includes only one or two substituent levels.
Bei Resten mit C-Atomen sind solche mit 1 bis 6 C-Atomen, vorzugsweise 1 bis 4 C- Atomen, insbesondere 1 oder 2 C-Atomen, bevorzugt. Bevorzugt sind in der Regel Substituenten aus der Gruppe Halogen, z.B. Fluor und Chlor, (Ci-C4)-Alkyl, vorzugsweise Methyl oder Ethyl, (Ci-C4)-Haloalkyl, vorzugsweise Trifluormethyl, (Cr C4)-Alkoxy, vorzugsweise Methoxy oder Ethoxy, (CrC4)-Haloalkoxy, Nitro und Cyano.For radicals with C atoms, those having 1 to 6 C atoms, preferably 1 to 4 C atoms, in particular 1 or 2 C atoms, are preferred. Preferred are usually Substituents from the group halogen, for example fluorine and chlorine, (Ci-C 4 ) alkyl, preferably methyl or ethyl, (Ci-C 4 ) haloalkyl, preferably trifluoromethyl, (C r C 4 ) alkoxy, preferably methoxy or ethoxy , (CrC4) haloalkoxy, nitro and cyano.
Gegenstand der Erfindung sind auch alle Stereoisomeren, die von Formel (I) umfaßt sind, und deren Gemische. Solche Verbindungen der Formel (I) enthalten ein oder mehrere asymmetrische C-Atome (= asymmetrisch substituierte C-Atome) und/oder asymmetrische Schwefelatome in der Form von Sulfoxiden (d.h. im Fall der Verbindungen der allgemeinen Formel (I) mit n = 1 ), die in zwei enantiomeren Formen existieren können, oder auch Doppelbindungen, die in den allgemeinen Formeln (I) nicht gesondert angegeben sind. Die durch ihre spezifische Raumform definierten möglichen Stereoisomeren, wie Enantiomere, Diastereomere, Z- und E- Isomere sind alle von der Formel (I) umfaßt und können nach üblichen Methoden aus Gemischen der Stereoisomeren erhalten oder auch durch stereoselektive Reaktionen in Kombination mit dem Einsatz von stereochemisch reinen Ausgangsstoffen hergestellt werden.The invention also relates to all stereoisomers which are encompassed by formula (I) and mixtures thereof. Such compounds of the formula (I) contain one or more asymmetric C atoms (= asymmetrically substituted C atoms) and / or asymmetric sulfur atoms in the form of sulfoxides (ie in the case of the compounds of the general formula (I) where n = 1) , which may exist in two enantiomeric forms, or also double bonds, which are not specified separately in the general formulas (I). The possible defined by their specific spatial form possible stereoisomers, such as enantiomers, diastereomers, Z and E isomers are all of the formula (I) and can be obtained by conventional methods from mixtures of stereoisomers or by stereoselective reactions in combination with the use of stereochemically pure starting materials are produced.
Gegenstand der vorliegenden Erfindung sind auch Methoden zur Herstellung der Verbindungen der allgemeinen Formel (I) und/oder deren Salze. Erfindungsgemäße Verbindungen der Formel (I) können alternativ über verschiedene analoge bekannte Methoden dargestellt werden, welche im Folgenden nicht abschließend beschrieben werden:The present invention also provides methods for the preparation of the compounds of general formula (I) and / or salts thereof. Alternatively, compounds of the formula (I) according to the invention can be prepared by various analogously known methods, which are not exhaustively described below:
a.)a.)
Zur Herstellung von optisch aktiven Sulfoxiden der Formel (III) bzw. Sulfonen der Formel (IV), worin R1, R2, R3, R4, R5, R6, R7, die gemäß Formel (I) zuvor angegebenen Bedeutungen haben, For the preparation of optically active sulfoxides of the formula (III) or sulfones of the formula (IV) in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , the formula (I) given above Have meanings
( III )(III)
( IV )(IV)
wird beispielsweise ein Thioether der allgemeinen Formel (II),For example, if a thioether of the general formula (II)
worin R1, R2, R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben, mit einem Äquivalent eines Oxidationsmittels zu den optisch aktiven Sulfoxiden (III) oxidiert, für die n die Zahl 1 bedeutet, oder mit zweiwherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given in formula (I) above, oxidized with one equivalent of an oxidizing agent to the optically active sulfoxides (III), for the n the number 1 means, or two
Äquivalenten eines Oxidationsmittels zu den Sulfonen (IV) oxidiert, für die n die Zahl 2 bedeutet. Man kann die Sulfone (IV) auch aus den optisch aktiven Sulfoxiden (III) gewinnen, wobei mit einem Äquivalent eines Oxidationsmittels zu den Sulfonen (IV) oxidiert wird.Oxidized equivalents of an oxidizing agent to the sulfones (IV), for which n is the number 2. The sulfones (IV) can also be obtained from the optically active sulfoxides (III), with one equivalent of an oxidizing agent oxidizing to the sulfones (IV).
Die Oxidationsmittel, welche für diese Umsetzung verwendet werden können, unterliegen keinen besonderen Bestimmungen und es können Oxidationsmittel verwendet werden, welche in der Lage sind, entsprechende Schwefelverbindungen in Sulfoxidverbindungen zu oxidieren.The oxidizing agents which can be used for this reaction are not subject to any special provisions and may contain oxidizing agents which are capable of oxidizing corresponding sulfur compounds into sulfoxide compounds.
Als Oxidationsmittel zur Herstellung der optisch aktiven Sulfoxide (n = 1 ) sind anorganische Peroxide wie z.B. Wasserstoffperoxid, Natriummetaperjodat, wahlweise in Gegenwart von einem Katalysator, wie z.B. Ruthenium(lll)-chlorid, organische Peroxide, wie z.B. tert.-Butylhydroperoxid oder organische Persäuren, wie Peressigsäure oder bevorzugt 3-Chlor-perbenzoesäure geeignet. Die Reaktion kann in halogenierten Kohlenwasserstoffen, z.B. Dichlormethan, 1 ,2-Dichlorethan, einem Alkohol, wie z.B. Methanol, oder in Dimethylformamid, Acetonitril, Wasser oder Essigsäure oder in einer Mischung der zuvor genannten Lösemittel durchgeführt werden. Die Reaktion wird in einer Temperaturbereich zwischen - 800C und 120 0C, bevorzugt zwischen - 200C bis 50 0C durchgeführt. Solche Verfahren sind in der Literatur bekannt und sind z.B. in J. Org. Chem., 58 (1993) 2791 , J. Org. Chem., 68 (2003) 3849 und J. Heterocyclic Chem., 15 (1978) 1361 beschrieben. Als Oxidationsmittel zur Herstellung der Sulfone (n = 2) sind z.B. Wasserstoffperoxid, organische Peroxide, wie z.B. tert.-Butylhydroperoxid oder organische Persäuren, wie Peressigsäure oder bevorzugt 3-Chlor-perbenzoesäure geeignet.As the oxidizing agent for the preparation of the optically active sulfoxides (n = 1) are inorganic peroxides such as hydrogen peroxide, sodium metaperiodate, optionally in the presence of a catalyst such as ruthenium (III) chloride, organic peroxides such as tert-butyl hydroperoxide or organic peracids , such as peracetic acid or preferably 3-chloro-perbenzoic acid suitable. The reaction can be carried out in halogenated hydrocarbons, for example dichloromethane, 1,2-dichloroethane, an alcohol, such as methanol, or in dimethylformamide, acetonitrile, water or acetic acid or in a mixture of the abovementioned solvents. The reaction is carried out in a temperature range between - 80 0 C and 120 0 C, preferably between - 20 0 C to 50 0 C. Such methods are known in the literature and are described, for example, in J. Org. Chem., 58 (1993) 2791, J. Org. Chem., 68 (2003) 3849 and J. Heterocyclic Chem., 15 (1978) 1361. Suitable oxidizing agents for the preparation of the sulfones (n = 2) are, for example, hydrogen peroxide, organic peroxides, such as, for example, tert-butyl hydroperoxide or organic peracids, such as peracetic acid or preferably 3-chloroperbenzoic acid.
Die enantioselektive Synthese von chiralen Sulfoxiden der Formel (III) in optisch angereicherter oder reiner Form kann, ausgehend von Thioverbindungen der Formel (II), nach Methoden erfolgen, wie sie beispielsweise in Chem. Rev., 103 (2003) 3651-3705, bzw. dort zitierter Literatur, und Adv. Synth. Catal., 347 (2005)19-31 , bzw. dort zitierter Literatur, beschrieben sind. Die absolute Konfiguration des Produkts hängt im Einzelfall von der Struktur des optisch aktiven Katalysators ab. The enantioselective synthesis of chiral sulfoxides of the formula (III) in optically enriched or pure form can be carried out starting from thio compounds of the formula (II) by methods as described, for example, in Chem. Rev., 103 (2003) 3651-3705, or US Pat literature cited therein, and Adv. Synth. Catal., 347 (2005) 19-31, or literature cited therein. The absolute configuration of the product depends in each case on the structure of the optically active catalyst.
( III )(III)
Verbindungen der allgemeinen Formel (IM) bestehen aus einem Gemisch der jeweiligen, an der Sulfoxid-Funktion chiralen Enantiomeren (Ml-S) und (IM-R)Compounds of the general formula (III) consist of a mixture of the respective enantiomers chiral to the sulfoxide function (Ml-S) and (III-R)
wobei die Reste R1, R2, R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebene Bedeutung haben.where the radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 have the meaning given above according to formula (I).
Sie weisen somit ein chirales Schwefelatom auf, welches in der oben dargestellten Struktur durch die Kennzeichneung (R/S) verdeutlicht ist. Gemäß den Regeln nach Cahn, Ingold und Prelog (CIP-Regeln) kann dieses Schwefelatom sowohl eine (R)- als auch eine (S)-Konfiguration aufweisen.They thus have a chiral sulfur atom, which is illustrated in the structure shown above by the characterization (R / S). According to the rules of Cahn, Ingold and Prelog (CIP rules), this sulfur atom can have both an (R) and an (S) configuration.
Von der vorliegenden Erfindung werden Verbindungen der allgemeinen Formel (IM) sowohl mit (S)- als auch mit (R)-Konfiguration erfasst, d.h., dass die vorliegende Erfindung die Verbindungen der allgemeinen Formel (Ml) erfasst, in welchen das betreffende Schwefelatom (1 ) eine (R)-Konfiguration; oder (2) eine (S)-Konfiguration aufweist.The present invention covers compounds of the general formula (III) having both (S) and (R) -configuration, that is to say that the present invention covers the compounds of the general formula (III) in which the relevant sulfur atom ( 1) an (R) configuration; or (2) an (S) configuration having.
Darüber hinaus werden im Rahmen der vorliegenden Erfindung auch (3) beliebige Mischungen von Verbindungen der allgemeinen Formel (IM), welche eine (R)-Konfiguation (Verbindungen der allgemeinen Formel (IM-(R)) aufweisen, mit Verbindungen der allgemeinen Formel (III), welche eine (S)- Konfiguration (Verbindungen der allgemeinen Formel (Ml-S)) aufweisen, erfasst.In addition, in the context of the present invention, (3) any mixtures of compounds of the general formula (III) which have an (R) -configuration (compounds of the general formula (III-R)) with compounds of the general formula III), which have an (S) - configuration (compounds of the general formula (Ml-S)) detected.
Die vorleigende Erfindung umfasst Verbindungen der allgemeienn Formel (IM), die racemisch sind, d.h. in welchen die Verbindungen der allgemeinen Formel (IM) mit (S)-Konfiguration (Verbindungen der allgemeinen Formel (IM-S)) im Vergleich zur (R)-Konfiguration (Verbindungen der allgemeinen Formel (Ml-R)) als 1 :1 Mischung (50% stereochemischen Reinheit ) vorliegen.The present invention includes compounds of the general formula (IM) which are racemic, i. in which the compounds of general formula (IM) with (S) configuration (compounds of general formula (IM-S)) compared to the (R) configuration (compounds of general formula (Ml-R)) as 1: 1 Mixture (50% stereochemical purity) are present.
Allerdings sind im Rahmen der vorliegenden Erfindung auch Verbindungen der allgemeinen Formel (IM) mit (S)-Konfiguration (Verbindungen der allgemeinen Formel (IM-S)) im Vergleich zur (R)-Konfiguration (Verbindungen der allgemeinen Formel (Ml-R)) mit einer stereochemischen Reinheit von im Allgemeinen über 50 % bis 100 %, vorzugsweise 60 bis 100 %, insbesondere 80 bis 100 %, ganz besonders 90 bis 100 %, speziell 95 bis 100 %, bevorzugt, wobei die jeweilige (S)-Verbindung mit einer Enantioselektivität von jeweils mehr als 50% ee, vorzugsweise 60 bis 100% ee, insbesondere 80 bis 100% ee, ganz besonders 90 bis 100% ee, meist bevorzugt 95 bis 100% ee, bezogen auf den Gesamtgehalt an betreffender (S)-Verbindung vorliegt, bevorzugt vorliegt.However, in the context of the present invention, compounds of the general formula (III) with (S) -configuration (compounds of the general formula (III-S)) in comparison with the (R) -configuration (compounds of the general formula (III-R) ) having a stereochemical purity of generally over 50% to 100%, preferably 60 to 100%, in particular 80 to 100%, very particularly 90 to 100%, especially 95 to 100%, preferred, wherein the respective (S) compound with an enantioselectivity of in each case more than 50% ee, preferably 60 to 100% ee, in particular 80 to 100% ee, very particularly 90 to 100% ee, most preferably 95 to 100% ee, based on the total content of (S) Compound present, preferably present.
Ferner sind im Rahmen der vorliegenden Erfindung auch Verbindungen der allgemeinen Formel (IM) mit (R)-Konfiguration (Verbindungen der allgemeinen Formel (Ml-R)) im Vergleich zur (S)-Konfiguration (Verbindungen der allgemeinen Formel (Hl-R)) mit einer stereochemischen Reinheit von im Allgemeinen über 50 % bis 100 %, vorzugsweise 60 bis 100 %, insbesondere 80 bis 100 %, ganz besonders 90 bis 100 %, speziell 95 bis 100 %, bevorzugt, wobei die jeweilige (R)-Verbindung mit einer Enantioselektivität von jeweils mehr als 50% ee, vorzugsweise 60 bis 100% ee, insbesondere 80 bis 100% ee, ganz besonders 90 bis 100% ee, meist bevorzugt 95 bis 100% ee, bezogen auf den Gesamtgehalt an betreffender (S)-Verbindung vorliegt, bevorzugt vorliegt.Furthermore, in the context of the present invention, compounds of the general formula (III) having (R) -configuration (compounds of the general formula (III-R)) in comparison with the (S) -configuration (compounds of the general formula (III-R) ) having a stereochemical purity of generally over 50% to 100%, preferably 60 to 100%, in particular 80 to 100%, very particularly 90 to 100%, especially 95 to 100%, preferred, wherein the respective (R) compound with an enantioselectivity of in each case more than 50% ee, preferably 60 to 100% ee, in particular 80 to 100% ee, very particularly 90 to 100% ee, most preferably 95 to 100% ee, based on the total content of (S) Compound present, preferably present.
Daher betrifft die vorliegende Erfindung auch Verbindungen der allgemeinen Formel (III), in welchen die stereochemische Konfiguration an dem mit (*) gekennzeichnet Schwefelatom (S) mit einer stereochemischen Reinheit von 60 bis 100 % (S), vorzugsweise 80 bis 100 % (S), insbesondere 90 bis 100 % (S), ganz besonders 95 bis 100 % (S), vorliegt.Therefore, the present invention also relates to compounds of general formula (III) in which the stereochemical configuration at the marked (*) sulfur atom (S) having a stereochemical purity of 60 to 100% (S), preferably 80 to 100% (S ), in particular 90 to 100% (S), very particularly 95 to 100% (S).
Für die Herstellung von Enantiomeren der allgemeinen Formel (III) kommen neben enantioselektiven Synthesen auch übliche Racemattrennungsmethoden in Frage (vgl. Handbücher der Stereochemie).For the preparation of enantiomers of the general formula (III), in addition to enantioselective syntheses, customary racemate resolution methods are also suitable (compare manuals of stereochemistry).
Racemische Gemische, beispielsweise von optisch aktiven Sulfoxiden der allgemeinen Formel (IM), lassen sich nach bekannten Verfahren trennen. Derartige Racemattrennungsmethoden sind in Handbüchern der Stereochemie beschrieben, beispielsweise in „Basic Organic Stereochemistry" (Eds.: Eliel, Ernest L.; Wilen, Samuel H.; Doyle, Michael P.; 2001 ; John Wiley & Sons) und „Stereochemisty of Organic Compounds (Eds.: Eliel, Ernest L.; Wilen, Samuel H.; Mander, Lewis N.; 1994; John Wiley & Sons). In Frage kommen hierbei z.B. die Adduktbildung mit einem optisch aktiven Hilfsreagens, die Trennung der diastereomeren Addukte in die entsprechenden Diastereomere, z.B. durch Kristallisation, Chromatographieverfah- ren, vor allem Säulenchromatographie und Hochdruckflüssigchromatographie, Destillation, gegebenenfalls unter reduziertem Druck, Extraktion und andere Verfahren und anschließende Rückspaltung der Diastereomeren in die Enantiomeren. Für präparative Mengen oder im industriellen Maßstab kommen Verfahren wie die Kristallisation diastereomerer Salze, die aus den Verbindungen (III) mit optisch aktiven Säuren und gegebenenfalls bei vorhandenen sauren Gruppen mit optisch aktiven Basen erhalten werden können, in Frage. Zur Racemattrennung durch Kristallisation diastereomerer Salze kommen als optisch aktive Säure z.B. Camphersulfonsäure, Camphersäure, Bromcamphersulfonsäure, Chinasäure, Weinsäure, Dibenzoylweinsäure und andere analoge Säuren in Betracht; als optisch aktive Basen kommen z.B. Chinin, Cinchonin, Chinidin, Brucin, 1-Phenylethylamin und andere analoge Basen in Frage.Racemic mixtures, for example of optically active sulfoxides of the general formula (III), can be separated by known processes. Such racemate resolution methods are described in handbooks of stereochemistry, for example in Basic Organic Stereochemistry (Eds .: Eliel, Ernest L, Wilen, Samuel H, Doyle, Michael P, 2001, John Wiley & Sons) and Stereochemistry of Organic Compounds (Eds .: Eliel, Ernest L .: Wilen, Samuel H., Mander, Lewis N, 1994, John Wiley & Sons), for example, the adduct formation with an optically active auxiliary reagent, the separation of the diastereomeric adducts in the corresponding diastereomers, for example by crystallization, chromatographic methods, especially column chromatography and high pressure liquid chromatography, distillation, optionally under reduced pressure, extraction and other methods and subsequent cleavage of the diastereomers in the enantiomers For preparative amounts or on an industrial scale are processes such as crystallization diastereomeric salts consisting of the compounds (III) with optically active acids and optionally b ei existing acidic groups can be obtained with optically active bases in question. For racemate separation by crystallization of diastereomeric salts come as optically active acid, for example, camphorsulfonic acid, camphoric acid, Bromcamphersulfonsäure, quinic acid, tartaric acid, dibenzoyltartaric acid and other analogous acids into consideration; quinine, cinchonine, quinidine, brucine, 1-phenylethylamine and other analogous bases are suitable as optically active bases.
Die Kristallisationen werden dann meist in wässrigen oder wässrig-organischen Lösemittel durchgeführt, wobei das Diastereomer mit der geringeren Löslichkeit gegebenenfalls nach Animpfen zunächst ausfällt. Das eine Enantiomer der Verbindung der Formel (III) wird danach aus dem ausgefällten Salz oder das andere aus dem Kristallisat durch Ansäuern bzw. mit Base freigesetzt.The crystallizations are then usually carried out in aqueous or aqueous-organic solvents, the diastereomer with the lower solubility optionally failing initially after inoculation. The one enantiomer of the compound of formula (III) is then released from the precipitated salt or the other from the crystals by acidification or with base.
Desweiteren können Racemate chromatographisch mit chiralen Stationärphasen getrennt werden. Derartige Enantiomerentrennungen lassen sich vom mg bis in den 100 kg Bereich mit präparativen HPLC Anlagen im Einzel- oder kontinuierlichen Betrieb durchführen.Furthermore, racemates can be separated chromatographically with chiral stationary phases. Enantiomer separations of this type can be carried out from mg to the 100 kg range with preparative HPLC systems in single or continuous operation.
Die Herstellung der Thioether der allgemeinen Formel (II), weche als Edukt für die oben unter a.) beschriebene Umsetzung dienen sowie auch Gegenstand der vorliegenden Erfindung sind, ist unter den Verfahren b.), c), d.), e.), f.), g.) und h.) nachfolgend beschrieben.The preparation of the thioethers of the general formula (II), which serve as starting material for the reaction described above under a.) And are also the subject of the present invention, is obtainable under the processes b.), C), d.), E.) , f.), g.) and h.) described below.
b.)b.)
Zur Herstellung eines Thioethers der allgemeinen Formel (II),For the preparation of a thioether of the general formula (II),
( H ) worin R1, R2, R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben, wird beispielsweise 2-Mercaptooxazol bzw. ein Salz desselben, bevorzugt ein Alkali- oder Erdalkalimetallsalz der allgemeinen Formel (V)1 ( H ) wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given in formula (I) above, for example, 2-mercaptooxazole or a salt thereof, preferably an alkali or alkaline earth metal salt of general formula (V) 1
( V ) M = Alkali-, Erdalkalimetall worin R1, R2 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben, mit einem Benzyl-Derivat der allgemeinen Formel (VI)(V) M = alkali metal, alkaline earth metal in which R 1 , R 2 have the meanings given above according to formula (I), with a benzyl derivative of the general formula (VI)
( Vl ) (VI)
worin R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben und Lg eine Abgangsgruppe bedeutet, in Gegenwart einer geeigneten Alkalioder Erdalkalimetall-Base, z.B. Kaliumcarbonat oder Natriumhydrid, oder einer organischen Base wie z.B. bevorzugt 1 ,8-Diazabicyclo(5.4.0)undec-7-en (DBU), in einem geigneten Lösemittel, z.B. Dimethylformamid, Tetrahydrofuran, Ethanol, oder bevorzugt Acetonitril, in einem Temperaturbereich zwischen 0 0C und 100 °C, und optional unter einer Inertgas-Atmosphäre, z.B. Stickstoff, umgesetzt.wherein R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given in formula (I) above and Lg is a leaving group, in the presence of a suitable alkali metal or alkaline earth metal base, for example potassium carbonate or sodium hydride, or an organic base such as For example, preferably 1, 8-diazabicyclo (5.4.0) undec-7-ene (DBU), in a suitable solvent, for example dimethylformamide, tetrahydrofuran, ethanol, or preferably acetonitrile, in a temperature range between 0 0 C and 100 ° C, and optionally reacted under an inert gas atmosphere, eg nitrogen.
Analoge Reaktionen für die Umsetzung von 2-Mercaptooxazolen bzw. deren Salzen sind in der Literatur beschrieben, z.B. in DE 26 25 229 A, WO 99/52874 A, WO 01/66529 A, WO 95/24403 A, Bradsher, C. K.; Jones, W. J. Jr; J. Org. Chem. 32, 2079 (1967). Anstelle der genannten Mercaptoverbindungen bzw. ein Salz denselben, bevorzugt ein Alkali- oder Erdalkalimetallsalz der allgemeinen Formel (V), können auch Mercaptanbildner, wie z.B. Isothiuroniumsalze verwendet werden.Analogous reactions for the reaction of 2-mercaptooxazoles or their salts are described in the literature, for example in DE 26 25 229 A, WO 99/52874 A, WO 01/66529 A, WO 95/24403 A, Bradsher, CK; Jones, WJ Jr; J. Org. Chem. 32, 2079 (1967). Instead of said mercapto compounds or a salt thereof, preferably an alkali metal or alkaline earth metal salt of the general formula (V), it is also possible to use mercaptan formers, for example isothiuronium salts.
Als Abgangsgruppen Lg sind Chlor, Brom, lod oder Sulfonat-Gruppen, wie Methan- Trifluormethan-, Ethan-, Benzol- oder Toluolsulfonat bevorzugt.As leaving groups Lg chlorine, bromine, iodine or sulfonate groups, such as methane trifluoromethane, ethane, benzene or toluenesulfonate are preferred.
Die im Verfahren b.) eingesetzten 2-Mercaptooxazol-Derivate bzw. entsprechenden Salze der 2-Mercaptooxazol-Derivate der allgemeinen Formel (V) sind demThe used in the process b.) 2-Mercaptooxazol derivatives or corresponding salts of 2-mercaptooxazole derivatives of the general formula (V) are the
Fachmann bekannt, und teilweise kommerziell erhältlich oder nach dem Fachmann bekannten Verfahren darstellbar, beispielsweise wie beschrieben in a) Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11 , Ed. E. Schaumann; b) Houben-Weyl (Methoden der organische Chemie), Band E8a, Hetarene Ill-Teil 1 , Ed. E. Schaumann; c) Can. J. Chem., Vol. 50, 3082-3083 (1972); d) WO 03/006442 A.Known to one skilled in the art, and partially commercially available or representable by methods known in the art, for example as described in a) Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann; b) Houben-Weyl (Methods of Organic Chemistry), Volume E8a, Hetarene Ill-Part 1, Ed. E. Schaumann; c) Can. J. Chem., Vol. 50, 3082-3083 (1972); d) WO 03/006442 A.
Die im Verfahren b.) eingesetzten Benzyl-Derivate der allgemeinen Formel (VI) sind dem Fachmann bekannt oder kommerziell erhältlich oder nach dem Fachmann bekannten Verfahren darstellbar [siehe z.B.: a) WO 01/12613 A, b) WO 02/062770 A, c) WO 03/000686 A, d) WO 2006/024820 A].The benzyl derivatives of the general formula (VI) used in process b.) Are known to the person skilled in the art or are commercially available or can be prepared by processes known to the person skilled in the art [see, for example: a) WO 01/12613 A, b) WO 02/062770 A, c) WO 03/000686 A, d) WO 2006/024820 A].
C)C)
Alternativ kann die Herstellung eines Thioethers der allgemeinen Formel (II),Alternatively, the preparation of a thioether of general formula (II),
worin R1, R2, R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben, durch die Umsetzung eines Oxazol-Derivates der allgemeinen Formel (VII), in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given above according to formula (I), by the reaction of an oxazole derivative of general formula (VII),
worin R1, R2 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben und Lg' eine Abgangsgruppe bedeutet, wobei als Abgangsgruppen u.a. Fluor, Chlor, Brom, lod, Sulfide-, Sulfoxide- oder Sulfonat-Gruppen fungieren können, mit einem Benzyl- Imidothiocarbamat-Salz der allgemeinen Formel (VIII)wherein R 1 , R 2 have the meanings given above according to formula (I) and Lg 'is a leaving group, which may function as leaving groups inter alia fluorine, chlorine, bromine, iodine, sulfide, sulfoxide or sulfonate groups, with a benzyl Imidothiocarbamate salt of general formula (VIII)
( VIII )(VIII)
worin R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebene Bedeutungen haben, Lg eine Abgangsgruppe bedeutet, in einem Eintopfverfahren in Gegenwart einer wäßrigen Alkali- oder Erdalkalimetall-Base erfolgen.wherein R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given in formula (I) above, Lg represents a leaving group, carried out in a one-pot process in the presence of an aqueous alkali or alkaline earth metal base.
Allgemein wird die Umsetzung durch das nachstehende Formelschema dargestellt: In general, the implementation is represented by the following formula scheme:
Die im Verfahren c.) eingesetzten Oxazol-Derivate der allgemeinen Formel (VII) sind dem Fachmann bekannt oder kommerziell erhältlich oder nach dem Fachmann bekannten Verfahren darstellbar [z.B. wie in „Science of Synthesis", Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11 , Ed. E. Schaumann und DE 26 25 229 A beschrieben].The oxazole derivatives of the general formula (VII) used in process c.) Are known to the person skilled in the art or are commercially available or can be prepared by processes known to the person skilled in the art [e.g. as described in "Science of Synthesis", Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed E. Schaumann and DE 26 25 229 A].
Die Verwendung von Imidothiocarbamat-Salzen (Isothiuroniumsalzen) im Sinne einer Eintopfreaktion zur Verseifung des Imidothiocarbamat-SalzesThe use of imidothiocarbamate salts (isothiuronium salts) in the sense of a one-pot reaction for the saponification of the imidothiocarbamate salt
(Isothiuroniurnsaizes) und Umsetzung des intermediär entstandenen Mercaptans in einer Austauschreaktion ist z.B. in in DE 39 42 946 A1 WO 2006/024820 A und WO 2006/037945 A, und unter Anwendung der Phasen-Transfer Katalyse in WO 2007/003294 A und WO 2007/003295 A beschrieben.(Isothiuroniurnsaizes) and reacting the resulting intermediate mercaptan in an exchange reaction is, for example, WO in in DE 39 42 946 A 1 2006/024820 A and WO 2006/037945 A, and using the phase-transfer catalysis in WO 2007/003294 A and WO 2007/003295 A described.
Verbindungen der allgemeinen Formel (VIII) lassen sich durch Umsetzung eines Alkylierungsmittels der allgemeinen Formel (VI), worin R3, R4, R5, R6, R7 die oben gemäß der allgemeinen Formel (I) angegebenen Bedeutungen haben und Lg eine Abgangsgruppe ist, mit Thioharnstoff erhalten.Compounds of the general formula (VIII) can be obtained by reacting an alkylating agent of the general formula (VI) in which R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given above according to the general formula (I) and Lg is a Leaving group is obtained with thiourea.
Die Herstellung der Imidothiocarbamat-Salze (VIII) durch Umsetzung eines Benzylierungsmittel der allgemeinen Formel (VI) mit Thioharnstoff erfolgt nach bekannten Verfahren (wie beispielsweise dem in DD 152557 A beschriebenen Verfahren), vorzugsweise durch Reaktion mit einer äquimolaren Menge an Thioharnstoff und wahlweise in Anwesenheit von Alkaliiodid, z.B. Natriumiodid,The preparation of the imidothiocarbamate salts (VIII) by reaction of a benzylating agent of the general formula (VI) with thiourea is carried out by known methods (such as the method described in DD 152557 A), preferably by reaction with an equimolar amount of thiourea and optionally in the presence of alkali iodide, eg sodium iodide,
Kaliumiodid, in einem inerten Lösemittel, wie niedrigen Alkoholen, wie beispielsweise Methanol, Ethanol oder Isopropanol; Kohlenwasserstoffen, wie beispielsweise Benzol oder Toluol; halogenierten Kohlenwasserstoffen, wie beispielsweise Dichlormethan oder Chloroform; oder Etherderivaten, wie beispielsweise Methyl- tert.-butylether, Tetrahydrofuran oder Dioxan bei Temperaturen zwischen 0 bis 1500C, vorzugsweise zwischen 20 bis 100 0C.Potassium iodide, in an inert solvent such as lower alcohols, such as methanol, ethanol or isopropanol; Hydrocarbons, such as Benzene or toluene; halogenated hydrocarbons, such as dichloromethane or chloroform; or ether derivatives, such as methyl tert-butyl ether, tetrahydrofuran or dioxane at temperatures between 0 to 150 0 C, preferably between 20 to 100 0 C.
Die in vielen Fällen durch Kristallisation erhaltenen Verbindungen der Imidothiocarbamat-Salze der allgemeinen Formel (VIII) werden bei dem erfindungsgemäßen Verfahren im Allgemeinen ohne weitere Reinigungsschritte unter starkem Rühren mit äquimolaren Mengen der Oxazol-Derivate der allgemeinen Formel (VII) unter Phasentransferbedingungen umgesetzt.The compounds of the imidothiocarbamate salts of the general formula (VIII) which are obtained in many cases by crystallization are generally reacted with equimolar amounts of the oxazole derivatives of the general formula (VII) under phase transfer conditions in the process according to the invention without further purification steps with vigorous stirring.
Vorteilhaft arbeitet man hier in einem Zweiphasensystem, wobei neben einer wäßrigen stark basischen Alkali- oder Erdalkalimetall-Hydroxid-Lösung, bevorzugt Natrium- oder Kaliumhydroxid, mit mindestens zwei Äquivalenten der Base, die organische Phase ein inertes Lösemittel wie Tetrahydrofuran, Diethylether, Acetonitril. Pentan, Hexan, Benzol, Toluo!, Xylo!, Chlorbenzol, Dichlormethan, Chloroform, Tetrachlorkohlenstoff, Nitrobenzol oder Mischungen dieser Lösemittel ist.Advantageously, one works here in a two-phase system, wherein in addition to an aqueous strongly basic alkali or alkaline earth metal hydroxide solution, preferably sodium or potassium hydroxide, with at least two equivalents of the base, the organic phase is an inert solvent such as tetrahydrofuran, diethyl ether, acetonitrile. Pentane, hexane, benzene, toluene, xylene, chlorobenzene, dichloromethane, chloroform, carbon tetrachloride, nitrobenzene or mixtures of these solvents.
Es ist auch möglich, das jeweils wertvollere Edukt der Formel (VIII) oder der Formel (VII) etwas im Unterschuß einzusetzen.It is also possible to use the respectively more valuable starting material of the formula (VIII) or of the formula (VII) in a slight amount.
Als Phasentransferkatalysatoren sind quatemäre Ammonium- oder Phosphoniumsalze sowie Kronenether, Kryptanden oder Polyethylenglykole geeignet. Beispiele solcher Katalysatoren finden sich z.B. in W. P. Weber, G. W. Gokel; Phase Transfer Catalysis in Organic Synthesis, Springer-Verlag, Berlin 1977 oder E. V. Dehmlow, S. S. Dehmlow, Phase Transfer Catalysis, Second Ed. Verlag Chemie, Weinheim 1983.Suitable phase transfer catalysts are quaternary ammonium or phosphonium salts and also crown ethers, cryptands or polyethylene glycols. Examples of such catalysts can be found e.g. in W.P. Weber, G.W. Gokel; Phase Transfer Catalysis in Organic Synthesis, Springer-Verlag, Berlin 1977 or E.V. Dehmlow, S.S. Dehmlow, Phase Transfer Catalysis, Second Ed. Verlag Chemie, Weinheim 1983.
Vorzugsweise werden die Reaktionspartner und der Katalysator bei Temperaturen von 20 bis 100 0C unter Schutzgasatmosphäre stark gerührt. Das unter den Reaktionsbedingungen intermediär entstehende Mercaptan der aallllggeemmeeiinneenn FFoorrmmeell ((IIXX)),, wwooririnn RR33,, RR44,, RR55,, RR66,, RR77 die oben gemäß der allgemeinen Formel (I) zuvor angegebene Bedeutung haben,Preferably, the reactants and the catalyst at temperatures of 20 to 100 0 C are stirred vigorously under a protective gas atmosphere. The intermediately formed under the reaction conditions Mercaptan allallggeemmeeiinnenn FFoorrmmeell ((IIXX)), wwooririnn RR 33 ,, RR 44 ,, RR 55 ,, RR 66 ,, RR 77 have the meaning given above according to the general formula (I) above,
( IX )(IX)
wird in situ sofort durch das Oxazol-Derivat der allgemeinen Formel (VII) abgefangen.is immediately trapped in situ by the oxazole derivative of general formula (VII).
d.)d.)
Alternativ kann die Herstellung von Thioethern der Formel (II) worin R 1 , D R2 , D R3 , D R4 , R5, R6, R7 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben,Alternatively, the preparation of thioethers of formula (II) wherein R 1, D R2, D R3, D R4, R 5, R 6, R 7 have the the formula (I) as defined above,
durch die Umsetzung eines Oxazol-Derivates der allgemeinen Formel (VII)by the reaction of an oxazole derivative of the general formula (VII)
worin R >1 , D R2 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben und Lg' eine Abgangsgruppe bedeutet, wobei als Abgangsgruppen u.a. Chlor, Brom oder Methylsulfonyl-Gruppen fungieren können, mit einem Benzyl-Imidothiocarbamat-Salz (Isothiuroniumsalz) der allgemeinen Formel (VIII)wherein R> 1, D R2 have the meanings given above according to formula (I) and Lg ' a leaving group, where as leaving groups, inter alia, chlorine, bromine or methylsulfonyl groups can act, with a benzyl imidothiocarbamate salt (isothiuronium salt) of the general formula (VIII)
( VIII )(VIII)
worin R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebene Bedeutungen haben, Lg eine Abgangsgruppe bedeutet, in einem Eintopfverfahren in Gegenwart einer Alkalimetall- oder Erdalkalimetall-Carbonatbase und eines Lösemittels, wie einem Alkohol, erfolgen.wherein R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given in formula (I) above, Lg is a leaving group, in a one-pot process in the presence of an alkali metal or alkaline earth metal carbonate base and a solvent such as an alcohol , respectively.
Allgemein wird die Umsetzung durch das nachstehende Formelschema dargestellt:In general, the implementation is represented by the following formula scheme:
Verbindungen der allgemeinen Formel (VIII) lassen sich durch Umsetzung eines Alkylierungsmittels der allgemeinen Formel (VI), worin R3, R4, R5, R6, R7 die oben gemäß der allgemeinen Formel (I) angegebenen Bedeutungen haben, und Lg eine Abgangsgruppe ist, mit Thioharnstoff erhalten, wie gemäß vorstehendem Verfahren c.) beschrieben.Compounds of the general formula (VIII) can be prepared by reacting an alkylating agent of the general formula (VI) in which R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given above according to the general formula (I), and Lg is a leaving group, obtained with thiourea, as described in process c. above).
Die Imidothiocarbamat-Salze (Isothiuroniumsalze) der allgemeinen Formel (VIII) werden bei dem erfindungsgemäßen Verfahren im Allgemeinen ohne weitere Reinigungsschritte unter starkem Rühren mit leichtem Überschuß der Oxazol- Derivate der allgemeinen Formel (VII) und mit leichtem Überschuß einer Carbonat- Base, z.B. Kaliumcarbonat, Natriumcarbonat oder Kaliumbicarbonat, oder eines Hydroxids, z.B. Kaliumhydroxid, oder ein Alkoxids, z.B. Natriumalkoxid, in Alkohol, z.B. Ethanol, Ether, z.B. 1 ,4-Dioxan, Tetrahydrofuran; einem polaren Lösemittel wie z.B. Wasser, Dimethylformamid; oder einer Mischung dieser Lösemittel in einer Temperaturbereich zwischen 20 bis 200 0C, bevorzugt zwischen 50 und 150 0C, optional unter einer Inertgas-Atmosphäre, z.B. Stickstoff, oder in einer Mikrowelle- Apparatur umgesetzt.The imidothiocarbamate salts (isothiuronium salts) of the general formula (VIII) be in the process of the invention generally without further purification steps with vigorous stirring with a slight excess of the oxazole derivatives of the general formula (VII) and with a slight excess of a carbonate base, for example potassium carbonate, sodium carbonate or potassium bicarbonate, or a hydroxide, for example potassium hydroxide, or an alkoxide, eg sodium alkoxide, in alcohol, eg ethanol, ethers, eg 1, 4-dioxane, tetrahydrofuran; a polar solvent such as water, dimethylformamide; or a mixture of these solvents in a temperature range between 20 and 200 ° C., preferably between 50 and 150 ° C., optionally under an inert gas atmosphere, for example nitrogen, or in a microwave apparatus.
Die Imidothiocarbamat-Salze (Isothiuroniumsalze) der allgemeinen Formel (VIII) können auch in situ, ohne Isolierung, weiter umgesetzt werden.The imidothiocarbamate salts (isothiuronium salts) of the general formula (VIII) can also be reacted further in situ, without isolation.
Vorteilhaft arbeitet man hier in einem Alkohol, bevorzugt Ethanol, mit mindestens 1.1 Äquivalenten der Base, bevorzugt Kaliumcarbonat (K2CO3).Advantageously, one works here in an alcohol, preferably ethanol, with at least 1.1 equivalents of the base, preferably potassium carbonate (K 2 CO 3 ).
Solche Verfahren sind in der Literatur bekannt und sind z.B. in WO 2006/024820 A, WO 01/012613 A und WO 2006/123088 A beschrieben.Such methods are known in the literature and are e.g. in WO 2006/024820 A, WO 01/012613 A and WO 2006/123088 A.
Die im Verfahren d.) eingesetzten Oxazol-Derivate der allgemeinen Formel (VII) sind dem Fachmann bekannt oder kommerziell erhältlich oder nach dem Fachmann bekannten Verfahren darstellbar [siehe z.B. Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11 , Ed. E. Schaumann].The oxazole derivatives of the general formula (VII) used in process d.) Are known to the person skilled in the art or are commercially available or can be prepared by processes known to the person skilled in the art [see, for example, US Pat. Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann].
e.)e.)
Alternativ kann die Herstellung eines Thioethers der allgemeinen Formel (II), Alternatively, the preparation of a thioether of general formula (II),
worin R1, R2, R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben, durch die Umsetzung eines Oxazol-Derivats der allgemeinen Formel (VII),in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given above according to formula (I), by the reaction of an oxazole derivative of general formula (VII),
worin R1, R2 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben und Lg' eine Abgangsgruppe bedeutet, wobei als Abgangsgruppen u.a. Fluor, Chlor, Brom, oder Sulfonat-Gruppen fungieren können, mit einem Benzyl-Mercaptan der allgemeinen Formel (IX),wherein R 1 , R 2 have the meanings given above in accordance with formula (I) and Lg ' denotes a leaving group, where as leaving groups inter alia fluorine, chlorine, bromine or sulfonate groups can function, with a benzyl mercaptan of the general formula (IX )
( IX )(IX)
worin R3, R4, R5, R6, R7 die oben gemäß der allgemeinen Formel (I) zuvor angegebene Bedeutung haben, in Gegenwart einer Alkali- oder Erdalkalimetall- Base, z.B. Kaliumcarbonat oder Natriumhydrid, oder organischen Base, z.B. bevorzugt 1 ,8-Diazabicyclo(5.4.0)undec-7-en (DBU)1 optional in einem Lösemittel, z.B. Dimethylformamid, Tetrahydrofuran, Ethanol, oder bevorzugt Acetonitril, in einem Temperaturbereich zwischen 0 und 100 °C, und optional unter einer Inertgas- Atmosphäre, z.B. Stickstoff, erfolgen.wherein R 3 , R 4 , R 5 , R 6 , R 7 have the meaning given above according to the general formula (I) above, in the presence of an alkali or alkaline earth metal base, for example potassium carbonate or sodium hydride, or organic base, for example 1, 8-diazabicyclo (5.4.0) undec-7-ene (DBU) 1 optionally in a solvent, for example dimethylformamide, tetrahydrofuran, ethanol, or preferably acetonitrile, in a temperature range between 0 and 100 ° C, and optionally under an inert gas - Atmosphere, such as nitrogen, take place.
Einige der Verfahren sind in der Literatur bekannt und sind z.B. in WO 2006/024820 A, WO 01/012613 A und WO 2006/123088 A beschrieben.Some of the methods are known in the literature and are e.g. in WO 2006/024820 A, WO 01/012613 A and WO 2006/123088 A.
Nucleophile Substitutionen an Oxazol-Derivate sind in der Literatur beschrieben, wie z.B. in Yamanaka, H.; Ohba, S.; Sakamoto, T.; Heterocycles (1990), 31(6), 1115-27.Nucleophilic substitutions on oxazole derivatives are described in the literature, e.g. in Yamanaka, H .; Ohba, S .; Sakamoto, T .; Heterocycles (1990), 31 (6), 1115-27.
Die im Verfahren e.) eingesetzten Oxazol-Derivate der allgemeinen Formel (VII) sind dem Fachmann bekannt oder kommerziell erhältlich oder nach dem Fachmann bekannten Verfahren darstellbar [siehe z.B. Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11 , Ed. E. Schaumann].The oxazole derivatives of the general formula (VII) used in process e.) Are known to the person skilled in the art or are commercially available or can be prepared by processes known to the person skilled in the art [see, for example, US Pat. Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann].
Die im Verfahren e.) eingesetzten Mercaptane der allgemeinen Formel (IX) sind dem Fachmann bekannt (siehe z.B. WO 2004/013106 A) oder in Analogie zu dem Fachmann bekannten Verfahren zur Mercaptan-Herstellung darstellbar.The mercaptans of the general formula (IX) used in process e.) Are known to the person skilled in the art (see, for example, WO 2004/013106 A) or can be prepared in analogy to processes known to the person skilled in the art for producing mercaptan.
f.)f.)
Die Herstellung von Thioethern der Formel (II) worin R1, R2, R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben, und R1 Halogen oder Nitro bedeutetThe preparation of thioethers of the formula (II) in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given above according to formula (I), and R 1 is halogen or nitro
kann beispielsweise durch die Umsetzung eines Oxazol-Derivats der allgemeinen Formel (X),For example, by the reaction of an oxazole derivative of the general Formula (X),
worin R2, R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebene Bedeutungen haben, erfolgen. Allgemein wird die Umsetzung durch das nachstehende Formelschema dargestellt:wherein R 2 , R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given in formula (I) above, take place. In general, the implementation is represented by the following formula scheme:
Die Verbindungen der allgemeinen Formel (X) werden mit einem halogenierenden Mittel, wie z.B. Halogen, wie Chlor, Brom, lod oder Halo-Succinimid, wie N- Chlorsuccinimid (NCS), N-Bromsuccinimid (NBS), N-Iodsuccinimid (NIS), oder für Nitro mit einen Nitrierungsmittel, wie z.B. Nitriersäure, hergestellt aus Schwefelsäure und Salpetersäure, behandelt und in geeigneten Lösemittel, wie Chlorkohlenwasserstoffen, z.B. Tetrachlormethan, Dichlormethan, 1 ,2-Dichlorethan, oder Dimethylformamid zu Verbindungen der Formel (II) umgesetzt.The compounds of general formula (X) are reacted with a halogenating agent, e.g. Halogen, such as chlorine, bromine, iodine or halo-succinimide, such as N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS), N-iodosuccinimide (NIS), or for nitro with a nitrating agent, such. Nitrating acid, prepared from sulfuric acid and nitric acid, and treated in suitable solvents, such as chlorinated hydrocarbons, e.g. Carbon tetrachloride, dichloromethane, 1, 2-dichloroethane, or dimethylformamide to give compounds of formula (II).
Die im Verfahren f.) eingesetzten analogen Thioether-Derivate der allgemeinen Formel (X) sind nach dem Fachmann bekannten Verfahren (siehe z.B.: DE 26 25 229 A, WO 99/52874 A, WO 01/66529 A, WO 95/24403 A; oder nach den unter b.), c), d.), e.) zuvor genannten Verfahren darstellbar. g )The analogous thioether derivatives of the general formula (X) used in process f.) Are processes known to the person skilled in the art (see, for example: DE 26 25 229 A, WO 99/52874 A, WO 01/66529 A, WO 95/24403 A or according to the methods mentioned under b.), c), d.), e.) above. g)
Die Herstellung von Thioethern der Formel (II) worin R1, R2, R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben,The preparation of thioethers of the formula (II) in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given above according to formula (I),
kann beispielsweise durch die Umsetzung eines Oxazol-Derivats der allgemeinen Formel (Xl),For example, by the reaction of an oxazole derivative of general formula (XI),
hergestellt aus einem Oxazol-Derivat der allgemeinen Formel (V), durch Umsetzung mit einem Alkylierungsmittel R12Lg', worin R2 die gemäß Formel (I) zuvor angegebenen Bedeutungen hat, R12 bevorzugt (CrC6)-Alkyl, welches unsubstituiert oder durch einen oder mehrere, gleiche oder verschiedene Reste aus der Gruppe Halogen substituiert ist, besonders bevorzugt Methyl oder Ethyl, bedeutet und Lg' eine Abgangsgruppe bedeutet, wobei als Abgangsgruppen u.a. Chlor, Brom oder Methylsulfonyl-Gruppen fungieren können, mit einer starken Base und einem Alkylierungsmittel R1Lg', worin R1 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben, nach dem Schema prepared from an oxazole derivative of general formula (V), by reaction with an alkylating agent R 12 Lg ' , wherein R 2 has the meanings given in formula (I) above, R 12 is preferably (C 1 -C 6 ) -alkyl which is unsubstituted or is substituted by one or more identical or different radicals from the group halogen, particularly preferably methyl or ethyl, and Lg ' denotes a leaving group, where as leaving groups, inter alia, chlorine, bromine or methylsulfonyl groups can act, with a strong base and a Alkylating agent R 1 Lg ' , wherein R 1 have the meanings given above according to formula (I), according to the scheme
( Xl ) ( XU ) n(XI) (XU) n
verlaufen, worin R1, R2, R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben und Lg bzw. Lg' eine Abgangsgruppe bedeutet, wobei als Abgangsgruppen u.a. Fluor, Chlor, Brom, lod oder Sulfonat-Gruppen wie Methan- Trifluormethan-, Ethan-, Phenyl- oder Toluolsulfonat fungieren können.in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given above according to formula (I) and Lg or Lg 'is a leaving group, said leaving groups include fluorine, chlorine , Bromine, iodine or sulfonate groups such as methane trifluoromethane, ethane, phenyl or toluenesulfonate can act.
Als starke Base kann Lithiumdiisopropylamid (LDA), Lithiumtetramethylpiperidin (LTMP), Lithiumhexamethyldisilazan (LHMDS) benutzt werden, bevorzugt LDA, die nach dem Fachmann bekannten Verfahren hergestellt sein können.As the strong base, lithium diisopropylamide (LDA), lithium tetramethylpiperidine (LTMP), lithium hexamethyldisilazane (LHMDS) may be used, preferably LDA, which may be prepared by methods known to those skilled in the art.
Hexamethylphosphoramid (HMPT) kann z.B. als Co-Lösemittel verwendet werden. Als Lösemittel dienen inerte Lösemittel wie Kohlenwasserstoffe, wie z.B. Hexan, Heptan, Cyclohexan, aromatische Kohlenwasserstoffe wie z.B. Benzol, Ether, wie z.B. Diethylether, Methyl-tert.-butylether (MTBE), Tetrahydrofuran und Dioxan, bevorzugt Tetrahydrofuran. Die zuvorgenannten Lösemittel können auch als Gemische eingesetzt werden. In dieser Reaktion werden die Verbindungen der Formel (Xl) und die Base bzw. das Alkylierungsmittel R1Lg' bevorzugt in 0.9-1.5 Mol von den Letzteren pro Mol der Ersteren eingesetzt. Die Reaktion wird bevorzugt in einem Temperaturbereich zwischen -90 0C und dem Siedepunkt des Lösemittels ausgeführt. Die Reaktionszeit unterliegt keiner Begrenzung, die Reaktionen sind allgemein nach 1 bis 24 Stunden abgeschlossen.Hexamethylphosphoramide (HMPT) can be used as co-solvent, for example. Suitable solvents are inert solvents such as hydrocarbons, such as hexane, heptane, cyclohexane, aromatic hydrocarbons such as benzene, ethers, such as diethyl ether, methyl tert-butyl ether (MTBE), tetrahydrofuran and dioxane, preferably tetrahydrofuran. The aforementioned solvents can also be used as mixtures. In this reaction, the compounds of the formula (XI) and the base or the alkylating agent R 1 Lg 'are preferably used in 0.9-1.5 mol of the latter per mole of the former. The reaction is preferably carried out in a temperature range between -90 0 C and the boiling point of the solvent. The reaction time is not limited, the reactions are generally completed after 1 to 24 hours.
Zur Herstellung der Sulfone und Sulfoxide der Verbindungen der Formel (II), worin R1, R2, R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben, kann die unter a) angegebene Methode angewendet werden.For the preparation of the sulfones and sulfoxides of the compounds of formula (II) wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given in formula (I) above, the under a ) method.
Besonders für den Fall dass R1 Fluor ist, werden bevorzugt Reagenzien für die elektrophile Fluorierung eingesetzt, wie z.B. 1-Chlormethyl-4-fluor-1 ,4-diazabicyclo- [2,2,2]octan-bis-tetrafluorborat (F-TEDA-BF4, SelectFluor™), N- Fluorbenzolsulfon- säureimid (NFBS oder NFSi), N-Fluor-o-benzenedisulfonimid (NFOBS), 1-Fluor-4- hydroxy-1 ,4-diazoniabicyclo[2.2.2]-octan bis(tetrafluorborat) (NFTh, AccuFluor™) und weitere wie in „Modern Fluoroorganic Chemistry", 2004, Wiley-VCH Verlag, Ed. P. Kirsch, beschrieben.Particularly in the case where R 1 is fluorine, preference is given to using reagents for electrophilic fluorination, for example 1-chloromethyl-4-fluoro-1,4-diazabicyclo- [2,2,2] octane-bis-tetrafluoroborate TEDA-BF4, SelectFluor ™), N-fluorobenzenesulfonic acid imide (NFBS or NFSi), N-fluoro-o-benzenedisulfonimide (NFOBS), 1-fluoro-4-hydroxy-1,4-diazoniabicyclo [2.2.2] octane bis (tetrafluoroborate) (NFTh, AccuFluor ™) and others as described in "Modern Fluoroorganic Chemistry", 2004, Wiley-VCH Verlag, Ed. P. Kirsch.
Die im Verfahren g.) eingesetzten 2-Mercaptooxazol-Derivate bzw. entsprechenden Salze der 2-Mercaptooxazol-Derivate der allgemeinen Formel (V) sind dem Fachmann bekannt, oder kommerziell erhältlich oder nach dem Fachmann bekannten Verfahren darstellbar, beispielsweise wie beschrieben in Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11 , Ed. E. Schaumann.The 2-mercaptooxazole derivatives or corresponding salts of the 2-mercaptooxazole derivatives of the general formula (V) used in process g.) Are known to the person skilled in the art, or are commercially available or can be prepared by processes known to those skilled in the art, for example as described in Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann.
Oxazol-Derivate (Xl) können, in Analogie zu dem Fachmann bekannten Verfahren, in 5-Position regioselektiv deprotoniert werden. Analoge Reaktionen unter Verwendung einer Alkylbase wie Buthyllithium sind in der Literatur beschrieben, z.B. in Boger, D. L. et al; J. Med. Chem. (2007) 50 (33), 1058-1068 und Molinski, T. F. et al; J. Org. Chem. (1998) 63, 551-555, und mit terf-Butyllithium und ein Kupfer-Salz in Marino, J. P. ; Nguyen, N. Tel Lett. (2003) 44, 7395-7398 und dort zitierte Literatur. Die im Verfahren g.) eingesetzten Oxazol-Derivate der allgemeinen Formel (Xl) können zum Beispiel entsprechend Verfahren b.) durch Reaktion eines 2-Mercapto- oxazol-Derivates der allgemeinen Formel (V) mit einem Alkylierungsmittel R12Lg' oder nach dem Fachmann bekannten Verfahren [siehe z.B. Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11 , Ed. E. Schaumann] hergestellt werden, oder sind kommerziell erhältlich.Oxazole derivatives (XI) can be deprotonated regioselectively in the 5-position, analogously to processes known to those skilled in the art. Analogous reactions using an alkyl base such as butyllithium have been described in the literature, eg in Boger, DL et al; J. Med. Chem. (2007) 50 (33), 1058-1068 and Molinski, TF et al; J. Org. Chem. (1998) 63, 551-555, and with terf-butyllithium and a copper salt in Marino, JP; Nguyen, N. Tel Lett. (2003) 44, 7395-7398 and literature cited therein. The oxazole derivatives of general formula (XI) used in process g.) Can be prepared, for example, according to process b.) By reaction of a 2-mercaptooxazole derivative of general formula (V) with an alkylating agent R 12 Lg ' or after Those skilled in the art [see, eg, Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann], or are commercially available.
Die im Verfahren g.) genannten Verbindungen der Formel (XIII) können aus den Verbindungen der Formel (XII) durch Oxidation nach vorstehendem Verfahren a) oder nach dem Fachmann bekannten Verfahren hergestellt werden. Die Verbindungen der allgemeinen Formel (XIII) wiederum können nach den vorstehenden Verfahren c.) oder d.) mit Benzyl-Imidothiocarbamat-Salzen (VIII) oder mit Benzyl- Mercaptanen der Formel (IX) nach vorstehenden Verfahren e.) zu Verbindungen des Typs (II) umgesetzt werden.The compounds of the formula (XIII) mentioned in process g.) Can be prepared from the compounds of the formula (XII) by oxidation according to the above process a) or by processes known to the person skilled in the art. The compounds of the general formula (XIII), in turn, can be prepared by the above processes c.) Or d.) With benzyl imidothiocarbamate salts (VIII) or with benzyl mercaptans of the formula (IX) according to the above process e.) To give compounds of the type (II) be implemented.
h.)H.)
Die Herstellung von Thioethern der Formel (II) worin R1, R2, R3, R4, R5 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben,The preparation of thioethers of the formula (II) in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above according to formula (I),
kann beispielsweise auch durch die Umsetzung eines Benzyldisulfid-Derivats der allgemeinen Formel (XV) mit 2-Amino-oxazolen der Formel (XIV) und einem Diazotierungsmittel wie in folgendem Schema dargestellt, may also be exemplified by the reaction of a benzyl disulfide derivative of the general formula (XV) with 2-amino-oxazoles of the formula (XIV) and a diazotizing agent as shown in the following scheme,
und worin R1, R2, R3, R4, R5 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben, erfolgen.and in which R 1 , R 2 , R 3 , R 4 , R 5 have the meanings given above according to formula (I).
Die Benzyldisulfide der allgemeinen Formel (XV) werden mit einem Diazotierungs- mittel und einem 2-Aminooxazol-Derivat der allgemeinen Formel (XIV) in einem geeigneten Lösemittel zu Verbindungen der Forme! (M) zur Reaktion gebracht.The benzyl disulfides of the general formula (XV) are reacted with a diazotization agent and a 2-aminooxazole derivative of the general formula (XIV) in a suitable solvent to form compounds! (M) reacted.
Geeignete Lösemittel sind gegenüber der Reaktion inerte Lösemittel, wie z.B. Kohlenwasserstoffe, so wie Hexan, Heptan, Cyclohexan; aromatische Kohlenwasserstoffe, wie Benzol, Chlorbenzol, Toluol, XyIoI; halogenierte Kohlenwasserstoffe, wie z.B. Dichlormethan, Dichlorethan, Chloroform und Tetrachlorkohlenstoff; Ester, wie z.B. Ethylacetat und Methylacetat; Ether, wie z.B. Diethylether, Methyl-tert.-butylether, Dioxan; Nitrile, wie z.B. Acetonitril; Alkohole, wie z.B. Methanol, Ethanol, Isopropylalkohol; Amide, wie z.B. N,N-Dimethylformamid und Sulfoxide, wie z.B. Dimethylsulfoxid.Suitable solvents are inert solvents to the reaction, e.g. Hydrocarbons, such as hexane, heptane, cyclohexane; aromatic hydrocarbons, such as benzene, chlorobenzene, toluene, xylene; halogenated hydrocarbons, e.g. Dichloromethane, dichloroethane, chloroform and carbon tetrachloride; Esters, e.g. Ethyl acetate and methyl acetate; Ethers, e.g. Diethyl ether, methyl tert-butyl ether, dioxane; Nitriles, e.g. acetonitrile; Alcohols, e.g. Methanol, ethanol, isopropyl alcohol; Amides, e.g. N, N-dimethylformamide and sulfoxides, e.g. Dimethyl sulfoxide.
Das Diazotierungsreagens kann z.B. ein Nitritester, wie Isoamylnitrit, oder ein Nitritsalz, wie Natriumnitrit, sein. Die Molverhältnisse können frei gewählt werden, bevorzugt sind äquimolare Mengen der Heteroarylalkyldisulfide und der Diazotierungsmittel. Bevorzugt wird die Reaktion bei einer Temperatur zwischen - 20 0C und dem Siedepunkt des gewählten Lösemittels durchgeführt und ist im Allgemeinen nach einer Zeit von 0,1 bis 40 Stunden vollständig abgeschlossen. Die Diazotierung eines 2-Aminooxazol-Derivats der allgemeinen Formel (XIV) ist z.B. beschrieben in Hodgetts, K. J.; Kershaw, M. T. Org. Lett. (2002), 4(17), 2905-2907.The diazotization reagent may be, for example, a nitrite ester such as isoamyl nitrite or a nitrite salt such as sodium nitrite. The molar ratios can be chosen freely, equimolar amounts of the heteroarylalkyl disulfides and the diazotization agents are preferred. Preferably, the reaction is carried out at a temperature between -20 0 C and the boiling point of the chosen solvent and is generally completely completed after a time of 0.1 to 40 hours. The diazotization of a 2-aminooxazole derivative of the general formula (XIV) is described, for example, in Hodgetts, KJ; Kershaw, MT Org. Lett. (2002), 4 (17), 2905-2907.
Die im Verfahren h.) eingesetzten Oxazol-Derivate der allgemeinen Formel (XIV) sind dem Fachmann bekannt oder kommerziell erhältlich, oder nach dem Fachmann bekannten Verfahren darstellbar [siehe z.B. Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations], Category 2, Volume 11 , Ed. E. Schaumann.The oxazole derivatives of the general formula (XIV) used in process h) are known to the person skilled in the art or are commercially available, or can be prepared by processes known to the person skilled in the art [see, for example, US Pat. Science of Synthesis, Houben-Weyl (Methods of Molecular Transformations), Category 2, Volume 11, Ed. E. Schaumann.
Die Benzyldisulfide der allgemeinen Formel (XV) können nach der Fachmann bekannten Verfahren hergestellt werden, wie z.B. in Gladysz, J. A., Wong, V. K., Jick, B. S.; Tetrahedron (1979) 35, 2329.The benzyl disulfides of the general formula (XV) can be prepared by methods known to those skilled in the art, e.g. in Gladysz, J.A., Wong, V.K., Jick, B.S. Tetrahedron (1979) 35, 2329.
Als Abgangsgruppen Lg sind Halogene, z.B. Chlor, Brom, lod, oder Alkyl- oder Aryl- Sulfonyl-Gruppen, wie Methyl-, Ethyl-, Phenyl- oder TolylsulfonyL oder eine Haloalkylsulfonyl-Gruppe, wie Trifluormethyl-, oder Nitro bevorzugt, besonders aber sind Chlor und Methylsulfonyl bevorzugt.As leaving groups Lg are halogens, e.g. Chlorine, bromine, iodine, or alkyl or aryl-sulfonyl groups, such as methyl, ethyl, phenyl or TolylsulfonyL or haloalkylsulfonyl group, such as trifluoromethyl, or nitro preferred, but especially chlorine and methylsulfonyl are preferred.
Als Abgangsgruppen Lg' sind Halogene, z.B. Chlor, Brom, lod, oder Alkyl- oder Arylsulfonyl-Gruppen, wie Methyl-, Ethyl-, Phenyl- oder Tolylsulfonyl, oder eine Haloalkylsulfonyl-Gruppe, wie Trifluormethyl-, oder Nitro bevorzugt, besonders aber sind Chlor und Methylsulfonyl bevorzugt.As leaving groups Lg ' are halogens, for example chlorine, bromine, iodine, or alkyl or arylsulfonyl groups, such as methyl, ethyl, phenyl or tolylsulfonyl, or a haloalkylsulfonyl group, such as trifluoromethyl, or nitro preferred, but especially Chlorine and methylsulfonyl are preferred.
Als Gruppe R12 ist (Ci-Cβ)-Alkyl bevorzugt, welche unsubstituiert oder gegebenenfalls durch einen oder mehrere, gleiche oder verschiedene Reste aus der Gruppe Halogen substituiert ist, besonders bevorzugt Methyl oder Ethyl.As group R 12 , preference is given to (C 1 -C 6) -alkyl, which is unsubstituted or optionally substituted by one or more, identical or different radicals from the group halogen, more preferably methyl or ethyl.
Die vorliegenden Verbindungen der allgemeinen Formel (I) mit n = 1 (Verbindungen der allgemeinen Formel (IM)) weisen ein chirales Schwefelatom auf, welches in der oben dargestellten Struktur durch die Kennzeichneung (*) verdeutlicht ist. Gemäß den Regeln nach Cahn, Ingold und Prelog (CIP-Regeln) kann dieses Schwefelatom sowohl eine (R)- als auch eine (S)-Konfiguration aufweisen.The present compounds of the general formula (I) with n = 1 (compounds of the general formula (IM)) have a chiral sulfur atom, which is illustrated in the above structure by the characterization (*). According to the rules of Cahn, Ingold and Prelog (CIP rules), this sulfur atom have both an (R) and an (S) configuration.
Sie weisen somit ein chirales Schwefelatom auf, welches in der oben dargestellten Struktur durch die Kennzeichneung (R/S) verdeutlicht ist. Gemäß den Regeln nach Cahn, Ingold und Prelog (CIP-Regeln) kann dieses Schwefelatom sowohl eine (R)- als auch eine (S)-Konfiguration aufweisen.They thus have a chiral sulfur atom, which is illustrated in the structure shown above by the characterization (R / S). According to the rules of Cahn, Ingold and Prelog (CIP rules), this sulfur atom can have both an (R) and an (S) configuration.
Von der vorliegenden Erfindung werden - wie bereits erwähnt - Verbindungen der allgemeinen Formel (III) sowohl mit (S)- als auch mit (R)-Konfiguration erfasst, d.h., dass die vorliegende Erfindung die Verbindungen der allgemeinen Formel (I) erfasst, in welchen das betreffende SchwefelatomAs already mentioned, the present invention encompasses compounds of the general formula (III) with both (S) and (R) -configuration, ie that the present invention covers the compounds of the general formula (I), in which the relevant sulfur atom
(1 ) eine (R)-Konfiguration; oder(1) an (R) configuration; or
(2) eine (S)-Konfiguration aufweist.(2) has an (S) configuration.
Darüber hinaus werden im Rahmen der vorliegenden Erfindung auchIn addition, in the context of the present invention also
(3) beliebige Mischungen von Verbindungen der allgemeinen Formel (III), welche eine (R)-Konfiguation (Verbindungen der allgemeinen Formel (MI-(R)) aufweisen, mit Verbindungen der allgemeinen Formel (IM), welche eine (S)- Konfiguration (Verbindungen der allgemeinen Formel (Ml-S)) aufweisen, erfasst.(3) any mixtures of compounds of the general formula (III) which have an (R) -configuration (compounds of the general formula (MI- (R)) with compounds of the general formula (III) which have a (S) - Configuration (compounds of the general formula (Ml-S)) detected.
Die vorliegende Erfindung umfasst Verbindungen der allgemeienn Formel (III), die racemisch sind, d.h. in welchen die Verbindungen der allgemeinen Formel (IM) mit (S)-Konfiguration (Verbindungen der allgemeinen Formel (Ml-S)) im Vergleich zur (R)-Konfiguration (Verbindungen der allgemeinen Formel (Ml-R)) als 1 :1 Mischung (50% stereochemischen Reinheit ) vorliegen.The present invention includes compounds of general formula (III) which are racemic, i. in which the compounds of general formula (IM) having (S) configuration (compounds of general formula (Ml-S)) compared to the (R) configuration (compounds of general formula (Ml-R)) as 1: 1 Mixture (50% stereochemical purity) are present.
Allerdings sind im Rahmen der vorliegenden Erfindung auch Verbindungen der allgemeinen Formel (Ml) mit (S)-Konfiguration (Verbindungen der allgemeinen Formel (Ml-S)) im Vergleich zur (R)-Konfiguration (Verbindungen der allgemeinen Formel (Ml-R)) mit einer stereochemischen Reinheit von im Allgemeinen über 50 % bis 100 %, vorzugsweise 60 bis 100 %, insbesondere 80 bis 100 %, ganz besonders 90 bis 100 %, speziell 95 bis 100 %, bevorzugt, wobei die jeweilige (S)- Verbindung mit einer Enantioselektivität von jeweils mehr als 50% ee, vorzugsweise 60 bis 100% ee, insbesondere 80 bis 100% ee, ganz besonders 90 bis 100% ee, meist bevorzugt 95 bis 100% ee, bezogen auf den Gesamtgehalt an betreffender (S)-Verbindung vorliegt, bevorzugt vorliegt.However, in the context of the present invention, compounds of the general formula (III) with (S) -configuration (compounds of the general formula (III-S)) in comparison with the (R) -configuration (compounds of the general formula (III-R) ) having a stereochemical purity of generally over 50% up to 100%, preferably 60 to 100%, in particular 80 to 100%, very particularly 90 to 100%, especially 95 to 100%, preferred, where the particular (S) compound having an enantioselectivity of more than 50% ee, preferably 60 to 100% ee, in particular 80 to 100% ee, very particularly 90 to 100% ee, most preferably 95 to 100% ee, based on the total content of the relevant (S) compound present, is preferably present.
Ferner sind im Rahmen der vorliegenden Erfindung auch Verbindungen der allgemeinen Formel (III) mit (R)-Konfiguration (Verbindungen der allgemeinen Formel (IM-R)) im Vergleich zur (S)-Konfiguration (Verbindungen der allgemeinen Formel (Ml-R)) mit einer stereochemischen Reinheit von im Allgemeinen über 50 % bis 100 %, vorzugsweise 60 bis 100 %, insbesondere 80 bis 100 %, ganz besonders 90 bis 100 %, speziell 95 bis 100 %, bevorzugt, wobei die jeweilige (R)-Verbindung mit einer Enantioselektivität von jeweils mehr als 50% ee, vorzugsweise 60 bis 100% ee, insbesondere 80 bis 100% ee, ganz besonders 90 bis 100% ee, meist bevorzugt 95 bis 100% ee, bezogen auf den Gesamtgehalt an betreffender (S)-Verbindung vorliegt, bevorzugt vorliegt.Furthermore, in the context of the present invention, compounds of the general formula (III) having (R) -configuration (compounds of the general formula (III-R)) in comparison with the (S) -configuration (compounds of the general formula (III-R) ) having a stereochemical purity of generally over 50% to 100%, preferably 60 to 100%, in particular 80 to 100%, very particularly 90 to 100%, especially 95 to 100%, preferred, wherein the respective (R) compound with an enantioselectivity of in each case more than 50% ee, preferably 60 to 100% ee, in particular 80 to 100% ee, very particularly 90 to 100% ee, most preferably 95 to 100% ee, based on the total content of (S) Compound present, preferably present.
Daher betrifft die vorliegende Erfindung auch Verbindungen der allgemeinen Formel (IM), in welchen die stereochemische Konfiguration an dem mit (*) gekennzeichnet Schwefelatom (S) mit einer stereochemischen Reinheit von 60 bis 100 % (S), vorzugsweise 80 bis 100 % (S), insbesondere 90 bis 100 % (S), ganz besonders 95 bis 100 % (S), vorliegt.Therefore, the present invention also relates to compounds of the general formula (III) in which the stereochemical configuration at the (S) sulfur atom (S) with a stereochemical purity of 60 to 100% (S), preferably 80 to 100% (S. ), in particular 90 to 100% (S), very particularly 95 to 100% (S).
Die Verbindungen der allgemeinen Formel (IM) können je nach Art und Verknüpfung der Substituenten weitere Chiralitätszentren als das in Formel (IM) mit einem Stern (*) markierte S-Atom enthalten und entsprechend als Stereoisomere vorliegen. Die durch ihre spezifische Raumform definierten möglichen Stereoisomeren, wie Enantiomere, Diastereomere, Z- und E-Isomere sind alle von der Formel (IM) umfaßt. Sind beispielsweise eine oder mehrere Alkenylgruppen vorhanden, so könnenDepending on the nature and linkage of the substituents, the compounds of the general formula (III) may contain further chiral centers as the S atom ( * ) marked with an asterisk ( * ) and correspondingly exist as stereoisomers. The possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers, Z and E isomers, are all encompassed by the formula (IM). For example, if one or more alkenyl groups are present, then
Diastereomere (Z- und E-Isomere) auftreten. Sind beispielsweise ein oder mehrere asymmetrische Kohlenstoffatome vorhanden, so können Enantiomere und Diastereomere auftreten. Stereoisomere lassen sich aus den bei der Herstellung anfallenden Gemischen nach üblichen Trennmethoden, beispielsweise durch chromatographische Trennverfahren, erhalten. Ebenso können Stereoisomere durch Einsatz stereoselektiver Reaktionen unter Verwendung optisch aktiver Aus-gangs- und/oder Hilfsstoffe selektiv hergestellt werden. Die Erfindung betrifft somit auch alle Stereoisomeren, die von der allgemeinen Formel (III) umfaßt, jedoch nicht mit ihrer spezifischen Stereoform angegeben sind und deren Gemische.Diastereomers (Z and E isomers) occur. For example, if one or more asymmetric carbon atoms are present, then enantiomers and Diastereomers occur. Stereoisomers can be obtained from the mixtures obtained in the preparation by customary separation methods, for example by chromatographic separation methods. Similarly, stereoisomers can be selectively prepared by using stereoselective reactions using optically active sources and / or adjuvants. The invention thus also relates to all stereoisomers which comprises the general formula (III), but are not specified with their specific stereoform and their mixtures.
Sind beispielsweise eine oder mehrere Alkenylgruppen vorhanden, so können Diastereomere (Z- und E-Isomere) auftreten.If, for example, one or more alkenyl groups are present, diastereomers (Z and E isomers) can occur.
Sind beispielsweise ein oder mehrere asymmetrische Kohlenstoffatome vorhanden, so können Enantiomere und Diastereomere auftreten.For example, if one or more asymmetric carbon atoms are present, enantiomers and diastereomers may occur.
Entsprechende Stereoisomere lassen sich aus den bei der Herstellung anfallenden Gemischen nach üblichen Trennmethoden, beispielsweise durch chromatographische Trennverfahren, erhalten. Ebenso können Stereoisomere durch Einsatz stereoselektiver Reaktionen unter Verwendung optisch aktiver Aus-gangs- und/oder Hilfsstoffe selektiv hergestellt werden. Die Erfindung betrifft somit auch alle Stereoisomeren, die von der allgemeinen Formel (I) umfaßt werden, jedoch nicht mit ihrer spezifischen Stereoform angegeben sind und deren Gemische.Corresponding stereoisomers can be obtained from the mixtures obtained in the preparation by customary separation methods, for example by chromatographic separation methods. Similarly, stereoisomers can be selectively prepared by using stereoselective reactions using optically active sources and / or adjuvants. The invention thus also relates to all stereoisomers which are encompassed by the general formula (I) but are not specified with their specific stereoform and their mixtures.
Mit den in den vorstehenden Verfahrensvarianten bezeichneten "inerten Lösemitteln" sind jeweils Lösemittel gemeint, die unter den jeweiligen Reaktionsbedingungen inert sind, jedoch nicht unter beliebigen Reaktionsbedingungen inert sein müssen.By the term "inert solvents" denoted in the preceding process variants are meant in each case solvents which are inert under the respective reaction conditions, but need not be inert under any reaction conditions.
Zur Herstellung der Säureadditionssalze der Verbindungen der Formel (I) kommen folgende Säuren in Frage:For the preparation of the acid addition salts of the compounds of the formula (I), the following acids are suitable:
Halogenwasserstoffsäuren wie Chlorwasserstoffsäure oder Bromwasserstoffsäure, weiterhin Phosphorsäure, Salpetersäure, Schwefelsäure, mono- oder bifunktionelle Carbonsäuren und Hydroxycarbonsäuren wie Essigsäure, Maleinsäure, Bernstein- säure, Fumarsäure, Weinsäure, Citronensäure, Salicylsäure, Sorbinsäure oder Milchsäure, sowie Sulfonsäuren wie p-Toluolsulfonsäure oder 1 ,5-Naphthalindisul- fonsäure. Die Säureadditionsverbindungen der Formel (I) können in einfacher Weise nach den üblichen Salzbildungsmethoden, z.B. durch Lösen einer Verbindung der Formel (I) in einem geeigneten organischen Lösemittel wie z.B. Methanol, Aceton, Methylenchlorid oder Benzin und Hinzufügen der Säure bei Temperaturen von 0 bis 100 0C erhalten werden und in bekannter Weise, z.B. durch Abfiltrieren, isoliert und gegebenfalls durch Waschen mit einem inerten organischen Lösemittel gereinigt werden.Hydrohalic acids such as hydrochloric acid or hydrobromic acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- or bifunctional carboxylic acids and hydroxycarboxylic acids such as acetic acid, maleic acid, amber acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid or lactic acid, as well as sulfonic acids such as p-toluenesulfonic acid or 1, 5-naphthalenedisulfonic acid. The acid addition compounds of the formula (I) can be prepared in a simple manner by the usual salt formation methods, for example by dissolving a compound of the formula (I) in a suitable organic solvent such as methanol, acetone, methylene chloride or benzene and adding the acid at temperatures of 0 to 100 0 C are obtained and in a known manner, for example by filtration, isolated and optionally purified by washing with an inert organic solvent.
Die Basenadditionssalze der Verbindungen der Formel (I) werden vorzugsweise in inerten polaren Lösemitteln wie z.B. Wasser, Methanol oder Aceton bei Temperaturen von 0 bis 100 CC hergestellt. Geeignete Basen zur Herstellung der erfindungsgemäßen Salze sind beispielsweise Alkalicarbonate, wie Kaliumcarbonat, Alkali- und Erdalkalihydroxide, wie z.B. NaOH oder KOH, Alkali- und Erdalkalihydride, wie z.B. NaH, Alkali- und Erdalkalialkoholate, wie z.B. Natriummethanolat oder Kalium-tert.-butylat, Ammoniak, Ethanolamin oder quartäres Ammoniumhydroxid der Formel [NRR'R"R'"]+ OH\The base addition salts of the compounds of the formula (I) are preferably prepared in inert polar solvents such as, for example, water, methanol or acetone at temperatures of 0 to 100 ° C. Suitable bases for the preparation of the salts according to the invention are, for example, alkali metal carbonates, such as potassium carbonate, alkali metal and alkaline earth metal hydroxides, for example NaOH or KOH, alkali metal and alkaline earth metal hydrides, for example NaH, alkali metal and alkaline earth metal alkoxides, for example sodium methoxide or potassium tert-butoxide. Ammonia, ethanolamine or quaternary ammonium hydroxide of the formula [NRR'R "R '"] + OH \
Kollektionen aus Verbindungen der Formel (I) und/oder deren Salzen, die nach den oben genannten Reaktionen synthetisiert werden können, können auch in parallelisierter Weise hergestellt werden, wobei dies in manueller, teilweise automatisierter oder vollständig automatisierter Weise geschehen kann. Dabei ist es beispielsweise möglich, die Reaktionsdurchführung, die Aufarbeitung oder die Reinigung der Produkte bzw. Zwischenstufen zu automatisieren. Insgesamt wird hierunter eine Vorgehensweise verstanden, wie sie beispielsweise durch D. Tiebes in Combinatorial Chemistry - Synthesis, Analysis, Screening (Herausgeber Günther Jung), Verlag Wiley 1999, auf den Seiten 1 bis 34 beschrieben ist.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 understood to mean a procedure as described, for example, by D. Tiebes in Combinatorial Chemistry - Synthesis, Analysis, Screening (publisher Günther Jung), Verlag Wiley 1999, on pages 1 to 34.
Zur parallelisierten Reaktionsdurchführung und Aufarbeitung können eine Reihe von im Handel erhältlichen Geräten verwendet werden, beispielsweise Calpyso- Reaktionsblöcke (Caylpso reaction blocks) der Firma Barnstead International, Dubuque, Iowa 52004-0797, USA oder Reaktionsstationen (reaction stations) der Firma Radleys, Shirehill, Saffron Waiden, Essex, CB 11 3AZ, England oder MultiPROBE Automated Workstations der Firma Perkin Elmar, Waltham, Massachusetts 02451 , USA. Für die parallelisierte Aufreinigung von Verbindungen der allgemeinen Formel (I) und deren Salzen beziehungsweise von bei der Herstellung anfallenden Zwischenprodukten stehen unter anderem Chromatographieapparaturen zur Verfügung, beispielsweise der Firma ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.For the parallelized reaction procedure and workup, a number of commercially available devices can be used, for example Calypyso 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 from Perkin Elmar, Waltham, Massachusetts 02451, USA. For the parallelized purification of compounds of the general formula (I) and their salts or of intermediates obtained during the preparation, among others, chromatography apparatuses are available, for example the company ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.
Die aufgeführten Apparaturen führen zu einer modularen Vorgehensweise, bei der die einzelnen Arbeitsschritte automatisiert sind, zwischen den Arbeitsschritten jedoch manuelle Operationen durchgeführt werden müssen. Dies kann durch den Einsatz von teilweise oder vollständig integrierten Automationssystemen umgangen werden, bei denen die jeweiligen Automationsmodule beispielsweise durch Roboter bedient werden. Derartige Automationssysteme können zum Beispiel von der Firma Caliper, Hopkinton, MA 01748, USA bezogen werden.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.
Die Durchführung einzelner oder mehrerer Syntheseschritte kann durch den Einsatz von Polymer-supported reagents/Scavanger-Harze unterstützt werden. In der Fachliteratur sind eine Reihe von Versuchsprotokollen beschrieben, beispielswiese in ChemFiles, Vol. 4, No. 1 , Polymer-Supported Scavengers and Reagents for Solution-Phase Synthesis (Sigma-Aldrich).The implementation of single or multiple synthetic steps can be supported by the use of polymer-supported reagents / Scavanger resins. A number of experimental protocols are described in the literature, for example in ChemFiles, Vol. 1, Polymer-Supported Scavengers and Reagents for Solution Phase Synthesis (Sigma-Aldrich).
Neben den hier beschriebenen Methoden kann die Herstellung von Verbindungen der allgemeinen Formel (I) und deren Salzen vollständig oder partiell durch Festphasen unterstützte Methoden erfolgen. Zu diesem Zweck werden einzelne Zwischenstufen oder alle Zwischenstufen der Synthese oder einer für die entsprechende Vorgehensweise angepassten Synthese an ein Syntheseharz gebunden. Festpha- sen-unterstützte Synthesemethoden sind in der Fachliteratur hinreichend beschrieben, z.B. Barry A. Bunin in "The Combinatorial Index", Vertag AcademicIn addition to the methods described herein, the preparation of compounds of general formula (I) and their salts can be carried out fully or partially by solid-phase assisted methods. For this purpose, individual intermediates or all intermediates of the synthesis or adapted for the appropriate approach synthesis are bound to a synthetic resin. Solid-phase assisted synthetic methods are well described in the literature, e.g. Barry A. Bunin in "The Combinatorial Index", Vertag Academic
Press, 1998 und Combinatorial Chemistry - Synthesis, Analysis, Screening (Herausgeber: Günther Jung), Verlag Wiley, 1999. Die Verwendung von Festphasen- unterstützten Synthesemethoden erlaubt eine Reihe von literaturbekannten Protokollen, die wiederum manuell oder automatisiert ausgeführt werden können. Die Reaktionen können beispielsweise mittels IRORI-Technologie in Mikroreaktoren (microreactors) der Firma Nexus Biosystems, 12140 Community Road, Poway, CA92064, USA durchgeführt werden.Press, 1998 and Combinatorial Chemistry - Synthesis, Analysis, Screening (Editor: Günther Jung), Verlag Wiley, 1999. The use of solid phase Supported synthesis methods allow a number of well-known protocols, 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.
Sowohl an fester als auch in flüssiger Phase kann die Durchführung einzelner oder mehrerer Syntheseschritte durch den Einsatz der Mikrowellen-Technologie unterstützt werden. In der Fachliteratur sind eine Reihe von Versuchsprotokollen be- schrieben, beispielsweise in Microwaves in Organic and Medicinal Chemistry (Herausgeber: C. O. Kappe und a. Stadler), Verlag Wiley, 2005.Both solid and liquid phases can be supported by the implementation of single or multiple synthetic steps through the use of microwave technology. A number of experimental protocols are described in the specialist literature, for example in Microwaves in Organic and Medicinal Chemistry (publisher: C. O. Kappe and A. Stadler), Verlag Wiley, 2005.
Die Herstellung gemäß der hier beschriebenen Verfahren liefert Verbindungen der Formel (I) und deren Salze in Form von Substanzkollektionen, die Bibliotheken genannt werden. Gegenstand der vorliegenden Erfindung sind auch Bibliotheken, die mindestens zwei Verbindungen der Formel (I) und deren Salzen enthalten.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.
Aufgrund ihrer herbiziden und pflanzenwachstumsregulatorischen Eigenschaften können die Wirkstoffe auch zur Bekämpfung von Schadpflanzen in Kulturen von bekannten oder noch zu entwickelnden gentechnisch veränderten Pflanzen eingesetzt werden. Die transgenen Pflanzen zeichnen sich in der Regel durch besondere vorteilhafte Eigenschaften aus, beispielsweise durch Resistenzen gegenüber bestimmten Pestiziden, vor allem bestimmten Herbiziden, Resistenzen gegenüber Pflanzenkrankheiten oder Erregern von Pflanzenkrankheiten wie bestimmten Insekten oder Mikroorganismen wie Pilzen, Bakterien oder Viren. Andere besondere Eigenschaften betreffen z.B. das Erntegut hinsichtlich Menge, Qualität, Lagerfähigkeit, Zusammensetzung und spezieller Inhaltsstoffe. So sind transgene Pflanzen mit erhöhtem Stärkegehalt oder veränderter Qualität der Stärke oder solche mit anderer Fettsäurezusammensetzung des Ernteguts bekannt. Weitere besondere Eigenschaften können in einer Toleranz oder Resistenz gegen abiotische Stressoren z.B. Hitze, Kälte, Trockenheit, Salz und ultraviolette Strahlung liegen. Bevorzugt ist die Anwendung der erfindungsgemäßen Verbindungen der Formel (I) oder deren Salze in wirtschaftlich bedeutenden transgenen Kulturen von Nutz-und Zierpflanzen, z.B. von Getreide wie Weizen, Gerste, Roggen, Hafer, Hirse, Reis, Maniok und Mais oder auch Kulturen von Zuckerrübe, Baumwolle, Soja, Raps, Kartoffel, Tomate, Erbse und anderen Gemüsesorten.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, for example, the crop in terms of quantity, quality, shelf life, composition and special ingredients. Thus, transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known. Other special properties may include tolerance or resistance to abiotic stressors such as heat, cold, drought, salt and ultraviolet radiation. 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, for example cereals such as wheat, barley, rye, oats, millet, rice, manioc and maize or also cultures of sugar beet , Cotton, soy, rapeseed, potato, tomato, pea and other vegetables.
Vorzugsweise können die Verbindungen der Formel (I) als Herbizide in Nutzpflanzenkulturen eingesetzt werden, welche gegenüber den phytotoxischen Wirkungen der Herbizide resistent sind bzw. gentechnisch resistent gemacht worden sind.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.
Herkömmliche Wege zur Herstellung neuer Pflanzen, die im Vergleich zu bisher vorkommenden Pflanzen modifizierte Eigenschaften aufweisen, bestehen beispielsweise in klassischen Züchtungsverfahren und der Erzeugung von Mutanten. Al- ternativ können neue Pflanzen mit veränderten Eigenschaften mit Hilfe gentechnischer Verfahren erzeugt werden (siehe z.B. EP 0221044, EP 0131624). Beschrieben wurden beispielsweise in mehreren Fällen gentechnische Veränderungen von Kulturpflanzen zwecks Modifikation der in den Pflanzen synthetisierten Stärke (z.B. WO 92/011376 A, WO 92/014827 A, WO 91/019806 A); transgene Kulturpflanzen, welche gegen bestimmte Herbizide vom Typ Glufosinate (vgl. z.B. EP 0 242 236 A, EP 0 242 246 A) oder Glyphosate (WO 92/000377 A) oder der Sulfonylharnstoffe (EP 0 257 993 A, US 5,013,659) oder Kombinationen oder Mischungen dieser Herbizide durch „gene stacking" resistent sind, wie transgenen Kulturpflanzen z. B. Mais oder Soja mit demConventional ways of producing new plants which have modified properties in comparison to previously occurring plants consist, for example, in classical breeding methods and the production of mutants. Alternatively, new plants with altered properties can be produced by genetic engineering methods (see, for example, EP 0221044, EP 0131624). For example, genetic engineering of crops has been described in several instances to modify the starch synthesized in the plants (e.g., WO 92/011376 A, WO 92/014827 A, WO 91/019806 A); transgenic crops which are resistant to certain glufosinate-type herbicides (cf., for example, EP 0 242 236 A, EP 0 242 246 A) or glyphosate (WO 92/000377 A) or the sulfonylureas (EP 0 257 993 A, US Pat. No. 5,013,659) or combinations or mixtures of these herbicides are "gene stacking" resistant, such as transgenic crops such as corn or soybean with the
Handelsnamen oder der Bezeichnung Optimum™ GAT™ (Glyphosate ALS Tolerant); transgene Kulturpflanzen, beispielsweise Baumwolle, mit der Fähigkeit Bacillus thuringiensis-Toxine (Bt-Toxine) zu produzieren, welche die Pflanzen gegen bestimmte Schädlinge resistent machen (EP 0 142 924 A, EP 0 193259 A); transgene Kulturpflanzen mit modifizierter Fettsäurezusammensetzung (WO 91/013972 A); gentechnisch veränderte Kulturpflanzen mit neuen Inhalts- oder Sekundärstoffen z.B. neuen Phytoalexinen, die eine erhöhte Krankheitsresistenz verursachen (EP 0 309 862 A, EP 0 464 461 A); gentechnisch veränderte Pflanzen mit reduzierter Photorespiration, die höhere Erträge und höhere Stresstoleranz aufweisen (EP 0 305 398 A); transgene Kulturpflanzen, die pharmazeutisch oder diagnostisch wichtige Proteine produzieren („molecular pharming"); transgene Kulturpflanzen, die sich durch höhere Erträge oder bessere Qualität auszeichnen; - transgene Kulturpflanzen die sich durch eine Kombinationen z.B. der o. g. neuen Eigenschaften auszeichnen („gene stacking").Trade name or designation Optimum ™ GAT ™ (Glyphosate ALS Tolerant); transgenic crops, for example cotton, capable of producing Bacillus thuringiensis toxins (Bt toxins) which render the plants resistant to certain pests (EP 0 142 924 A, EP 0 193259 A); Transgenic crop plants with modified fatty acid composition (WO 91/013972 A); genetically modified crops with new content or secondary substances, for example new phytoalexins, which cause increased disease resistance (EP 0 309 862 A, EP 0 464 461 A); genetically modified plants with reduced photorespiration, which have higher yields and higher stress tolerance (EP 0 305 398 A); transgenic crops that produce pharmaceutically or diagnostically important proteins ("molecular pharming"), transgenic crops that are characterized by higher yields or better quality, - transgenic crops that are characterized by a combination of the above-mentioned new properties ("gene stacking") ,
Zahlreiche molekularbiologische Techniken, mit denen neue transgene Pflanzen mit veränderten Eigenschaften hergestellt werden können, sind im Prinzip bekannt; siehe z.B. I. Potrykus und G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin. Heidelberg, oder Christou, "Trends in Plant Science" 1 (1996) 423-431 ).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).
Für derartige gentechnische Manipulationen können Nucleinsäuremoleküle in Plasmide eingebracht werden, die eine Mutagenese oder eine Sequenzveränderung durch Rekombination von DNA-Sequenzen erlauben. Mit Hilfe von Standardverfahren können z.B. Basenaustausche vorgenommen, Teilsequenzen entfernt oder natürliche oder synthetische Sequenzen hinzugefügt werden. Für die Verbindung der DNA-Fragmente untereinander können an die Fragmente Adaptoren oder Linker angesetzt werden, siehe z.B. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2. Aufl. CoId Spring Harbor Laboratory Press, CoId Spring Harbor, NY; oder Winnacker "Gene und Klone", VCH Weinheim 2. Auflage 1996.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, e.g. Base exchanges are 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 e.g. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., CoId Spring Harbor Laboratory Press, CoId Spring Harbor, NY; or Winnacker "Genes and Clones", VCH Weinheim 2nd edition 1996.
Die Herstellung von Pflanzenzellen mit einer verringerten Aktivität eines Genpro- dukts kann beispielsweise erzielt werden durch die Expression mindestens einer entsprechenden antisense-RNA, einer sense-RNA zur Erzielung eines Cosuppressions- effektes oder die Expression mindestens eines entsprechend konstruierten Ribozyms, das spezifisch Transkripte des obengenannten Genprodukts spaltet.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 for the purpose of achieving a co-suppression effect or the expression of at least one appropriately designed one Ribozyme which specifically cleaves transcripts of the above-mentioned gene product.
Hierzu können zum einen DNA-Moleküle verwendet werden, die die gesamte codierende Sequenz eines Genprodukts einschließlich eventuell vorhandener flankierender Sequenzen umfassen, als auch DNA-Moleküle, die nur Teile der codierenden Sequenz umfassen, wobei diese Teile lang genug sein müssen, um in den Zellen einen antisense-Effekt zu bewirken. Möglich ist auch die Verwendung von DNA-Sequenzen, die einen hohen Grad an Homologie zu den codiereden Sequenzen eines Genprodukts aufweisen, aber nicht vollkommen identisch sind.For this purpose, DNA molecules may be used which comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules which comprise only parts of the coding sequence, which parts must be long enough to be present in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical.
Bei der Expression von Nucleinsäuremolekülen in Pflanzen kann das synthetisierte Protein in jedem beliebigen Kompartiment der pflanzlichen Zelle lokalisiert sein. Um aber die Lokalisation in einem bestimmten Kompartiment zu erreichen, kann z.B. die codierende Region mit DNA-Sequenzen verknüpft werden, die die Lokalisierung in einem bestimmten Kompartiment gewährleisten. Derartige Sequenzen sind dem Fachmann bekannt (siehe beispielsweise Braun et al., EMBO J. 11 (1992), 3219- 3227; Wolter et al., Proc. Natl. Acad. Sei. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991 ), 95-106). Die Expression der Nukleinsäuremoleküle kann auch in den Organellen der Pflanzenzellen stattfinden.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.
Die transgenen Pflanzenzellen können nach bekannten Techniken zu ganzen Pflanzen regeneriert werden. Bei den transgenen Pflanzen kann es sich prinzipiell um Pflanzen jeder beliebigen Pflanzenspezies handeln, d.h., sowohl monokotyle als auch dikotyle Pflanzen.The transgenic plant cells can be regenerated to whole plants by known techniques. The transgenic plants may, in principle, be plants of any plant species, that is, both monocotyledonous and dicotyledonous plants.
So sind transgene Pflanzen erhältlich, die veränderte Eigenschaften durch Überexpression, Suppression oder Inhibierung homologer (= natürlicher) Gene oder Gensequenzen oder Expression heterologer (= fremder) Gene oder Gensequenzen aufweisen.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.
Vorzugsweise können die erfindungsgemäßen Verbindungen (I) in transgenen Kulturen eingesetzt werden, welche gegen Wuchsstoffe, wie z.B. Dicamba oder gegen Herbizide, die essentielle Pflanzenenzyme, z.B. Acetolactatsynthasen (ALS), EPSP Synthasen, Glutaminsynthasen (GS) oder Hydoxyphenylpyruvat Dioxy- genasen (HPPD) hemmen, respektive gegen Herbizide aus der Gruppe der Sulfonylharnstoffe, der Glyphosate, Glufosinate oder Benzoylisoxazole und analogen Wirkstoffe oder gegen beliebige Kombinationen dieser Wirkstoffe resistent sind.Preferably, the compounds (I) according to the invention can be used in transgenic cultures which are resistant to growth substances, such as Dicamba or against herbicides which inhibit essential plant enzymes, eg acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD), respectively against herbicides from the group of sulfonylureas, glyphosates, glufosinates or benzoylisoxazoles and analogues or against Any combinations of these agents are resistant.
Besonders bevorzugt können die erfindungsgemäßen Verbindungen in transgenen Kulturpflanzen eingesetzt werden, die gegen eine Kombination von Glyphosaten und Glufosinaten, Glyphosaten und Sulfonylharnstoffen oder Imidazolinonen resistent sind. Ganz besonders bevorzugt können die erfindungsgemäßen Verbindungen in transgenen Kulturpflanzen wie z. B. Mais oder Soja mit dem Handelsnamen oder der Bezeichnung Optimum™ GAT™ (Glyphosate ALS Tolerant) eingesetzt werden.The compounds according to the invention can particularly preferably be used 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.
Bei der Anwendung der erfindungsgemäßen Wirkstoffe in transgenen Kulturen treten neben den in anderen Kulturen zu beobachtenden Wirkungen gegenüber Schadpflanzen oftmals Wirkungen auf, die für die Applikation in der jeweiligen transgenen Kultur spezifisch sind, beispielsweise ein verändertes oder speziell erweitertes Unkrautspektrum, das bekämpft werden kann, veränderte Aufwandmengen, die für die Applikation eingesetzt werden können, vorzugsweise gute Kombinierbarkeit mit den Herbiziden, gegenüber denen die transgene Kultur resistent ist, sowie Beeinflussung von Wuchs und Ertrag der transgenen Kulturpflanzen.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.
Gegenstand der Erfindung ist deshalb auch die Verwendung der erfindungsgemäßen Verbindungen der Formel (I) als Herbizide zur Bekämpfung von Schadpflanzen in transgenen Kulturpflanzen.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.
Die erfindungsgemäßen Verbindungen können in Form von Spritzpulvern, emulgierbaren Konzentraten, versprühbaren Lösungen, Stäubemitteln oder Granulaten in den üblichen Zubereitungen angewendet werden. Gegenstand der Erfindung sind deshalb auch Herbizide und pflanzenwachstumsregulierende Mittel, welche die erfindungsgemäßen Verbindungen enthalten. Die Verbindungen der allgemeinen Formel (I) können auf verschiedene Art formuliert werden, je nachdem welche biologischen und/oder chemisch-physikalischen Parameter vorgegeben sind. Als Formulierungsmöglichkeiten kommen beispielsweise in Frage: Spritzpulver (WP), wasserlösliche Pulver (SP), wasserlösliche Konzentrate, emulgierbare Konzentrate (EC), Emulsionen (EW), wie Öl-in-Wasser- und Wasser-in-ÖI-Emulsionen, versprühbare Lösungen, Suspensionskonzentrate (SC), Dispersionen auf Öl- oder Wasserbasis, ölmischbare Lösungen, Kapselsuspensionen (CS), Stäubemittel (DP), Beizmittel, Granulate für die Streu- und Bodenapplikation, Granulate (GR) in Form von Mikro-, Sprüh-, Aufzugs- und Adsorptionsgranulaten, wasserdispergierbare Granulate (WG), wasserlösliche Granulate (SG), ULV-Formulierungen, Mikrokapseln und Wachse.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 provides herbicides and plant growth-regulating agents which contain the compounds according to the invention. The compounds of the general formula (I) can be formulated in various ways, depending on which biological and / or chemical-physical parameters are predetermined. Possible formulation options are, for example: wettable powder (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions , Suspension concentrates (SC), oil or water based dispersions, oil miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for litter and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
Diese einzelnen Formulierungstypen sind im Prinzip bekannt und werden beispielsweise beschrieben in: Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hanser Verlag München, 4. Aufl. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.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.
Die notwendigen Formulierungshilfsmittel wie Inertmaterialien, Tenside, Lösemittel und weitere Zusatzstoffe sind ebenfalls bekannt und werden beispielsweise beschrieben in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Grenzflächenaktive Äthylenoxidaddukte", Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hanser Verlag München, 4. Aufl. 1986. Auf der Basis dieser Formulierungen lassen sich auch Kombinationen mit anderen Pestizid wirksamen Stoffen, wie z. B. Insektiziden, Akariziden, Herbiziden, Fungiziden, sowie mit Safenern, Düngemitteln und/oder Wachstumsregulatoren herstellen, z. B. in Form einer Fertigformulierung oder als Tankmix. Spritzpulver sind in Wasser gleichmäßig dispergierbare Präparate, die neben dem Wirkstoff außer einem Verdünnungs- oder Inertstoff noch Tenside ionischer und/oder nichtionischer Art (Netzmittel, Dispergiermittel), z. B. polyoxyethylierte Alkylphenole, polyoxethylierte Fettalkohole, polyoxethylierte Fettamine, Fettalkoholpolyglykolethersulfate, Alkansulfonate, Alkylbenzolsulfonate, ligninsulfonsaures Natrium, 2,2'-Dinaphthylmethan-6,6l-disulfonsaures Natrium, dibutylnaphthalin-sulfonsaures Natrium oder auch oleoylmethyltaurinsaures Natrium enthalten. Zur Herstellung der Spritzpulver werden die herbiziden Wirkstoffe beispielsweise in üblichen Apparaturen wie Hammermühlen, Gebläsemühlen und Luftstrahlmühlen feingemahlen und gleichzeitig oder anschließend mit den Formulierungshilfsmitteln vermischt.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 NJ, Hv Olphen, "Introduction to Clay Colloid Chemistry "; 2nd Ed., J. Wiley & Sons, NY; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, NY 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood NJ; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., NY 1964; Schönfeldt, "Grenzflächenaktive Äthylenoxidaddukte", Wiss. Publishing company, Stuttgart 1976; Winnacker-Kuchler, "Chemical Technology", Volume 7, C. Hanser Verlag Munich, 4th ed. 1986. On the basis of these formulations, combinations with other pesticide-active substances such. As insecticides, acaricides, herbicides, fungicides, and with safeners, fertilizers and / or growth regulators produce, for. B. in the form of a finished formulation or as a tank mix. Injection powders are preparations which are uniformly dispersible in water and, in addition to the active ingredient, also contain ionic and / or nonionic surfactants (wetting agent, dispersant) in addition to a diluent or inert substance, eg. Example, polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthylmethane-6,6 l disulfonate, sodium dibutylnaphthalene or sodium oleoylmethyltaurinsaures. 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.
Emulgierbare Konzentrate werden durch Auflösen des Wirkstoffes in einem organischen Lösemittel z. B. Butanol, Cyclohexanon, Dimethylformamid, XyIoI oder auch höhersiedenden Aromaten oder Kohlenwasserstoffen oder Mischungen der organischen Lösemittel unter Zusatz von einem oder mehreren Tensiden ionischer und/oder nichtionischer Art (Emulgatoren) hergestellt. Als Emulgatoren können beispielsweise verwendet werden: Alkylarylsulfonsaure Calzium-Salze wie Ca-dodecylbenzolsulfonat oder nichtionische Emulgatoren wie Fettsäurepolyglykol- ester, Alkylarylpolyglykolether, Fettalkoholpolyglykolether, Propylenoxid-Ethylenoxid- Kondensationsprodukte, Alkylpolyether, Sorbitanester wie z. B. Sorbitanfettsäu- reester oder Polyoxethylensorbitanester wie z. B. Polyoxyethylensorbitanfettsäu- reester.Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent z. B. butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers). Examples of emulsifiers which can be used are: alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide / ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as, for example, B. Sorbitanfettsäu- ester or Polyoxethylenensorbitanester such. B. Polyoxyethylensorbitanfettsäu- ester.
Stäubemittel erhält man durch Vermählen des Wirkstoffes mit fein verteilten festen Stoffen, z. B. Talkum, natürlichen Tonen, wie Kaolin, Bentonit und Pyrophyllit, oder Diatomeenerde. Suspensionskonzentrate können auf Wasser- oder Ölbasis sein. Sie können beispielsweise durch Naß-Vermahlung mittels handelsüblicher Perlmühlen und gegebenenfalls Zusatz von Tensiden, wie sie z. B. oben bei den anderen Formulierungstypen bereits aufgeführt sind, hergestellt werden.Dusts are obtained by grinding the active ingredient with finely divided solids, eg. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth. Suspension concentrates may be water or oil based. You can, for example, by wet grinding using commercially available bead mills and optionally added surfactants, such as. B. are already listed above in the other formulation types, are produced.
Emulsionen, z. B. ÖI-in-Wasser-Emulsionen (EW), lassen sich beispielsweise mittels Rühren, Kolloidmühlen und/oder statischen Mischern unter Verwendung von wäßrigen organischen Lösemitteln und gegebenenfalls Tensiden, wie sie z. B. oben bei den anderen Formulierungstypen bereits aufgeführt sind, herstellen.Emulsions, eg. As oil-in-water emulsions (EW) can be, for example, by means of stirring, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as. B. are listed above in the other types of formulation produced.
Granulate können entweder durch Verdüsen des Wirkstoffes auf adsorptionsfähiges, granuliertes Inertmaterial hergestellt werden oder durch Aufbringen von Wirkstoffkonzentraten mittels Klebemitteln, z. B. Polyvinylalkohol, polyacrylsaurem Natrium oder auch Mineralölen, auf die Oberfläche von Trägerstoffen wie Sand, Kaolinite oder von granuliertem Inertmaterial. Auch können geeignete Wirkstoffe in der für die Herstellung von Düngemittelgranulaten üblichen Weise - ge- wünschtenfalls in Mischung mit Düngemitteln - granuliert werden.Granules can be prepared either by spraying the active ingredient on adsorptive, granulated inert material or by applying active substance concentrates by means of adhesives, for. As polyvinyl alcohol, polyacrylic acid sodium or mineral oils, on the surface of carriers such as sand, kaolinites or granulated inert material. It is also possible to granulate suitable active ingredients in the manner customary for the production of fertilizer granules, if desired mixed with fertilizers.
Wasserdispergierbare Granulate werden in der Regel nach den üblichen Verfahren wie Sprühtrocknung, Wirbelbett-Granulierung, Teller-Granulierung, Mischung mit Hochgeschwindigkeitsmischern und Extrusion ohne festes Inertmaterial hergestellt.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.
Zur Herstellung von Teller-, Fließbett-, Extruder- und Sprühgranulate siehe z. B. Verfahren in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, Seiten 147 ff; "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, S. 8-57.For the preparation of plate, fluidized bed, extruder and spray granules see, for. B. Methods in "Spray-Drying Handbook" 3rd Ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff; Perry's Chemical Engineer's Handbook, 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.
Für weitere Einzelheiten zur Formulierung von Pflanzenschutzmitteln siehe z. B. G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961 , Seiten 81-96 und J. D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, Seiten 101-103. Die agrochemischen Zubereitungen enthalten in der Regel 0,1 bis 99 Gew.-%, insbesondere 0,1 bis 95 Gew.-%, Wirkstoff der Formel (I).For more details on pesticide formulation see, e.g. BGC Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96 and JD Freyer, SA Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford , 1968, pages 101-103. The agrochemical preparations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of active compound of the formula (I).
In Spritzpulvern beträgt die Wirkstoffkonzentration z. B. etwa 10 bis 90 Gew.-%, der Rest zu 100 Gew.-% besteht aus üblichen Formulierungsbestandteilen. Bei emulgierbaren Konzentraten kann die Wirkstoffkonzentration etwa 1 bis 90, vorzugsweise 5 bis 80 Gew.-% betragen. Staubförmige Formulierungen enthalten 1 bis 30 Gew.-% Wirkstoff, vorzugsweise meistens 5 bis 20 Gew.-% an Wirkstoff, versprühbare Lösungen enthalten etwa 0,05 bis 80, vorzugsweise 2 bis 50 Gew.-% Wirkstoff. Bei wasserdispergierbaren Granulaten hängt der Wirkstoffgehalt zum Teil davon ab, ob die wirksame Verbindung flüssig oder fest vorliegt und welche Granulierhilfsmittel, Füllstoffe u.a. verwendet werden. Bei den in Wasser dispergierbaren Granulaten liegt der Gehalt an Wirkstoff beispielsweise zwischen 1 und 95 Gew.-%, vorzugsweise zwischen 10 und 80 Gew.-%.In wettable powders, the active ingredient concentration z. B. about 10 to 90 wt .-%, the remainder to 100 wt .-% consists of conventional formulation components. For emulsifiable concentrates, the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%. Dusty formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% of active ingredient. In the case of water-dispersible granules, the active ingredient content depends, in part, on whether the active compound is liquid or solid and which granulating aids, fillers and the like are present. be used. In the case of the water-dispersible granules, the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
Daneben enthalten die genannten Wirkstofformulierungen gegebenenfalls die jeweils üblichen Haft-, Netz-, Dispergier-, Emulgier-, Penetrations-, Konservierungs-, Frostschutz- und Lösemittel, Füll-, Träger- und Farbstoffe, Entschäumer, Verdunstungshemmer und den pH-Wert und die Viskosität beeinflussende Mittel.In addition, the active substance formulations mentioned optionally contain the customary adhesion, wetting, dispersing, emulsifying, penetrating, preserving, antifreezing and solvent-based agents, fillers, carriers and colorants, defoamers, evaporation inhibitors and the pH value and Viscosity-influencing agent.
Die Verbindungen der allgemeinen Formel (I) oder deren Salze können als solche oder in Form ihrer Zubereitungen (Formulierungen) mit anderen pestizid wirksamen Stoffen, wie z. B. Insektiziden, Akariziden, Nematiziden, Herbiziden, Fungiziden, Safenern, Düngemitteln und/oder Wachstumsregulatoren kombiniert eingesetzt wer- den, z. B. als Fertigformulierung oder als Tankmischungen.The compounds of the general formula (I) or salts thereof can be used as such or in the form of their preparations (formulations) with other pesticidal substances, such. As insecticides, acaricides, nematicides, herbicides, fungicides, safeners, fertilizers and / or growth regulators are used, z. B. as a ready-made formulation or as tank mixes.
Als Kombinationspartner für die erfindungsgemäßen Verbindungen der allgemeinen Formel (I) in Mischungsformulierungen oder im Tank-Mix sind beispielsweise bekannte Wirkstoffe, die auf einer Inhibition von beispielsweise Acetolactat- Synthase, Acetyl-CoA-Carboxylase, Cellulose-Synthase, Enolpyruvylshikimat-3- phosphat-Synthase, Glutamin-Synthetase, p-Hydroxyphenylpyruvat-Dioxygenase, Phytoendesaturase, Photosystem I, Photosystem II, Protoporphyrinogen-Oxidase beruhen, einsetzbar, wie sie z.B. aus Weed Research 26 (1986) 441 445 oder "The Pesticide Manual", 14th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2003 und dort zitierter Literatur beschrieben sind. Als bekannte Herbizide oder Pflanzenwachstumsregulatoren, die mit den erfindungsgemäßen Verbindungen kombiniert werden können, sind z.B. folgende Wirkstoffe zu nennen (die Verbindungen sind entweder mit dem "common name" nach der International Organization for Standardization (ISO) oder mit dem chemischen Namen oder mit der Codenummer bezeichnet) und umfassen stets sämtliche Anwendungsformen wie Säuren, Salze, Ester und Isomere wie Stereoisomere und optische Isomere. Dabei sind beispielhaft eine und zum Teil auch mehrere Anwendungsformen genannt:Examples of combination partners for the compounds of general formula (I) according to the invention in mixture formulations or in tank mix are known active compounds which are based on 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 for example from Weed Research 26 (1986) 441 445 or "The Pesticide Manual", 14th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2003 and cited therein. Examples of known herbicides or plant growth regulators which can be combined with the compounds according to the invention are the following active substances (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 and always include all forms of use such as acids, salts, esters and isomers such as stereoisomers and optical isomers. Here are an example and partly also called several application forms:
Acetochlor, Acibenzolar, Acibenzolar-S-methyl, Acifluorfen, Acifluorfen-sodium, Aclonifen, Alachlor, Allidochlor, Alloxydim, Alloxydim-sodium, Ametryn, Amicarbazone, Amidochlor, Amidosulfuron, Aminocyclopyrachlor, Aminopyralid, Amitrole, Ammoniumsulfamat, Ancymidol, Anilofos, Asulam, Atrazine. Azafenidin, Azimsulfuron, Aziprotryn, BAH-043, BAS-140H, BAS-693H, BAS-714H, BAS-762H, BAS-776H, BAS-800H, Beflubutamid, Benazolin, Benazolin-ethyl, bencarbazone, Benfluralin, Benfuresate, Bensulide, Bensulfuron-methyl, Bentazone, Benzfendizone, Benzobicyclon, Benzofenap, Benzofluor, Benzoylprop, Bifenox, Bilanafos, Bilanafos- natrium, Bispyribac, Bispyribac-natrium, Bromacil, Bromobutide, Bromofenoxim, Bromoxynil, Bromuron, Buminafos, Busoxinone, Butachlor, Butafenacil, Butamifos, Butenachlor, Butralin, Butroxydim, Butylate, Cafenstrole, Carbetamide, Carfentrazone, Carfentrazone-ethyl, Chlomethoxyfen, Chloramben, Chlorazifop, Chlorazifop-butyl, Chlorbromuron, Chlorbufam, Chlorfenac, Chlorfenac-natrium, Chlorfenprop, Chlorflurenol, Chlorflurenol-methyl, Chloridazon, Chlorimuron, Chlorimuron-ethyl, Chlormequat-chlorid, Chlornitrofen, Chlorophthalim, Chlorthal- dimethyl, Chlorotoluron, Chlorsulfuron, Cinidon, Cinidon-ethyl, Cinmethylin, Cinosulfuron, Clethodim, Clodinafop Clodinafop-propargyl, Clofencet, Clomazone, Clomeprop, Cloprop, Clopyralid, Cloransulam, Cloransulam-methyl, Cumyluron, Cyanamide, Cyanazine, Cyclanilide, Cycloate, Cyclosulfamuron, Cycloxydim, Cycluron, Cyhalofop, Cyhalofop-butyl, Cyperquat, Cyprazine, Cyprazole, 2,4-D, 2,4- DB, Daimuron/Dymron, Dalapon, Daminozide, Dazomet, n-Decanol, Desmedipham, Desmetryn, Detosyl-Pyrazolate (DTP), Diallate, Dicamba, Dichlobenil, Dichlorprop, Dichlorprop-P, Diclofop, Diclofop-methyl, Diclofop-P-methyl, Diclosulam, Diethatyl, Diethatyl-ethyl, Difenoxuron, Difenzoquat, Diflufenican, Diflufenzopyr, Diflufenzopyr- natrium, Dimefuron, Dikegulac-sodium, Dimefuron, Dimepiperate, Dimethachlor, Dimethametryn, Dimethenamid, Dimethenamid-P, Dimethipin, Dimetrasulfuron, Dinitramine, Dinoseb, Dinoterb, Diphenamid, Dipropetryn, Diquat, Diquat-dibromide, Dithiopyr, Diuron, DNOC, Eglinazine-ethyl, Endothal, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron-methyl, Ethephon, Ethidimuron, Ethiozin, Ethofumesate, Ethoxyfen, Ethoxyfen-ethyl, Ethoxysulfuron, Etobenzanid, F-5331 , d.h. N-[2-Chlor-4-fluor-5-[4- (3fluorpropyl)-4,5-dihydro-5-oxo-1 H-tetrazol-1-yl]-phenyl]-ethansulfonamid, Fenoprop, Fenoxaprop, Fenoxaprop-P, Fenoxaprop-ethyl, Fenoxaprop-P-ethyl, Fentrazamide, Fenuron, Flamprop, Flamprop-M-isopropyl, Flamprop-M-methyl, Flazasulfuron, Florasulam, Fluazifop, Fluazifop-P, Fluazifop-butyl, Fluazifop-P-butyl, Fluazolate, Flucarbazone, Flucarbazone-sodium, Flucetosulfuron, Fluchloralin, Flufenacet (Thiafluamide), Flufenpyr, Flufenpyr-ethyl, Flumetralin, Flumetsulam, Flumiclorac, Flumiclorac-pentyl, Flumioxazin, Flumipropyn, Fluometuron, Fluorodifen, Fluoroglycofen, Fluoroglycofen-ethyl, Flupoxam, Flupropacil, Flupropanate, Flupyrsulfuron, Flupyrsulfuron-methyl-sodium, Flurenol, Flurenol-butyl, Fluridone, Flurochloridone, Fluroxypyr, Fluroxypyr-meptyl, Flurprimidol, Flurtamone, Fluthiacet, Fluthiacet-methyl, Fluthiamide, Fomesafen, Foramsulfuron, Forchlorfenuron, Fosamine, Furyloxyfen, Gibberellinsäure, Glufosinate, L- Glufosinate, L-Glufosinate-ammonium, Glufosinate-ammonium, Glyphosate, Glyphosate-isopropylammonium, H-9201 , Halosafen, Halosulfuron, Halosulfuron- methyl, Haloxyfop, Haloxyfop-P, Haloxyfop-ethoxyethyl, Haloxyfop-P-ethoxyethyl, Haloxyfop-methyl, Haloxyfop-P-methyl, Hexazinone, HNPC-9908, HOK-201 , HW-02, Imazamethabenz, Imazamethabenz-methyl, Imazamox, Imazapic, Imazapyr, Imazaquin, Imazethapyr, Imazosulfuron, Inabenfide, Indanofan, Indolessigsäure (IAA), 4-lndol-3-ylbuttersäure (IBA), lodosulfuron, lodosulfuron-methyl-natrium, loxynil, Isocarbamid, Isopropalin, Isoproturon, Isouron, Isoxaben, Isoxachlortole, Isoxaflutole, Isoxapyrifop, KUH-043, KUH-071 , Karbutilate, Ketospiradox, Lactofen, Lenacil, Linuron, Maleinsäurehydrazid, MCPA, MCPB, MCPB-methyl, -ethyl und - natrium, Mecoprop, Mecoprop-natrium, Mecoprop-butotyl, Mecoprop-P-butotyl, Mecoprop-P-dimethylammonium, Mecoprop-P-2-ethylhexyl, Mecoprop-P-kalium, Mefenacet, Mefluidide, Mepiquat-chlorid, Mesosulfuron, Mesosulfuron-methyl, Mesotrione, Methabenzthiazuron, Metam, Metamifop, Metamitron, Metazachlor, Methazole, Methoxyphenone, Methyldymron, 1-Methylcyclopropen,Acetochlor, acibenzolar, acibenzolar-S-methyl, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, aminocyclopyrachlor, aminopyralid, amitrole, ammonium sulfamate, ancymidol, anilofos, asulam, Atrazine. Azafenidin, Azimsulfuron, Aziprotryn, BAH-043, BAS-140H, BAS-693H, BAS-714H, BAS-762H, BAS-776H, BAS-800H, Beflubutamide, Benazoline, Benazolin-ethyl, bencarbazone, Benfluralin, Benfuresate, Bensulide, Bensulfuron-methyl, Bentazone, Benzofendizone, Benzobicyclone, Benzofenap, Benzofluor, Benzoylprop, Bifenox, Bilanafos, Bilanafos-Sodium, Bispyribac, Bispyribac-Sodium, Bromacil, Bromobutide, Bromofenoxime, Bromoxynil, Bromuron, Buminafos, Busoxinone, Butachlor, Butafenacil, Butamifos, Butenachlor, Butraline, Butroxydim, Butylates, Cafenstrols, Carbetamides, Carfentrazone, Carfentrazone-ethyl, Chlomethoxyfen, Chloramben, Chlorazifop, Chlorazifop-butyl, Chlorobromuron, Chlorobufam, Chlorfenac, Chlorfenac Sodium, Chlorfenprop, Chlorflurenol, Chlorflurenol-methyl, Chloridazon, Chlorimuron, Chlorimuron-ethyl, Chlormequat-chloride, Chlornitrofen, Chlorophthalim, Chlorthal-dimethyl, Chlorotoluron, Chlorsulfuron, Cinidon, Cinidon-ethyl, Cinmethylin, Cinosulfuron, Clethodim, Clodinafop Clodinafop-prop Argyl, Clofencet, Clomazone, Clomeprop, Cloprop, Clopyralid, Cloransulam, Cloransulam-methyl, Cumyluron, Cyanamide, Cyanazine, Cyclanilide, Cycloate, Cyclosulfamuron, Cycloxydim, Cycluron, Cyhalofop, Cyhalofop-butyl, Cyperquat, Cyprazine, Cyprazole, 2,4- D, 2,4- DB, daimurone / dymron, dalapon, daminozide, dazomet, n-decanol, desmedipham, desmetryne, detosyl-pyrazolate (DTP), dialkylate, dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl , Diclosulam, diethatyl, diethyl ethyl, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyrsodium, dimefuron, dikegulac-sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipine, dimetrasulfuron, dinitramine, dinoseb, dinoterb , Diphenamid, Dipropetryn, Diquat, Diquat-dibromide, Dithiopyr, Diuron, DNOC, Eglinazine-ethyl, Endothal, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron-methyl, Ethephon, Ethidimuron, Ethiozine, Ethofumesate, Ethoxyfen, Ethoxyfen-ethyl, Ethoxysulfuron, Etobenzanide , F-5331, ie N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo-1H-tetrazol-1-yl] -phenyl] -ethanesulfonamide , Fenoprop, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fentrazamide, fenuron, Flamprop, Flam prop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-p-butyl, fluazolates, flucarbazones, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet (thiafluamide), flufenpyr , Flufenpyr-ethyl, Flumetralin, Flumetsulam, Flumiclorac, Flumiclorac-pentyl, Flumioxazin, Flumipropyn, Fluometuron, Fluorodifen, Fluoroglycofen, Fluoroglycofen-ethyl, Flupoxam, Flupropacil, Flupropanate, Flupyrsulfuron, Flupyrsulfuron-methyl-sodium, Flurenol, Flurenol-butyl, Fluridone , Flurochloridone, Fluroxypyr, Fluroxypyr-meptyl, Flurprimidol, Flurtamone, Fluthiacet, Fluthiacet-methyl, Fluthiamide, Fomesafen, Foramsulfuron, Forchlorfenuron, Fosamine, Furyloxyfen, Gibberellin, Glufosinate, L-Glufosinate, L-Glufosinate-ammonium, Glufosinate-ammonium, Glyphosate , Glyphosate isopropylammonium, H-9201, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfopethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfo pP-methyl, hexazinone, HNPC-9908, HOK-201, HW-02, imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, inabenfide, indanofan, indoleacetic acid (IAA), 4-indole-3 -ylbutyric acid (IBA), iodosulfuron, iodosulfuron-methyl-sodium, loxynil, isocarbamide, isopropalin, isoproturon, isourone, isoxaben, isoxachlorotole, isoxaflutole, isoxapyrifop, KUH-043, KUH-071, carbutilate, ketospiradox, lactofen, lenacil, linuron, Maleic hydrazide, MCPA, MCPB, MCPB-methyl, -ethyl and - sodium, mecoprop, mecoprop-sodium, mecoprop-butotyl, mecoprop-p-butotyl, mecoprop-P-dimethylammonium, mecoprop-P-2-ethylhexyl, mecoprop-potassium, mefenetacet, mefluidides, mepiquat chloride, mesosulfuron, mesosulfuron methyl, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, methazoles, methoxyphenones, methyldymron, 1-methylcyclopropene,
Methylisothiocyanat, Metobenzuron, Metobenzuron, Metobromuron, Metolachlor, S- Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron, Metsulfuron-methyl, Molinate, Monalide, Monocarbamide, Monocarbamide-dihydrogensulfat, Monolinuron, Monosulfuron, Monuron, MT 128, MT-5950, d. h. N-[3-Chlor-4-(1- methylethyl)-phenyl]-2-methylpentanamid, NGGC-011 , Naproanilide, Napropamide, Naptalam, NC-310, d.h. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole, Neburon, Nicosulfuron, Nipyraclofen, Nitralin, Nitrofen, Nitrophenolat-natrium (Isomerengemisch), Nitrofluorfen, Nonansäure, Norflurazon, Orbencarb, Orthosulfamuron, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefone, Oxyfluorfen, Paclobutrazol, Paraquat, Paraquat-dichlorid, PelargonsäureMethylisothiocyanate, metobenzuron, metobenzuron, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinates, monalides, monocarbamides, monocarbamide dihydrogen sulfate, monolinuron, monosulfuron, monuron, MT 128, MT-5950, d , H. N- [3-chloro-4- (1-methylethyl) phenyl] -2-methylpentanamide, NGGC-011, naproanilides, napropamide, naptalam, NC-310, i. 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazoles, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrophenolate sodium (isomeric mixture), nitrofluorocane, nonanoic acid, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon , Oxasulfuron, oxaziclomefones, oxyfluorfen, paclobutrazole, paraquat, paraquat-dichloride, pelargonic acid
(Nonansäure), Pendimethalin, Pendralin, Penoxsulam, Pentanochlor. Pentoxazone, Perfluidone, Pethoxamid, Phenisopham, Phenmedipham, Phenmedipham-ethyl, Picloram, Picolinafen, Pinoxaden, Piperophos, Pirifenop, Pirifenop-butyl, Pretilachlor, Primisulfuron, Primisulfuron-methyl, Probenazole, Profluazol, Procyazine, Prodiamine, Prifluraline, Profoxydim, Prohexadione, Prohexadione-calcium, Prohydrojasmone, Prometon, Prometryn, Propachlor, Propanil, Propaquizafop, Propazine, Propham, Propisochlor, Propoxycarbazone, Propoxycarbazone-natrium, Propyzamide, Prosulfalin, Prosulfocarb, Prosulfuron, Prynachlor, Pyraclonil, Pyraflufen, Pyraflufen-ethyl, Pyrasulfotole, Pyrazolynate (Pyrazolate), Pyrazosulfuron-ethyl, Pyrazoxyfen, Pyribambenz, Pyribambenz-isopropyl,(Nonanoic acid), pendimethalin, pendralin, penoxsulam, pentanochlor. Pentoxazone, Perfluidone, Pethoxamide, Phenisopham, Phenmedipham, Phenmediphamethyl, Picloram, Picolinafen, Pinoxaden, Piperophos, Pirifenop, Pirifenopbutyl, Pretilachlor, Primisulfuron, Primisulfuron-methyl, Probenazoles, Profluazole, Procyazine, Prodiamine, Prifluralines, Profoxydim, Prohexadione, Prohexadione-calcium, Prohydrojasmone, Prometon, Prometry, Propachlor, Propanil, Propaquizafop, Propazine, Prophet, Propisochlor, Propoxycarbazone, Propoxycarbazone-Sodium, Propyzamide, Prosulfine, Prosulfocarb, Prosulfuron, Prynachlor, Pyraclonil, Pyraflufen, Pyraflufen-ethyl, Pyrasulfotole, Pyrazolynate ( Pyrazolates), pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl,
Pyribenzoxim, Pyributicarb, Pyridafol, Pyridate, Pyriftalid, Pyriminobac, Pyriminobac- methyl, Pyrimisulfan, Pyrithiobac, Pyrithiobac-natrium, Pyroxasulfone, Pyroxsulam, Quinclorac, Quinmerac, Quinoclamine, Quizalofop, Quizalofop-ethyl, Quizalofop-P, Quizalofop-P-ethyl, Quizalofop-P-tefuryl, Rimsulfuron, Saflufenacil, Secbumeton, Sethoxydim, Siduron, Simazine, Simetryn, SN-106279, Sulcotrione, SulfallatePyribenzoxim, Pyributicarb, Pyridafol, Pyridate, Pyriftalid, Pyriminobac, Pyriminobacmethyl, Pyrimisulfan, Pyrithiobac, Pyrithiobac Sodium, Pyroxasulfones, Pyroxsulam, Quinclorac, Quinmerac, Quinoclamine, Quizalofop, Quizalofop-ethyl, Quizalofop-P, Quizalofop-P-ethyl, Quizalofop P-tefuryl, rimsulfuron, saflufenacil, secbumetone, sethoxydim, siduron, simazine, simetryn, SN-106279, sulcotrione, sulfallates
(CDEC), Sulfentrazone, Sulfometuron, Sulfometuron-methyl, Sulfosate (Glyphosate- trimesium), Sulfosulfuron, SYN-523, SYP-249, SYP-298, SYP-300, Tebutam, Tebuthiuron, Tecnazene, Tefuryltrione, Tembotrione, Tepraloxydim, Terbacil, Terbucarb, Terbuchlor, Terbumeton, Terbuthylazine, Terbutryn, TH-547, Thenylchlor, Thiafluamide, Thiazafluron, Thiazopyr, Thidiazimin, Thidiazuron, Thiencarbazone, Thiencarbazone-methyl, Thifensulfuron, Thifensulfuron-methyl, Thiobencarb, Tiocarbazil, Topramezone, Tralkoxydim, Triallate, Triasulfuron, Triaziflam, Triazofenamide, Tribenuron, Tribenuron-methyl, Trichloressigsäure (TCA), Triclopyr, Tridiphane, Trietazine, Trifloxysulfuron, Trifloxysulfuron-natrium, Trifluralin, Triflusulfuron, Triflusulfuron-methyl, Trimeturon, Trinexapac, Trinexapac- ethyl, Tritosulfuron, Tsitodef, Uniconazole, Uniconazole-P, Vernolate, ZJ-0166, ZJ- 0270, ZJ-0543, ZJ-0862 sowie die folgenden Verbindungen(CDEC), sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosate (glyphosate trimesium), sulfosulfuron, SYN-523, SYP-249, SYP-298, SYP-300, tebutam, Tebuthiuron, tecnazenes, tefuryltriones, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumetone, terbuthylazine, terbutryn, TH-547, thenylchloro, thiafluamides, thiazafluron, thiazopyr, thidiazimine, thidiazuron, thiencarbazones, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, Thiobencarb, tiocarbazil, toprame zone, tralkoxydim, triallate, triasulfuron, triaziflam, triazofenamide, tribenuron, tribenuron-methyl, trichloroacetic acid (TCA), triclopyr, tridiphane, trietazine, trifloxysulfuron, trifloxysulfuron sodium, trifluralin, triflusulfuron, triflusulfuron-methyl, trimeturon, trinexapac , Trinexapacethyl, tritosulfuron, Tsitodef, Uniconazole, Uniconazole-P, Vernolate, ZJ-0166, ZJ-0270, ZJ-0543, ZJ-0862 and the following compounds
Von besonderem Interesse ist die selektive Bekämpfung von Schadpflanzen in Kulturen von Nutz- und Zierpflanzen. Obgleich die erfindungsgemäßen Verbindungen der allgemeinen Formel (I) bereits in vielen Kulturen sehr gute bis ausreichende Selektivität aufweisen, können prinzipiell in einigen Kulturen und vor allem auch im Falle von Mischungen mit anderen Herbiziden, die weniger selektiv sind, Phytotoxizi- täten an den Kulturpflanzen auftreten. Diesbezüglich sind Kombinationen erfindungsgemäßer Verbindungen der allgemeinen Formel (I) von besonderem Interesse, welche die Verbindungen der allgemeinen Formel (I) bzw. deren Kombinationen mit anderen Herbiziden oder Pestiziden und Safenern enthalten. Die Safener, welche in einem antidotisch wirksamen Gehalt eingesetzt werden, reduzieren die phytotoxischen Nebenwirkungen der eingesetzten Herbizide/Pestizide, z. B. in wirtschaftlich bedeutenden Kulturen wie Getreide (Weizen, Gerste, Roggen, Mais, Reis, Hirse), Zuckerrübe, Zuckerrohr, Raps, Baumwolle und Soja, vorzugswiese Getreide. Folgende Gruppen von Verbindungen kommen beispielsweise als Safener für die Verbindungen (I) alleinig oder aber in deren Kombinationen mit wieteren Pestiziden in Frage:Of particular interest is the selective control of harmful plants in crops of commercial and ornamental plants. Although the compounds of the general formula (I) according to the invention already have very good to sufficient selectivity in many cultures, phytotoxicity of the crop plants can in principle occur in some crops and, above all, in the case of mixtures with other herbicides which are less selective , In this regard, combinations of inventive compounds of general formula (I) are of particular interest, which are the compounds of general formula (I) or their combinations with other herbicides or pesticides and safeners. The safeners, which are used in an antidote effective content, reduce the phytotoxic side effects of the herbicides / pesticides used, eg. B. in economically important crops such as cereals (wheat, barley, rye, corn, rice, millet), sugar beet, sugar cane, rapeseed, cotton and soybeans, preferably cereals. The following groups of compounds are suitable, for example, as safeners for the compounds (I), alone or in combinations thereof with other pesticides:
S1 ) Verbindungen der Formel (S1 ),S1) compounds of the formula (S1),
wobei die Symbole und Indizes folgende Bedeutungen haben: ΠA ist eine natürliche Zahl von 0 bis 5, vorzugsweise 0 bis 3;where the symbols and indices have the following meanings: ΠA is a natural number from 0 to 5, preferably 0 to 3;
RA1 ist Halogen, (Ci-C4)Alkyl, (Ci-C4)AIkOXy, Nitro oder (Ci-C4)Haloalkyl; WA ist ein unsubstituierter oder substituierter divalenter heterocyclischer Rest aus der Gruppe der teilungesättigten oder aromatischen Fünfring-Heterocyclen mit 1 bis 3 Heteroringatomen aus der Gruppe N und O, wobei mindestens ein N- Atom und höchstens ein O-Atom im Ring enthalten ist, vorzugsweise ein Rest aus der Gruppe (WA 1) bis (WA 4),RA 1 is halogen, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, nitro or (C 1 -C 4 ) haloalkyl; W A is an unsubstituted or substituted divalent heterocyclic radical from the group of the unsaturated or unsaturated five-membered ring heterocycles having 1 to 3 hetero ring atoms from the group N and O, wherein at least one N atom and at most one O atom is contained in the ring, preferably a radical from the group (W A 1 ) to (W A 4 ),
RA2 ist ORA3, SRA3 oder NRA3RA4 oder ein gesättigter oder ungesättigter 3- bis 7- gliedriger Heterocyclus mit mindestens einem N-Atom und bis zu 3 Hetero- atomen, vorzugsweise aus der Gruppe O und S, der über das N-Atom mit der Carbonylgruppe in (S1) verbunden ist und unsubstituiert oder durch Reste aus der Gruppe (d-C-OAlkyl, (CrC4)AIkOXy oder gegebenenfalls substituiertes Phenyl substituiert ist, vorzugsweise ein Rest der Formel ORA 3, NHRA4 oder N(CH3)2, insbesondere der Formel ORA 3; RA 2 is ORA 3 , SRA 3 or NRA 3 RA 4 or a saturated or unsaturated 3- to 7-membered heterocycle having at least one N atom and up to 3 heteroatoms, preferably from the group O and S, via the N atom is connected to the carbonyl group in (S1) and is unsubstituted or substituted by radicals from the group (dC-OAlkyl, (CrC 4 ) AIkOXy or optionally substituted phenyl, preferably a radical of the formula OR A 3 , NHRA 4 or N (CH 3 ) 2 , in particular the formula OR A 3 ;
RA3 ist Wasserstoff oder ein unsubstituierter oder substituierter aliphatischer Kohlenwasserstoffrest, vorzugsweise mit insgesamt 1 bis 18 C-Atomen; RA 4 ist Wasserstoff, (C1-C6)Alkyl, (CrC6)Alkoxy oder substituiertes oder unsubstituiertes Phenyl;RA 3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having in total 1 to 18 carbon atoms; R A 4 is hydrogen, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkoxy or substituted or unsubstituted phenyl;
RA 5 ist H, (Ci-C8)Alkyl, (d-C8)Haloalkyl, (C1-C4)Alkoxy(Ci-C8)Alkyl, Cyano oder COORA9, worin RA 9 Wasserstoff, (d-C8)Alkyl, (d-CβJHaloalkyl, (C1- C4)Alkoxy-(Ci-C4)alkyl, (CrC6)Hydroxyalkyl, (C3-Ci2)Cycloalkyl oder Tri-(d- C4)-alkyl-silyl ist;R A 5 is H, (Ci-C 8 ) alkyl, (dC 8 ) haloalkyl, (C 1 -C 4 ) alkoxy (Ci-C 8 ) alkyl, cyano or COORA 9 , wherein R A 9 is hydrogen, (dC 8 ) alkyl, (d-CβJHaloalkyl, (C 1 - C 4) alkoxy (Ci-C 4) alkyl, (CrC 6) hydroxyalkyl, (C3-Ci2) -cycloalkyl or tri- (d-C4) -alkyl -silyl is;
RA6, RA7, RA8 sind gleich oder verschieden Wasserstoff, (Ci-C8)Alkyl; (Ci-C8)HaIo- alkyl, (C3-C-i2)Cycloalkyl oder substituiertes oder unsubstituiertes Phenyl;RA 6 , RA 7 , RA 8 are identical or different hydrogen, (Ci-C 8 ) alkyl ; (Ci-C 8) alkyl halo-, (C 3 -C 2) cycloalkyl or substituted or unsubstituted phenyl;
vorzugsweise: a) Verbindungen vom Typ der Dichlorphenylpyrazolin-3-carbonsäure (S1a), vorzugsweise Verbindungen wie i^^-DichlorphenyO-δ^ethoxycarbonyO-δ-methyl^-pyrazolin-S-carbonsäure, 1-(2,4-Dichlorphenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazolin-3-carbonsäure- ethylester (S1-1 ) ("Mefenpyr-diethyl"), und verwandte Verbindungen, wie sie in der WO-A-91/07874 beschrieben sind; b) Derivate der Dichlorphenylpyrazolcarbonsäure (S1b), vorzugsweise Verbindungen wie 1 -^^-DichlorphenyO-δ-methyl-pyrazol-S-carbonsäureethyl- ester (S1 -2), 1 -(2,4-Dichlorphenyl)-5-isopropyl-pyrazol-3-carbonsäureethyl- ester (S1-3), 1-(2,4-Dichlorphenyl)-5-(1 ,1-dimethyl-ethyl)pyrazol-3-carbon- säureethyl-ester (S1-4) und verwandte Verbindungen, wie sie inpreferably: a) compounds of the type dichlorophenylpyrazoline-3-carboxylic acid (S1 a ), preferably compounds such as i ^^ -DichlorphenyO-δ ^ ethoxycarbonyO-δ-methyl ^ -pyrazolin-S-carboxylic acid, 1- (2,4-dichlorophenyl ) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylic acid ethyl ester (S1-1) ("mefenpyr-diethyl"), and related compounds as described in WO-A-91/07874 are; b) dichlorophenylpyrazolecarboxylic acid derivatives (S1 b), preferably compounds such as 1 - ^^ - DichlorphenyO-δ-methyl-pyrazol-S-carbonsäureethyl- ester (S1 -2), 1 - (2,4-dichlorophenyl) -5-isopropyl pyrazole-3-carboxylic acid ethyl ester (S1-3), 1- (2,4-dichlorophenyl) -5- (1, 1-dimethyl-ethyl) pyrazole-3-carboxylic acid ethyl ester (S1-4) and related compounds, as in
EP-A-333 131 und EP-A-269 806 beschrieben sind; c) Derivate der 1 ,5-Diphenylpyrazol-3-carbonsäure (S1C), vorzugsweise Ver- bindungen wie 1 -(2,4-Dichlorphenyl)-5-phenylpyrazol-3-carbonsäureethyl- ester (S1-5), 1-(2-Chlorphenyl)-5-phenylpyrazol-3-carbonsäuremethylester (S 1-6) und verwandte Verbindungen wie sie beispielsweise in der EP-A- 268554 beschrieben sind; d) Verbindungen vom Typ der Triazolcarbonsäuren (S1d), vorzugsweise Verbindungen wie Fenchlorazol(-ethylester), d.h. 1-(2,4-Dichlorphenyl)-5-trichlormethyl-(1 H)-1 ,2,4-triazol-3-carbonsäure- ethylester (S1-7), und verwandte Verbindungen wie sie in EP-A-174 562 und EP-A-346 620 beschrieben sind; e) Verbindungen vom Typ der 5-Benzyl- oder 5-Phenyl-2-isoxazolin-3- carbonsäure oder der 5,5-Diphenyl-2-isoxazolin-3-carbonsäure (S1e), vorzugsweise Verbindungen wie 5-(2,4-Dichlorbenzyl)-2-isoxazolin-3-carbonsäureethylester (S1-8) oder 5-Phenyl-2-isoxazolin-3-carbonsäureethylester (S1-9) und verwandte Verbindungen, wie sie in WO-A-91/08202 beschrieben sind, bzw. 5,5-Diphenyl-2-isoxazolin-carbonsäure (S1-10) oder 5,5-Diphenyl-2- isoxazolin-carbonsäureethylester (S1-11) ("Isoxadifen-ethyl") oder -n-propylester (S1-12) oder der 5-(4-Fluorphenyl)-5-phenyl-2-isoxazolin-3- carbonsäureethylester (S1-13), wie sie in der Patentanmeldung WO-A-95/07897 beschrieben sind.EP-A-333,131 and EP-A-269,806 are described; c) derivatives of 1, 5-diphenylpyrazole-3-carboxylic acid (S1 C), preferably comparison compounds such as ethyl 1- (2,4-dichlorophenyl) -5-phenylpyrazole-3-carboxylate (S1-5), 1- (2-chlorophenyl) -5-phenylpyrazole-3-carboxylic acid methyl ester (S 1-6) and related Compounds as described, for example, in EP-A-268554; d) compounds of the type of the triazolecarboxylic acids (S1 d ), preferably compounds such as fenchlorazole (ethyl ester), ie 1- (2,4-dichlorophenyl) -5-trichloromethyl- (1 H) -1, 2,4-triazole-3 ethyl carboxylic acid ester (S1-7), and related compounds as described in EP-A-174 562 and EP-A-346 620; e) Compounds of the 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (S1 e), preferably compounds such as 5- (2, 4-dichlorobenzyl) -2-isoxazoline-3-carboxylic acid ethyl ester (S1-8) or 5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-9) and related compounds as described in WO-A-91/08202 , or 5,5-diphenyl-2-isoxazoline-carboxylic acid (S1-10) or ethyl 5,5-diphenyl-2-isoxazoline-carboxylate (S1-11) ("isoxadifen-ethyl") or n-propyl ester (S1 -12) or the 5- (4-fluorophenyl) -5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-13), as described in the patent application WO-A-95/07897.
S2) Chinolinderivate der Formel (S2),S2) quinoline derivatives of the formula (S2)
wobei die Symbole und Indizes folgende Bedeutungen haben: R8 1 ist Halogen, (C1-C4)AIKyI, (C1-C4)AIkOXy, Nitro oder (CrC4)Haloalkyl; nB ist eine natürliche Zahl von 0 bis 5, vorzugsweise 0 bis 3; R8 2 ist ORB 3, SRB 3 oder NR8 3RB4 oder ein gesättigter oder ungesättigter 3- bis 7-gliedriger Heterocyclus mit mindestens einem N-Atom und bis zu 3 Heteroatomen, vorzugsweise aus der Gruppe O und S, der über das N-Atom mit der Carbonylgruppe in (S2) verbunden ist und unsubstituiert oder durch Reste aus der Gruppe (Ci-C4)Alkyl, (CrC4)Alkoxy oder gegebenenfalls substituiertes Phenyl substituiert ist, vorzugsweise ein Rest der Formel ORB 3, NHR8 4 oder N(CH3)2, insbesondere der Formel ORB 3;wherein the symbols and indices have the following meanings: R 8 1 is halogen, (C 1 -C 4 ) AIKyI, (C 1 -C 4 ) alkoxy, nitro or (C r C 4 ) haloalkyl; n B is a natural number from 0 to 5, preferably 0 to 3; R 8 2 is OR B 3 , SR B 3 or NR 8 3 RB 4 or a saturated or unsaturated 3- to 7-membered heterocycle having at least one N atom and up to 3 heteroatoms, preferably from the group O and S, which is connected via the N atom with the carbonyl group in (S2) and unsubstituted or by radicals from the group (Ci-C 4 ) alkyl, (CrC 4 ) alkoxy or optionally substituted phenyl is substituted, preferably a radical of the formula OR B 3 , NHR 8 4 or N (CH 3 ) 2 , in particular of the formula OR B 3 ;
RB3 ist Wasserstoff oder ein unsubstituierter oder substituierter aliphatischer Kohlenwasserstoffrest, vorzugsweise mit insgesamt 1 bis 18 C-Atomen;RB 3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having a total of 1 to 18 C atoms;
RB4 ist Wasserstoff, (CrC6)Alkyl, (C-ι-C6)Alkoxy oder substituiertes oder unsubstituiertes Phenyl; T5 ist eine (Ci oder C2)-Alkandiylkette, die unsubstituiert oder mit einem oder zwei (Ci-C4)Alkylresten oder mit [(Ci-C3)-Alkoxy]-carbonyl substituiert ist;RB 4 is hydrogen, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) alkoxy or substituted or unsubstituted phenyl; T 5 is a (C 1 or C 2 ) alkanediyl chain which is unsubstituted or substituted by one or two (C 1 -C 4 ) alkyl radicals or by [(C 1 -C 3 ) alkoxy] carbonyl;
vorzugsweise: a) Verbindungen vom Typ der 8-Chinolinoxyessigsäure (S2a), vorzugsweise (5-Chlor-8-chinolinoxy)essigsäure-(1 -methylhexyl)ester ("Cloquintocet-mexyl")preferably: a) Compounds of the 8-quinolinoxyacetic acid (S2 a), preferably (5-chloro-8-quinolinoxy) acetic acid (1 -methylhexyl) ester ( "cloquintocet-mexyl")
(S2-1 ),(S2-1),
(5-Chlor-8-chinolinoxy)essigsäure-(1 ,3-dimethyl-but-1 -yl)ester (S2-2), (5-Chlor-8-chinolinoxy)essigsäure-4-allyloxy-butylester (S2-3), (5-Chlor-8-chinolinoxy)essigsäure-1-allyloxy-prop-2-ylester (S2-4), (5-Chlor-8-chinolinoxy)essigsäureethylester (S2-5),(5-Chloro-8-quinolinoxy) acetic acid (1, 3-dimethylbut-1-yl) ester (S2-2), (5-chloro-8-quinolinoxy) acetic acid 4-allyloxy-butyl ester (S2- 3), (5-chloro-8-quinolinoxy) acetic acid 1-allyloxy-prop-2-yl ester (S2-4), (5-chloro-8-quinolinoxy) acetic acid ethyl ester (S2-5),
(5-Chlor-8-chinolinoxy)essigsäuremethylester (S2-6), (5-Chlor-8-chinolinoxy)essigsäureallylester (S2-7), (δ-Chlor-δ-chinolinoxyJessigsäure^^-propyliden-iminoxyJ-i-ethylester (S2-8), (5-Chlor-8-chinolinoxy)essigsäure-2-oxo-prop-1-ylester (S2-9) und verwandte Verbindungen, wie sie in EP-A-86 750, EP-A-94 349 und(5-chloro-8-quinolinoxy) acetic acid methyl ester (S2-6), (5-chloro-8-quinolinoxy) allyl acetate (S2-7), (δ-chloro-δ-quinolinoxy-acetic acid ^^ - propylidene-iminoxy-i-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 oder EP-A-O 492 366 beschrieben sind, sowie (5-Chlor-8- chinolinoxy)essigsäure (S2-10), deren Hydrate und Salze, beispielsweise deren Lithium-, Natrium- Kalium-, Kalzium-, Magnesium-, Aluminium-, Eisen-, Ammonium-, quartäre Ammonium-, Sulfonium-, oder Phosphoniumsalze wie sie in der WO-A-2002/34048 beschrieben sind; b) Verbindungen vom Typ der (5-Chlor-8-chinolinoxy)malonsäure (S2b), vorzugsweise Verbindungen wie (5-Chlor-8-chinolinoxy)malonsäurediethyl- ester, (5-Chlor-8-chinolinoxy)malonsäurediallylester, (5-Chlor-8-chinolin- oxy)malonsäure-methyl-ethylester und verwandte Verbindungen, wie sie in EP-A-O 582 198 beschrieben sind.EP-A-191 736 or EP-AO 492 366, and (5-chloro-8-quinolinoxy) acetic acid (S2-10), their hydrates and salts, for example their lithium, sodium, potassium, calcium, Magnesium, aluminum, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salts as described in WO-A-2002/34048; b) compounds of the (5-chloro-8-quinolinoxy) malonic acid type (S2 b ), preferably compounds such as (5-chloro-8-quinolinoxy) malonic acid diethyl ester, (5-chloro-8-quinolinoxy) malonic acid diallyl ester, (5-chloro-8-quinolineoxy) malonic acid methyl ethyl ester and related compounds, as described in EP-AO 582 198.
S3) Verbindungen der Formel (S3)S3) compounds of the formula (S3)
wobei die Symbole und Indizes folgende Bedeutungen haben: Rc1 ist (C1-C4)AIRyI, (Ci-C4)Haloalkyl, (C2-C4)Alkenyl, (C2-C4)Haloalkenyl,where the symbols and indices have the following meanings: Rc 1 is (C 1 -C 4) AIRyI, (Ci-C 4) haloalkyl, (C 2 -C 4) alkenyl, (C 2 -C 4) haloalkenyl,
(C3-C7)Cycloalkyl, vorzugsweise Dichlormethyl; Rc2, Rc3 sind gleich oder verschieden Wasserstoff, (CrC^Alkyl, (C2-C4)Alkenyl,(C 3 -C 7 ) cycloalkyl, preferably dichloromethyl; Rc 2 , Rc 3 are identical or different hydrogen, (C 1 -C 4 alkyl, (C 2 -C 4 ) alkenyl,
(C2-C4)AI kinyl, (CrC4)Haloalkyl, (C2-C4)Haloalkenyl, (CrC4)Alkylcarbamoyl-(C 2 -C 4) AI kinyl, (C r C4) haloalkyl, (C 2 -C 4) haloalkenyl, (C r C4) alkylcarbamoyl
(CrC4)aikyi, (C2-C4)Alkenylcarbamoyl-(Ci-C4)alkyl, (CrC4)Alkoxy-(Ci- C4)alkyl, Dioxolanyl-(Ci-C4)alkyl, Thiazolyl, Furyl, Furylalkyl, Thienyl,(CrC 4) aikyi, (C 2 -C 4) Alkenylcarbamoyl- (Ci-C 4) alkyl, (C r C4) alkoxy- (Ci C4) alkyl, dioxolanyl (Ci-C4) alkyl, thiazolyl , Furyl, furylalkyl, thienyl,
Piperidyl, substituiertes oder unsubstituiertes Phenyl, oder Rc2 und Rc3 bilden zusammen einen substituierten oder unsubstituierten heterocyclischen Ring, vorzugsweise einen Oxazolidin-, Thiazolidin-, Piperidin-, Morpholin-, Hexa- hydropyrimidin- oder Benzoxazinring;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;
vorzugsweise:preferably:
Wirkstoffe vom Typ der Dichloracetamide, die häufig als VorauflaufsafenerActive substances of the dichloroacetamide type, often as pre-emergence safeners
(bodenwirksame Safener) angewendet werden, wie z. B.(soil-active safeners) are used, such. B.
"Dichlormid" (N,N-Diallyl-2,2-dichloracetamid) (S3-1 ), "R-29148" (3-Dichloracetyl-2,2,5-trimethyl-1 ,3-oxazolidin) der Firma Stauffer"Dichloromid" (N, N-diallyl-2,2-dichloroacetamide) (S3-1), "R-29148" (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer
(S3-2),(S3-2),
"R-28725" (3-Dichloracetyl-2,2,-dimethyl-1 ,3-oxazolidin) der Firma Stauffer"R-28725" (3-dichloroacetyl-2,2, -dimethyl-1,3-oxazolidine) from Stauffer
(S3-3),(S3-3),
"Benoxacor" (4-Dichloracetyl-3,4-dihydro-3-methyl-2H-1 ,4-benzoxazin) (S3-4), "PPG-1292" (N-Allyl-N-KI .S-dioxolan^-yO-methyn-dichloracetamid) der Firma PPG Industries (S3-5),"Benoxacor" (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4), "PPG-1292" (N-Allyl-N-KI.S-dioxolane-cyano-methyn-dichloroacetamide) from PPG Industries (S3-5),
"DKA-24" (N-Allyl-N-KallylaminocarbonyOmethylJ-dichloracetamid) der Firma Sagro-Chem (S3-6), "AD-67" oder "MON 4660" (3-Dichloracetyl-1 -oxa-3-aza-spiro[4,5]decan) der"DKA-24" (N-allyl-N-kallylaminocarbony-methyl-dichloroacetamide) from Sagro-Chem (S3-6), "AD-67" or "MON 4660" (3-dichloroacetyl-1-oxa-3-aza) spiro [4,5] decane) the
Firma Nitrokemia bzw. Monsanto (S3-7),Company Nitrokemia or Monsanto (S3-7),
"TI-35" (1-Dichloracetyl-azepan) der Firma TRI-Chemical RT (S3-8), "Diclonon" (Dicyclonon) oder "BAS145138" oder "LAB145138" (S3-9) (3-Dichloracetyl-2,5,5-trimethyl-1 ,3-diazabicyclo[4.3.0]nonan) der Firma BASF,"TI-35" (1-dichloroacetyl-azepane) from TRI-Chemical RT (S3-8), "diclonone" (dicyclonone) or "BAS145138" or "LAB145138" (S3-9) (3-dichloroacetyl-2, 5,5-trimethyl-1,3-diazabicyclo [4.3.0] nonane) from BASF,
"Furilazol" oder "MON 13900" ((RS)-3-Dichloracetyl-5-(2-furyl)-2,2-dimethyl- oxazolidin) (S3-10); sowie dessen (R)-Isomer (S3-11 )."Furilazole" or "MON 13900" ((RS) -3-dichloroacetyl-5- (2-furyl) -2,2-dimethyl-oxazolidine) (S3-10); and its (R) isomer (S3-11).
S4) N-Acylsulfonamide der Formel (S4) und ihre Salze,S4) N-acylsulfonamides of the formula (S4) and their salts,
worin die Symbole und Indizes folgende Bedeutungen haben: X0 ist CH oder N; RD1 ist CO-NRD5RD6 oder NHCO-RD7; R0 2 ist Halogen, (Ci-C4)Haloalkyl, (CrC4)Haloalkoxy, Nitro, (d-C4)Alkyl, (C1-C4)AIkOXy, (Ci-C4)Alkylsulfonyl, (CrC4)Alkoxycarbonyl oder (CrC^OAlkylcarbonyl; wherein the symbols and indices have the following meanings: X 0 is CH or N; RD 1 is CO-NRD 5 RD 6 or NHCO-RD 7 ; R 0 2 is halogen, (Ci-C 4) haloalkyl, (C r C4) haloalkoxy, nitro, (dC 4) alkyl, (C 1 -C 4) -alkoxy, (Ci-C 4) alkylsulfonyl, (CrC 4 ) Alkoxycarbonyl or (C 1 -C 4) alkylcarbonyl;
R0 3 ist Wasserstoff, (CrC4)Alkyl, (C2-C4)Alkenyl oder (C2-C4)Alkinyl; R0 4 ist Halogen, Nitro, (CrC4)Alkyl, (Ci-C4)Haloalkyl, (C1-C4)HaIOaIkOXy, (C3-C6)Cycloalkyl, Phenyl, (C1-C4)AIkOXy, Cyano, (CrC4)Alkylthio,R 0 3 is hydrogen, (C r C 4 ) alkyl, (C 2 -C 4 ) alkenyl or (C 2 -C 4 ) alkynyl; R 0 4 is halogen, nitro, (C r C 4 ) alkyl, (Ci-C 4 ) haloalkyl, (C 1 -C 4 ) haloalkoxy, (C 3 -C 6 ) cycloalkyl, phenyl, (C 1 -C 4 ) AIkOXy, cyano, (CrC 4 ) alkylthio,
(CrC4)Alkylsulfinyl, (C1-C4)Alkylsulfonyl, (CrC4)Alkoxycarbonyl oder (CrC4)Alkylcarbonyl; RD5 ist Wasserstoff, (CrCeJAlkyl, (C3-C6)Cycloalkyl, (C2-C6)Alkenyl, (C2-C6)Alkinyl, (C5-C6)Cycloalkenyl, Phenyl oder 3- bis 6-gliedriges Heterocyclyl enthaltend VD Heteroatome aus der Gruppe Stickstoff, Sauerstoff und Schwefel, wobei die sieben letztgenannten Reste durch vD Substituenten aus der Gruppe Halogen, (CrC6)Alkoxy, (CrC6)Haloalkoxy, (d-C2)Alkylsulfinyl, (d- C2)Alkylsulfonyl, (C3-C6)Cycloalkyl, (CrC4)Alkoxycarbonyl, (Cr (CrC 4) alkylsulfinyl, (C 1 -C 4) alkylsulfonyl, (CrC 4) alkoxycarbonyl or (CrC 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 -C 6 ) cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl containing V D heteroatoms from the group nitrogen, oxygen and sulfur, wherein the seven latter radicals by v D substituents from the group halogen, (CrC 6 ) alkoxy , (CrC 6) haloalkoxy, (dC 2) alkylsulfinyl, (dC 2) alkylsulfonyl, (C 3 -C 6) cycloalkyl, (C r C4) alkoxycarbonyl, (C r
C4)Alkylcarbonyl und Phenyl und im Falle cyclischer Reste auch (C1-C4) Alkyl und (d-C-OHaloalkyl substituiert sind; RD6 ist Wasserstoff, (d-C6)Alkyl, (C2-C6)Alkenyl oder (C2-C6)Alkinyl, wobei die drei letztgenannten Reste durch VD Reste aus der Gruppe Halogen, Hydroxy, (Ci-C4)AIlCyI1 (Ci-C4)Alkoxy und (CrC4)Alkylthio substituiert sind, oderC 4 ) alkylcarbonyl and phenyl and in the case of cyclic radicals also (C 1 -C 4 ) alkyl and (dC-OHaloalkyl substituted; RD 6 is hydrogen, (dC 6 ) alkyl, (C 2 -C 6 ) alkenyl or (C 2 -C 6) -alkynyl, where the three last-mentioned radicals are substituted by VD radicals from the group halogen, hydroxy, (Ci-C 4) AIlCyI 1 (Ci-C 4) alkoxy and (C r C 4) alkylthio, or
RD5 und R0 6 gemeinsam mit dem dem sie tragenden Stickstoffatom einenRD 5 and R 0 6 together with the nitrogen atom carrying them
Pyrrolidinyl- oder Piperidinyl-Rest bilden; RD7 ist Wasserstoff, (d-C^Alkylamino, DKd^alkylamino, (CrC6)Alkyl,Pyrrolidinyl or piperidinyl moiety; RD 7 is hydrogen, (dC ^ alkylamino, DKD ^ alkylamino, (C r C6) alkyl,
(C3-C6)Cycloalkyl, wobei die 2 letztgenannten Reste durch vD Substituenten aus der Gruppe Halogen, (C-i-C4)Alkoxy, (Ci-CβJHaloalkoxy und(C 3 -C 6 ) cycloalkyl, where the 2 latter radicals by v D substituents selected from the group consisting of halogen, (CiC 4 ) alkoxy, (Ci-CβJHaloalkoxy and
(CrC4)Alkylthio und im Falle cyclischer Reste auch (Ci-C-4)A!ky! und (C-ι-C4)Haloalkyl substituiert sind; nD ist 0, 1 oder 2; vD ist 0, 1 , 2 oder 3;(C r C 4 ) alkylthio and in the case of cyclic radicals also (Ci-C-4) A! Ky! and (C 1 -C 4 ) haloalkyl are substituted; n D is 0, 1 or 2; v D is 0, 1, 2 or 3;
davon bevorzugt sind Verbindungen von Typ der N-Acylsulfonamide, z.B. der nachfolgenden Formel (S4a), die z. B. bekannt sind aus WO-A-97/45016preferred are compounds of the type of N-acylsulfonamides, for example the following formula (S4 a ), the z. B. are known from WO-A-97/45016
worin wherein
RD7 (C-i-CβJAlkyl, (Cs-CβJCycloalkyl, wobei die 2 letztgenannten Reste durch vD RD 7 (Ci-CβJAlkyl, (Cs-CβJCycloalkyl, where the latter two radicals by v D
Substituenten aus der Gruppe Halogen, (CrC4)AIkOXy, (CrCβJHaloalkoxy und (CrC4)Alkylthio und im Falle cyclischer Reste auch (CrC4)Alkyl und (CrC4)Haloalkyl substituiert sind; RD 4 Halogen, (CrC4)Alkyl, (C1-C4)AIkOXy, CF3; rriD 1 oder 2;Substituents from the group halogen, (CrC 4 ) AIkOXy, (CrCβJHaloalkoxy and (C r C 4 ) alkylthio and in the case of cyclic radicals are also (CrC 4 ) alkyl and (CrC 4 ) haloalkyl substituted; R D 4 is halogen, (C r C 4 ) alkyl, (C 1 -C 4 ) alkoxy, CF 3 ; limit 1 or 2;
V0 ist 0, 1 , 2 oder 3 bedeutet;V 0 is 0, 1, 2 or 3;
sowiesuch as
Acylsulfamoylbenzoesäureamide, z.B. der nachfolgenden Formel (S4b), die z.B. bekannt sind aus WO-A-99/16744,Acylsulfamoylbenzoesäureamide, for example, the following formula (S4 b ), for example, are known from WO-A-99/16744,
z.B. solche worin eg those in which
R0 5 = Cyclopropyl und (R0 4) = 2-OMe istfCyprosulfamide", S4-1 ),R 0 5 = cyclopropyl and (R 0 4 ) = 2-OMe isfyprosulfamide ", S4-1),
RD 5 = Cyclopropyi und (RD 4) = 5-Ci-2-OMe ist (S4-2),R D 5 = cyclopropyl and (R D 4 ) = 5-Ci-2-OMe is (S4-2),
R0 5 = Ethyl und (R0 4) = 2-OMe ist (S4-3),R 0 5 = ethyl and (R 0 4 ) = 2-OMe is (S4-3),
RD5 = Isopropyl und (R0 4) = 5-CI-2-OMe ist (S4-4) undRD 5 = isopropyl and (R 0 4 ) = 5-CI-2-OMe is (S4-4) and
RD5 = Isopropyl und (R0 4) = 2-OMe ist(S4-5).RD 5 = isopropyl and (R 0 4 ) = 2-OMe (S4-5).
sowiesuch as
Verbindungen vom Typ der N-Acylsulfamoylphenylharnstoffe der Formel (S4C), die z.B. bekannt sind aus der EP-A-365484,Compounds of the type of N-acylsulfamoylphenylureas of the formula (S4 C ) which are known, for example, from EP-A-365484,
worinwherein
R0 8 und RD 9 unabhängig voneinander Wasserstoff, (CrC8)Alkyl, (C3-C8)Cycloalkyl, (C3-C6)Alkenyl, (C3-C6)Alkinyl, RD 4 Halogen, (Ci-C4)Alkyl, (C1-C4)AIkOXy, CF3 ITID 1 oder 2 bedeutet;R 0 R 8 and D 9 are independently hydrogen, (CrC 8) alkyl, (C 3 -C 8) cycloalkyl, (C 3 -C 6) alkenyl, (C 3 -C 6) alkynyl, R D ITID 4 is halogen, (Ci-C 4) alkyl, (C 1 -C 4) -alkoxy, CF 3 1 or 2;
beispielsweisefor example
1-[4-(N-2-Methoxybenzoylsulfamoyl)phenyl]-3-methylharnstoff,1- [4- (N-2-Methoxybenzoylsulfamoyl) phenyl] -3-methyl-urea,
1-[4-(N-2-Methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylhamstoff, 1-[4-(N-4,5-Dimethylbenzoylsulfamoyl)phenyl]-3-methylharnstoff.1- [4- (N-2-Methoxybenzoylsulfamoyl) phenyl] -3,3-dimethylurea, 1- [4- (N-4,5-dimethylbenzoylsulfamoyl) phenyl] -3-methylurea.
S5) Wirkstoffe aus der Klasse der Hydroxyaromaten und der aromatisch- aliphatischen Carbonsäurederivate (S5), z.B.S5) Active ingredients from the class of hydroxyaromatics and aromatic-aliphatic carboxylic acid derivatives (S5), e.g.
3,4,5-Triacetoxybenzoesäureethylester, 3,5-Dimethoxy-4-hydroxybenzoe- säure, 3,5-Dihydroxybenzoesäure, 4-Hydroxysalicylsäure, 4-Fluorsalicycl- säure, 2-Hydroxyzimtsäure, 2,4-Dichlorzimtsäure, wie sie in der WO-A- 2004/084631 , WO-A-2005/015994, WO-A-2005/016001 beschrieben sind.3,4,5-triacetoxybenzoic acid ethyl ester, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicyclic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid, as described in US Pat WO-A-2004/084631, WO-A-2005/015994, WO-A-2005/016001.
56) Wirkstoffe aus der Klasse der 1 ,2-Dihydrochinoxalin-2-one (S6), z.B. 1-Methyl-3-(2-thienyl)-1 ,2-dihydrochinoxalin-2-on, 1 -Methyl-3-(2-thienyl)-1 ,2- dihydrochinoxalin-2-thion, 1 -(2-Aminoethyl)-3-(2-thienyl)-1 ,2-dihydro- chinoxalin-2-on-hydrochlorid, 1-(2-Methylsulfonylaminoethyl)-3-(2-thienyl)-1 ,2- dihydro-chinoxalin-2-on, wie sie in der WO-A-2005/112630 beschrieben sind.56) Agents from the class of 1, 2-dihydroquinoxaline-2-ones (S6), e.g. 1-Methyl-3- (2-thienyl) -1,2-dihydroquinoxalin-2-one, 1-methyl-3- (2-thienyl) -1,2-dihydroquinoxaline-2-thione, 1- (2-aminoethyl ) -3- (2-thienyl) -1,2-dihydroquinoxaline-2-one hydrochloride, 1- (2-methylsulfonylaminoethyl) -3- (2-thienyl) -1, 2-dihydroquinoxaline-2 on, as described in WO-A-2005/112630.
57) Verbindungen der Formel (S7),wie sie in der WO-A-1998/38856 beschrieben sind57) Compounds of the formula (S7) as described in WO-A-1998/38856
worin die Symbole und Indizes folgende Bedeutungen haben: RE 1, RE2 sind unabhängig voneinander Halogen, (CrC4)Alkyl, (Ci-C4)Alkoxy,wherein the symbols and indices have the following meanings: R E 1 , RE 2 are each independently halogen, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy,
(CrC4)Haloalkyl, (Ci-C4)Alkylamino, Di-(CrC4)Alkylamino, Nitro; AE ist COORE3 oder COSRE 4 (CrC 4) haloalkyl, (Ci-C 4) alkylamino, di- (C r C 4) alkylamino, nitro; A E is COORE 3 or COSR E 4
RE3, RE4 sind unabhängig voneinander Wasserstoff, (Ci-C4)Alkyl, (C2- C6)Alkenyl, (C2-C4)AI kinyl, Cyanoalkyl, (CrC4)Haloalkyl, Phenyl,RE 3, RE 4 are independently hydrogen, (Ci-C 4) alkyl, (C 2 - C 6) alkenyl, (C 2 -C 4) AI kinyl, cyanoalkyl, (CrC 4) haloalkyl, phenyl,
Nitrophenyl, Benzyl, Halobenzyl, Pyridinylalkyl und Alkylammonium, nE 1 ist 0 oder 1 ΓIE2, nE 3 sind unabhängig voneinander 0, 1 oder 2,Nitrophenyl, benzyl, halobenzyl, pyridinylalkyl and alkylammonium, n E 1 is 0 or 1 ΓIE 2 , n E 3 are independently 0, 1 or 2,
vorzugsweise:preferably:
Diphenylmethoxyessigsäure,diphenylmethoxy,
Diphenylmethoxyessigsäureethylester,Diphenylmethoxyessigsäureethylester,
Diphenylmethoxyessigsäuremethylester (CAS-Reg.Nr. 41858-19-9) (S7-1 ). S8) Verbindungen der Formel (S8),wie sie in der WO-A-98/27049 beschrieben sindMethyl diphenylmethoxyacetate (CAS No. 41858-19-9) (S7-1). S8) compounds of the formula (S8) as described in WO-A-98/27049
worin nF für den Fall, dass XF=N ist, eine ganze Zahl von 0 bis 4 und für den Fall, dass XF=CH ist, eine ganze Zahl von 0 bis 5 ,wherein n F for the case that XF = N, an integer from 0 to 4 and for the case that X F = CH, an integer from 0 to 5,
RF1 Halogen, (CrC4)Alkyl, (CrC4)Haloalkyl, (Ci-C4)Alkoxy, (CrC4)Haloalkoxy, Nitro, (CrC4)Alkylthio, (CrC4)-Alkylsulfonyl, (d-C4)Alkoxycarbonyl, ggf. substituiertes. Phenyl, ggf. substituiertes Phenoxy, RF2 Wasserstoff oder (CrC4)AlkylRF 1 is halogen, (C r C4) alkyl, (C r C 4) haloalkyl, (Ci-C 4) alkoxy, (CrC 4) haloalkoxy, nitro, (C r C4) alkylthio, (C r C 4) Alkylsulfonyl, (dC 4 ) alkoxycarbonyl, optionally substituted. Phenyl, optionally substituted phenoxy, RF 2 hydrogen or (C r C 4 ) alkyl
RF3 Wasserstoff, (CrC8)Alkyl, (C2-C4)Alkenyl, (C2-C4)Alkinyl, oder Aryl, wobei jeder der vorgenannten C-haltigen Reste unsubstituiert oder durch einen oder mehrere, vorzugsweise bis zu drei gleiche oder verschiedene Reste aus der Gruppe, bestehend aus Halogen und Alkoxy substituiert ist, bedeuten, oder deren Salze,RF 3 is hydrogen, (C 1 -C 8 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, or aryl, wherein each of the aforementioned C-containing radicals is unsubstituted or substituted by one or more, preferably up to three the same or different radicals from the group consisting of halogen and alkoxy is substituted, mean, or their salts,
vorzugsweise Verbindungen worinpreferably compounds wherein
XF CH,X F CH,
ΠF eine ganze Zahl von 0 bis 2 ,ΠF is an integer from 0 to 2,
RF1 Halogen, (C1-C4)AIkVl, (C1-C4)HaIOaIkVl1 (C1-C4)AIkOXy, (C1-C4)HaIOaIkOXy, RF2 Wasserstoff oder (C1-C4)AIk^, RF3 Wasserstoff, (CrC8)Alkyl, (C2-C4)Alkenyl, (C2-C4)Alkinyl, oder Aryl, wobei jeder der vorgenannten C-haltigen Reste unsubstituiert oder durch einen oder mehrere, vorzugsweise bis zu drei gleiche oder verschiedene Reste aus der Gruppe, bestehend aus Halogen und Alkoxy substituiert ist, bedeuten, oder deren Salze.RF 1 halogen, (C 1 -C 4 ) Al kVl, (C 1 -C 4 ) halogenoalkyl 1 (C 1 -C 4 ) alkoxy, (C 1 -C 4 ) haloalkoxy, RF 2 hydrogen or (C 1 -C 4 ) AIk ^, RF 3 is hydrogen, (C 1 -C 8 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, or aryl, where each of the abovementioned C-containing radicals is unsubstituted or substituted by one or more preferably up to three identical or different radicals from the group consisting of halogen and alkoxy is substituted, mean, or their salts.
S9) Wirkstoffe aus der Klasse der 3-(5-Tetrazolylcarbonyl)-2-chinolone (S9), z.B. 1 ,2-Dihydro-4-hydroxy-1 -ethyl-3-(5-tetrazolylcarbonyl)-2-chinolon (CAS-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.Nr. 219479-18-2), 1 ,2-Dihydro-4-hydroxy-1-methy!-3-(5-tetrazo!yl- carbonyl)-2-chinolon (CAS-Reg.Nr. 95855-00-8), wie sie in der WO-A- 1999/000020 beschrieben sind.Registration number. 219479-18-2), 1, 2-dihydro-4-hydroxy-1-methyl-3- (5-tetrazo-1-ylcarbonyl) -2-quinolone (CAS reference 95855-00-8) as described in WO-A-1999/000020.
S10) Verbindungen der Formeln (S10a) oder (S10b), wie sie in der WO-A- 2007/023719 und WO-A-2007/023764 beschrieben sindS10) compounds of the formulas (S10 a ) or (S10 b ), as described in WO-A-2007/023719 and WO-A-2007/023764
(S10a) (S10b)(S10 a) (S10 b)
worinwherein
RG 1 Halogen, (CrC4)Alkyl, Methoxy, Nitro, Cyano, CF3, OCF3 R G 1 is halogen, (C r C 4 ) alkyl, methoxy, nitro, cyano, CF 3 , OCF 3
YG, ZG unabhängig voneinander O oder S, nc eine ganze Zahl von 0 bis 4, RG2 (Ci-Ci6)Alkyl, (C2-C6)Alkenyl, (C3-C6)Cycloalkyl, Aryl; Benzyl, Halogenbenzyl, RG3 Wasserstoff oder (CrC6)Alkyl bedeutet.YG, Z G independently of one another O or S, nc is an integer from 0 to 4, RG 2 (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 3 -C 6 ) cycloalkyl, aryl; Benzyl, halobenzyl, RG 3 is hydrogen or (C r C 6 ) alkyl.
511 ) Wirkstoffe vom Typ der Oxyimino-Verbindungen (S 11 ), die als Saatbeizmittel bekannt sind, wie z. B.511) oxyimino compound type compounds (S 11) known as seed dressings, such as. B.
"Oxabetrinil" ((Z)-1 ,3-Dioxolan-2-ylmethoxyimino(phenyl)acetonitril) (S11-1 ), das als Saatbeiz-Safener für Hirse gegen Schäden von Metolachlor bekannt ist,"Oxabetrinil" ((Z) -1, 3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile) (S11-1), which is known as a seed dressing safener for millet against damage by metolachlor,
"Fluxofenim" (1 -(4-Chlorphenyl)-2,2,2-trifluor-1 -ethanon-O-(1 ,3-dioxolan-2- ylmethyl)-oxim) (S11 -2), das als Saatbeiz-Safener für Hirse gegen Schäden von Metolachlor bekannt ist, und"Fluxofenim" (1- (4-chlorophenyl) -2,2,2-trifluoro-1-ethanone-O- (1,3-dioxolan-2-ylmethyl) oxime) (S11-2) which was used as seed dressing Safener for millet is known against damage from metolachlor, and
"Cyometrinil" oder "CGA-43089" ((Z)-Cyanomethoxyimino(phenyl)acetonitril)"Cyometrinil" or "CGA-43089" ((Z) -cyanomethoxyimino (phenyl) acetonitrile)
(S11-3), das als Saatbeiz-Safener für Hirse gegen Schäden von Metolachlor bekannt ist.(S11-3), known as millet safener for millet against damage from metolachlor.
512) Wirkstoffe aus der Klasse der Isothiochromanone (S12), wie z.B. Methy!-[(3- oxo-1 H-2-benzothiopyran-4(3H)-yliden)methoxy]acetate (CAS-Reg.Nr. 205121-04-6) (S12-1 ) und verwandte Verbindungen aus WO-A-1998/13361.512) Isothiochromanone (S12) class agents, e.g. Methy! - [(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.
S13) Eine oder mehrere Verbindungen aus Gruppe (S13):S13) One or more compounds from group (S13):
"Naphthalic anhydrid" (1 ,8-Naphthalindicarbonsäureanhydrid) (S13-1 ), das als"Naphthalene anhydride" (1,8-naphthalenedicarboxylic anhydride) (S13-1), which is known as
Saatbeiz-Safener für Mais gegen Schäden von Thiocarbamatherbiziden bekannt ist,Seed pickling safener for maize known for damage from thiocarbamate herbicides
"Fenclorim" (4,6-Dichlor-2-phenylpyrimidin) (S13-2), das als Safener für Pretilachlor in gesätem Reis bekannt ist,"Fenclorim" (4,6-dichloro-2-phenylpyrimidine) (S13-2), known as safener for pretilachlor in sown rice,
"Flurazole" (Benzyl-2-chlor-4-trifluormethyl-1 ,3-thiazol-5-carboxylat) (S13-3), das als Saatbeiz-Safener für Hirse gegen Schäden von Alachlor und"Flurazole" (benzyl-2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (S13-3) used as a seed dressing safener for millet against damage by alachlor and
Metolachlor bekannt ist,Metolachlor is known
"CL 304415" (CAS-Reg.Nr. 31541-57-8) (4-Carboxy-3,4-dihydro-2H-1 -benzopyran-4-essigsäure) (S13-4) der Firma"CL 304415" (CAS Reg. No. 31541-57-8) (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4) of the company
American Cyanamid, das als Safener für Mais gegen Schäden vonAmerican Cyanamid, which acts as a safener for maize against damage from
Imidazolinonen bekannt ist, "MG 191" (CAS-Reg.Nr. 96420-72-3) (2-Dichlormethyl-2-methyl-1 ,3-dioxolan) (S13-5) der Firma Nitrokemia, das als Safener für Mais bekannt ist, "MG-838" (CAS-Reg.Nr. 133993-74-5)Imidazolinones are known "MG 191" (CAS Reg. No. 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia, which is known as safener for corn, " MG-838 "(CAS Reg. No. 133993-74-5)
(2-propenyl 1-oxa-4-azaspiro[4.5]decane-4-carbodithioate) (S13-6) der Firma Nitrokemia,(2-propenyl 1-oxa-4-azaspiro [4.5] decane-4-carbodithioate) (S13-6) from Nitrokemia,
"Disulfoton" (O,O-Diethyl S-2-ethylthioethyl phosphordithioat) (S13-7), "Dietholate" (O,O-Diethyl-O-phenylphosphorotioat) (S13-8), "Mephenate" (4-Chlorphenyl-methylcarbamat) (S13-9)."Disulfonone" (O, O-diethyl S-2-ethylthioethyl phosphorodithioate) (S13-7), "dietholate" (O, O-diethyl-O-phenyl phosphorotioate) (S13-8), "mephenate" (4-chlorophenyl) methylcarbamate) (S13-9).
S14) Wirkstoffe, die neben einer herbiziden Wirkung gegen Schadpflanzen auch Safenerwirkung an Kulturpflanzen wie Reis aufweisen, wie z. B. "Dimepiperate" oder "MY-93" (S-1-Methyl-1-phenylethyl-piperidin-1- carbothioat), das als Safener für Reis gegen Schäden des Herbizids Molinate bekannt ist, "Daimuron" oder "SK 23" (1 -(1 -Methyl-1 -phenylethyl)-3-p-tolyl-harnstoff), das als Safener für Reis gegen Schäden des Herbizids Imazosulfuron bekannt ist, "Cumyluron" = "JC-940" (3-(2-Chlorphenylmethyl)-1-(1-methyl-1-phenyl- ethyl)harnstoff, siehe JP-A-60087254), das als Safener für Reis gegen Schäden einiger Herbizide bekannt ist, "Methoxyphenon" oder "NK 049" (3,3'-Dimethyl-4-methoxy-benzophenon), das als Safener für Reis gegen Schäden einiger Herbizide bekannt ist, "CSB" (1-Brom-4-(chlormethylsulfonyl)benzol) von Kumiai, (CAS-Reg.Nr. 54091-06-4), das als Safener gegen Schäden einiger Herbizide in Reis bekannt ist.S14) active substances, in addition to a herbicidal activity against harmful plants and safener action on crop plants such as rice, such as. "Dimepiperate" or "MY-93" (S-1-methyl-1-phenylethyl-piperidine-1-carbothioate) known as a safener for rice against damages of the herbicide Molinate, "daimuron" or "SK 23" (1 - (1-methyl-1-phenylethyl) -3-p-tolyl-urea) known as safener for rice against damage of the herbicide imazosulfuron, "cumyluron" = "JC-940" (3- (2- Chlorophenylmethyl) -1- (1-methyl-1-phenylethyl) urea, see JP-A-60087254) known as safener for rice against damage of some herbicides, "methoxyphenone" or "NK 049" (3,3 'Dimethyl-4-methoxy-benzophenone) known as safener for rice against damage of some herbicides,' COD '(1-bromo-4- (chloromethylsulfonyl) benzene) from Kumiai, (CAS Reg. 54091- 06-4), which is known as safener against damage of some herbicides in rice.
S15) Wirkstoffe, die vorrangig als Herbizide eingesetzt werden, jedoch auch Safenerwirkung auf Kulturpflanzen aufweisen, z.B. (2,4-Dichlorphenoxy)essigsäure (2,4-D), (4-Chlorphenoxy)essigsäure, (R,S)-2-(4-Chlor-o-tolyloxy)propionsäure (Mecoprop),S15) 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-Dichlorphenoxy)buttersäure (2,4-DB), (4-Chlor-o-tolyloxy)essigsäure (MCPA), 4-(4-Chlor-o-tolyloxy)buttersäure,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-Chlorphenoxy)buttersäure,4- (4-chlorophenoxy) butyric acid,
3,6-Dichlor-2-methoxybenzoesäure (Dicamba),3,6-dichloro-2-methoxybenzoic acid (Dicamba),
1-(Ethoxycarbonyl)ethyl-3,6-dichlor-2-methoxybenzoat (Lactidichlor-ethyl).1- (ethoxycarbonyl) ethyl 3,6-dichloro-2-methoxybenzoate (lactidichloroethyl).
Einige der Safener sind bereits als Herbizide bekannt und entfalten somit neben der Herbizidwirkung bei Schadpflanzen zugleich auch Schutzwirkung bei den Kulturpflanzen.Some of the safeners are already known as herbicides and therefore, in addition to the herbicidal effect on harmful plants, also have a protective effect on the crop plants.
Die Gewichtsverhältnisse von Herbizid(mischung) zu Safener hängt im Allgemeinen von der Aufwandmenge an Herbizid und der Wirksamkeit des jeweiligen Safeners ab und kann innerhalb weiter Grenzen variieren, beispielsweise im Bereich von 200:1 bis 1 :200, vorzugsweise 100:1 bis 1 :100, insbesondere 20:1 bis 1 :20. Die Safener können analog den Verbindungen der Formel (I) oder deren Mischungen mit weiteren Herbiziden/Pestiziden formuliert werden und als Fertigformulierung oder Tankmischung mit den Herbiziden bereitgestellt und angewendet werden.The weight ratio of herbicide (mixture) to safener generally depends on the application rate of herbicide and the effectiveness of the particular safener and can vary within wide limits, for example in the range from 200: 1 to 1: 200, preferably 100: 1 to 1: 100, in particular 20: 1 to 1:20. The safeners can be formulated analogously to the compounds of the formula (I) or mixtures thereof with further herbicides / pesticides and provided and used as finished formulation or tank mixture with the herbicides.
Zur Anwendung werden die in handelsüblicher Form vorliegenden Formulierungen gegebenenfalls in üblicher weise verdünnt z. B. bei Spritzpulvern, emulgierbaren Konzentraten, Dispersionen und wasserdispergierbaren Granulaten mittels Wasser. Staubförmige Zubereitungen, Boden- bzw. Streugranulate sowie versprühbare Lösungen werden vor der Anwendung üblicherweise nicht mehr mit weiteren inerten Stoffen verdünnt.For application, the formulations present in commercial form are optionally diluted in the usual way, for. As in wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Dust-like preparations, ground or scattered granules and sprayable solutions are usually no longer diluted with other inert substances before use.
Mit den äußeren Bedingungen wie Temperatur, Feuchtigkeit, der Art des verwendeten Herbizids, u.a. variiert die erforderliche Aufwandmenge der Verbindungen der allgemeinen Formel (I). Sie kann innerhalb weiter Grenzen schwanken, z. B. zwischen 0,001 und 10,0 kg/ha oder mehr Aktivsubstanz, vorzugsweise liegt sie jedoch zwischen 0,005 und 5 kg/ha.With the external conditions such as temperature, humidity, the type of herbicide used, u.a. varies the required application rate of the compounds of general formula (I). It can vary within wide limits, eg. B. between 0.001 and 10.0 kg / ha or more active substance, but it is preferably between 0.005 and 5 kg / ha.
Die vorliegende Erfindung wird anhand der nachfolgenden Beispiele näher erläutert, welche die vorliegende Erfindung jedoch keineswegs einschränken. SynthesebeispieleThe present invention will be further illustrated by the following examples, which by no means limit the present invention. synthesis Examples
Nachfolgend sind einige Synthesebeispiele von Verbindungen der allgemeinen Formel (I) oder deren Salze beispielhaft beschrieben.Hereinafter, some synthesis examples of compounds of the general formula (I) or salts thereof are exemplified.
(1 ) 2-[(2,5-Dimethylbenzyl)sulfanyl]-1 ,3-oxazol (Bsp. 130)(1) 2 - [(2,5-dimethylbenzyl) sulfanyl] -1,3-oxazole (Ex. 130)
1 ,3-Oxazol-2(3H)-thion (0,500 g, 5 mmol, hergestellt gemäß WO 03/006442 A) wird in 15 ml Acetonitril vorgelegt. Unter Eisbadkühlung wird 1 ,8-Diazabicyclo(5.4.0)- undec-7-en (DBU, 0,81 ml, 5 mmol) zugetropft. Es wird 10 Minuten bei 25 0C nachgerührt. Eine Lösung von 2-(Brommethyl)-1 ,4-dimethylbenzol (0,984 g, 5 mmol), gelöst in Acetonitril, wird zugetropft. Man rührt weitere 4 Stunden bei 25 0C und lässt über Nacht stehen. Zur Aufarbeitung wird das Reaktionsgemisch auf Wasser gegeben und zweimal mit Dichlormethan extrahiert, danach mit Wasser und schließlich mit gesättigter NaCI-Lösung gewaschen. Die vereinigten organischen Phasen werden über Magnesiumsulfat getrocknet, abfiltriert und eingeengt. Das Rohprodukt wird chromatographisch gereinigt (Heptan : Ethylacetat, Gradient 10 : 0 bis 8 : 2). Man erhält 0,78 g Produkt (68,3 % d. Th.).1, 3-oxazol-2 (3H) -thione (0.500 g, 5 mmol, prepared according to WO 03/006442 A) is initially charged in 15 ml of acetonitrile. With ice bath cooling, 1,8-diazabicyclo (5.4.0) undec-7-ene (DBU, 0.81 ml, 5 mmol) is added dropwise. It is stirred for 10 minutes at 25 0 C. A solution of 2- (bromomethyl) -1, 4-dimethylbenzene (0.984 g, 5 mmol) dissolved in acetonitrile is added dropwise. The mixture is stirred for a further 4 hours at 25 0 C and allowed to stand overnight. For workup, the reaction mixture is added to water and extracted twice with dichloromethane, then washed with water and finally with saturated NaCl solution. The combined organic phases are dried over magnesium sulfate, filtered off and concentrated. The crude product is purified by chromatography (heptane: ethyl acetate, gradient 10: 0 to 8: 2). This gives 0.78 g of product (68.3% of theory).
NMR (CDCI3, 400 MHz): 2.28 (s, 3H, CH3); 2.38 (s, 3H, CH3); 4.40 (s, 2H1 SCH2); 7.01 (m, 1 H, Ar); 7.07 (m, 1 H, Ar); 7.12 (br s, 1 H); 7.13 (br s, 1 H, Ar); 7.66 (br s, 1 H).NMR (CDCl 3 , 400 MHz): 2.28 (s, 3H, CH 3 ); 2:38 (s, 3H, CH 3); 4.40 (s, 2H 1 SCH 2 ); 7.01 (m, 1H, Ar); 7.07 (m, 1H, Ar); 7.12 (br s, 1 H); 7.13 (br s, 1 H, Ar); 7.66 (br s, 1 H).
(2) 2-[(2,6-Dichlorbenzyl)sulfinyl]-1 ,3-oxazol (Bsp. 44)(2) 2 - [(2,6-dichlorobenzyl) sulfinyl] -1,3-oxazole (Ex. 44)
a) Herstellung von 2-[(2,6-Dichlorbenzyl)sulfanyl]-1 ,3-oxazola) Preparation of 2 - [(2,6-dichlorobenzyl) sulfanyl] -1,3-oxazole
1 ,3-Oxazol-2(3H)-thion (0,500 g, 5 mmol, hergestellt gemäß WO 03/006442 A) wird in 10 ml Acetonitril vorgelegt. Unter Eisbadkühlung wird 1 ,8-Diazabicyclo(5.4.0)- undec-7-en (DBU, 0,812 ml, 5 mmol) zugetropft. Es wird 10 Minuten bei 25 0C nachgerührt. Eine Lösung von 2-(Brommethyl)-1 ,3-dichlorbenzol (1 ,186 g, 5 mmol), gelöst in Acetonitril, wird zugetropft. Man rührt weitere 5 Stunden bei 25 0C und lässt über Nacht stehen. Zur Aufarbeitung wird das Reaktionsgemisch auf Wasser gegeben und zweimal mit Dichlormethan extrahiert, danach mit Wasser und schließlich mit gesättigter NaCI-Lösung gewaschen. Die vereinigten organischen Phasen werden über Magnesiumsulfat getrocknet, abfiltriert und eingeengt. Das Rohprodukt wird chromatographisch gereinigt (Heptan : Ethylacetat, Gradient 10 : 0 bis 7 : 3). Man erhält 0,66 g Produkt (48,7 % d. Th.).1, 3-oxazol-2 (3H) -thione (0.500 g, 5 mmol, prepared according to WO 03/006442 A) is initially charged in 10 ml of acetonitrile. With ice-bath cooling, 1,8-diazabicyclo (5.4.0) undec-7-ene (DBU, 0.812 ml, 5 mmol) is added dropwise. It is stirred for 10 minutes at 25 0 C. A solution of 2- (bromomethyl) -1,3-dichlorobenzene (1.186 g, 5 mmol) dissolved in acetonitrile is added dropwise. The mixture is stirred for a further 5 hours at 25 0 C and allowed to stand overnight. For workup, the reaction mixture is water and extracted twice with dichloromethane, then washed with water and finally with saturated NaCl solution. The combined organic phases are dried over magnesium sulfate, filtered off and concentrated. The crude product is purified by chromatography (heptane: ethyl acetate, gradient 10: 0 to 7: 3). This gives 0.66 g of product (48.7% of theory).
NMR (CDCI3, 400 MHz): 4.71 (s, 2H, SCH2); 7.16 (br s, 1 H); 7.19 (m, 1H, Ar); 7.31 (m, 2H1 Ar); 7.70 (br s, 1 H).NMR (CDCl 3 , 400 MHz): 4.71 (s, 2H, SCH 2 ); 7.16 (br s, 1 H); 7.19 (m, 1H, Ar); 7.31 (m, 2H 1 Ar); 7.70 (brs, 1h).
b) Herstellung von 2-[(2,6-Dichlorbenzyl)sulfinyl]-1 ,3-oxazolb) Preparation of 2 - [(2,6-dichlorobenzyl) sulfinyl] -1,3-oxazole
2-[(2,6-Dichlorbenzyl)sulfanyl]-1 ,3-oxazol (0,298 g, 1 mmol) wird in 50 ml Dichlormethan unter einer Argonatmosphäre vorgelegt. Dann wird unter Rühren und Eiskühlung portionsweise 3-Chlor-perbenzoesäure (0,257 g, 1 mmol, 77 %ig) zugegeben und weitere 6 Stunden bei 0 °C gerührt. Zur Aufarbeitung wird das Reaktionsgemisch zweimal mit 2-molarer Natriumhydroxid-Lösung, danach mit Wasser und schließlich mit gesättigter NaCI-Lösung gewaschen. Die vereinigten organischen Phasen werden über Magnesiumsulfat getrocknet, abfiltriert und eingeengt. Man erhält 0,290 g Produkt (87 % d. Th.).2 - [(2,6-Dichlorobenzyl) sulfanyl] -1,3-oxazole (0.298 g, 1 mmol) is placed in 50 ml of dichloromethane under argon atmosphere. Then 3-chloro-perbenzoic acid (0.257 g, 1 mmol, 77% strength) is added in portions with stirring and ice cooling and stirred at 0 ° C for a further 6 hours. For workup, the reaction mixture is washed twice with 2 molar sodium hydroxide solution, then with water and finally with saturated NaCl solution. The combined organic phases are dried over magnesium sulfate, filtered off and concentrated. 0.290 g of product (87% of theory) are obtained.
NMR (CDCI3, 400 MHz): 4.97 (br s, 2H, S(O)CH2); 7.23 (t, 1 H, Ar); 7.31 (d, 2H, Ar); 7.35 (br s, 1 H); 7.91 (br s, 1 H).NMR (CDCl 3 , 400 MHz): 4.97 (br s, 2H, S (O) CH 2 ); 7.23 (t, 1H, Ar); 7.31 (d, 2H, Ar); 7.35 (br s, 1 H); 7.91 (brs, 1h).
2-[(S)-{[(2,6-Dichlorbenzyl)sulfinyl]}-1 ,3-oxazol (Bsp. 2517) und 2-[(R)-{[(2,6- Dichlorbenzyl)sulfinyl]}-1 ,3-oxazol (Bsp. 3351)2 - [(S) - {[(2,6-dichlorobenzyl) sulfinyl]} - 1,3-oxazole (Ex 2517) and 2 - [(R) - {[(2,6-dichlorobenzyl) sulfinyl]} -1, 3-oxazole (Ex.3,351)
Das erhaltene racemische 2-[(2,6-Dichlorbenzyl)sulfinyl]-1 ,3-oxazol (0.8 g, 99%ig) wird durch präparative chirale HPLC (Säule: Chiralcel® OD; Eluent: n-Hexan/2- Propanol 80:20; Flow: 0.6 ml/min; Säulentemperatur: 25 0C) in die Enantiomeren getrennt. Man erhält so 0.3 g (37.5 % d. Th.) 2-[(S)-{[(2,6-Dichlorbenzyl)sulfinyl]}-1 ,3- oxazol (R1 = 10.801 min, [α]D = +11.4°) und 0.3 g (37.5 % d. Th.) 2-[(R)-{[(2,6- Dichlorbenzyl)sulfinyl]}-1 ,3-oxazol (R1 = 14.963 min, [α]D = -12.4°). (3) 2-[(2,6-Difluorbenzyl)sulfonyl]-1 ,3-oxazol (Bsp. 12)The resulting racemic 2 - [(2,6-dichlorobenzyl) sulfinyl] -1, 3-oxazole (0.8 g, 99% pure) is separated by preparative chiral HPLC (column: Chiralcel ® OD; eluent: n-hexane / 2-propanol 80:20; flow: 0.6 ml / min; column temperature: 25 ° C.) into the enantiomers. This gives 0.3 g (37.5% of theory) of 2 - [(S) - {[(2,6-dichlorobenzyl) sulfinyl]} -1,3-oxazole (R 1 = 10.801 min, [α] D = + 11.4 °) and 0.3 g (37.5% of theory) of 2 - [(R) - {[(2,6-dichlorobenzyl) sulfinyl]} - 1,3-oxazole (R 1 = 14.963 min, [α] D = -12.4 °). (3) 2 - [(2,6-Difluorobenzyl) sulfonyl] -1,3-oxazole (Ex. 12)
a) Herstellung von 2-[(2,6-Difluorbenzyl)sulfanyl]-1 ,3-oxazola) Preparation of 2 - [(2,6-difluorobenzyl) sulfanyl] -1,3-oxazole
1 ,3-Oxazol-2(3H)-thion (0,500 g, 5 mmol, hergestellt gemäß WO 03/006442 A) wird in 10 ml Acetonitril vorgelegt. Unter Eisbadkühlung wird 1 ,8-Diazabicyclo(5.4.0)- undec-7-en (DBU, 0,812 ml, 5 mmol) zugetropft. Es wird 10 Minuten bei 25 0C nachgerührt. Eine Lösung von 2-(Brommethyl)-1 ,3-difluorbenzol (1 ,024 g, 5 mmol), gelöst in Acetonitril, wird zugetropft. Man rührt weitere 5 Stunden bei 25 0C und lässt über Nacht stehen. Zur Aufarbeitung wird das Reaktionsgemisch auf Wasser gegeben und zweimal mit Dichlormethan extrahiert, danach mit Wasser und schließlich mit gesättigter NaCI-Lösung gewaschen. Die vereinigten organischen Phasen werden über Magnesiumsulfat getrocknet, abfiltriert und eingeengt. Das Rohprodukt wird chromatographisch gereinigt (Heptan : Ethylacetat, Gradient 10 : 0 bis 8 : 2). Man erhält 0,69 g Produkt (58,3 % d. Th.).1, 3-oxazol-2 (3H) -thione (0.500 g, 5 mmol, prepared according to WO 03/006442 A) is initially charged in 10 ml of acetonitrile. With ice-bath cooling, 1,8-diazabicyclo (5.4.0) undec-7-ene (DBU, 0.812 ml, 5 mmol) is added dropwise. It is stirred for 10 minutes at 25 0 C. A solution of 2- (bromomethyl) -1,3-difluorobenzene (1.024 g, 5 mmol) dissolved in acetonitrile is added dropwise. The mixture is stirred for a further 5 hours at 25 0 C and allowed to stand overnight. For workup, the reaction mixture is added to water and extracted twice with dichloromethane, then washed with water and finally with saturated NaCl solution. The combined organic phases are dried over magnesium sulfate, filtered off and concentrated. The crude product is purified by chromatography (heptane: ethyl acetate, gradient 10: 0 to 8: 2). This gives 0.69 g of product (58.3% of theory).
NMR (CDCI3, 400 MHz): 4.47 (s, 2H, SCH2); 6.90 (m, 2H, Ar); 7.20 (br s, 1 H); 7.24 (m, 1 H, Ar); 7.69 (br s, 1 H).NMR (CDCl 3 , 400 MHz): 4.47 (s, 2H, SCH 2 ); 6.90 (m, 2H, Ar); 7.20 (br s, 1 H); 7.24 (m, 1H, Ar); 7.69 (brs, 1h).
b) Herstellung von 2-[(2,6-Difluorbenzyl)sulfonyl]-1 ,3-oxazolb) Preparation of 2 - [(2,6-difluorobenzyl) sulfonyl] -1,3-oxazole
2-[(2,6-Difluorbenzyl)sulfanyl]-1 ,3-oxazol (0,326 g, 1 mmol) wird in 50 ml Dichlormethan unter einer Argonatmosphäre vorgelegt. Dann wird unter Rühren und Eiskühlung portionsweise 3-Chlor-perbenzoesäure (0,810 g, 3.6 mmol, 77 %ig) zugegeben und weitere 6 Stunden bei 25 0C gerührt und über Nacht stehengelassen. Zur Aufarbeitung wird das Reaktionsgemisch zweimal mit 2-molarer Natriumhydroxid-Lösung, danach mit Wasser und schließlich mit gesättigter NaCI- Lösung gewaschen. Die vereinigten organischen Phasen werden über Magnesiumsulfat getrocknet, abfiltriert und eingeengt. Man erhält 0.312 g Produkt (75,4 % d. Th.). NMR (CDCI3, 400 MHz): 4.72 (s, 2H, S(O)2CH2); 6.92 (m, 2H, Ar); 7.37 (m, 1H, Ar); 7.39 (br s, 1 H); 7.86 (br s, 1 H).2 - [(2,6-Difluorobenzyl) sulfanyl] -1,3-oxazole (0.326 g, 1 mmol) is placed in 50 ml of dichloromethane under an argon atmosphere. Then 3-chloroperbenzoic acid (0.810 g, 3.6 mmol, 77%) is added in portions with stirring and ice cooling and stirred for a further 6 hours at 25 0 C and allowed to stand overnight. For workup, the reaction mixture is washed twice with 2 molar sodium hydroxide solution, then with water and finally with saturated NaCl solution. The combined organic phases are dried over magnesium sulfate, filtered off and concentrated. 0.312 g of product (75.4% of theory) are obtained. NMR (CDCl 3 , 400 MHz): 4.72 (s, 2H, S (O) 2 CH 2 ); 6.92 (m, 2H, Ar); 7.37 (m, 1H, Ar); 7.39 (br s, 1 H); 7.86 (brs, 1h).
(4) 2-[(2,3,6-Trichlorbenzyl)sulfanyl]-1 ,3-oxazol (Bsp. 64)(4) 2 - [(2,3,6-trichlorobenzyl) sulfanyl] -1,3-oxazole (Ex. 64)
a) Herstellung von 2-(Methylsulfonyl)-1 ,3-oxazola) Preparation of 2- (methylsulfonyl) -1,3-oxazole
1 ,3-Oxazol-2(3H)-thion (1 ,00 g, 10 mmol; hergestellt gemäß WO 03/006442 A) wird unter Schutzgasatmosphäre in 20 ml Acetonitril vorgelegt, lodmethan (1 ,544 g, 0,677 ml, 11 mmol) wird zugetropft, dann wird Kaliumcarbonat (1 ,503 g, 11 mmol) zugegeben. Es wird 6 Stunden bei 25 0C nachgerührt. Zur Aufarbeitung wird das Reaktionsgemisch auf Wasser gegeben und zweimal mit Dichlormethan extrahiert (100 ml), danach mit Wasser und schließlich mit gesättigter NaCI-Lösung gewaschen. Die vereinigten organischen Phasen werden über Magnesiumsulfat getrocknet, abfiltriert und direkt weiter umgesetzt. Zu der somit erhaltenten Dichlormethan-Lösung wird dann unter Rühren und Eiskühlung portionsweise 3- Chlor-perbenzoesäure (5,100 g, 23 mmol, 77 %ig) zugegeben, weitere 6 Stunden bei 25 0C nachgerührt und über Nacht stehengelassen. Zur Aufarbeitung wird das Reaktionsgemisch zweimal mit 2-molarer Natriumhydroxid-Lösung, danach mit Wasser und schließlich mit gesättigter NaCI-Lösung gewaschen. Die vereinigten organischen Phasen werden über Magnesiumsulfat getrocknet, abfiltriert und eingeengt. Man erhält 0,820 g Produkt (50,7 % d. Th.).1, 3-oxazol-2 (3H) -thione (1, 00 g, 10 mmol, prepared according to WO 03/006442 A) is placed under an inert gas atmosphere in 20 ml of acetonitrile, iodomethane (1, 544 g, 0.677 ml, 11 mmol ) is added dropwise, then potassium carbonate (1, 503 g, 11 mmol) is added. It is stirred for 6 hours at 25 0 C. For workup, the reaction mixture is added to water and extracted twice with dichloromethane (100 ml), then washed with water and finally with saturated NaCl solution. The combined organic phases are dried over magnesium sulfate, filtered off and reacted further directly. Portionwise 3- chloroperbenzoic acid (5.100 g, 23 mmol, 77% strength) is added to the thus obtained ducks dichloromethane solution under stirring and ice-cooling, stirred for a further 6 hours at 25 0 C and allowed to stand overnight. For workup, the reaction mixture is washed twice with 2 molar sodium hydroxide solution, then with water and finally with saturated NaCl solution. The combined organic phases are dried over magnesium sulfate, filtered off and concentrated. 0.820 g of product (50.7% of theory) are obtained.
NMR (CDCI3, 400 MHz): 3.35 (s, 3H, CH3); 7.38 (br s, 1 H); 7.88 (br s, 1 H).NMR (CDCl 3 , 400 MHz): 3.35 (s, 3H, CH 3 ); 7.38 (br s, 1 H); 7.88 (brs, 1h).
b) Herstellung von 2-[(2, 3, 6-Trichlorbenzyl)sulfanyl]-1 ,3-oxazolb) Preparation of 2 - [(2, 3, 6-trichlorobenzyl) sulfanyl] -1,3-oxazole
2,3,6-Trichlorbenzylbromid (0,267 g, 1 mmol) wird in Ethanol (10 ml) vorgelegt. Thioharnstoff (0,074 g, 1 mmol) wird zugegeben und die Mischung wird 2 Stunden unter Rückfluss erhizt. Die Lösung wird dann auf 25 0C abgekühlt und 2- (Methylsulfonyl)-1 ,3-oxazol (0,130 mg, 1 mmol) wird zugegeben, gefolgt von Kaliumcarbonat (0.183 g, 1 mmol). Die Mischung wird 6 h Stunden unter Rückfluss erhizt. Zur Aufarbeitung wird die Reaktionslösung auf Wasser gegeben und mit Dichlormethan extrahiert. Die vereinigten organischen Phasen werden getrocknet und eingeengt. Man erhält 0,063 g Produkt (23 % d. Th.).2,3,6-Trichlorobenzylbromide (0.267 g, 1 mmol) is presented in ethanol (10 ml). Thiourea (0.074 g, 1 mmol) is added and the mixture is refluxed for 2 hours. The solution is then cooled to 25 ° C. and 2- (methylsulfonyl) -1,3-oxazole (0.130 mg, 1 mmol) is added, followed by potassium carbonate (0.183 g, 1 mmol). The mixture is refluxed for 6 hours erhizt. For workup, the reaction solution is added to water and extracted with dichloromethane. The combined organic phases are dried and concentrated. This gives 0.063 g of product (23% of theory).
NMR (CDCI3, 400 MHz): 4.72 (s, 2H, SCH2); 7.17 (br s, 1 H); 7.27 (d, 1 H); 7.38 (d, 1 H); 7.71 (br s, 1 H).NMR (CDCl 3 , 400 MHz): 4.72 (s, 2H, SCH 2 ); 7.17 (br s, 1 H); 7.27 (d, 1H); 7.38 (d, 1H); 7.71 (brs, 1h).
Retentionszeiten (Rt, in Minuten) und Enatiomerenverhältnisse (ee) von chiralen Verbindungen wurden mittels analytischer chiralen HPLC ermittelt [Chiralcel® OD Säule (250 x 4.6 mm, Korngröße 5 μm), Temperatur 25 0C, Fluss 1 ml/min, Hexan / 2-Propanol 90:10 v/v].Retention times (R t, in minutes) and Enatiomerenverhältnisse (ee) of chiral compounds were determined by analytical chiral HPLC [Chiralcel ® OD column (250 x 4.6 mm, particle size 5 .mu.m), temperature 25 0 C, flow 1 ml / min, hexane / 2-propanol 90:10 v / v].
Racemate oder enantiomeren Gemische wurden mittels präparative chiralen HPLC in den jeweiligen enantiomeren getrennt [Chiralcel® OD Säule (250 x 5 mm, Korngröße 10 μm), Temperatur 25 CC, Fluss 0.6 ml/min, Hexan / 2-Propanol 90:10 v/v]. Racemates or enantiomeric mixtures were separated by preparative chiral HPLC into the respective enantiomeric [Chiralcel ® OD column (250 x 5 mm, particle size 10 .mu.m), temperature 25 C C, flow 0.6 ml / min, hexane / 2-propanol 90:10 v / v].
Die in den nachfolgenden Tabellen 1 - 3 beschriebenen Verbindungen erhält man gemäß oder analog zu den oben beschriebenen Synthesebeispielen.The compounds described in Tables 1 to 3 below are obtained according to or analogously to the synthesis examples described above.
In den Tabellen bedeuten:In the tables mean:
Me = MethylMe = methyl
Et = EthylEt = ethyl
F = FluorF = fluorine
Cl = Chlor Cl = chlorine
Tabelle 1: Verbindungen der Formel (I) Table 1: Compounds of the formula (I)
NMR Daten augewählten Verbindungen der Tabelle 1:NMR data of selected compounds of Table 1:
2-[(2,6-Difluorbenzyl)sulfanyl]-1,3-oxazol (Verbindung Nr.10):2 - [(2,6-Difluorobenzyl) sulfanyl] -1,3-oxazole (Compound No. 10):
NMR (CDCI3, 400 MHz): 4.47 (s, 2H, SCH2); 6.90 (m, 2H, Ar); 7.20 (br s, 1 H); 7.24 (m, 1H,Ar); 7.69(brs, 1H).NMR (CDCl 3 , 400 MHz): 4.47 (s, 2H, SCH 2 ); 6.90 (m, 2H, Ar); 7.20 (br s, 1 H); 7.24 (m, 1H, Ar); 7.69 (brs, 1H).
2-[(2,5-Difluorbenzyl)sulfanyl]-1 ,3-oxazol (Verbindung Nr.7):2 - [(2,5-Difluorobenzyl) sulfanyl] -1,3-oxazole (Compound No. 7):
NMR (CDCI3, 400 MHz): 4.38 (s, 2H, SCH2); 6.93 (m, 1H, Ar); 7.00 (m, 1H, Ar); 7.12 (br s, 1 H); 7.18 (m, 1 H, Ar); 7.68 (br s, 1 H).NMR (CDCl 3 , 400 MHz): 4.38 (s, 2H, SCH 2 ); 6.93 (m, 1H, Ar); 7.00 (m, 1H, Ar); 7.12 (br s, 1 H); 7.18 (m, 1H, Ar); 7.68 (brs, 1h).
2-[(2,6-Dichlorbenzyl)sulfanyl]-1,3-oxazol (Verbindung Nr.43):2 - [(2,6-dichlorobenzyl) sulfanyl] -1,3-oxazole (Compound No. 43):
NMR (CDCI3, 400 MHz): 4.71 (s, 2H, SCH2); 7.16 (br s, 1H); 7.19 (m, 1H, Ar); 7.31 (m,2H, Ar); 7.70 (br s, 1H).NMR (CDCl 3 , 400 MHz): 4.71 (s, 2H, SCH 2 ); 7.16 (br s, 1H); 7.19 (m, 1H, Ar); 7.31 (m, 2H, Ar); 7.70 (brs, 1H).
2-[(2,6-Difluor-3-methylbenzyl)sulfanyl]-1,3-oxazol (Verbindung Nr.13):2 - [(2,6-Difluoro-3-methylbenzyl) sulfanyl] -1,3-oxazole (Compound No. 13):
NMR (CDCI3, 400 MHz): 2.22 (s, 3H, CH3); 4.44 (s, 2H, SCH2); 6.78 (m, 1H, Ar); 7.09 (m, 1 H, Ar); 7.13 (br s, 1H); 7.69 (br s, 1H).NMR (CDCl 3 , 400 MHz): 2.22 (s, 3H, CH 3 ); 4.44 (s, 2H, SCH 2 ); 6.78 (m, 1H, Ar); 7.09 (m, 1H, Ar); 7.13 (br s, 1H); 7.69 (br s, 1H).
2-[(2,6-Dichlorbenzyl)sulfonyl]-1 ,3-oxazol (Verbindung Nr.45):2 - [(2,6-dichlorobenzyl) sulfonyl] -1,3-oxazole (Compound No.45):
NMR (CDCI3, 400 MHz): 5.11 (s, 2H, S(O)2CH2); 7.29 (m, 1H, Ar); 7.36 (m, 2H, Ar); 7.41 (brs, 1H); 7.88(brs, 1H).NMR (CDCl 3 , 400 MHz): 5.11 (s, 2H, S (O) 2 CH 2 ); 7.29 (m, 1H, Ar); 7.36 (m, 2H, Ar); 7.41 (brs, 1H); 7.88 (brs, 1h).
2-[(2-Chlor-3,6-difluorbenzyl)sulfonyl]-1,3-oxazol (Verbindung Nr.204):2 - [(2-Chloro-3,6-difluorobenzyl) sulfonyl] -1,3-oxazole (Compound No. 204):
NMR(CDCI3, 400 MHz): 4.89 (s, 2H, S(O)2CH2); 7.04 (m, 1H, Ar); 7.21 (m, 1H, Ar); 7.41 (brs, 1H); 7.89 (brs, 1H). 2-[(2-Chlor-3,6-difluorbenzyl)sulfinyl]-1 ,3-oxazol (Verbindung Nr. 203):NMR (CDCl 3 , 400 MHz): 4.89 (s, 2H, S (O) 2 CH 2 ); 7.04 (m, 1H, Ar); 7.21 (m, 1H, Ar); 7.41 (brs, 1H); 7.89 (brs, 1H). 2 - [(2-Chloro-3,6-difluorobenzyl) sulfinyl] -1,3-oxazole (Compound No. 203):
NMR (CDCI3, 400 MHz): 4.57 (s, 2H, S(O)CH2); 6.98 (m, 1 H1 Ar); 7.09 (m, 1 H1 Ar); 7.17 (br s, 1H); 7.70 (br s, 1 H).NMR (CDCl 3 , 400 MHz): 4.57 (s, 2H, S (O) CH 2 ); 6.98 (m, 1H 1 Ar); 7.09 (m, 1H 1 Ar); 7.17 (br s, 1H); 7.70 (brs, 1h).
2-[(2,5-Difluorbenzyl)sulfonyl]-1 ,3-oxazol (Verbindung Nr. 9):2 - [(2,5-Difluorobenzyl) sulfonyl] -1,3-oxazole (Compound No. 9):
NMR (CDCI3, 400 MHz): 4.69 (s, 2H, S(O)2CH2); 7.00 - 7.11 (m, 3H, Ar); 7.40 (br s, 1 H); 7.86 (br s, 1 H).NMR (CDCl 3 , 400 MHz): 4.69 (s, 2H, S (O) 2 CH 2 ); 7.00 - 7.11 (m, 3H, Ar); 7.40 (br s, 1 H); 7.86 (brs, 1h).
2-[(2,5-Difluorbenzyl)sulfinyl]-1 ,3-oxazol (Verbindung Nr. 8):2 - [(2,5-Difluorobenzyl) sulfinyl] -1,3-oxazole (Compound No. 8):
NMR (CDCI3, 400 MHz): 4.49 (d, 1 H, S(O)CH2); 4.61 (d, 1 H, S(O)CH2); 6.95 (m, 1 H, Ar); 7.05 (m, 2H, Ar); 7.34 (br s, 1 H); 7.89 (br s, 1 H).NMR (CDCl 3 , 400 MHz): 4.49 (d, 1 H, S (O) CH 2 ); 4.61 (d, 1 H, S (O) CH 2 ); 6.95 (m, 1H, Ar); 7.05 (m, 2H, Ar); 7.34 (br s, 1 H); 7.89 (brs, 1h).
2-[(2,6-Difluor-3-methylbenzyl)sulfinyl]-1 ,3-oxazol (Verbindung Nr. 14):2 - [(2,6-Difluoro-3-methylbenzyl) sulfinyl] -1,3-oxazole (Compound No. 14):
NMR (CDCI3, 400 MHz): 2.21 (s, 3H, CH3); 4.68 (d, 1 H, S(O)CH2); 4.80 (d, 1 H1 S(O)CH2); 6.79 (m, 1 H, Ar); 7.15 (m, 1 H, Ar); 7.30 (br s, 1 H); 7.90 (br s, 1 H).NMR (CDCl 3 , 400 MHz): 2.21 (s, 3H, CH 3 ); 4.68 (d, 1 H, S (O) CH 2 ); 4.80 (d, 1 H 1 S (O) CH 2 ); 6.79 (m, 1H, Ar); 7.15 (m, 1H, Ar); 7.30 (br s, 1 H); 7.90 (br s, 1 H).
2-[(2,6-Difluor-3-methylbenzyl)sulfonyl]-1 ,3-oxazol (Verbindung Nr. 15):2 - [(2,6-Difluoro-3-methylbenzyl) sulfonyl] -1,3-oxazole (Compound No. 15):
NMR (CDCI3, 400 MHz): 2.22 (s, 3H, CH3); 4.72 (s, 2H, S(O)2CH2); 6.81 (m, 1 H1 Ar); 7.20 (m, 1 H, Ar); 7.40 (br s, 1 H); 7.88 (br s, 1 H).NMR (CDCl 3 , 400 MHz): 2.22 (s, 3H, CH 3 ); 4.72 (s, 2H, S (O) 2 CH 2 ); 6.81 (m, 1H 1 Ar); 7.20 (m, 1H, Ar); 7.40 (br s, 1 H); 7.88 (brs, 1h).
2-[(2,6-Difluorbenzyl)sulfinyl]-1 ,3-oxazol (Verbindung Nr. 11 ):2 - [(2,6-Difluorobenzyl) sulfinyl] -1,3-oxazole (Compound No. 11):
NMR (CDCI3, 400 MHz): 4.59 (d, 1 H, S(O)CH2); 4.68 (d, 1 H, S(O)CH2); 6.91 (m, 2H, Ar); 7.30 (br s, 1 H); 7.31 (m, 1 H, Ar); 7.90 (br s, 1 H).NMR (CDCl 3 , 400 MHz): 4.59 (d, 1 H, S (O) CH 2 ); 4.68 (d, 1 H, S (O) CH 2 ); 6.91 (m, 2H, Ar); 7.30 (br s, 1 H); 7.31 (m, 1H, Ar); 7.90 (br s, 1 H).
2-[(2,5-Dimethylbenzyl)sulfinyl]-1 ,3-oxazol (Verbindung Nr. 131 ): NMR (CDCI3, 400 MHz): 2.24 (s, 3H, CH3); 2.37 (s, 3H, CH3); 4.52 (d, 1H, S(O)CH2); 4.59 (d, 1 H, S(O)CH2); 6.87 (br s, 1 H, Ar); 7.04 (m, 1 H, Ar); 7.09 (br s, 1 H, Ar); 7.31 (brs, 1H); 7.88(brs, 1H).2 - [(2,5-Dimethylbenzyl) sulfinyl] -1,3-oxazole (Compound No. 131): NMR (CDCl 3 , 400 MHz): 2.24 (s, 3H, CH 3 ); 2:37 (s, 3H, CH 3); 4:52 (d, 1 H, S (O) CH 2); 4.59 (d, 1 H, S (O) CH 2 ); 6.87 (br s, 1 H, Ar); 7.04 (m, 1H, Ar); 7.09 (brs, 1H, Ar); 7.31 (brs, 1H); 7.88 (brs, 1h).
2-[(2,5-Dimethylbenzyl)sulfonyl]-1,3-oxazol (Verbindung Nr.132):2 - [(2,5-Dimethylbenzyl) sulfonyl] -1,3-oxazole (Compound No. 132):
NMR (CDCI3, 400 MHz): 2.25 (s, 3H, CH3); 2.35 (s, 3H, CH3); 4.66 (s, 2H, S(O)2CH2); 6.90 (br s, 1 H, Ar); 7.09 (m, 2H, Ar); 7.39 (br s, 1 H, Ar); 7.80 (br s, 1 H).NMR (CDCl 3 , 400 MHz): 2.25 (s, 3H, CH 3 ); 2:35 (s, 3H, CH 3); 4.66 (s, 2H, S (O) 2 CH 2 ); 6.90 (br s, 1 H, Ar); 7.09 (m, 2H, Ar); 7.39 (br s, 1 H, Ar); 7.80 (br s, 1 H).
2-[(2-Chlor-3,6-difluorbenzyl)sulfanyl]-1 ,3-oxazol (Verbindung Nr.202):2 - [(2-Chloro-3,6-difluorobenzyl) sulfanyl] -1,3-oxazole (Compound No. 202):
NMR (CDCI3, 400 MHz): 4.55 (s, 2H, SCH2); 6.98 (m, 1 H, Ar); 7.10 (m, 1 H, Ar); 7.17 (brs, 1H); 7.70(brs, 1H).NMR (CDCl 3 , 400 MHz): 4.55 (s, 2H, SCH 2 ); 6.98 (m, 1H, Ar); 7.10 (m, 1H, Ar); 7.17 (brs, 1H); 7.70 (brs, 1H).
2-[(2,3,6-Trichlorbenzyl)sulfinyl]-1 ,3-oxazol (Verbindung Nr.65):2 - [(2,3,6-Trichlorobenzyl) sulfinyl] -1,3-oxazole (Compound No.65):
NMR (CDCI3, 400 MHz): 4.97 (d, 1 H, S(O)CH2); 5.03 (d, 1 H, S(O)CH2); 7.30 (d, 1 H, Ar); 7.33 (br s, 1 H); 7.42 (d, 1 H, Ar); 7.95 (br s, 1 H).NMR (CDCl 3 , 400 MHz): 4.97 (d, 1 H, S (O) CH 2 ); 5.03 (d, 1 H, S (O) CH 2 ); 7.30 (d, 1H, Ar); 7.33 (br s, 1 H); 7.42 (d, 1H, Ar); 7.95 (brs, 1h).
2-[(2,3,6-Trichlorbenzyl)sulfonyl]-1 ,3-oxazol (Verbindung Nr.66):2 - [(2,3,6-trichlorobenzyl) sulfonyl] -1,3-oxazole (Compound No.66):
NMR(CDCI3, 400 MHz): 5.14 (s, 2H, S(O)2CH2); 7.31 (d, 1H, Ar); 7.42 (brs, 1H); 7.46 (d, 1 H, Ar); 7.89 (brs, 1H). NMR (CDCl 3 , 400 MHz): 5.14 (s, 2H, S (O) 2 CH 2 ); 7.31 (d, 1H, Ar); 7.42 (brs, 1H); 7.46 (d, 1H, Ar); 7.89 (brs, 1H).
Tabelle 2: Optisch aktive Verbindungen der Formel (IM-S)Table 2: Optically active compounds of the formula (IM-S)
) )
Tabelle 3: Optisch aktive Verbindungen der Formel (HI-R) Table 3: Optically active compounds of the formula (HI-R)
Die zuvor angegebenen NMR-Daten wurden bei 400 MHz und in CDCI3 als Lösemittel gemessen. Die chemische Verschiebung δ ist in ppm angegeben (TMS- Standard). The NMR data given above were measured at 400 MHz and in CDCl 3 as the solvent. The chemical shift δ is given in ppm (TMS standard).
B. FormulierungsbeispieleB. Formulation Examples
a) Ein Stäubemittel wird erhalten, indem man 10 Gew. Teile einer Verbindung der Formel (I) und/oder deren Salze und 90 Gew. Teile Talkum als Inertstoff mischt und in einer Schlagmühle zerkleinert.a) A dust is obtained by mixing 10 parts by weight of a compound of formula (I) and / or salts thereof and 90 parts by weight of talc as an inert material and comminuted in a hammer mill.
b) Ein in Wasser leicht dispergierbares, benetzbares Pulver wird erhalten, indem man 25 Gewichtsteile einer Verbindung der Formel (I) und/oder deren Salze, 64 Gew. Teile kaolinhaltigen Quarz als Inertstoff, 10 Gewichtsteile ligninsulfonsaures Kalium und 1 Gew. Teil oleoylmethyltaurinsaures Natrium als Netz und Dispergiermittel mischt und in einer Stiftmühle mahlt.b) A wettable powder readily dispersible in water is obtained by reacting 25 parts by weight of a compound of the formula (I) and / or its salts, 64 parts by weight of kaolin-containing quartz as inert material, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of oleoylmethyl tauric acid sodium as a wetting and dispersing agent and grinding in a pin mill.
c) Ein in Wasser leicht dispergierbares Dispersionskonzentrat wird erhalten, indem man 20 Gew. Teile einer Verbindung der Formel (I) und/oder deren Salze mit 6 Gew. Teilen Alkylphenolpolyglykolether (©Triton X 207), 3 Gew. Teilen Isotridecanolpolyglykolether (8 EO) und 71 Gew. Teilen paraffinischem Mineralöl (Siedebereich z.B. ca. 255 bis über 277 C) mischt und in einer Reibkugelmühle auf eine Feinheit von unter 5 Mikron vermahlt.c) A dispersion concentrate readily dispersible in water is obtained by reacting 20 parts by weight of a compound of the formula (I) and / or salts thereof with 6 parts by weight of alkylphenol polyglycol ether (© Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO ) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to about 277 C) and milled in a ball mill to a fineness of less than 5 microns.
d) Ein emulgierbares Konzentrat wird erhalten aus 15 Gew. Teilen einer Verbindung der Formel (I) und/oder deren Salze, 75 Gew. Teilen Cyclohexanon als Lösungsmittel und 10 Gew. Teilen oxethyliertes Nonylphenol als Emulgator.d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I) and / or salts thereof, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.
e) Ein in Wasser dispergierbares Granulat wird erhalten indem mane) A water-dispersible granules are obtained by
75 Gew. Teile einer Verbindung der Formel (I) und/oder deren Salze,75 parts by weight of a compound of the formula (I) and / or salts thereof,
10 Gew. Teile ligninsulfonsaures Calcium,10 parts by weight of lignosulfonic acid calcium,
5 Gew. Teile Natriumlaurylsulfat,5 parts by weight of sodium lauryl sulfate,
3 Gew. Teile Polyvinylalkohol und3 parts by weight of polyvinyl alcohol and
7 Gew. Teile Kaolin mischt, auf einer Stiftmühle mahlt und das Pulver in einem Wirbelbett durch7 parts by weight kaolin mixed, ground on a pin mill and the powder in a fluidized bed by
Aufsprühen von Wasser als Granulierflüssigkeit granuliert. Ein in Wasser dispergierbares Granulat wird auch erhalten, indem man 25 Gew. Teile einer Verbindung der Formel (I) und/oder deren Salze, 5 Gew. Teile 2,2' dinaphthylmethan 6,6' disulfonsaures Natrium 2 Gew. Teile oleoylmethyltaurinsaures Natrium, 1 Gew. Teil Polyvinylalkohol, 17 Gew. Teile Calciumcarbonat und 50 Gew. Teile Wasser auf einer Kolloidmühle homogenisiert und vorzerkleinert, anschließend auf einer Perlmühle mahlt und die so erhaltene Suspension in einem Sprühturm mittels einer Einstoffdüse zerstäubt und trocknet. Spraying of water as granulating liquid granulated. A water-dispersible granule is also obtained by reacting 25 parts by weight of a compound of formula (I) and / or salts thereof, 5 parts by weight of 2,2'-dinaphthylmethane 6,6'-disulfonic acid sodium 2 parts by weight of sodium oleoylmethyltaurate, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water homogenized on a colloid mill and pre-crushed, then grinded on a bead mill and the resulting suspension in a spray tower by means of a Einstoffdüse atomized and dried.
C. Biologische BeispieleC. Biological examples
Die erfindungsgemäßen Verbindungen der Formel (I) (und/oder deren Salze), im folgenden zusammen als „erfindungsgemäße Verbindungen" bezeichnet, weisen eine ausgezeichnete herbizide Wirksamkeit gegen ein breites Spektrum wirtschaftlich wichtiger mono- und dikotyler annueller Schadpflanzen auf. Auch schwer bekämpfbare perennierende Schadpflanzen, die aus Rhizomen, Wurzelstöcken oder anderen Dauerorganen austreiben, werden durch die Wirkstoffe gut erfaßt.The compounds of the formula (I) (and / or their salts) according to the invention, 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 expel from rhizomes, rhizomes or other permanent organs are well detected by the active ingredients.
Gegenstand der vorliegenden Erfindung ist daher auch ein Verfahren zur Bekämpfung von unerwünschten Pflanzen oder zur Wachstumsregulierung von Pflanzen, vorzugsweise in Pflanzenkulturen, worin eine oder mehrere erfindungsgemäße Verbindung(en) auf die Pflanzen (z.B. Schadpflanzen wie mono- oder dikotyle Unkräuter oder unerwünschte Kulturpflanzen), das Saatgut (z.B. Körner, Samen oder vegetative Vermehrungsorgane wie Knollen oder Sprossteile mit Knospen) oder die Fläche, auf der die Pflanzen wachsen (z.B. die Anbaufläche), ausgebracht werden. Dabei können die erfindungsgemäßen Verbindungen z.B. im Vorsaat- (ggf. auch durch Einarbeitung in den Boden), Vorauflauf- oder Nachauflaufverfahren ausgebracht werden. Im einzelnen seien beispielhaft einige Vertreter der mono- und dikotylen Unkrautflora genannt, die durch die erfindungsgemäßen Verbindungen kontrolliert werden können, ohne dass durch die Nennung eine Beschränkung auf bestimmte Arten erfolgen soll.The present invention therefore also provides a method for controlling undesirable plants or for regulating the growth of plants, preferably in plant crops, wherein one or more compounds of the invention are applied to the plants (eg harmful plants such as monocotyledonous or dicotyledonous weeds or undesired crop plants), the seeds (eg grains, seeds or vegetative propagules such as tubers or sprout parts with buds) or the area on which the plants grow (eg the acreage) are applied. The compounds of the invention may be e.g. in pre-sowing (possibly also by incorporation into the soil), pre-emergence or Nachauflaufverfahren be applied. Specifically, by way of example, some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned, which can be controlled by the compounds according to the invention, without the intention of limiting them to certain species.
Monokotyle Schadpflanzen der Gattungen: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.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.
Dikotyle Unkräuter der Gattungen: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, BeIMs, 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, Salsola, Senecio, Sesbania, Sida, Sinapis, Solarium, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, BeIMs, 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, Salsola, Senecio, Sesbania, Sida, Sinapis, Solarium, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
Werden die erfindungsgemäßen Verbindungen vor dem Keimen auf die Erdoberfläche appliziert, so wird entweder das Auflaufen der Unkrautkeimlinge vollständig verhindert oder die Unkräuter wachsen bis zum Keimblattstadium heran, stellen jedoch dann ihr Wachstum ein und sterben schließlich nach Ablauf von drei bis vier Wochen vollkommen ab.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.
Bei Applikation der Wirkstoffe auf die grünen Pflanzenteile im Nachauflaufverfahren tritt nach der Behandlung Wachstumsstop ein und die Schadpflanzen bleiben in dem zum Applikationszeitpunkt vorhandenen Wachstumsstadium stehen oder sterben nach einer gewissen Zeit ganz ab, so dass auf diese Weise eine für die Kulturpflanzen schädliche Unkrautkonkurrenz sehr früh und nachhaltig beseitigt wird.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.
Obgleich die erfindungsgemäßen Verbindungen eine ausgezeichnete herbizide Aktivität gegenüber mono- und dikotylen Unkräutern aufweisen, werden Kulturpflanzen wirtschaftlich bedeutender Kulturen z.B. dikotyler Kulturen der Gattungen Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, oder monokotyler Kulturen der Gattungen Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Seeale, Sorghum, Triticale, Triticum, Zea, insbesondere Zea und Triticum, abhängig von der Struktur der jeweiligen erfindungsgemäßen Verbindung und deren Aufwandmenge nur unwesentlich oder gar nicht geschädigt. Die vorliegenden Verbindungen eignen sich aus diesen Gründen sehr gut zur selektiven Bekämpfung von unerwünschtem Pflanzenwuchs in Pflanzenkulturen wie landwirtschaftlichen Nutzpflanzungen oder Zierpflanzungen.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. For these reasons, the present compounds are very well suited for the selective control of undesired ones Plant growth in crops such as agricultural crops or ornamental plantings.
Darüberhinaus weisen die erfindungsgemäßen Verbindungen (abhängig von ihrer jeweiligen Struktur und der ausgebrachten Aufwandmenge) hervorragende wachstumsregulatorische Eigenschaften bei Kulturpflanzen auf. Sie greifen regulierend in den pflanzeneigenen Stoffwechsel ein und können damit zur gezielten Beeinflussung von Pflanzeninhaltsstoffen und zur Ernteerleichterung wie z.B. durch Auslösen von Desikkation und Wuchsstauchung eingesetzt werden. Desweiteren eignen sie sich auch zur generellen Steuerung und Hemmung von unerwünschtem vegetativen Wachstum, ohne dabei die Pflanzen abzutöten. Eine Hemmung des vegetativen Wachstums spielt bei vielen mono- und dikotylen Kulturen eine große Rolle, da beispielsweise die Lagerbildung hierdurch verringert oder völlig verhindert werden kann.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.
Aufgrund ihrer herbiziden und pflanzenwachstumsregulatorischen Eigenschaften können die Wirkstoffe auch zur Bekämpfung von Schadpflanzen in Kulturen von gentechnisch oder durch konventionelle Mutagenese veränderten Pflanzen eingesetzt werden. Die transgenen Pflanzen zeichnen sich in der Regel durch besondere vorteilhafte Eigenschaften aus, beispielsweise durch Resistenzen gegenüber bestimmten Pestiziden, vor allem bestimmten Herbiziden, Resistenzen gegenüber Pflanzenkrankheiten oder Erregern von Pflanzenkrankheiten wie bestimmten Insekten oder Mikroorganismen wie Pilzen, Bakterien oder Viren. Andere besondere Eigenschaften betreffen z. B. das Erntegut hinsichtlich Menge, Qualität, Lagerfähigkeit, Zusammensetzung und spezieller Inhaltsstoffe. So sind transgene Pflanzen mit erhöhtem Stärkegehalt oder veränderter Qualität der Stärke oder solche mit anderer Fettsäurezusammensetzung des Ernteguts bekannt.Because of their herbicidal and plant growth regulatory properties, the active compounds can also be used to control harmful plants in crops of genetically engineered or conventional mutagenized plants. The transgenic plants are usually characterized by particular advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties relate to z. B. the crop in terms of quantity, quality, shelf life, composition and special ingredients. Thus, transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known.
Bevorzugt bezüglich transgener Kulturen ist die Anwendung der erfindungsgemäßen Verbindungen in wirtschaftlich bedeutenden transgenen Kulturen von Nutz und Zierpflanzen, z. B. von Getreide wie Weizen, Gerste, Roggen, Hafer, Hirse, Reis und Mais oder auch Kulturen von Zuckerrübe, Baumwolle, Soja, Raps, Kartoffel, Tomate, Erbse und anderen Gemüsesorten.Preferred with respect to transgenic cultures is the use of the compounds of the invention in economically important transgenic crops of useful and ornamental plants, eg. As cereals such as wheat, barley, rye, oats, millet, rice and corn or even crops of sugar beet, cotton, soybeans, rapeseed, potato, tomato, Pea and other vegetables.
Vorzugsweise können die erfindungsgemäßen Verbindungen als Herbizide inPreferably, the compounds of the invention as herbicides in
Nutzpflanzenkulturen eingesetzt werden, welche gegenüber den phytotoxischenCrop crops are used, which compared to the phytotoxic
Wirkungen der Herbizide resistent sind bzw. gentechnisch resistent gemacht worden sind.Effects of the herbicides are resistant or have been made genetically resistant.
1. Herbizide Wirkung bzw. Kulturpflanzenverträglichkeit im Vorauflauf1. Herbicidal action or crop plant compatibility in the pre-emergence
Samen von mono- bzw. dikotylen Unkraut- bzw. Kulturpflanzen werden in Holzfasertöpfen in sandiger Lehmerde ausgelegt und mit Erde abgedeckt. Die in Form von benetzbaren Pulvern (WP) formulierten erfindungsgemäßen Verbindungen werden dann als wäßrige Suspension mit einer Wasseraufwandmenge von umgerechnet 600 l/ha unter Zusatz von 0,2% Netzmittel auf die Oberfläche der Abdeckerde appliziert.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 according to the invention formulated in the form of wettable powders (WP) are then applied to the surface of the cover soil as an aqueous suspension having a water application rate of 600 l / ha, with the addition of 0.2% wetting agent.
Nach der Behandlung werden die Töpfe im Gewächshaus aufgestellt und unter guten Wachstumsbedingungen für die Testpflanzen gehalten. Nach ca. 3 Wochen wird die Wirkung der Präparate visuell im Vergleich zu unbehandelten Kontrollen bonitiert (herbizide Wirkung in Prozent (%): 100% Wirkung = Pflanzen sind abgestorben, 0 % Wirkung = wie Kontrollpflanzen).After the treatment, the pots are placed in the greenhouse and kept under good growth conditions for the test plants. After approx. 3 weeks, the effect of the preparations is scored visually in comparison to untreated controls (herbicidal action in percent (%): 100% action = plants have died, 0% action = like control plants).
Wie die Ergebnisse zeigen, weisen erfindungsgemäße Verbindungen eine gute herbizide Vorauflaufwirksamkeit gegen ein breites Spektrum von Ungräsern und Unkräutern auf. Beispielsweise haben die Verbindungen Nr. 11 , 14, 131 , 44, 65, 66 203, 2517 und andere Verbindungen aus der Tabellen 1 - 3 sehr gute herbizide Wirkung gegen Schadpflanzen wie beispielsweise Echinochloa crus galli, Lolium multiflorum, Veronica persica und Alopecurus myosuroides im Vorauflaufverfahren bei einer Aufwandmenge von 0.32 kg und weniger Aktivsubstanz pro Hektar.As the results show, compounds of the invention have a good herbicidal pre-emergence activity against a broad spectrum of grass weeds and weeds. For example, compounds Nos. 11, 14, 131, 44, 65, 66, 203, 2517 and other compounds of Tables 1-3 have very good herbicidal activity against harmful plants such as Echinochloa crus galli, Lolium multiflorum, Veronica persica and Alopecurus myosuroides Pre-emergence method at an application rate of 0.32 kg and less active substance per hectare.
Gleichzeitig lassen erfindungsgemäße Verbindungen zweikeimblättrige Kulturen wie Raps im Vorauflaufverfahren selbst bei hohen Wirkstoffdosierungen ungeschädigt. Einige Substanzen schonen darüber hinaus auch Gramineen Kulturen wie Weizen und Mais. Die erfindungsgemäßen Verbindungen zeigen teilweise eine hohe Selektivität und eignen sich deshalb im Vorauflaufverfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs in landwirtschaftlichen Kulturen.At the same time, compounds according to the invention leave dicotyledonous crops, such as rape seed pre-emergence, undamaged even at high doses of active ingredient. In addition, some substances also protect graminaceous crops such as wheat and corn. Some of the compounds according to the invention show a high selectivity and are therefore suitable in the pre-emergence process for controlling undesired plant growth in agricultural crops.
2. Herbizide Wirkung bzw. Kulturpflanzenverträglichkeit im Nachauflauf2. Herbicidal action or crop plant compatibility postemergence
Samen von mono- bzw. dikotylen Unkraut- bzw. Kulturpflanzen werden in Holzfasertöpfen in sandigem Lehmboden ausgelegt, mit Erde abgedeckt und im Gewächshaus unter guten Wachstumsbedingungen angezogen. 2 bis 3 Wochen nach der Aussaat werden die Versuchspflanzen im Einblattstadium behandelt. Die in Form von benetzbaren Pulvern (WP) formulierten erfindungsgemäßen Verbindungen werden dann als wäßrige Suspension mit einer Wasseraufwandmenge von umgerechnet 600 l/ha unter Zusatz von 0,2% Netzmittel auf die grünen Pflanzenteile gesprüht. Nach ca. 3 Wochen Standzeit der Versuchspflanzen im Gewächshaus unter optimalen Wachstumsbedingungen wird die Wirkung der Präparate visuell im Vergleich zu unbehandelten Kontrollen bonitiert (herbizide Wirkung in Prozent (%): 100% Wirkung = Pflanzen sind abgestorben, 0 % Wirkung = wie Kontrollpflanzen).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 according to the invention formulated in the form of wettable powders (WP) are then sprayed onto the green plant parts as an aqueous suspension having a water application rate of 600 l / ha, with the addition of 0.2% wetting agent. After about 3 weeks of life of the test plants in the greenhouse under optimal growth conditions, the effect of the preparations is scored visually compared to untreated controls (herbicidal activity in percent (%): 100% effect = plants are dead, 0% effect = like control plants).
Wie die Ergebnisse zeigen, weisen erfindungsgemäße Verbindungen eine gute herbizide Nachauflaufwirksamkeit gegen einige Ungräser bzw. Unkräuter auf. Beispielsweise haben die Verbindungen Nr. 44, 65, 131 , 203, 2517 und andere Verbindungen aus der Tabellen 1 - 3 sehr gute herbizide Wirkung gegen Schadpflanzen wie beispielsweise Echinochloa crus galli und Lolium multiflorum im Nachauflaufverfahren bei einer Aufwandmenge von 0.32 kg und weniger Aktivsubstanz pro Hektar.As the results show, compounds according to the invention have a good herbicidal postemergence activity against some weeds or weeds. For example, the compounds Nos. 44, 65, 131, 203, 2517 and other compounds from Tables 1-3 have very good herbicidal activity against harmful plants such as Echinochloa crus galli and Lolium multiflorum postemergence at an application rate of 0.32 kg and less active ingredient per hectares.
Gleichzeitig lassen erfindungsgemäße Verbindungen zweikeimblättrige Kulturen wie Raps im Nachauflaufverfahren selbst bei hohen Wirkstoffdosierungen ungeschädigt. Einige Substanzen schonen darüber hinaus auch Gramineen Kulturen wie Weizen und Mais. Die erfindungsgemäßen Verbindungen zeigen teilweise eine hohe Selektivität und eignen sich deshalb im Nachauflaufverfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs in landwirtschaftlichen Kulturen. At the same time, compounds according to the invention leave dicotyledonous crops, such as rapeseed, undamaged even after high doses of active ingredient. In addition, some substances also protect graminaceous crops such as wheat and corn. 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.

Claims

Patentansprüche claims
1. Verbindungen der allgemeinen Formel (I) und deren agrochemisch verträglichen Salze1. Compounds of general formula (I) and their agrochemically acceptable salts
worinwherein
n gleich 0, 1 , 2 entspricht; die Substituenten R1 und R2, jeweils unabhängig voneinander, ausgewählt sind aus der Gruppe, bestehend ausn equals 0, 1, 2; the substituents R 1 and R 2 , each independently, are selected from the group consisting of
Wasserstoff, Haiogen, Nitro, Cyano, Formyl, -C(O)OH, Hydroxy, undHydrogen, halogen, nitro, cyano, formyl, -C (O) OH, hydroxy, and
Amino;amino;
(d-C6)-Alkyl, (d-C6)-Alkylcarbonyl, (d-CeJ-AlkylcarbonyKCrd)- alkyl und (Ci-C6)-Alkylcarbonyloxy;(dC 6) alkyl, (dC 6) alkylcarbonyl, (d-CeJ-AlkylcarbonyKCrd) - alkyl and (Ci-C 6) alkylcarbonyloxy;
(Ci-C6)-Alkoxy, (CrC6)-Alkoxycarbonyl, (CrC6)-Alkoxycarbonyl-(d-(Ci-C 6) alkoxy, (CrC 6) alkoxycarbonyl, (C r C6) alkoxycarbonyl (d-
C6)-alkyl, (C1-C6)-Alkoxy-(d-C6)-alkylI (C1-C6)-Alkoxy-(CrC6)-alkoxy und (C1-C6)-Alkoxycarbonyl-(d-C6)-alkoxy;C 6) alkyl, (C 1 -C 6) alkoxy (dC 6) alkyl I (C 1 -C 6) alkoxy (CrC 6) alkoxy and (C 1 -C 6) alkoxycarbonyl (dC 6 ) alkoxy;
(C2-C6)-Alkenyl, (C2-C6)-Alkenyloxy, (C2-C6)-Alkinyl und (C2-C6)-(C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyl and (C 2 -C 6 ) -
Alkinyloxy;alkynyloxy;
(d-C6)-Alkylthio, (d-C6)-Alkylsulfinyl, (d-C6)-Alkylsulfonyl, (C1-C6)-(dC 6) alkylthio, (dC 6) alkylsulfinyl, (dC 6) alkylsulfonyl, (C 1 -C 6) -
Alkylsulfonyloxy, (d-CeO-AlkylsulfonyKd-CeO-alkyl, (C1-C6)-Alkylsulfonyloxy, (d-CeO-AlkylsulfonyKd-CeO-alkyl, (C 1 -C 6 ) -
Alkylsulfinyl-(d-C6)-alkyl, d-C6)-Alkylthio-(CrC6)-alkyl und (C1-C6)-Alkylsulfinyl (dC 6) alkyl, dC 6) alkylthio (CrC 6) alkyl and (C 1 -C 6) -
Alkylthio-(CrC6)-alkoxy;Alkylthio (C r C6) alkoxy;
Mono-((CrC6)-alkyl)-amino, Di-((CrC6)-alkyl)-amino, NK(C1-C6)-Mono - ((CrC 6) alkyl) amino, di - ((C r C6) alkyl) amino, NK (C 1 -C 6) -
Alkanoyl)-amino, AminocarbonyKCrCβJ-alkyl, Mono-((d-C6)-alkyl)- aminocarbonyl, Di-((C1-C6)-alkyl)-aminocarbonyl, Mono-((CrC6)-alkyl)- aminosulfonyl und Di-((C1-C6)-alkyl)-aminosulfonyl; (C3-C8)-Cycloalkyl, (C3-C8)-Cycloalkoxy, (C3-C8)-Cycloalkyl-(Ci-C6)- alkyl, (C3-C8)-Cycloalkyl-(C1-C6)-alkoxy> (C3-C8)-Cycloalkylcarbonyl und (C3-C8)-Cycloalkoxycarbonyl;Alkanoyl) -amino, aminocarbonyKCrCβJ-alkyl, mono - ((dC 6 ) -alkyl) -aminocarbonyl, di- ((C 1 -C 6 ) -alkyl) -aminocarbonyl, mono - ((CrC 6 ) -alkyl) -aminosulfonyl and di - ((C 1 -C 6 ) alkyl) -aminosulfonyl; (C 3 -C 8) cycloalkyl, (C 3 -C 8) cycloalkoxy, (C 3 -C 8) -cycloalkyl- (Ci-C 6) - alkyl, (C 3 -C 8) -cycloalkyl- ( C 1 -C 6 ) alkoxy > (C 3 -C 8 ) cycloalkylcarbonyl and (C 3 -C 8 ) cycloalkoxycarbonyl;
(C3-C8)-Cycloalkenyl, (C3-C8)-Cycloalkenyloxy, (C3-C8)-Cycloalkylthio, (C3-C8)-Cycloalkylsulfinyl, (C3-C8)-Cycloalkylsulfonyl und (C3-C8)- Cycloalkylsulfonyloxy;(C 3 -C 8 ) -cycloalkenyl, (C 3 -C 8 ) -cycloalkenyloxy, (C 3 -C 8 ) -cycloalkylthio, (C 3 -C 8 ) -cycloalkylsulfinyl, (C 3 -C 8 ) -cycloalkylsulfonyl and (C 3 -C 8 ) cycloalkylsulfonyloxy;
Cyano-(C-ι-C6)-alkoxy und Cyano-(CrC6)-alkyl; -CONH-SO2-(CrC6)-Alkyl, -NHCHO1 -NHCO-(CrC6)-Alkyl, -NHCO2- (CrC6)-Alkyl, -NHCONH-(CrC6)-Alkyl, -NHSO2-(CrC6)-Alkyl, -OCONH-(Ci-Cβ)-Alkyl, (Ci-C6)-Alkylaminosulfonyl-(CrC2)-alkylf Di- (d-CeJ-alkylaminosulfonyl^CrC^-alkyl, -C(O)NHR9, -C(O)NR9R10, wobei R9 und R10, jeweils unabhängig voneinander, ausgewählt werden aus der Gruppe, bestehend aus Wasserstoff, (CrCe)-AIkVl, (C3-C6)-Cycloalkyl, (CrC6)-Haloalkyl, oder wo R9 und R10 zusammen eine (CrCβJ-Alkylen-Gruppe bilden, die ein Sauerstoff-, oder Schwefel-Atom oder ein oder zwei Arnino oder (CrCeJ-Alkylamino- Gruppen enthalten kann, die Substituenten R3 bis R7, jeweils unabhängig voneinander, ausgewählt sind aus der Gruppe, bestehend ausCyano (C 1 -C 6 ) alkoxy and cyano (C 1 -C 6 ) alkyl; -CONH-SO 2 - (CrC 6) alkyl, -NHCHO 1 -NHCO- (C r C6) alkyl, -NHCO 2 - (C r C6) alkyl, -NHCONH- (CrC 6) alkyl , -NHSO 2 - (CrC 6) alkyl, -OCONH- (Ci-Cβ) alkyl, (Ci-C6) alkylaminosulfonyl (CRC2) -alkyl f di- (d-CeJ-alkylaminosulfonyl ^ CrC ^ - alkyl, -C (O) NHR 9 , -C (O) NR 9 R 10 , wherein each of R 9 and R 10 , independently of one another, is selected from the group consisting of hydrogen, (C 1 -C 6) -AlkVl, (C 3 -C 6 ) -cycloalkyl, (C r C 6 ) -haloalkyl, or where R 9 and R 10 together form a (CrCβJ-alkylene group which is an oxygen or sulfur atom or one or two arnino or (CrCeJ -Alkylamino groups, the substituents R 3 to R 7 , each independently selected from the group consisting of
Wasserstoff, Halogen, Hydroxy, Cyano, Nitro, Amino, C(O)OH und Formyl;Hydrogen, halogen, hydroxy, cyano, nitro, amino, C (O) OH and formyl;
(CrC6)-Alkyl, (CrC6)-Halogenalkyl, (CrC6)-Alkyicarbonyi, (C1- CβJ-Haloalkylcarbonyl, (CrCβJ-Alkylcarbonyloxy, (CrCβJ-Halogen- alkylcarbonyloxy, (C1-C6)-Alkylcarbonyl-(C1-C4)-alkyl, (C1-Ce)-Ha- loalkylcarbonyl-(CrC4)-alkyl, (C1-C6)-Alkylcarbonyl-(C1-C4)-ha- loalkyl und (C1-C6)-Haloalkylcarbonyl-(C1-C4)-haloalkyl; (CrC6)-Alkoxy, (CrC6)-Halogenalkoxy, (CrC6)-Alkoxycarbonyl, (Ci-C6)-Haloalkoxycarbonyl, (CrC6)-Alkoxycarbonyl-(CrC6)-alkyl, (CrC6)-Haloalkoxycarbonyl-(CrC6)-alkyl, (C-i-CβJ-Alkoxycarbonyl- (CrCβJ-halogenalkyl und (CrCβJ-HalogenalkoxycarbonyKCrCe)- halogenalkyl; (C2-C6)-Alkenyl, (C2-C6)-Halogenalkenyl, (C2-C6)-Alkenylcarbonyl, (C2-C6)-Haloalkenylcarbonyl, (C2-C6)-Alkenyloxy, (C2-Ce)-HaIo- alkenyloxy, (C2-C6)-Alkenyloxycarbonyl und (C2-C6)-Haloalkenyl- oxycarbonyl;(C r C6) alkyl, (C r C 6) haloalkyl, (CrC 6) -Alkyicarbonyi, (C 1 - CβJ-haloalkylcarbonyl, (CrCβJ alkylcarbonyloxy, (CrCβJ halogen alkylcarbonyloxy, (C 1 -C 6) alkylcarbonyl (C 1 -C 4) alkyl, (C 1 -Ce) -Ha- loalkylcarbonyl- (CrC 4) alkyl, (C 1 -C 6) alkylcarbonyl (C 1 -C 4) -ha- loalkyl, and (C 1 -C 6) -Haloalkylcarbonyl- (C 1 -C 4) -haloalkyl, (CrC 6) alkoxy, (CrC 6) -haloalkoxy, (C r C6) -alkoxycarbonyl, (C -C 6 ) -haloalkoxycarbonyl, (CrC 6 ) -alkoxycarbonyl- (CrC 6 ) -alkyl, (CrC 6 ) -haloalkoxycarbonyl- (CrC 6 ) -alkyl, (Ci-CβJ-alkoxycarbonyl- (CrCβJ-haloalkyl and (CrCβJ-) HaloalkoxycarbonyKCrCe) - haloalkyl; (C 2 -C 6 ) -alkenyl, (C 2 -C 6 ) -haloalkenyl, (C 2 -C 6 ) -alkenylcarbonyl, (C 2 -C 6 ) haloalkenylcarbonyl, (C 2 -C 6 ) alkenyloxy, (C 2 -Ce) -haloalkenyloxy, (C 2 -C 6 ) -alkenyloxycarbonyl and (C 2 -C 6 ) -haloalkenyl - oxycarbonyl;
(C2-C6)-Alkinyl, (C2-C6)-Halogenalkinyl, (C2-C6)-Alkinylcarbonyl, (C2-C6)-Haloalkinylcarbonyl, (C2-C6)-Alkinyloxy, (C2-C6)-Haloalki- nyloxy, (C2-C6)-Alkinyloxycarbonyl und (C2-C6)-Halogenalkinyloxy- carbonyl;(C 2 -C 6 ) -alkynyl, (C 2 -C 6 ) -haloalkynyl, (C 2 -C 6 ) -alkynylcarbonyl, (C 2 -C 6 ) -haloalkynylcarbonyl, (C 2 -C 6 ) -alkynyloxy, (C 2 -C 6 ) -haloalkynyloxy, (C 2 -C 6 ) -alkynyloxycarbonyl and (C 2 -C 6 ) -haloalkynyloxycarbonyl;
(d-C6)-Alkylthiocarbonyl, (d-CeJ-Haloalkylthiocarbonyl, (C1-C6)- Alkylthiocarbonyloxy und (d-CeJ-Haloalkylthiocarbonyloxy; (CrC6)-Alkylthio-(Ci-C6)-alkoxy, (d-C6)-Alkylthio-(CrC6)-alkylcar- bonyl und (d-C6)-Alkylthio-(Ci-C6)-alkylcarbonyloxy; (Ci-C6)-Alkylsulfonyl, (d-C6)-Alkylthio, (d-C6)-Alkylsulfinyl, (Cr C6)-Haloalkylsulfonyl, (d-C6)-Halogenalkylthio, (CrC6)-Halogen- alkylsulfinyl^d-CeJ-Alkylsulfonyl^d-CeJ-alkyl, (d-C6)-Alkylthio- (Ci-C6)-alkyl, (d-CeJ-Alkylsulfinyl^d-CeJ-alkyl, (C1-C6)- Ha!oa!ky!su!fony!-(d-C6)-aikyi, (CrCerHaioaikyithio^CrCej-aikyi, (CrC6)-Haloalkylsulfinyl-(d-C6)-alkyl, (d-C6)-Alkylsulfonyl-(Cr C6)-haloalkyl, (d-C6)-Alkylthio-(d-C6)-haloalkyl, (C1-C6)- Alkylsulfinyl-(CrC6)-haloalkyl, (CrCeJ-Haloalkylsulfonyl^CrCe)- haloalkyl, (CrCeJ-Haloalkylthio^CrCeJ-haloalkyl, (C1-Ce)-Ha- loalkylsulfinyl-(d-C6)-haloalkyl, (CrC6)-Alkylsulfonyloxy und (C1- C6)-Halogenalkylsulfonyloxy;(dC 6 ) alkylthiocarbonyl, (d-CeJ-haloalkylthiocarbonyl, (C 1 -C 6 ) -alkylthiocarbonyloxy and (d-CeJ-haloalkylthiocarbonyloxy; (CrC 6 ) -alkylthio (C 1 -C 6 ) -alkoxy, (dC 6 ) alkylthio (C r C6) -alkylcar- carbonyl and (dC 6) alkylthio (Ci-C 6) alkylcarbonyloxy, (Ci-C 6) alkylsulfonyl, (dC 6) alkylthio, (dC 6 ) alkylsulfinyl, (C r C6) haloalkylsulfonyl, (dC 6) -haloalkylthio, (C r C6) alkylsulfinyl-halo ^ d-CeJ-alkylsulfonyl ^ d-CeJ-alkyl, (dC 6) alkylthio (Ci-C6) alkyl, (d-CeJ alkylsulfinyl ^ d-CeJ alkyl, (C1-C6) -! Ha oa ky sulphonyl - (dC 6) -alkyl, (CrCerHaioaikyithio ^ CrCej-aikyi, (C r C6) -Haloalkylsulfinyl- (dC 6) alkyl, (dC 6) alkylsulphonyl (C r C6) -haloalkyl, (dC 6) alkylthio (dC 6) -haloalkyl , (C1-C6) - alkylsulphinyl (C r C6) -haloalkyl, (CrCeJ-haloalkylsulfonyl CRCE ^) - haloalkyl, (CrCeJ-haloalkylthio ^ CrCeJ-haloalkyl, (C 1 -Ce) -Ha- loalkylsulfinyl- (dC 6) -haloalkyl, (C r C6) alkylsulfonyloxy and (C 1 - C 6) -Halogenalkylsulfonyloxy;
Mono-((d-C6)-alkyl)-amino, Mono-((d-C6)-haloalkyl)-amino, Di- ((CrCeJ-alkyO-amino, Di-((d-C6)-haloalkyl)-amino, ((d-C6)-Alkyl- (CrCeJ-haloalkyO-amino, N-((C1-C6)-Alkanoyl)-amino, N-((CrC6)- Haloalkanoyl)-amino, Aminocarbonyl-(d-C6)-alkyl, MOnO-(C1-C6)- AlkylaminocarbonyKCrCeJ-alkyl, Di-(d-C6)-Alkylaminocarbonyl- (CrCe)-alkyl und Mono-((d-C6)-alkyl)-aminocarbonyl; C6)-Alkoxycarbonyl-(d-C6)-alkoxy,Mono (- (C 1 -C 6 ) -alkyl) -amino, mono - ((C 1 -C 6 ) -haloalkyl) -amino, di- (C 1 -C 6 -alkyl-amino, di- ((C 1 -C 6 ) -haloalkyl) -amino, ( (dC 6) alkyl- (CrCeJ-haloalkyO-amino, N - ((C 1 -C 6) alkanoyl) amino, N - ((C r C6) - haloalkanoyl) amino, aminocarbonyl (dC 6 ) -alkyl, MOnO- (C 1 -C 6 ) -alkylaminocarbonyKCrCeJ-alkyl, di (dC 6 ) -alkylaminocarbonyl (CrCe) -alkyl and mono - ((dC 6 ) -alkyl) -aminocarbonyl; C 6 ) -alkoxycarbonyl- (dC 6 ) -alkoxy,
(C3-C8)-Cycloalkyl, (C3-C8)-Cycloalkoxy, (C3-C8)-Cycloalkyl-(d- C6)-alkyl, (Ca-CβJ-CycloalkyKCrCeJ-haloalkyl, (C3-C8)-Cycloalkyl- (CrC6)-alkoxy, (Cs-QO-CycloalkyKd-CeJ-haloalkoxy, (C3-C8)- Cycloalkylcarbonyl, (C3-C8)-Cycloalkoxycarbonyl, (C3-C8)-Cy- cloalkyl-Cd-CeJ-alkylcarbonyUCs-CsJ-Cycloalkyl-CCrCeJ-halo- alkylcarbonyl, (C3-C8)-Cycloalkyl-(CrC6)-alkoxycarbonyl, (C3-C8)- Cycloalkyl-(CrC6)-haloalkoxycarbonyl, (C3-C8)-Cycloalkylcarbo- nyloxy, (C3-C8)-Cycloalkoxycarbonyloxy, (C3-C8)-Cycloalkyl-(d- CβJ-alkylcarbonyloxy, (C3-C8)-Cycloalkyl-(Ci-C6)-halogen- alkylcarbonyloxy, (C3-C8)-Cycloalkyl-(CrC6)-alkoxycarbonyloxy und (C3-C8)-Cycloalkyl-(CrC6)-haloalkoxycarbonyloxy; (C3-C8)-Cycloalkenyl, (C3-C8)-Cycloalkenyloxy, (C3-C8)-Cycloalke- nyl-(Ci-C6)-alkyl, (C3-C8)-Cycloalkenyl-(CrC6)-halogenalkyl, (C3- C8)-Cycloalkenyl-(d-C6)-alkoxy, (C3-C8)-Cycloalkenyl-(CrC6)- halogenalkoxy, (C3-C8)-Cycloalkenylcarbonyl, (C3-C8)-Cycloal- kenyloxycarbonyl, (C3-C8)-Cycloalkenyl-(C1-C6)-alkylcarbonyl, (C3- C8)-Cycloalkenyl-(Ci-C6)-halogenalkylcarbonyl, (C3-C8)-Cyclo- a!keny!-(C-i-C6)-a!koxycarbonyl, (C3-C8)-Cycioaikenyi-(Ci-C6)-ha- loalkoxycarbonyl, (C3-C8)-Cycloalkenylcarbonyloxy, (C3-C8)-Cyclo- alkenyloxycarbonyloxy, (C3-C8)-Cycloalkenyl-(Ci-C6)-alkylcar- bonyloxy, (C3-C8)-Cycloalkenyl-(Ci-C6)-halogenalkylcarbonyloxy, (C3-C8)-Cycloalkenyl-(CrC6)-alkoxycarbonyloxy und (C3-Cs)-Cy- cloalkenyl-(CrC6)-haloalkoxycarbonyloxy; (C3-C8)-Cycloalkylthio, (C3-C8)-Alkenylthio, (C3-C8)-Cycloalkenyl- thio und (C3-C6)-Alkinylthio;(C 3 -C 8 ) -cycloalkyl, (C 3 -C 8 ) -cycloalkoxy, (C 3 -C 8 ) -cycloalkyl- (dC 6 ) -alkyl, (Ca-CβJ -cycloalkyKCrCeJ-haloalkyl, (C 3 -C 8 ) -cycloalkyl- (C r C6) -alkoxy, (Cs-QO-CycloalkyKd-CeJ-haloalkoxy, (C 3 -C 8) - cycloalkylcarbonyl, (C 3 -C 8) -cycloalkoxycarbonyl, (C 3 -C 8) -Cy- cloalkyl-Cd-CeJ-alkylcarbonyUCs-CsJ-cycloalkyl-CCrCeJ-halo-alkylcarbonyl, (C 3 -C 8 ) -cycloalkyl- (CrC 6 ) -alkoxycarbonyl, (C 3 -C 8 ) -cycloalkyl- (CrC 6 ) - haloalkoxycarbonyl, (C 3 -C 8 ) -cycloalkylcarbonyloxy, (C 3 -C 8 ) -cycloalkoxycarbonyloxy, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 6 -alkylcarbonyloxy, (C 3 -C 8 ) -cycloalkyl - (C 1 -C 6 ) -haloalkylcarbonyloxy, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 6) -alkoxycarbonyloxy and (C 3 -C 8 ) -cycloalkyl- (C 1 -C 6 ) -haloalkoxycarbonyloxy; (C 3 -C 8 ) -cycloalkenyl, (C 3 -C 8 ) -cycloalkenyloxy, (C 3 -C 8 ) -cycloalkynyl- (C 1 -C 6 ) -alkyl, (C 3 -C 8 ) -cycloalkenyl- (C 1 -C 6 ) haloalkyl, (C 3 - C 8) cycloalkenyl (d-C6) alkoxy, (C 3 -C 8) cycloalkenyl (C r C6) - haloalkoxy, (C 3 -C 8) -Cycloalkenylcarbonyl, (C 3 -C 8) -Cycloal- alkenyloxycarbonyl, (C 3 -C 8) cycloalkenyl (C 1 -C 6) alkylcarbonyl, (C 3 - C 8) cycloalkenyl (Ci-C 6 ) -haloalkylcarbonyl, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 6 ) -alkoxycarbonyl, (C 3 -C 8 ) -cycloalkyl- (C 1 -C 6 ) -haloalkoxycarbonyl, ( C 3 -C 8 ) -cycloalkenylcarbonyloxy, (C 3 -C 8 ) -cycloalkenyloxycarbonyloxy, (C 3 -C 8 ) -cycloalkenyl- (C 1 -C 6 ) -alkylcarbonyloxy, (C 3 -C 8 ) - Cycloalkenyl- (C 1 -C 6 ) -haloalkylcarbonyloxy, (C 3 -C 8 ) -cycloalkenyl- (C 1 -C 6 ) -alkoxycarbonyloxy and (C 3 -Cs) -cycloalkenyl- (C 1 -C 6 ) -haloalkoxycarbonyloxy; (C 3 -C 8 ) -cycloalkylthio, (C 3 -C 8 ) -alkenylthio, (C 3 -C 8 ) -cycloalkenylthio and (C 3 -C 6 ) -alkynylthio;
Hydroxy-(Ci-C6)-alkyl, Hydroxy-(Ci-C6)-alkoxy, Cyano-(CrC6)- alkoxy und Cyano-(CrC6)-alkyl; 3-Oxetanyloxy-,Hydroxy (Ci-C 6) alkyl, hydroxy (Ci-C 6) alkoxy, cyano (C r C6) - alkoxy and cyano- (CrC 6) alkyl; 3-Oxetanyloxy-,
-C(O)NHR9 oder -C(O)NR9R10, wobei R9 und R10, jeweils unabhängig voneinander, ausgewählt werden aus der Gruppe, bestehend aus Wasserstoff, (CrC6)-Alkyl, (C3-C6)-Cycloalkyl, (Cr C6)-Haloalkyl, oder wo R9 und R10 zusammen eine (Ci-C6)- Alkylen-Gruppe bilden, die ein Sauerstoff-, oder Schwefel-Atom oder ein oder zwei Amino oder (CrCβJ-Alkylamino-Gruppen enthalten kann, wobei-C (O) NHR 9 or -C (O) NR 9 R 10 , wherein R 9 and R 10 are each independently selected from the group consisting of hydrogen, (C 1 -C 6 ) alkyl, (C 3 -) C 6 ) -cycloalkyl, (C r C 6 ) -haloalkyl, or where R 9 and R 10 together form a (Ci-C 6 ) - alkylene group which is an oxygen or sulfur atom or one or two amino or (CrCβJ-alkylamino groups can contain, where
(1 ) die zuvor für R3 bis R7 definierten Reste gegebenenfalls untereinander zyklisch verknüpft sein können, unter der Voraussetzung, dass sie o/t/70-ständig sind; und/oder(1) the radicals previously defined for R 3 to R 7 may optionally be cyclically linked with each other, provided that they are o / t / 70-continuous; and or
(2) zwei ortho-ständige Substituenten zusammen eine (d-Cβ)- Alkylengruppe bilden, die ein oder mehrere Sauerstoff- und/oder Schwefelatome enthalten können, wobei die (C-i-CβJ-Alkylengruppe durch Halogen einfach oder mehrfach substituiert sein kann und die jeweilgen Halogensubstituenten gleich oder verschieden sein können; und/oder(2) two ortho-substituents together form a (d-Cβ) - alkylene group which may contain one or more oxygen and / or sulfur atoms, wherein the (Ci-CβJ-alkylene group may be monosubstituted or polysubstituted by halogen and the each halogen substituent may be the same or different; and / or
(3) die zuvor genannten Reste R1 bis R2 einfach oder mehrfach und unabhängig voneinander durch Reste substituiert sein können, welche ausgewählt sind aus der Gruppe, bestehend aus Halogen und (C-i-Cβ)- Alkyl; und(3) the abovementioned radicals R 1 to R 2 may be mono- or polysubstituted and independently of one another by radicals which are selected from the group consisting of halogen and (C 1 -C 6) -alkyl; and
(4) mindestens ein Rest, ausgewählt aus der Gruppe der Reste R3 bis R7 ungleich Wasserstoff ist,(4) at least one radical selected from the group of radicals R 3 to R 7 is not hydrogen,
wobei die Verbindung 2-[(1 ,3-Benzodioxol-5-ylmethyl)sulfanyl]-4-methyl-1 ,3- oxazol ausgenommen ist.wherein the compound 2 - [(1, 3-benzodioxol-5-ylmethyl) sulfanyl] -4-methyl-1,3-oxazole is excluded.
2. Verbindungen der allgemeinen Formel (I), deren agrochemisch verträglichen Salze oder deren agrochemisch verträglichen quatemierten Stickstoff- Derivate nach Anspruch 1 , dadurch gekennzeichnet, dass der Rest R1 ausgewählt ist aus der Gruppe, bestehend aus Wasserstoff, Halogen, Nitro, Cyano, Carboxyl, (d-C6)-Alkyl, (C3-C6)-Cycloalkyl, (C3-C6)-Cycloalkoxy, (d- C6)-Alkoxy, (CrC6)-Alkylcarbonyl, (C3-C6)-Cycloalkylcarbonyl, (CrC6)- Alkoxycarbonyl, (C3-C6)-Cycloalkoxycarbonyl, Mono-((Ci-C4)-alkyl)-aminocar- bonyl, Di-((Ci-C4)-alkyl)-aminocarbonyl, Mono-((Ci-C4)-alkyl)-aminosulfonyl, Di-((CrC4)-alkyl)-aminosulfonyl, (CrC4)-Alkylthio, (C3-C6)-Cycloalkylthio, (C1- C4)-Alkylsulfinyl, (C3-C6)-Cycloalkylsulfinyl, (CrC4)-Alkylsulfonyl, (C3-C6)- Cycloalkylsulfonyl, (CrC4)-Alkylsulfonyloxy, (C3-C6)-Cycloalkylsulfonyloxy, (C2-C3)-Alkenyl, (C2-C3)-Alkinyl, (C2-C3)-Alkenyloxy, (C2-C3)-Alkinyloxy, - N HCO-(C1 -C3)-Alkyl, -N HCO2-(C1 -C3)-Alkyl, -NHCONH-(d-C3)-Alkyl, - NHSO2-(d-C3)-Alkyl, -OCONH-(CrC3)-Alkyl, -CONHR9, -CONR9R10, wobei R9 und R10 unabhängig voneinander ausgewählt sind aus der Gruppe, bestehend aus Wasserstoff, (Ci-C6)-Alkyl, (C3-C6)-Cycloalkyl und (CrC6)-Haloalkyl; und wobei der Rest R1 einfach oder mehrfach durch Reste substituiert sein kann, welche ausgewählt sind aus der Gruppe, bestehend aus Halogen und (d-C6)-Alkyl.2. Compounds of general formula (I), their agrochemically acceptable salts or their agrochemically compatible quaternized nitrogen derivatives according to claim 1, characterized in that the radical R 1 is selected from the group consisting of hydrogen, halogen, nitro, cyano, carboxyl, (dC 6) alkyl, (C 3 -C 6) -cycloalkyl, (C 3 -C 6) cycloalkoxy, (dC 6) alkoxy, (C r C6) alkylcarbonyl, (C 3 -C 6) cycloalkylcarbonyl, (C r C6) - alkoxycarbonyl, (C 3 -C 6) cycloalkoxycarbonyl, mono - ((Ci-C 4) alkyl) -aminocar- bonyl, di - ((Ci-C 4) -alkyl) aminocarbonyl, mono - ((Ci-C4) -alkyl) aminosulfonyl, di - ((CrC 4) alkyl) aminosulfonyl, (C r C4) alkylthio, (C 3 -C 6) -cycloalkylthio, (C 1 - C 4) alkylsulfinyl, (C 3 -C 6) cycloalkylsulfinyl, (C r C 4) alkylsulfonyl, (C 3 -C 6) - cycloalkylsulfonyl, (C r C 4) Alkylsulfonyloxy, (C 3 -C 6 ) -cycloalkylsulfonyloxy, (C 2 -C 3 ) alkenyl, (C 2 -C 3 ) alkynyl, (C 2 -C 3 ) alkenyloxy, (C 2 -C 3 ) alkynyloxy, -N HCO- (C 1 -C 3 ) -Alkyl, -NHCO 2 - (C 1 -C 3 ) -alkyl, -NHCONH- (dC 3 ) -alkyl, - NHSO 2 - (dC 3 ) -alkyl, -OCONH- (C r C 3 ) - Alkyl, -CONHR 9 , -CONR 9 R 10 , wherein R 9 and R 10 are independently selected from the group consisting of hydrogen, (Ci-C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl and ( CrC 6 ) haloalkyl; and wherein the radical R 1 may be monosubstituted or polysubstituted by radicals selected from the group consisting of halogen and (C 1 -C 6 ) -alkyl.
3. Verbindungen der allgemeinen Formel (I), deren agrochemisch verträglichen Salze oder deren agrochemisch verträglichen quaternierten Stickstoff- Derivate nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Rest R2 ausgewählt ist aus der Gruppe, bestehend aus Wasserstoff, Halogen, Nitro, Cyano, Carboxyl, (d-C6)-Alkyl, (C3-C6)-Cycloalkyl, (C3-C6)-Cycloalkoxy, (C1- C6)-Alkoxy, (CrC6)-Alkylcarbonyl, (C3-C6)-Cycloalkylcarbonyl, (C1-C6)- Alkoxycarbonyl, (Cs-C-eJ-Cycloalkoxycarbonyl, Mono-((C1-C4)-a!kyl)-aminocar- bonyl, Di-((CrC4)-alkyl)-aminocarbonyl, Mono-((CrC4)-alkyl)-aminosulfonyl, Di-((CrC4)-alkyl)-aminosulfonyl, (d-C4)-Alkylthio, (C3-C6)-Cycloalkylthio, (C1- C4)-Alkylsulfinyl, (C3-C6)-Cycloalkylsulfinyl, (CrC4)-Alkylsulfonyl, (C3-C6)- Cycloalkylsulfonyl, (d-dJ-Alkylsulfonyloxy, (C3-C6)-Cycloalkylsulfonyloxy, (C2-C3)-Alkenyl, (C2-C3)-Alkinyl, (C2-C3)-Alkenyloxy, (C2-C3)-Alkinyloxy, - NHCO-(Ci-C3)-Alkyl, -NHCO2-(d-C3)-Alkyl, -NHCONH-td-CcO-Alkyl, - NHSO2-(CrC3)-Alkyl, -OCONH-(CrC3)-Alkyl, -CONHR9,3. Compounds of general formula (I), their agrochemically acceptable salts or their agrochemically compatible quaternized nitrogen derivatives according to claim 1 or 2, characterized in that the radical R 2 is selected from the group consisting of hydrogen, halogen, nitro, cyano, carboxyl, (dC 6) alkyl, (C 3 -C 6) -cycloalkyl, (C 3 -C 6) cycloalkoxy, (C 1 - C 6) alkoxy, (C r C6) alkylcarbonyl, (C 3 -C 6 ) -cycloalkylcarbonyl, (C 1 -C 6 ) -alkoxycarbonyl, (Cs-C-eJ-cycloalkoxycarbonyl, mono - ((C 1 -C 4 ) -alkyl) -aminocarbonyl, di - ((C 1 -C 4 ) -alkyl) -aminocarbonyl, mono - ((C 1 -C 4 ) -alkyl) -aminosulfonyl, di- ((C 1 -C 4 ) -alkyl) -aminosulfonyl, (C 1 -C 4 ) -alkylthio, (C 3 -C 6 ) cycloalkylthio, (C 1 - C 4) alkylsulfinyl, (C 3 -C 6) cycloalkylsulfinyl, (CrC 4) alkylsulfonyl, (C 3 -C 6) - cycloalkylsulfonyl, (d-dj-alkylsulfonyloxy, (C 3 -C 6 ) -cycloalkylsulfonyloxy, (C 2 -C 3 ) -alkenyl, (C 2 -C 3 ) -alkynyl, (C 2 -C 3 ) -alkenyloxy, (C 2 -C 3 ) -alkynyloxy, -NHCO - (C 1 -C 3 ) -alkyl , -NHCO 2 - (dC 3 ) -alkyl, -NHCONH-td-CcO-alkyl, - NHSO 2 - (C r C 3 ) -alkyl, -OCONH- (C r C 3 ) -alkyl, -CONHR 9 ,
-CONR9R10, wobei R9 und R10 unabhängig voneinander ausgewählt sind aus der Gruppe, bestehend aus Wasserstoff, (d-C6)-Alkyl, (C3-C6)-Cycloalkyl und (d-C6)-Haloalkyl; und wobei der Rest R2 einfach oder mehrfach durch Reste substituiert sein kann, welche ausgewählt sind aus der Gruppe, bestehend aus Halogen und (d-C6)-Alkyl.-CONR 9 R 10 wherein R 9 and R 10 are independently selected from the group consisting of hydrogen, (dC 6) alkyl, (C 3 -C 6) cycloalkyl, and (dC 6) -haloalkyl; and wherein the radical R 2 may be monosubstituted or polysubstituted by radicals selected from the group consisting of halogen and (C 1 -C 6 ) -alkyl.
4. Verbindungen der allgemeinen Formel (I), deren agrochemisch verträglichen Salze oder deren agrochemisch verträglichen quaternierten Stickstoff- Derivate nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Rest R3 ausgewählt ist aus der Gruppe, bestehend aus Wasserstoff, Hydroxy, Halogen, Cyano, Nitro, Amino, C(O)OH, (CrC4)-Alkyl, (C3-C6)- Cycloalkyl, (CrC4)-Haloalkyl, (C1-C4J-AIkOXy, (CrC4)-Haloalkoxy, (C1-C4)- Alkoxy-(CrC2)-alkyl, (CrC3)-Alkylcarbonyl, (CrC^-Alkylcarbonyloxy, (C1-C4)- Alkoxycarbonyl, (C3-C6)-Cycloalkoxycarbonyl, (C3-C6)-Cycloalkyl-(C1-C2)- alkoxy, (C3-C6)-Cycloalkoxy, (C1-C4)-Alkoxycarbonyl-(C1-C2)-alkoxy, (C3-C4)- Alkenyloxy, (C3-C4)-Alkinyloxy, (Ci-C4)-Alkylthio, (d-C^-Haloalkylthio, (C1- C4)-Alkylsulfinyl, (CrC4)-Haloalkylsulfinyl, (d-C^Alkylsulfonyl, (C1-C4)- Haloalkylsulfonyl, (CrC4)-Alkylsulfonyloxy, Di-(CrC4)-Alkylamino, (C3-C4)- Alkenyloxycarbonyl, (C2-C4)-Alkinyloxycarbonyl, Formyl, (C2-C4)-Alkenyl, (C2- C4)-Alkinyl, -C(O)NR9R10, wobei R9 und R10, unabhängig voneinander, ausgewählt sind aus der Gruppe, bestehend aus Wasserstoff, (Ci-C6)-Alkyl, (C3-C6)-Cycloalkyl, (d-CβJ-Haloalkyl, oder worin R9 und R10 zusammen eine (CrC6)-Alkylen-Gruppe bilden, die ein Sauerstoff- oder Schwefel-Atom oder ein oder zwei Amino- oder (CrC6)-Alkylamino-Gruppen enthalten kann.4. Compounds of general formula (I), their agrochemically acceptable salts or their agrochemically compatible quaternized nitrogen derivatives according to one of claims 1 to 3, characterized in that R 3 is selected from the group consisting of hydrogen, hydroxy, halogen, cyano, nitro, amino, C (O) OH, (C r C4) alkyl, (C 3 -C 6) - cycloalkyl, ( C r C 4) -haloalkyl, (C 1 -C 4 J -alkoxy, (C r C 4) -haloalkoxy, (C 1 -C 4) - alkoxy (-C 2) alkyl, (C r C 3) Alkylcarbonyl, (C 1 -C 4 ) -alkylcarbonyloxy, (C 1 -C 4 ) -alkoxycarbonyl, (C 3 -C 6 ) -cycloalkoxycarbonyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 2 ) -alkoxy, ( C 3 -C 6 ) -cycloalkoxy, (C 1 -C 4 ) -alkoxycarbonyl- (C 1 -C 2 ) -alkoxy, (C 3 -C 4 ) -alkenyloxy, (C 3 -C 4 ) -alkynyloxy, ( Ci-C 4) alkylthio, (^ dC haloalkylthio, (C 1 - C 4) alkylsulfinyl, (CrC 4) haloalkylsulfinyl, (dC ^ alkylsulfonyl, (C 1 -C 4) - haloalkylsulfonyl, (C r C 4) alkylsulfonyloxy, di- (C r C 4) alkylamino, (C 3 -C 4) - alkenyloxycarbonyl, (C 2 -C 4) alkynyloxycarbonyl, formyl, (C2 -C4) alkenyl, (C 2 -C 4 ) -alkynyl, -C (O) NR 9 R 10 , where R 9 and R 10 , independently of one another, are selected from the group consisting of hydrogen, (C 1 -C 6 ) -alkyl, ( C 3 -C 6 ) -cycloalkyl, (d-CβJ-haloalkyl or wherein R 9 and R 10 together form a (CrC 6 ) -alkylene group which is an oxygen or sulfur atom or one or two amino or (CrC 6 ) -Alkylamino groups may contain.
5. Verbindungen der allgemeinen Formel (I), deren agrochemisch verträglichen Salze oder deren agrochemisch verträglichen quaternierten Stickstoff- Derivate nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Rest R4 ausgewählt ist aus der Gruppe, bestehend aus Wasserstoff, Hydroxy, Halogen, Cyano, Nitro, Amino, C(O)OH, (CrC4)-Alkyl, (C3-C6)- Cycloalkyl, (CrC4)-Haloalkyl, (CrC4)-Alkoxy, (C1-C4J-HaIOaIkOXy, (C1-C4)- Alkoxy-(CrC2)-alkyl, (CrC3)-Alkylcarbonyl, (d-C3)-Alkylcarbonyloxy, (C1-C4)- Alkoxycarbonyl, (C3-C6)-Cycloalkoxycarbonyl, (C3-C6)-Cycloalkyl-(Ci-C2)- alkoxy, (C3-C6)-Cycloalkoxy, (C1-C4)-Alkoxycarbonyl-(C1-C2)-alkoxy, (C3-C4)- Alkenyloxy, (C3-C4)-Alkinyloxy, (CrC4)-Alkylthio, (CrC4)-Haloalkylthio, (C1- C4)-Alkylsulfinyl, (d-C4)-Haloalkylsulfinyl, (CrC4)-Alkylsulfonyl, (C1-C4)- Haloalkylsulfonyl, (CrC4)-Alkylsulfonyloxy, Di-(d-C4)-Alkylamino, (C3-C4)- Alkenyloxycarbonyl, (C2-C4)-Alkinyloxycarbonyl, Formyl, (C2-C4)-Alkenyl, (C2- C4)-Alkinyl, -C(O)NR9R10, wobei R9 und R10, unabhängig voneinander, ausgewählt sind aus der Gruppe, bestehend aus Wasserstoff, (CrC6)-Alkyl, (C3-C6)-Cycloalkyl, (CrCβJ-Haloalkyl, oder worin R9 und R10 zusammen eine (CrCβJ-Alkylen-Gruppe bilden, die ein Sauerstoff- oder Schwefel-Atom oder ein oder zwei Amino- oder (Ci-C6)-Alkylamino-Gruppen enthalten kann.5. Compounds of general formula (I), their agrochemically acceptable salts or their agrochemically compatible quaternized nitrogen derivatives according to one of claims 1 to 4, characterized in that the radical R 4 is selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C (O) OH, (C r C4) alkyl, (C 3 -C 6) - cycloalkyl, (C r C4) -haloalkyl, (C r C4) alkoxy , (C 1 -C 4 J-HaIOaIkOXy, (C 1 -C 4) - alkoxy (-C 2) alkyl, (C r C 3) alkylcarbonyl, (dC 3) alkylcarbonyloxy, (C 1 -C 4 ) - alkoxycarbonyl, (C 3 -C 6 ) -cycloalkoxycarbonyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 2 ) -alkoxy, (C 3 -C 6 ) -cycloalkoxy, (C 1 -C 4 ) alkoxycarbonyl (C 1 -C 2) alkoxy, (C 3 -C 4) - alkenyloxy, (C 3 -C 4) alkynyloxy, (C r C4) alkylthio, (C r C4) haloalkylthio , (C 1 - C 4) alkylsulfinyl, (dC 4) haloalkylsulfinyl, (C r C4) -alkylsulfonyl, (C 1 -C 4) - haloalkylsulfonyl, (C r C4) alkylsulfonyloxy, di- (dC 4 ) -alkylamino, (C 3 -C 4 ) -alkenyloxyca rbonyl, (C 2 -C 4 ) -alkynyloxycarbonyl, formyl, (C 2 -C 4 ) -alkenyl, (C 2 -C 4 ) -alkynyl, -C (O) NR 9 R 10 , wherein R 9 and R 10 , independently of one another, are selected from the group consisting of hydrogen, (CrC 6) alkyl, (C 3 -C 6) cycloalkyl, (CrCβJ-haloalkyl, or R 9 and R 10 together form a Form (CrCβJ alkylene group which may contain an oxygen or sulfur atom or one or two amino or (Ci-C 6 ) alkylamino groups.
6. Verbindungen der allgemeinen Formel (I), deren agrochemisch verträglichen Salze oder deren agrochemisch verträglichen quaternierten Stickstoff- Derivate nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Rest R5 ausgewählt ist aus der Gruppe, bestehend aus Wasserstoff, Hydroxy, Halogen, Cyano, Nitro, Amino, C(O)OH, (CrC4)-Alkyl, (C3-C6)- Cycloalkyl, (d-C4)-Haloalkyl, (C1-C4J-AIkOXy, (C1-C4J-HaIOaIkOXy, (C1-C4)- Alkoxy-(C1-C2)-alkyl, (CrC3)-Alkylcarbonyl, (CrC3)-Alkylcarbonyloxy, (Ci-C4)- Alkoxycarbonyl, (C3-C6)-Cycloalkoxycarbonyl, (C3-C6)-Cycloalkyl-(Ci-C2)- alkoxy, (C3-C6)-Cycloalkoxy, (CrOO-AlkoxycarbonyKC^J-alkoxy, (C3-C4)- Alkenyloxy, (C3-C4)-Alkinyloxy, (CrC^-Alkylthio, (CrC4)-Haloalkylthio, (C1- C4)-Alkylsulfinyl, (CrC4)-Haloalkylsulfinyl, (CrC4)-Alkylsulfonyl, (C1-C4)- Haloalkylsulfonyl, (CrC4)-Alkylsulfonyloxy, Di-(C1-C4)-Alkylamino, (C3-C4)- Alkenyloxycarbonyl, (C2-C4)-A!kiny!oxycarbonyl, Formyl, (C2-C4)-Aikenyi, (C2- C4)-Alkinyl, -C(O)NR9R10, wobei R9 und R10, unabhängig voneinander, ausgewählt sind aus der Gruppe, bestehend aus Wasserstoff, (CrCβJ-Alkyl, (C3-C6)-Cycloalkyl, (CrCβJ-Haloalkyl, oder worin R9 und R10 zusammen eine (C-ι-C6)-Alkylen-Gruppe bilden, die ein Sauerstoff- oder Schwefel-Atom oder ein oder zwei Amino- oder (C-i-CβJ-Alkylamino-Gruppen enthalten kann.6. Compounds of general formula (I), their agrochemically acceptable salts or their agrochemically compatible quaternized nitrogen derivatives according to one of claims 1 to 5, characterized in that the radical R 5 is selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C (O) OH, (CrC 4) alkyl, (C 3 -C 6) - cycloalkyl, (dC 4) -haloalkyl, (C 1 -C 4 J -alkoxy, (C J-1 -C 4 HaIOaIkOXy, (C 1 -C 4) - alkoxy- (C 1 -C 2) alkyl, (CrC 3) alkylcarbonyl, (CrC 3) alkylcarbonyloxy, (Ci-C4) - alkoxycarbonyl , (C 3 -C 6 ) -cycloalkoxycarbonyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 2 ) -alkoxy, (C 3 -C 6 ) -cycloalkoxy, (C 1 -C -alkoxycarbonyKC 1, -J-alkoxy, ( C 3 -C 4) - alkenyloxy, (C 3 -C 4) alkynyloxy, (CrC ^ alkylthio, (C r C4) haloalkylthio, (C 1 - C 4) alkylsulfinyl, (C r C 4) haloalkylsulfinyl, (C r C4) -alkylsulfonyl, (C 1 -C 4) - haloalkylsulfonyl, (C r C4) -alkylsulfonyloxy, di- (C 1 -C 4) alkylamino, (C 3 -C 4) Alkenyloxycarbonyl, (C 2 -C 4 ) Alkyloxycarbonyl, formyl, (C 2 -C 4 ) -alkyl, (C 2 -C 4 ) -alkynyl, -C (O) NR 9 R 10 , where R 9 and R 10 , independently of one another, are selected from the group consisting of hydrogen, (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (C 1 -C 6 -haloalkyl, or in which R 9 and R 10 together form a (C 1 -C 6 ) -alkylene Form a group which may contain an oxygen or sulfur atom or one or two amino or (Ci-CβJ-alkylamino groups.
7. Verbindungen der allgemeinen Formel (I), deren agrochemisch verträglichen Salze oder deren agrochemisch verträglichen quaternierten Stickstoff- Derivate nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass der Rest R6 ausgewählt ist aus der Gruppe, bestehend aus Wasserstoff, Hydroxy, Halogen, Cyano, Nitro, Amino, C(O)OH, (CrC4)-Alkyl, (C3-C6)- Cycloalkyl, (CrC4)-Haloalkyl, (CrC4)-Alkoxy, (CrC4)-Haloalkoxy, (C1-C4)- Alkoxy-(C-ι-C2)-alkyl, (CrC3)-Alkylcarbonyl, (CrC3)-Alkylcarbonyloxy, (C1-C4)- Alkoxycarbonyl, (C3-C6)-Cycloalkoxycarbonyl, (C3-C6)-Cycloalkyl-(Ci-C2)- alkoxy, (C3-C6)-Cycloalkoxy, (C1-C4)-Alkoxycarbonyl-(C1-C2)-alkoxy, (C3-C4)- Alkenyloxy, (C3-C4)-Alkinyloxy, (CrC4)-Alkylthio, (CrC4)-Haloalkylthio, (C1- C4)-Alkylsulfinyl, (Ci-C4)-Haloalkylsulfinyl, (d-C4)-Alkylsulfonyl, (C1-C4)- Haloalkylsulfonyl, (CrC4)-Alkylsulfonyloxy, Di-(CrC4)-Alkylamino, (C3-C4)- Alkenyloxycarbonyl, (C2-C4)-Alkinyloxycarbonyl, Formyl, (C2-C4)-Alkenyl, (C2- C4)-Alkinyl, -C(O)NR9R10, wobei R9 und R10, unabhängig voneinander, ausgewählt sind aus der Gruppe, bestehend aus Wasserstoff, (d-C6)-Alkyl, (C3-C6)-Cycloalkyl, (CrC6)-Haloalkyl, oder worin R9 und R10 zusammen eine (C-rCβJ-Alkylen-Gruppe bilden, die ein Sauerstoff- oder Schwefel-Atom oder ein oder zwei Amino- oder (CrC-6)-Alkylamino-Gruppen enthalten kann.7. Compounds of general formula (I), their agrochemically acceptable salts or their agrochemically compatible quaternized nitrogen derivatives according to one of claims 1 to 6, characterized in that the radical R 6 is selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C (O) OH, (CrC 4) alkyl, (C 3 -C 6) - cycloalkyl, (C r C4) -haloalkyl, (C r C4) alkoxy, ( C r C 4) -haloalkoxy, (C 1 -C 4) - alkoxy- (C-ι-C 2) alkyl, (C r C 3) alkylcarbonyl, (C r C 3) alkylcarbonyloxy, (C 1 -C 4 ) - alkoxycarbonyl, (C 3 -C 6 ) -cycloalkoxycarbonyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 2 ) -alkoxy, (C 3 -C 6 ) -cycloalkoxy, (C 1 - C 4) alkoxycarbonyl (C 1 -C 2) alkoxy, (C 3 -C 4) - alkenyloxy, (C 3 -C 4) alkynyloxy, (C r C4) alkylthio, (C r C 4 ) Haloalkylthio, (C 1 - C 4) alkylsulfinyl, (Ci-C4) haloalkylsulfinyl, (dC 4) -alkylsulfonyl, (C 1 -C 4) - haloalkylsulfonyl, (C r C4) -alkylsulfonyloxy, di- (C r C4) alkylamino , (C 3 -C 4 ) -alkenyloxycarbonyl, (C 2 -C 4 ) -alkynyloxycarbonyl, formyl, (C 2 -C 4 ) -alkenyl, (C 2 -C 4 ) -alkynyl, -C (O) NR 9 R 10 wherein R 9 and R 10, independently of one another, are selected from the group consisting of hydrogen, (dC 6) alkyl, (C 3 -C 6) -cycloalkyl, (CrC 6) haloalkyl, or R 9 and R 10 together form a (C 1 -C 6 ) alkylene group which may contain an oxygen or sulfur atom or one or two amino or (C 1 -C 6 ) alkylamino groups.
8. Verbindungen der allgemeinen Formel (I), deren agrochemisch verträglichen Salze oder deren agrochemisch verträglichen quaternierten Stickstoff- Derivate nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass der Rest R7 ausgewählt ist aus der Gruppe, bestehend aus Wasserstoff, Hydroxy, Halogen, Cyano, Nitro, Amino, C(O)OH, (Ci-C4)-Alkyl, (C3-C6)- CycloalkyL (CrC4)-Haloalkyl, (Ci-C4)-A!koxy, (d-C4)-Haioaikoxy, (C1-C4)- Alkoxy-(Ci-C2)-alkyl, (CrC3)-Alkylcarbonyl, (d-C3)-Alkylcarbonyloxy, (C1-C4)- Alkoxycarbonyl, (C3-C6)-Cycloalkoxycarbonyl, (C3-C6)-Cycloalkyl-(C1-C2)- alkoxy, (C3-C6)-Cycloalkoxy, (C1-C4)-Alkoxycarbonyl-(C1-C2)-alkoxy, (C3-C4)- Alkenyloxy, (C3-C4)-Alkinyloxy, (d-C4)-Alkylthio, (C1-C4)-Haloalkylthio, (C1- C4)-Alkylsulfinyl, (CrC4)-Haloalkylsulfinyl, (d-C4)-Alkylsulfonyl, (C1-C4)- Haloalkylsulfonyl, (d-C4)-Alkylsulfonyloxy, Di-(d-C4)-Alkylamino, (C3-C4)- Alkenyloxycarbonyl, (C2-C4)-Alkinyloxycarbonyl, Formyl, (C2-C4)-Alkenyl, (C2- C4)-Alkinyl, -C(O)NR9R10, wobei R9 und R10, unabhängig voneinander, ausgewählt sind aus der Gruppe, bestehend aus Wasserstoff, (CrC6)-Alkyl, (C3-C6)-Cycloalkyl, (d-C6)-Haloalkyl, oder worin R9 und R10 zusammen eine (d-C6)-Alkylen-Gruppe bilden, die ein Sauerstoff- oder Schwefel-Atom oder ein oder zwei Amino- oder (CrCβJ-Alkylamino-Gruppen enthalten kann.8. Compounds of general formula (I), their agrochemically acceptable salts or their agrochemically compatible quaternized nitrogen derivatives according to one of claims 1 to 7, characterized in that the radical R 7 is selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C (O) OH, (Ci-C 4) -alkyl, (C 3 -C 6) - cycloalkyl (CrC 4) -haloalkyl, (Ci-C 4) -alkoxy -A! (dC 4) -Haioaikoxy, (C 1 -C 4) - alkoxy- (Ci-C 2) alkyl, (C r C 3) alkylcarbonyl, (dC 3) alkylcarbonyloxy, (C 1 -C 4) - Alkoxycarbonyl, (C 3 -C 6 ) -cycloalkoxycarbonyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 2 ) -alkoxy, (C 3 -C 6 ) -cycloalkoxy, (C 1 -C 4 ) - alkoxycarbonyl (C 1 -C 2) alkoxy, (C 3 -C 4) - alkenyloxy, (C 3 -C 4) alkynyloxy, (dC 4) alkylthio, (C 1 -C 4) haloalkylthio, ( C 1 - C 4) alkylsulfinyl, (CrC 4) haloalkylsulfinyl, (dC 4) -alkylsulfonyl, (C 1 -C 4) - haloalkylsulfonyl, (dC 4) alkylsulfonyloxy, di- (dC 4) alkylamino, ( C 3 -C 4 ) -alkenyloxycarbonyl, (C 2 -C 4 ) alkynyloxycarbonyl, formyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, -C (O) NR 9 R 10 , wherein R 9 and R 10 are independently selected are selected from the group consisting of hydrogen, (CrC 6) alkyl, (C 3 -C 6) -cycloalkyl, (dC 6) haloalkyl, or wherein R 9 and R 10 together form a (dC 6) alkylene group form, which may contain an oxygen or sulfur atom or one or two amino or (CrCβJ-alkylamino groups.
9. Verbindungen nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass in der allgemeinen Formel n gleich 1 ist. 9. Compounds according to one of claims 1 to 8, characterized in that n is 1 in the general formula.
10. Verbindungen nach Anspruch 9, dadurch gekennzeichnet, dass die Verbindung der allgemeinen Formel (I) mit n = 1 mit einer (R)- oder (S)- Konfiguration mit einer stereochemischen Reinheit von über 50 % bis 100 % vorliegt.10. Compounds according to claim 9, characterized in that the compound of the general formula (I) with n = 1 with an (R) - or (S) - configuration with a stereochemical purity of over 50% to 100% is present.
11. Verfahren zur Herstellung einer Verbindung der allgemeinen Formel (IM) oder einer Verbindung der allgemeinen Formel (IV), worin R1, R2, R3, R4, R5, R6, R7, die gemäß Formel (I) zuvor angegebenen Bedeutungen haben,11. A process for the preparation of a compound of the general formula (III) or a compound of the general formula (IV) in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , which according to formula (I ) have previously given meanings,
( IV )(IV)
dadurch gekennzeichnet, dass ein Thioether der allgemeinen Formel (II),characterized in that a thioether of the general formula (II),
worin R1, Rz, Rά, R4, Rb, Rb, R' die gemäß Formel (I) zuvor angegebenen Bedeutungen haben, mit einem Äquivalent eines Oxidationsmittels zu den optisch aktiven Sulfoxiden (IM) oxidiert wird, für die n die Zahl 1 bedeutet, oder mit zwei Äquivalenten eines Oxidationsmittels zu den Sulfonen (IV) oxidiert wird, für die n die Zahl 2 bedeutet.wherein R 1 , R z , R ά , R 4 , R b , R b , R 'are as defined above according to formula (I) Have oxidized with one equivalent of an oxidizing agent to the optically active sulfoxides (IM), for which n is the number 1, or is oxidized with two equivalents of an oxidizing agent to the sulfones (IV), for which n is the number 2.
12. Verfahren zur Herstellung eins Thioethers der allgemeinen Formel (II)12. Process for the preparation of a thioether of the general formula (II)
worin R1, R2, R3, R4, R5, R6 und R7 die gemäß einem der Ansprüche 1 bis 8 aufweisenden Bedeutungen haben, gemäß einem der folgenden Verfahren:wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 have the meanings according to one of claims 1 to 8, according to one of the following processes:
(a) Umsetzung von 2-Mercaptooxazol oder einem Oxazol-2(3H)-thion oder einem Salz davon(a) Reaction of 2-mercaptooxazole or an oxazole-2 (3H) -thione or a salt thereof
( V ) M = Alkali-, Erdalkalimetall worin R1, R2 die gemäß einem der Ansprüche 1 bis 8 aufweisenden Bedeutungen haben, mit einem Benzyl-Derivat der allgemeinen Formel (VI) (V) M = alkali metal, alkaline earth metal in which R 1 , R 2 have the meanings according to one of Claims 1 to 8, with a benzyl derivative of the general formula (VI)
( VI )(VI)
worin R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben und Lg eine Abgangsgruppe bedeutet, in Gegenwart einer Alkali- oder Erdalkalimetall-Base oder einer organischen Base in einem Lösemittel;wherein R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given in formula (I) above and Lg is a leaving group, in the presence of an alkali or alkaline earth metal base or an organic base in a solvent;
(b) Umsetzung eines Oxazol-Derivates der allgemeinen Formel (VII),(b) reaction of an oxazole derivative of the general formula (VII),
worin R1, R2 die gemäß einem der Ansprüche 1 bis 8 aufweisenden Bedeutungen haben und Lg' eine Abgangsgruppe bedeutet mit einem Benzyl- Imidothiocarbamat-Salz der allgemeinen Formel (VIII)in which R 1 , R 2 have the meanings according to one of Claims 1 to 8 and Lg ' denotes a leaving group with a benzyl-imidothiocarbamate salt of the general formula (VIII)
( VIII )(VIII)
worin R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebene Bedeutungen haben, Lg eine Abgangsgruppe bedeutet, in einem Eintopfverfahren in Gegenwart einer wäßrigen Alkali- oder Erdalkalimetall- Base oder einer Alkalimetall- oder Erdalkalimetall-Carbonatbase und eines Lösemittels;in which R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given above according to formula (I), Lg represents a leaving group, in a one-pot process in the presence of an aqueous alkali metal or alkaline earth metal Base or an alkali metal or alkaline earth metal carbonate base and a solvent;
(c) Umsetzung eines Oxazol-Derivats der allgemeinen Formel (VII),(c) reacting an oxazole derivative of general formula (VII),
worin R1, R2 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben und Lg' eine Abgangsgruppe bedeutet mit einem Benzyl-Imidothiocarbamat- SaIz (Isothiuroniumsalz) der allgemeinen Formel (VIII) in which R 1 , R 2 have the meanings given above according to formula (I) and Lg ' denotes a leaving group with a benzyl-imidothiocarbamate salt (isothiuronium salt) of the general formula (VIII)
( VIII )(VIII)
worin R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebene Bedeutungen haben, Lg eine Abgangsgruppe bedeutet, in einem Eintopfverfahren in Gegenwart einer Alkalimetall- oder Erdalkalimetall- Carbonatbase und eines Lösemittels;wherein R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given in formula (I) above, Lg represents a leaving group, in a one-pot process in the presence of an alkali metal or alkaline earth metal carbonate base and a solvent;
(d) Umsetzung eines Oxazol-Derivats der allgemeinen Formel (VII),(d) reacting an oxazole derivative of general formula (VII),
( VII ) worin R1, R2 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben und Lg' eine Abgangsgruppe bedeutet mit einem Benzyl-Mercaptan der allgemeinen Formel (IX),(VII) in which R 1 , R 2 have the meanings given above according to formula (I) and Lg ' denotes a leaving group with a benzyl mercaptan of the general formula (IX),
( IX )(IX)
worin R3, R4, R5, R6, R7 die oben gemäß der allgemeinen Formel (I) zuvor angegebene Bedeutung haben in Gegenwart einer Alkali- oder Erdalkalimetall-Baseoder organischen Baseoptional in einem Lösemittel;wherein R 3 , R 4 , R 5 , R 6 , R 7 have the meaning given above according to the general formula (I) above in the presence of an alkali or alkaline earth metal base or organic base optionally in a solvent;
(e) Umsetzung eines Oxazol-Derivats der allgemeinen Formel (X),(e) reacting an oxazole derivative of the general formula (X)
worin R2, R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebene Bedeutungen haben, gemäß nachstehendem Formelschema:in which R 2 , R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given above according to formula (I), according to the following formula scheme:
wobei die Verbindungen der allgemeinen Formel (X) mit einem halogenierenden Mitteloder mit einen Nitrierungsmittelbehandelt und in geeigneten Lösemittel zu Verbindungen der Formel (II) umgesetzt werden;wherein the compounds of general formula (X) having a halogenating agent or with a nitrating agent and reacted in suitable solvents to give compounds of formula (II);
(f) Umsetzung eines Oxazol-Derivats der allgemeinen Formel (Xl),(f) reaction of an oxazole derivative of the general formula (XI),
hergestellt aus einem Oxazol-Derivat der allgemeinen Formel (V), durch Umsetzung mit einem Alkylierungsmittel R12Lg', worin R2 die gemäß Formel (I) zuvor angegebenen Bedeutungen hat, R12 bevorzugt (Ci-C6)-Alkyl, welches unsubstituiert oder durch einen oder mehrere, gleiche oder verschiedene Reste aus der Gruppe Halogen substituiert ist bedeutet und Lg' eine Abgangsgruppe bedeutet, mit einer starken Base und einem Alkylierungsmittel R1Lg', worin R1 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben, nach dem Schema prepared from an oxazole derivative of general formula (V), by reaction with an alkylating agent R 12 Lg ' , wherein R 2 has the meanings given in formula (I) above, R 12 is preferably (Ci-C 6 ) alkyl, which is unsubstituted or substituted by one or more identical or different radicals from the group halogen and Lg 'is a leaving group, with a strong base and an alkylating agent R 1 Lg ' , wherein R 1 have the meanings given in formula (I) above , according to the scheme
( Xl ) ( XII ) n(XI) (XII) n
worin R1, R2, R3, R4, R5, R6, R7 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben und Lg bzw. Lg' eine Abgangsgruppe bedeutet;wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 have the meanings given above according to formula (I) and Lg or Lg 'is a leaving group;
(g) Umsetzung eines Benzyldisulfid-Derivats der allgemeinen Formel (XV) mit 2- Amino-oxazolen der Formel (XIV) und einem Diazotierungsmittel wie in folgendem Schema dargestellt,(g) reacting a benzyl disulfide derivative of general formula (XV) with 2-amino-oxazoles of formula (XIV) and a diazotizing agent as shown in the following scheme,
worin R1, R2, R3, R4, R5 die gemäß Formel (I) zuvor angegebenen Bedeutungen haben. wherein R 1 , R 2 , R 3 , R 4 , R 5 have the meanings given in formula (I) above.
13. Verfahren nach Anspruch 11 , dadurch gekennzeichnet, dass die Verbindung der allgemeinen Formel (II), welche gemäß dem Verfahren nach Anspruch 12 erhalten wird, als Ausgangsverbindung in dem Verfahren nach Anspruch 11 eingesetzt wird.13. The method according to claim 11, characterized in that the compound of general formula (II), which is obtained according to the method of claim 12, is used as starting compound in the process according to claim 11.
14. Zusammensetzungen, enthaltend mindestens eine Verbindung der allgemeinen Formel (I) gemäß einem der Ansprüche 1 bis 8.14. Compositions comprising at least one compound of the general formula (I) according to one of claims 1 to 8.
15. Zusammensetzung nach Anspruch 14, dadurch gekennzeichnet, dass die Zusammensetzung mindestens einen weiteren Wirkstoff umfasst, welcher ausgewählt ist aus der Gruppe, bestehend aus mindestens einem weiteren Herbizid und mindestens einem Safener.A composition according to claim 14, characterized in that the composition comprises at least one further active ingredient which is selected from the group consisting of at least one further herbicide and at least one safener.
16. Verwendung der Verbindungen der allgemeinen Formel (I) gemäß einem der Ansprüche 1 bis 8 als Pflanzenwachstumsregulatoren.16. Use of the compounds of general formula (I) according to any one of claims 1 to 8 as plant growth regulators.
17. Verwendung der Zusammensetzungen gemäß Anspruch 15 oder 16 als Pflanzenwachstumsregulatoren.17. Use of the compositions according to claim 15 or 16 as plant growth regulators.
18. Verwendung nach Anspruch 16 oder 17 zur Pflanzenbekämpfung in speziellen Pflanzenkulturen oder als Pflanzenschutzregulator. 18. Use according to claim 16 or 17 for plant control in specific crops or as a plant protection regulator.
EP09735369A 2008-04-22 2009-04-15 2-(benzylsulfonyl)-oxazole derivatives, chiral 2- (benzylsulfinyl) -oxazole derivatives and 2-(benzylsulfanyl)-oxazole derivatives, methods for the production thereof, and use thereof as herbicides and plant growth regulators Withdrawn EP2294058A1 (en)

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PCT/EP2009/002741 WO2009129953A1 (en) 2008-04-22 2009-04-15 2-(benzylsulfonyl)-oxazole derivatives, chiral 2- (benzylsulfinyl) -oxazole derivatives and 2-(benzylsulfanyl)-oxazole derivatives, methods for the production thereof, and use thereof as herbicides and plant growth regulators
EP09735369A EP2294058A1 (en) 2008-04-22 2009-04-15 2-(benzylsulfonyl)-oxazole derivatives, chiral 2- (benzylsulfinyl) -oxazole derivatives and 2-(benzylsulfanyl)-oxazole derivatives, methods for the production thereof, and use thereof as herbicides and plant growth regulators

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EP09735369A Withdrawn EP2294058A1 (en) 2008-04-22 2009-04-15 2-(benzylsulfonyl)-oxazole derivatives, chiral 2- (benzylsulfinyl) -oxazole derivatives and 2-(benzylsulfanyl)-oxazole derivatives, methods for the production thereof, and use thereof as herbicides and plant growth regulators

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EA023797B1 (en) * 2011-03-15 2016-07-29 Байер Интеллектуэль Проперти Гмбх Herbicide safener compositions
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Family Cites Families (68)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3960542A (en) 1975-03-17 1976-06-01 Uniroyal Inc. Herbicidal 2-sulfinyl and 2-sulfonyl pyridine N-oxide derivatives
GB1552125A (en) 1975-06-07 1979-09-05 Lilly Industries Ltd 2-acylamino oxazoles
US4022607A (en) 1975-06-09 1977-05-10 Sandoz, Inc. Substituted oxazoles and thiazoles as herbicides
DD152557A1 (en) 1980-08-14 1981-12-02 Siegfried Dr Rer Nat D Andreae PROCESS FOR THE PREPARATION OF NEW FURANIDE-CONTAINING ISOTHIONIC FRUIT SALTS
MA19709A1 (en) 1982-02-17 1983-10-01 Ciba Geigy Ag APPLICATION OF QUINOLEIN DERIVATIVES TO THE PROTECTION OF CULTIVATED PLANTS.
EP0094349B1 (en) 1982-05-07 1994-04-06 Ciba-Geigy Ag Use of quinoline derivatives for the protection of cultivated plants
JPS60500438A (en) 1983-01-17 1985-04-04 モンサント　カンパニ− Plasmids for transforming plant cells
BR8404834A (en) 1983-09-26 1985-08-13 Agrigenetics Res Ass METHOD TO GENETICALLY MODIFY A PLANT CELL
JPS6087254A (en) 1983-10-19 1985-05-16 Japan Carlit Co Ltd:The Novel urea compound and herbicide containing the same
DE3525205A1 (en) 1984-09-11 1986-03-20 Hoechst Ag, 6230 Frankfurt PLANT PROTECTIVE AGENTS BASED ON 1,2,4-TRIAZOLE DERIVATIVES AND NEW DERIVATIVES OF 1,2,4-TRIAZOLE
BR8600161A (en) 1985-01-18 1986-09-23 Plant Genetic Systems Nv CHEMICAL GENE, HYBRID, INTERMEDIATE PLASMIDIO VECTORS, PROCESS TO CONTROL INSECTS IN AGRICULTURE OR HORTICULTURE, INSECTICIDE COMPOSITION, PROCESS TO TRANSFORM PLANT CELLS TO EXPRESS A PLANTINIDE TOXIN, PRODUCED BY CULTURES, UNITED BY BACILLA
DE3680212D1 (en) 1985-02-14 1991-08-22 Ciba Geigy Ag USE OF CHINOLINE DERIVATIVES FOR PROTECTING CROPS.
JPS6239583A (en) * 1985-08-14 1987-02-20 Yamanouchi Pharmaceut Co Ltd Benzodioxazole derivative and production thereof
EP0221044B1 (en) 1985-10-25 1992-09-02 Monsanto Company Novel plant vectors
ES2018274T5 (en) 1986-03-11 1996-12-16 Plant Genetic Systems Nv VEGETABLE CELLS RESISTANT TO GLUTAMINE SYNTHETASE INHIBITORS, PREPARED BY GENETIC ENGINEERING.
WO1987006766A1 (en) 1986-05-01 1987-11-05 Honeywell Inc. Multiple integrated circuit interconnection arrangement
IL83348A (en) 1986-08-26 1995-12-08 Du Pont Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase
US5013659A (en) 1987-07-27 1991-05-07 E. I. Du Pont De Nemours And Company Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase
DE3633840A1 (en) 1986-10-04 1988-04-14 Hoechst Ag PHENYLPYRAZOLIC CARBONIC ACID DERIVATIVES, THEIR PRODUCTION AND USE AS PLANT GROWTH REGULATORS AND SAFENERS
DE3775527D1 (en) 1986-10-22 1992-02-06 Ciba Geigy Ag 1,5-DIPHENYLPYRAZOLE-3-CARBONIC ACID DERIVATIVES FOR THE PROTECTION OF CROPS.
DE3733017A1 (en) 1987-09-30 1989-04-13 Bayer Ag Stilbene synthase gene
DE3808896A1 (en) 1988-03-17 1989-09-28 Hoechst Ag PLANT PROTECTION AGENTS BASED ON PYRAZOL CARBON SEA DERIVATIVES
DE3817192A1 (en) 1988-05-20 1989-11-30 Hoechst Ag PLANT-PROTECTIVE AGENTS CONTAINING 1,2,4-TRIAZOLE DERIVATIVES AND NEW DERIVATIVES OF 1,2,4-TRIAZOLE
ATE84302T1 (en) 1988-10-20 1993-01-15 Ciba Geigy Ag SULFAMOYLPHENYL UREAS.
DE3939010A1 (en) 1989-11-25 1991-05-29 Hoechst Ag ISOXAZOLINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A PLANT PROTECTIVE AGENT
DE3939503A1 (en) 1989-11-30 1991-06-06 Hoechst Ag NEW PYRAZOLINE FOR THE PROTECTION OF CULTURAL PLANTS AGAINST HERBICIDES
DE3942946A1 (en) 1989-12-23 1991-06-27 Hoechst Ag METHOD FOR PRODUCING 1,1-DISUBSTITUTED CYCLOPROPAN DERIVATIVES
FR2656612B1 (en) 1989-12-28 1992-03-27 Rhone Poulenc Agrochimie HERBICIDES WITH ALCENYL OR HETEROARYL GROUP THIO, SULFONE, SULFOXIDE.
WO1991013972A1 (en) 1990-03-16 1991-09-19 Calgene, Inc. Plant desaturases - compositions and uses
AU644203B2 (en) 1990-06-18 1993-12-02 Monsanto Company Increased starch content in plants
DK0536330T3 (en) 1990-06-25 2002-04-22 Monsanto Technology Llc Glyphosate tolerant plants
DE4107396A1 (en) 1990-06-29 1992-01-02 Bayer Ag STYLE SYNTHASE GENES FROM VINEYARD
SE467358B (en) 1990-12-21 1992-07-06 Amylogene Hb GENETIC CHANGE OF POTATISE BEFORE EDUCATION OF AMYLOPECT TYPE STARCH
DE59108636D1 (en) 1990-12-21 1997-04-30 Hoechst Schering Agrevo Gmbh New 5-chloroquinoline-8-oxyalkanecarboxylic acid derivatives, process for their preparation and their use as antidots of herbicides
DE4104782B4 (en) 1991-02-13 2006-05-11 Bayer Cropscience Gmbh Novel plasmids containing DNA sequences that cause changes in carbohydrate concentration and carbohydrate composition in plants, as well as plants and plant cells containing these plasmids
TW259690B (en) 1992-08-01 1995-10-11 Hoechst Ag
DE4331448A1 (en) 1993-09-16 1995-03-23 Hoechst Schering Agrevo Gmbh Substituted isoxazolines, processes for their preparation, compositions containing them and their use as safeners
IL112721A0 (en) 1994-03-10 1995-05-26 Zeneca Ltd Azole derivatives
DE19621522A1 (en) 1996-05-29 1997-12-04 Hoechst Schering Agrevo Gmbh New N-acylsulfonamides, new mixtures of herbicides and antidots and their use
DE69707907T2 (en) 1996-09-26 2002-05-16 Syngenta Participations Ag, Basel HERBICIDAL COMPOSITION
DE19652961A1 (en) 1996-12-19 1998-06-25 Hoechst Schering Agrevo Gmbh New 2-fluoroacrylic acid derivatives, new mixtures of herbicides and antidots and their use
US6071856A (en) 1997-03-04 2000-06-06 Zeneca Limited Herbicidal compositions for acetochlor in rice
DE19727410A1 (en) 1997-06-27 1999-01-07 Hoechst Schering Agrevo Gmbh 3- (5-tetrazolylcarbonyl) -2-quinolones and crop protection agents containing them
DE19742951A1 (en) 1997-09-29 1999-04-15 Hoechst Schering Agrevo Gmbh Acylsulfamoylbenzoic acid amides, crop protection agents containing them and process for their preparation
WO1999052874A1 (en) 1998-04-10 1999-10-21 Ube Industries, Ltd. Difluoroalkene derivatives, process for producing the same, and agricultural or horticultural pest control agent
CZ301045B6 (en) 1999-08-10 2009-10-21 Kumiai Chemical Industry Co., Ltd. Isoxazoline derivative and herbicidal agent containing this derivative as active component
JP2001322988A (en) 2000-03-09 2001-11-20 Nippon Bayer Agrochem Co Ltd Nematicidal trifluorobutenes
AR031027A1 (en) 2000-10-23 2003-09-03 Syngenta Participations Ag AGROCHEMICAL COMPOSITIONS
JP4465133B2 (en) 2001-02-08 2010-05-19 クミアイ化学工業株式会社 Isoxazoline derivatives and herbicides containing the same as active ingredients
DE60238194D1 (en) 2001-06-21 2010-12-16 Kumiai Chemical Industry Co ISOXAZOLINE DERIVATIVES AND HERBICIDES
JP2003081949A (en) 2001-07-04 2003-03-19 Bayer Ag Method for producing 1,3-oxazole-2-thiol
JP2003096059A (en) 2001-09-21 2003-04-03 Otsuka Chem Co Ltd Thiazole compound and herbicidal composition containing the same
US20060014805A1 (en) 2002-08-01 2006-01-19 Markus Kordes Pesticidal fluoroalkene derivatives
PL218431B1 (en) 2002-08-01 2014-12-31 Ihara Chemical Ind Co Pyrazole derivatives and process for the production thereof
DE10254876A1 (en) 2002-11-25 2004-06-03 Bayer Cropscience Ag Use of 1,1-difluoro-omega-heterocyclylthio-alk-1-ene derivatives as herbicides, for total or selective weed control, pre- or post-emergence
CA2520228A1 (en) 2003-03-26 2004-10-07 Bayer Cropscience Gmbh Use of aromatic compounds as safeners
DE10335726A1 (en) 2003-08-05 2005-03-03 Bayer Cropscience Gmbh Use of hydroxyaromatics as safener
DE10335725A1 (en) 2003-08-05 2005-03-03 Bayer Cropscience Gmbh Safener based on aromatic-aliphatic carboxylic acid derivatives
DE102004023332A1 (en) 2004-05-12 2006-01-19 Bayer Cropscience Gmbh Quinoxaline-2-one derivatives, crop protection agents containing them, and processes for their preparation and their use
US8680290B2 (en) 2004-09-03 2014-03-25 Syngenta Limited Isoxazoline derivatives and their use as herbicides
PL1799657T3 (en) 2004-10-05 2010-05-31 Syngenta Ltd Isoxazoline derivatives and their use as herbicides
GB0510151D0 (en) 2005-05-18 2005-06-22 Syngenta Ltd Novel herbicides
DE102005031583A1 (en) 2005-07-06 2007-01-25 Bayer Cropscience Gmbh Process for the preparation of 3-arylmethylthio and 3-heteroarylmethylthio-4,5-dihydro-isoxazoline derivatives
DE102005031412A1 (en) 2005-07-06 2007-01-11 Bayer Cropscience Gmbh 3- [1-Halo-1-aryl-methane-sulfonyl] and 3- [1-halo-1-heteroaryl-methanesulfonyl] -isoxazoline derivatives, processes for their preparation and use as herbicides and plant growth regulators
WO2007006409A2 (en) * 2005-07-07 2007-01-18 Bayer Cropscience Ag Herbicide-safener combination
WO2007023719A1 (en) 2005-08-22 2007-03-01 Kumiai Chemical Industry Co., Ltd. Agent for reducing chemical injury and herbicide composition with reduced chemical injury
WO2007023764A1 (en) 2005-08-26 2007-03-01 Kumiai Chemical Industry Co., Ltd. Agent for reduction of harmful effect of herbicide and herbicide composition having reduced harmful effect
GB0526044D0 (en) 2005-12-21 2006-02-01 Syngenta Ltd Novel herbicides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009129953A1 *

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