EP2294058A1 - Dérivés de 2-(benzylsulfonyl)-oxazole, dérivés chiraux de 2-(benzylsulfinyl)-oxazole, dérivés de 2- (benzylsulfanyl) -oxazole, procédé pour produire ces dérivés ainsi que leur utilisation comme herbicides et régulateurs de la croissance des plantes - Google Patents

Dérivés de 2-(benzylsulfonyl)-oxazole, dérivés chiraux de 2-(benzylsulfinyl)-oxazole, dérivés de 2- (benzylsulfanyl) -oxazole, procédé pour produire ces dérivés ainsi que leur utilisation comme herbicides et régulateurs de la croissance des plantes

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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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EP
European Patent Office
Prior art keywords
alkyl
crc
alkoxy
cycloalkyl
general formula
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EP09735369A
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German (de)
English (en)
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/fr
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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

L'invention concerne des dérivés de 2-(benzylsulfonyl)-oxazole, des dérivés chiraux de 2-(benzylsulfinyl)-oxazole, et des dérivés de 2-(benzylsulfanyl)-oxazole de formule générale (I), et leurs sels, les différents groupes et références ayant les significations indiquées dans la description. L'invention porte également sur des procédés pour préparer ces composés, de même que sur l'utilisation desdits composés comme herbicides ou régulateurs de la croissance des plantes, en particulier comme herbicides pour l'élimination sélective des mauvaises herbes dans les cultures de plantes utilitaires.
EP09735369A 2008-04-22 2009-04-15 Dérivés de 2-(benzylsulfonyl)-oxazole, dérivés chiraux de 2-(benzylsulfinyl)-oxazole, dérivés de 2- (benzylsulfanyl) -oxazole, procédé pour produire ces dérivés ainsi que leur utilisation comme herbicides et régulateurs de la croissance des plantes Withdrawn EP2294058A1 (fr)

Priority Applications (1)

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EP09735369A EP2294058A1 (fr) 2008-04-22 2009-04-15 Dérivés de 2-(benzylsulfonyl)-oxazole, dérivés chiraux de 2-(benzylsulfinyl)-oxazole, dérivés de 2- (benzylsulfanyl) -oxazole, procédé pour produire ces dérivés ainsi que leur utilisation comme herbicides et régulateurs de la croissance des plantes

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EP08007743A EP2112143A1 (fr) 2008-04-22 2008-04-22 Dérivés de 2-(benzylsulfinyle)-oxazole, dérivés chirales de 2-(benzylsulfinyle) et dérivés d'oxazole 2-(benzylsulfanyle), leur procédé de preparation ainsi que leur utilisation en tant qu'herbicides et régulateurs de croissances des plantes
EP09735369A EP2294058A1 (fr) 2008-04-22 2009-04-15 Dérivés de 2-(benzylsulfonyl)-oxazole, dérivés chiraux de 2-(benzylsulfinyl)-oxazole, dérivés de 2- (benzylsulfanyl) -oxazole, procédé pour produire ces dérivés ainsi que leur utilisation comme herbicides et régulateurs de la croissance des plantes
PCT/EP2009/002741 WO2009129953A1 (fr) 2008-04-22 2009-04-15 Dérivés de 2-(benzylsulfonyl)-oxazole, dérivés chiraux de 2-(benzylsulfinyl)-oxazole, dérivés de 2- (benzylsulfanyl) -oxazole, procédé pour produire ces dérivés ainsi que leur utilisation comme herbicides et régulateurs de la croissance des plantes

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EP2294058A1 true EP2294058A1 (fr) 2011-03-16

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EP09735369A Withdrawn EP2294058A1 (fr) 2008-04-22 2009-04-15 Dérivés de 2-(benzylsulfonyl)-oxazole, dérivés chiraux de 2-(benzylsulfinyl)-oxazole, dérivés de 2- (benzylsulfanyl) -oxazole, procédé pour produire ces dérivés ainsi que leur utilisation comme herbicides et régulateurs de la croissance des plantes

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CA2830090C (fr) * 2011-03-15 2019-07-16 Bayer Intellectual Property Gmbh Compositions d'herbicides et de phytoprotecteurs
WO2023137309A2 (fr) 2022-01-14 2023-07-20 Enko Chem, Inc. Inhibiteurs de protoporphyrinogène oxydase

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 (de) 1980-08-14 1981-12-02 Siegfried Dr Rer Nat D Andreae Verfahren zur herstellung von neuen furanrestenthaltenden isothionharnstoffsalzen
MA19709A1 (fr) 1982-02-17 1983-10-01 Ciba Geigy Ag Application de derives de quinoleine a la protection des plantes cultivees .
EP0094349B1 (fr) 1982-05-07 1994-04-06 Ciba-Geigy Ag Utilisation de dérivés de quinoléine pour protéger des plantes cultivées
WO1984002919A1 (fr) 1983-01-17 1984-08-02 Monsanto Co Plasmides de transformation de cellules vegetales
BR8404834A (pt) 1983-09-26 1985-08-13 Agrigenetics Res Ass Metodo para modificar geneticamente uma celula vegetal
JPS6087254A (ja) 1983-10-19 1985-05-16 Japan Carlit Co Ltd:The 新規尿素化合物及びそれを含有する除草剤
DE3525205A1 (de) 1984-09-11 1986-03-20 Hoechst Ag, 6230 Frankfurt Pflanzenschuetzende mittel auf basis von 1,2,4-triazolderivaten sowie neue derivate des 1,2,4-triazols
BR8600161A (pt) 1985-01-18 1986-09-23 Plant Genetic Systems Nv Gene quimerico,vetores de plasmidio hibrido,intermediario,processo para controlar insetos em agricultura ou horticultura,composicao inseticida,processo para transformar celulas de plantas para expressar uma toxina de polipeptideo produzida por bacillus thuringiensis,planta,semente de planta,cultura de celulas e plasmidio
DE3680212D1 (de) 1985-02-14 1991-08-22 Ciba Geigy Ag Verwendung von chinolinderivaten zum schuetzen von kulturpflanzen.
JPS6239583A (ja) * 1985-08-14 1987-02-20 Yamanouchi Pharmaceut Co Ltd ベンゾジオキソ−ル誘導体及びその製造法
EP0221044B1 (fr) 1985-10-25 1992-09-02 Monsanto Company Vecteurs de plantes
EP0242236B2 (fr) 1986-03-11 1996-08-21 Plant Genetic Systems N.V. Cellules végétales résistantes aux inhibiteurs de la synthétase de glutamine, produites par génie génétique
EP0305398B1 (fr) 1986-05-01 1991-09-25 Honeywell Inc. Agencement d'interconnexion de plusieurs circuits integres
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
IL83348A (en) 1986-08-26 1995-12-08 Du Pont Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase
DE3633840A1 (de) 1986-10-04 1988-04-14 Hoechst Ag Phenylpyrazolcarbonsaeurederivate, ihre herstellung und verwendung als pflanzenwachstumsregulatoren und safener
US5078780A (en) 1986-10-22 1992-01-07 Ciba-Geigy Corporation 1,5-diphenylpyrazole-3-carboxylic acid derivatives for the protection of cultivated plants
DE3733017A1 (de) 1987-09-30 1989-04-13 Bayer Ag Stilbensynthase-gen
DE3808896A1 (de) 1988-03-17 1989-09-28 Hoechst Ag Pflanzenschuetzende mittel auf basis von pyrazolcarbonsaeurederivaten
DE3817192A1 (de) 1988-05-20 1989-11-30 Hoechst Ag 1,2,4-triazolderivate enthaltende pflanzenschuetzende mittel sowie neue derivate des 1,2,4-triazols
EP0365484B1 (fr) 1988-10-20 1993-01-07 Ciba-Geigy Ag Sulfamoylphénylurées
DE3939010A1 (de) 1989-11-25 1991-05-29 Hoechst Ag Isoxazoline, verfahren zu ihrer herstellung und ihre verwendung als pflanzenschuetzende mittel
DE3939503A1 (de) 1989-11-30 1991-06-06 Hoechst Ag Neue pyrazoline zum schutz von kulturpflanzen gegenueber herbiziden
DE3942946A1 (de) 1989-12-23 1991-06-27 Hoechst Ag Verfahren zur herstellung von 1,1-disubstituierten cyclopropanderivaten
FR2656612B1 (fr) 1989-12-28 1992-03-27 Rhone Poulenc Agrochimie Herbicides a groupe alcenyle ou heteroaryle thio, sulfone, sulfoxyde.
CA2077896C (fr) 1990-03-16 2008-02-19 Gregory A. Thompson Desaturases vegetales - compositions et utilisations
ATE212670T1 (de) 1990-06-18 2002-02-15 Monsanto Technology Llc Erhöhter stärkegehalt in pflanzen
DK0536330T3 (da) 1990-06-25 2002-04-22 Monsanto Technology Llc Glyphosattolerante planter
DE4107396A1 (de) 1990-06-29 1992-01-02 Bayer Ag Stilbensynthase-gene aus weinrebe
SE467358B (sv) 1990-12-21 1992-07-06 Amylogene Hb Genteknisk foeraendring av potatis foer bildning av staerkelse av amylopektintyp
EP0492366B1 (fr) 1990-12-21 1997-03-26 Hoechst Schering AgrEvo GmbH Nouveaux dérivés de chloro-5-quinoline-8-acide oxyalkanecarboniques, procédé pour leur préparation et leur utilisation comme antidote d'herbicides
DE4104782B4 (de) 1991-02-13 2006-05-11 Bayer Cropscience Gmbh Neue Plasmide, enthaltend DNA-Sequenzen, die Veränderungen der Karbohydratkonzentration und Karbohydratzusammensetzung in Pflanzen hervorrufen, sowie Pflanzen und Pflanzenzellen enthaltend dieses Plasmide
TW259690B (fr) 1992-08-01 1995-10-11 Hoechst Ag
DE4331448A1 (de) 1993-09-16 1995-03-23 Hoechst Schering Agrevo Gmbh Substituierte Isoxazoline, Verfahren zu deren Herstellung, diese enthaltende Mittel und deren Verwendung als Safener
IL112721A0 (en) 1994-03-10 1995-05-26 Zeneca Ltd Azole derivatives
DE19621522A1 (de) 1996-05-29 1997-12-04 Hoechst Schering Agrevo Gmbh Neue N-Acylsulfonamide, neue Mischungen aus Herbiziden und Antidots und deren Verwendung
WO1998013361A1 (fr) 1996-09-26 1998-04-02 Novartis Ag Composition herbicide
DE19652961A1 (de) 1996-12-19 1998-06-25 Hoechst Schering Agrevo Gmbh Neue 2-Fluoracrylsäurederivate, neue Mischungen aus Herbiziden und Antidots und deren Verwendung
US6071856A (en) 1997-03-04 2000-06-06 Zeneca Limited Herbicidal compositions for acetochlor in rice
DE19727410A1 (de) 1997-06-27 1999-01-07 Hoechst Schering Agrevo Gmbh 3-(5-Tetrazolylcarbonyl)-2-chinolone und diese enthaltende nutzpflanzenschützende Mittel
DE19742951A1 (de) 1997-09-29 1999-04-15 Hoechst Schering Agrevo Gmbh Acylsulfamoylbenzoesäureamide, diese enthaltende nutzpflanzenschützende Mittel und Verfahren zu ihrer Herstellung
WO1999052874A1 (fr) 1998-04-10 1999-10-21 Ube Industries, Ltd. Derives difluoroalcene, procede de production associe, et agent de lutte contre les ravageurs dans l'agriculture et l'horticulture
CN1170825C (zh) 1999-08-10 2004-10-13 组合化学工业株式会社 异噁唑啉衍生物和含此为有效成分的除草剂
JP2001322988A (ja) 2000-03-09 2001-11-20 Nippon Bayer Agrochem Co Ltd 殺センチュウ性トリフルオロブテン類
AR031027A1 (es) 2000-10-23 2003-09-03 Syngenta Participations Ag Composiciones agroquimicas
JP4465133B2 (ja) 2001-02-08 2010-05-19 クミアイ化学工業株式会社 イソオキサゾリン誘導体及びこれを有効成分とする除草剤
WO2003000686A1 (fr) 2001-06-21 2003-01-03 Kumiai Chemical Industry Co., Ltd. Dérivés d'isoxazoline et herbicides
JP2003081949A (ja) 2001-07-04 2003-03-19 Bayer Ag １，３−オキサゾール−２−チオールの製造方法
JP2003096059A (ja) 2001-09-21 2003-04-03 Otsuka Chem Co Ltd チアゾール化合物及び除草剤組成物
US20060014805A1 (en) 2002-08-01 2006-01-19 Markus Kordes Pesticidal fluoroalkene derivatives
AU2003252447B2 (en) 2002-08-01 2008-06-05 Kumiai Chemical Industry Co., Ltd. Pyrazole derivatives and process for the production thereof
DE10254876A1 (de) 2002-11-25 2004-06-03 Bayer Cropscience Ag Verwendung von heterocyclischen Fluoralkenylthioethern und deren Derivaten als Herbizide
KR20060002857A (ko) 2003-03-26 2006-01-09 바이엘 크롭사이언스 게엠베하 독성 완화제로서의 방향족 하이드록시 화합물의 용도
DE10335726A1 (de) 2003-08-05 2005-03-03 Bayer Cropscience Gmbh Verwendung von Hydroxyaromaten als Safener
DE10335725A1 (de) 2003-08-05 2005-03-03 Bayer Cropscience Gmbh Safener auf Basis aromatisch-aliphatischer Carbonsäuredarivate
DE102004023332A1 (de) 2004-05-12 2006-01-19 Bayer Cropscience Gmbh Chinoxalin-2-on-derivate, diese enthaltende nutzpflanzenschützende Mittel und Verfahren zu ihrer Herstellung und deren Verwendung
JP2008511596A (ja) 2004-09-03 2008-04-17 シンジェンタ リミテッド イソオキサゾリン誘導体と、その除草剤としての利用法
ES2333977T3 (es) 2004-10-05 2010-03-03 Syngenta Limited Derivados de isoxazolina y su uso como herbicidas.
GB0510151D0 (en) 2005-05-18 2005-06-22 Syngenta Ltd Novel herbicides
DE102005031412A1 (de) 2005-07-06 2007-01-11 Bayer Cropscience Gmbh 3-[1-Halo-1-aryl-methan-sulfonyl]-und 3-[1-Halo-1-heteroaryl-methan-sulfonyl]-isoxazolin-Derivate, Verfahren zu deren Herstellung und Verwendung als Herbizide und Pflanzenwachstumsregulatoren
DE102005031583A1 (de) 2005-07-06 2007-01-25 Bayer Cropscience Gmbh Verfahren zur Herstellung von von 3-Arylmethylthio- und 3-Heteroarylmethylthio-4,5-dihydro-isoxazolin-Derivaten
WO2007006409A2 (fr) * 2005-07-07 2007-01-18 Bayer Cropscience Ag Association herbicide-phytoprotecteur
JPWO2007023719A1 (ja) 2005-08-22 2009-02-26 クミアイ化学工業株式会社 薬害軽減剤及び薬害が軽減された除草剤組成物
WO2007023764A1 (fr) 2005-08-26 2007-03-01 Kumiai Chemical Industry Co., Ltd. Agent servant à réduire les effets nocifs d’un herbicide et composition d’herbicide ayant des effets nocifs réduits
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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CA2722214A1 (fr) 2009-10-29
AU2009240244A1 (en) 2009-10-29
WO2009129953A1 (fr) 2009-10-29
US20110190125A1 (en) 2011-08-04

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