Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole 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
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
  • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
  • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
  • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
  • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

• a 5- or 6-membered heteroaryl having one to four nitrogen atoms, or having one to three nitrogen atoms and one oxygen or sulfur atom, or with a
• Oxygen or sulfur atom may be that partially or fully halogenated and / or 1 to 3 radicals from the group cyano, Ci-C6-alkyl, C3-C6 - cycloalkyl, d-Ce-haloalkyl, Ci-C6-alkoxy, dC 6 -haloalkoxy and Ci-C 6 - can carry alkoxy-Ci-C4-alkyl;
• R 1 , R 2 are hydrogen, hydroxy or C 1 -C 6 -alkoxy
• R 4 is hydrogen or C 1 -C 6 -alkyl
• R 5 is hydrogen, Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Ci-C 6 haloalkyl, C 2 -C 6 - haloalkenyl, C2-C6 haloalkynyl, C -C 6 cyanoalkyl, C 2 -C 6 -Cyanoalkenyl, C 2 - C ⁇ -cyanoalkynyl, Ci-C ⁇ hydroxyalkyl, C2-C6-hydroxyalkenyl, C -C ⁇ ⁇ -hydroxyalkynyl, C3-C6-cycloalkyl, Cs-C ⁇ - Cycloalkenyl, 3- to 6-membered heterocyclyl, wherein the aforementioned cycloalkyl, cycloalkenyl or 3- to 6-membered heterocyclyl may be partially or fully halogenated and / or one to three radicals from the group oxo, cyano,
• R 7 is hydrogen, Ci-C 6 alkyl or Ci-C 6 -Halogenalkyi;
• R 8 is hydrogen, Ci-C 6 alkyl or C 6 haloalkyl
• R 9 and R 10 are hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 3 -C 6 -haloalkenyl, C 3 -C 6 - haloalkynyl, formyl, CrC ⁇ alkyl-carbonyl, Ci-C ⁇ -alkylthiocarbonyl, C 3 -C 6 cycloalkylcarbonyl, C2-C6-alkenylcarbonyl, C2-C6-alkynylcarbonyl, -C 6 alkoxycarbonyl, Cs-C ⁇ -alkenyloxycarbonyl, Cs-C ⁇ -Alki ⁇ yloxycarbonyl , aminocarbonyl, CrC ⁇ -alkylaminocarbonyl, C 3 - Ce-alkenylaminocarbonyl, Cs-C ⁇ -alkynyla
• phenyl aminocarbonyl, phenyl-CrC ⁇ -alkylcarbonyl, where the phenyl radical may be partially or fully halogenated and / or may carry one to three of the following groups: nitro, cyano, -C 4 alkyl, -C 4 haloalkyl, dC 4 alkoxy or CrC 4 - haloalkoxy; or
• R 11 is hydrogen, -C 6 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 -alkyl kinyl, C 3 -C 6 -
• the invention relates to processes and intermediates for the preparation of compounds of formula I, compositions containing them and the use of these derivatives or agents containing them for controlling harmful plants.
• heteroaroyl-substituted alanines of the formula I and their herbicidal activity were found.
• herbicidal agents were found which contain the compounds I and have a very good herbicidal activity.
• methods for the preparation of these compositions and methods for controlling undesired plant growth with the compounds I have been found.
• the compounds of the formula I contain two or more chiral centers and are then present as enantiomer or diastereomer mixtures.
• the invention provides both the pure enantiomers or diastereomers and mixtures thereof.
• the compounds of the formula I can also be in the form of their agriculturally useful salts, whereby the type of salt generally does not matter.
• the salts of those cations or the acid addition salts of those acids come into consideration whose cations, or anions, do not adversely affect the herbicidal activity of the compounds I.
• the cations used are, in particular, ions of the alkali metals, preferably lithium, sodium and potassium, the alkaline earth metals, preferably calcium and magnesium, and the transition metals, preferably manganese, copper, zinc and iron, and also ammonium, in which case, if desired, one to four hydrogen atoms Ci-C4-alkyl, hydroxy-CrC 4 alkyl, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C 4 alkyl, phenyl or benzyl may be replaced , preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2- (2-hydroxyeth-1-oxy) eth-1-ylammonium, di (2-hydroxyeth-1-yl) -ammonium, trimethylbenzylammonium, and furthermore phosphonium ions
• Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of dC 4 -alkanoic acids, preferably formate, acetate, propionate and butyrate.
• All hydrocarbon chains e.g. all alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, cyanoalkyl, cyanoalkenyl, cyanoalkynyl, hydroxyalkyl, hydroxyalkenyl, Huydroxyalkinyl-, alkoxy, haloalkoxy and alkylthio parts can be straight-chain or branched.
• halogenated substituents preferably carry one to five identical or different halogen atoms.
• the meaning halogen in each case represents fluorine, chlorine, bromine or iodine.
• C 1 -C 4 -alkyl as mentioned above, and also, for example, n-pentyl, 1-methyl-butyl, 2-
• Methylpentyl 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl-butyl, 2 Ethylbutyl, 1, 1, 2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-3-methylpropyl;
• C 1 -C 4 -alkylcarbonyl for example methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl or 1,1-dimethylethylcarbonyl;
• C 3 -C 6 -cycloalkyl and the cycloalkyl parts of C 5 -C 6 -cycloalkylcarbonyl monocyclic, saturated hydrocarbon having 3 to 6 ring members, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
• Cs-C ⁇ -cycloalkenyl e.g. 1-Cyciopropenyl, 2-cyclopropenyl, 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 1, 3-cyclopentadienyl, 1, 4-
• Alkenyl) -N- (C 1 -C 6 alkoxy) aminocarbonyl e.g. 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1 - Methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1 - Dimethyl 2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethy
• C 1 -C 4 -cyanoalkyl for example, cyanomethyl, 1-cyanoeth-1-yl, 2-cyanoeth-1-yl, 1-cyano-prop-1-yl, 2-cyanoprop-1-yl, 3-cyanoprop-1 -yl, 1-cyanoprop-2-yl, 2-cyanoprop-2-yl, 1-cyanobut-1-yl, 2-cyanobut-1-yl, 3-cyanobut-1-yl, 4-cyanobut-1-yl , 1-cyano-but-2-yl, 2-cyanobut-2-yl, 1-cyanobut-3-yl, 2-cyanobut-3-yl, 1-cyano-2-methyl-prop-3-yl, 2 Cyano-2-methyl-prop-3-yl, 3-cyano-2-methyl-prop-3-yl and 2-cyano-methyl-prop-2-yl;
• C 1 -C 8 -hydroxyalkyl C 1 -C 4 -hydroxyalkyl as mentioned above, and also, for example, 1-hydroxy-pent-5-yl, 2-hydroxy-pent-5-yl, 3-hydroxy-pent-5-yl, 4-hydroxy -pent-5-yl, 5-hydroxy-pent-5-yl, 1-hydroxypent-4-yl, 2-hydroxy-4-yl, 3-hydroxypent-4-yl, A-
• Hydroxypent-4-yl 1-hydroxy-pent-3-yl, 2-hydroxy-pent-3-yl, 3-hydroxy-pent-3-yl, 1-hydroxy-2-methylbut-3-yl, 2-hydroxy-2-methyl-but-3-yl, 3-hydroxy-2-methyl-but-3-yl, 1-hydroxy-2-methyl-but-4-yl, 2-hydroxy-2-methyl but-4-yl, 3-hydroxy-2-methyl-buM-yl, 4-hydroxy-2-methyl-but-4-yl, 1-hydroxy-3-methyl-but-4-yl, 2-hydroxy 3-methylbut-4-yl, 3-hydroxy-3-methylbut-4-yl, 4-hydroxy-3-methyl-but-4-yl, 1
• Heteroaryl-C 1 -C 4 -haloalkyl a C 1 -C 4 -alkyl radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, eg chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl methyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, bromomethyl, iodomethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-
• Trifluoroethyl 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2, 2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2, 2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1-
• C 3 -C 6 -haloalkenyl a C 1 -C 6 -alkenyl radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, eg 2-chloroprop-2-en-1 yl, 3-chloroprop-2-en-1-yl, 2,3-dichloroprop-2-en-1-yl, 3,3-dichloroprop-2-en-1-yl, 2,3,3-trichloro 2-en-1-yl, 2,3-dichlorobut-2-en-1-yl, 2-bromoprop-2-en-1-yl, 3-bromoprop-2-en-1-yl, 2,3- Dibromoprop-2-en-1-yl, 3,3-dibromoprop-2-en-1-yl, 2,3,3-
• C2-C6 cyanoalkenyl e.g. 2-cyanovinyl, 2-cyanoallyl, 3-cyanoallyl, 2,3-dicyanoallyl, 3,3-dicyanoallyl, 2,3,3-tricyanoallyl, 2,3-dicyanobut-2-enyl;
• Ca-C ⁇ -haloalkynyl a Ca-C ⁇ -alkynyl radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, e.g. 1, 1 - Difluoro-prop-2-yn-1-yl, 3-iodo-prop-2-yn-1-yl, 4-fluorobut-2-yn-1-yl, 4-chlorobut-2in-1 - yl, 1, 1-difluorobut-2-yn-1-yl, 4-iodobut-3-yn-1-yl, 5-fluoropent-3-yn-1-yl, 5-iodopent-4-yn-1 - yl, 6-fluorohex-4-yn-1-yl or 6-iodohex-5-yn-1-yl;
• Heteroaryl-C 2 -C 4 -hydroxyalkynyl e.g. 1, 1-dihydroxy-prop-2-yn-1-yl, 3-hydroxyprop-2-yn-1-yl, 4-hydroxy-but-2-yn-1-yl, 1,1-dihydroxybutyl 2-yn-1-yl, 4-hydroxybut-3-yn-1-yl, 5-hydroxypent-3-yn-1-yl, 5-hydroxypent-4-yn-1-yl, 6-hydroxyhex-4 in-1-yl or 6-hydroxyhex-5-yn-1-yl;
• C 1 -C 6 -alkylsulfinyl (C 1 -C 6 -alkyl-S (OO) -) and the C 1 -C 6 -alkylsulfinyl parts of C 1 -C 6 -alkylsulfinyl-C 1 -C 4 -alkyl: for example methylsulfinyl, ethylsulfinyl, Propylsulfinyl, 1-methylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1,1-dimethylethylsulfinyl, pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropy
• Ci-C ⁇ -haloalkylsulfinyl and the Ci-C ⁇ -Halogenalkylsulfinyl parts of Ci-C ⁇ - haloalkylsulfinyl-Ci-C4-alkyl Ci-C ⁇ -Alkylsulfinylrest as mentioned above, which partially or completely by fluorine, chlorine, bromine and / or iodine is substituted, eg Fluoromethylsulfinyl, difluoromethylsulfinyl, trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethylsulfinyl, 2-fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2,2-difluoroethylsulf
• Alkylsulfonyl as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, thus e.g. Fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2-chloro 2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro
• C 1 -C 4 -haloalkoxy a C 1 -C 4 -alkoxy radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, thus e.g. Fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro 2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy,
• Ci-C 4 alkyl eg methoxymethyl, ethoxymethyl, propoxymethyl, (I -Methylethoxy) methyl, butoxymethyl, (I-methylpropoxy) methyl, (2-methyl-prop oxy) methyl , (1, 1-dimethylethoxy) methyl, 2- (methoxy) ethyl, 2- (ethoxy) ethyl, 2-
• C 1 -C 4 -alkylthio as mentioned above, and also, for example, pentylthio, 1-methylbutylthio, 2-methylbutylthio , 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1, 1-dimethylpropylthio, 1, 2-dimethylpropylthio, 1-methylpentylthio, 2-
• Di (C 1 -C 4 -alkyl) amino for example N, N-dimethylamino, N, N-diethylamino, N, N-dipropylamino, N 1 N -di (1-methylethyl) amino, N, N -Dibutylamino, N 1 N-di- (I -methylpropyl) - amino, N, N-di- (2-methylpropyl) amino, N 1 N-di (1, 1-dimethylethyl) amino, N-ethyl -N-methylamino, N-methyl-N-propylamino, N -methyl-N- (1-methylethyl) amino, N-butyl-N-methylamino, N -methyl-N- (1-methylpropyl) amino, N -methyl N- (2-methylpropyl) amino, N- (1, 1-dimethyl-ethyl) -N-methylamino, N-ethyl-
• C 1 -C 4 -alkyl amino as mentioned above and: e.g. N, N-dipentylamino, N, N-dihexylamino, N-methyl-N-pentylamino, N-ethyl-N-pentylamino, N-methyl-N-hexylamino and N-ethyl-N-hexylamino; (C 1 -C 4 -alkylamino ) carbonyl: eg Methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, 1-methyl-ethylaminocarbonyl, butylaminocarbonyl, 1-methylpropylaminocarbonyl, 2-
• N- (1,2,2-trimethylpropyl) aminocarbonyl N-ethyl-N- (1-ethyl-1-methylpropyl) -aminocarbonyl, N-ethyl-N- (1-ethyl-2-methylpropyl) aminocarbonyl, N- Propyl-N-pentylaminocarbonyl, N-butyl-N-pentylaminocarbonyl, N, N-dipentylaminocarbonyl, N-propyl-N-hexylaminocarbonyl, N-butyl-N-hexylaminocarbonyl, N-pentyl-N-hexylaminocarbonyl or N, N-dihexylaminocarbonyl;
• Di (C 1 -C 6 -alkyl) aminothiocarbonyl for example N, N-dimethylaminothiocarbonyl, N, N-diethylaminothiocarbonyl, N, N-di- (1-methylethyl) aminothiocarbonyl, N, N-dipropylaminothiocarbonyl, N, N-dibutylaminothiocarbonyl, N 1 N-di- (I -methylpropyl) aminothiocarbonyl, N, N-di- (2-methylpropyl) aminothiocarbonyl, N, N-di (1, 1-dimethylethyl) - aminothiocarbonyl, N-ethyl-N- methylaminothiocarbonyl, N-methyl-N-propylamino-thiocarbonyl, N-methyl-N- (1-methylethyl) aminothiocarbonyl, N-butyl-N-methylaminothiocarbon
• N-ethylaminothiocarbonyl N-ethyl-N- (1-methylpropyl) aminothiocarbonyl, N-ethyl-N- (2-methylpropyl) aminothiocarbonyl, N-ethyl-N- (1, 1-dimethylethyl) aminothio-carbonyl, N - (1-methylethyl) -N-propylaminothiocarbonyl, N-butyl-N-propylaminothio-carbonyl, N- (1-methylpropyl) -N-propylaminothiocarbonyl, N- (2-methylpropyl) -N-propylamino-thiocarbonyl, N- ( 1, 1-dimethylethyl) -N-propylaminothiocarbonyl, N-
• N- (1-methylethyl) aminothiocarbonyl N- (1-methylethyl) -N- (1-methylpropyl) -aminothiocarbonyl, N- (1-methylethyl) -N- (2-methylpropyl) aminothiocarbonyl, N- (1 , 1-dimethylethyl) -N- (i-methylethyl) aminothiocarbonyl, N-butyl-N- (i-methylpropyl) - aminothiocarbonyl, N-butyl-N- (2-methylpropyl) aminothiocarbonyl, N-butyl-N- (1, 1-dimethylethyl) aminothiocarbonyl, N- (1-methylpropyl) -N- (2-methylpropyl) aminothiocarbonyl, N- (1, 1-dimethylethyl) -N- (1-methylpropyl) aminothiocarbonyl, N- (1, 1-dimethylethyl)
• 3- to 6-membered heterocyclyl monocyclic, saturated or partially unsaturated hydrocarbons having three to six ring members as mentioned above which contain, in addition to carbon atoms, one to four nitrogen atoms, or one to three nitrogen atoms and one oxygen or sulfur atom, or one to three oxygen atoms. or may contain one to three sulfur atoms, and which may be linked via a C atom or an N atom, for example
• 4,5-dihydropyrrol-1-yl 2,5-dihydropyrrol-1-yl, 4,5-dihydroisoxazol-2-yl, 2,3-dihydroisoxazol-1-yl, 4,5-dihydroisothiazol-1-yl , 2,3-dihydroisothiazol-1-yl, 2,3-di- hydropyrazol-1-yl, 4,5-dihydropyrazol-1-yl, 3,4-dihydropyrazol-1-yl, 2,3-dihydroimidazol-1-yl, 4,5-dihydroimidazol-1-yl, 2, 5-dihydroimidazol-1-yl, 2,3-dihydro-oxazol-2-yl, 3,4-dihydro-oxazol-2-yl, 2,3-dihydrothiazol-2-yl, 3,4-dihydrothiazol-2-yl
• pyridyl eg pyridin-2-yl, pyridin-3-yl, pyridin-4-yl
• pyrazinyl eg pyridazin-3-yl, Pyridazin-4-yl
• pyrimidinyl eg pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl
• pyrazine-2-yl triazinyl (eg 1, 3,5-triazine-2-yl) yl, 1, 2,4-triazin-3-yl, 1, 2,4-triazin-5-yl, 1, 2,4-triazin-6-yl), tetrazinyl (eg 1, 2,4,5- Tetrazine-3-yl); such as
• Bicyclic compounds such as the benzanellated derivatives of the aforementioned monocycles, e.g. Quinolinyl, isoquinolinyl, indolyl, benzthienyl, benzofuranyl, benzoxazolyl, benzothiazolyl, benzisothiazolyl, benzimidazolyl, benzopyrazolyl, benzthiadiazolyl, benzotriazolyl;
• 5- or 6-membered heteroaryl having one to four nitrogen atoms, or one to three nitrogen atoms and one oxygen or sulfur atom, or with an oxygen or sulfur atom: e.g. C-atom linked aromatic 5-membered heterocycles which may contain, besides carbon atoms, one to four nitrogen atoms, or one to three nitrogen atoms and one sulfur or oxygen atom, or a sulfur or oxygen atom as ring members, e.g.
• Oxadiazol-3-yl 1, 2,4-oxadiazol-5-yl, 1, 2,4-thiadiazol-3-yl, 1, 2,4-thiadiazol-5-yl, 1, 2,4-triazole 3-yl, 1, 3,4-oxadiazol-2-yl, 1, 3,4-thiadiazol-2-yl and 1, 3,4-triazol-2-yl;
• aromatic 6-membered ring heterocycles linked via a carbon atom which may contain, besides carbon atoms, one to four, preferably one to three, nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrazidinyl, 2-pyrazinyl, 1, 3,5-triazin-2-yl and 1, 2,4-triazine-3-yl.
• the variables of the heteroaroyl-substituted alanines of the formula I have the following meanings, these being considered singularly and in combination with one another in particular embodiments of the compounds of the formula I: Preference is given to the heteroaroyl-substituted alanines of the formula I in which
• a 5- or 6-membered heteroaryl having one to four nitrogen atoms, or having one to three nitrogen atoms and one oxygen or sulfur atom, or having one oxygen or sulfur atom which is represented by a C 1 -C 6 -haloalkyl radical, is preferably substituted in the 2-position by a C 1 -C 6 -haloalkyl radical, and 1 to 3 radicals from the group cyano, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -haloalkyl, C 1 -C 3 -cycloalkyl Alkoxy, C 1 -C 6 -haloalkoxy and C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl; means.
• heteroaroyl-substituted alanines of the formula I 1 in the A 5 or 6-membered heteroaryl selected from the group pyrrolyl, thienyl,
• heteroaryl radicals may be partially or fully halogenated and / or may carry from 1 to 3 radicals selected from the group consisting of C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl and C 1 -C 6 haloalkyl;
• heteroaryl selected from the group of thienyl, furyl, pyrazolyl, imidazolyl, thiazolyl and oxazolyl; where said heteroaryl radicals may be partially halogenated and / or may carry from 1 to 2 radicals selected from the group consisting of C 1 -C 6 -alkyl and C 1 -C 4 -haloalkyl;
• heteroaryl radicals may be partially halogenated and / or may carry from 1 to 2 radicals selected from the group consisting of C 1 -C 6 -alkyl and C 1 -C 4 -haloalkyl;
• heteroaryl radicals can be partially halogenated and / or 1 to 2 radicals from the group consisting of C 1 -C 6 -alkyl and C 1 -C 4 -alkyl radicals
• Ci-C ⁇ -alkyl and Ci-C4-haloalkyl can gene gene;
• heteroaroyl-substituted alanines of the formula I in which A is 5-membered heteroaryl having one to four nitrogen atoms, or one to three nitrogen atoms and one oxygen or sulfur atom, or one oxygen atom; particularly preferably 5-membered heteroaryl selected from the group of thienyl, furyl, pyrazolyl, imidazolyl, thiazolyl and oxazolyl; especially preferred 5-membered heteroaryl selected from the group thienyl, furyl, pyrazolyl and imidazolyl; most preferably pyrazolyl; wherein said heteroaryl are substituted by a Ci-C ⁇ -haloalkyl, preferably in the 2-position by a Ci-C ⁇ -haloalkyl, and 1 to 3 radicals from the group halogen, cyano, Ci-C ⁇ -alkyl, C3-Ce-cycloalkyl that can carry 6 haloalkoxy and Ci-C 6 alkoxy
• heteroaroyl-substituted alanines of the formula I in which A is 5-membered heteroaryl having one to four nitrogens; preferably 5-membered heteroaryl having one to three nitrogens; very preferably 5-membered heteroaryl having one to two nitrogens; particularly preferred 5-membered heteroaryl with two nitrogens; most preferably pyrazolyl; wherein the heteroaryl radicals mentioned by 1 to 3 radicals from the group halogen, cyano, Ci-C 6 alkyl, C 3 -C 6 cycloalkyl, Ci-Ce-haloalkyl, Ci-C 6 -
• R 13 is hydrogen, halogen, Ci-C 6 alkyl or Ci-C6 haloalkyl; particularly preferably hydrogen, Ci-C 4 alkyl or Ci-C 4 haloalkyl; especially preferably hydrogen or C 1 -C 4 -alkyl; most preferably hydrogen;
• R 14 is halogen, Ci-C 6 alkyl, Ci-C6 haloalkyl or Ci-C 6 haloalkoxy; particularly preferably halogen, C 1 -C 4 -alkyl or C 1 -C 6 -haloalkyl; especially preferably halogen or C 1 -C 6 -haloalkyl; very preferably C 1 -C 6 -haloalkyl; extremely preferably C 1 -C 4 -haloalkyl very particularly preferably CF 3;
• R 15 is hydrogen, halogen, C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl; particularly preferably hydrogen, halogen or C 1 -C 4 -haloalkyl; especially preferably hydrogen or halogen; most preferably hydrogen; and
• R 16 is hydrogen, Ci-C 6 alkyl, C 3 -C 6 cycloalkyl, Ci-C 6 haloalkyl or C C6 alkoxy-Ci-C4-alkyl; particularly preferably Ci-C4-alkyl, C3-C6 cycloalkyl, Ci-C4-haloalkyl or Ci-C4-alkoxy-Ci-C4-alkyl; particularly preferably Ci-C 4 alkyl or Ci-C 4 haloalkyl; extremely preferably C 1 -C 4 -alkyl; very preferably CH3;
• R 13 to R 16 are defined as mentioned above;
• heteroaroyl-substituted alanines of the formula I in which
• R 1 is hydrogen; means.
• heteroaryl heteroaryl-Ci-C4-alkyl, heteroaryl-Ci-C4-hydroxyalkyl, heteroaryloxy- Ci-C4-alkyl, heteroarylthio-Ci-C4-alkyl, heteroarylsulfinyl-Ci-C4-alkyl, or hetero- roarylsulfonyl -Ci-C 4 alkyl, wherein the above-mentioned phenyl and heteroaryl may be partially or fully halogenated and / or one to three radicals from the
• Cyano group nitro, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, hydroxy, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, hydroxycarbonyl, C 1 -C 6 -alkoxycarbonyl, hydroxycarbonyl-C 1 -C 6 -alkoxy, C i -C6-alkylsulfonylamino and Ci-C ⁇ -haloalkylsulfonylamino;
• C 2 -C 6 -alkenyl particularly preferably C 2 -C 6 -alkenyl, C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, phenyl or heteroaryl; means.
• heteroaroyl-substituted alanines of the formula I 1 in the R 9 and R 10 are each independently
• Ci-C 6 alkyl C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, formyl
• Ci-C 6 - alkylcarbonyl C ⁇ -Ce-alkenylcarbonyl, C 3 -C 6 cycloalkylcarbonyl, C -C 6 - alkoxycarbonyl, aminocarbonyl, Ci-C ⁇ -alkylaminocarbonyl, Ci-C 6 - Alkylsulfonylaminocarbonyl, di (C 1 -C 6 -alkyl) aminocarbonyl, N- (C 1 -C 6 -alkoxy) -N- (C 1 -C 6 -alkyl) aminocarbonyl, [(C 1 -C 6 -alkyl) aminocarbonyl (C 1 -C 6 -alkyl ) amino] - carbonyl, (d-Ce-Alky ⁇ aminothicarbonyl, di (Ci-C
• C 1 -C 6 -alkyl particularly preferably hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkenyl, C 1 -C 6 -alkynyl, formyl, C 1 -C 6 -alkylcarbonyl, C 2 -C 6 -alkenylcarbonyl, C 1 -C 6 -alkoxycarbonyl, aminocarbonyl, (C 1 -C 6 -alkyl) aminocarbonyl, d-Ce-alkylsulfonylaminocarbonyl, di (C 1 -C 6 -alkyl) aminocarbonyl, N- (C 1 -C 6 -alkoxy) -N- (C 1 -C 6 -alkyl) aminocarbonyl, [(C 1 -C 6 -alkyl) aminocarbonyl (Ci C 6 -alkyl) amino] carbonyl, (C 1 -C 6 -alkyl) amino
• C 1 -C 6 -alkyl particularly preferably hydrogen, C 1 -C 6 -alkyl, formyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -haloalkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, aminocarbonyl, (C 1 -C 6 -alkyl) aminocarbonyl, di (C 1 -C 6 -alkyl) aminocarbonyl, N- (C 1 -C 6 -alkoxy) -N- (C 1 -C 6 -alkyl) aminocarbonyl, [(C 1 -C 6 -alkyl) aminocarbonyl (C 1 -C 6 -alkyl) amino] carbonyl or di (C 1 -C 6 -alkyl) alkyl) aminothiocarbonyl; or
• heteroaroyl-substituted alanines of the formula I 1 in the R 9 and R 10 are each independently
• heteroaroyl-substituted alanines of the formula I in which R 12 d-Ce-alkyl, CrC 6 -haloalkyl, di (CrC 6 alkyl) amino or phenyl, where the phenyl radical may be partially halogenated or partially and / or may be substituted by C 1 -C 4 -alkyl; particularly preferably C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, di (C 1 -C 6 -alkyl) amino or phenyl; especially preferably methyl, trifluoromethyl or phenyl; means.
• heteroaroyl-substituted alanines of the formula I in which A is 5- or 6-membered heteroaryl selected from the group consisting of thienyl, furyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl and pyridyl; wherein said heteroaryl may be partially or completely halogenated and / or may carry from 1 to 3 radicals selected from the group consisting of CrC ⁇ -alkyl, Ca-C ⁇ -cycloalkyl and CrC ⁇ -haloalkyl; R 1 and R 2 are hydrogen; R 3 is C 1 -C 4 -alkyl, more preferably CH 3 ; R 4 is hydrogen; R 5 is C 2 -C 6 -alkenyl, C 1 -C 6 -haloalkyl, 3 to 6-membered heterocyclyl, C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 6
• R 7 and R 8 are hydrogen
• R 9 and R 10 is hydrogen, C r C 6 alkyl, formyl, d-Ce-alkylcarbonyl, halo-dC 6 alkylcarbonyl, Ci-C ⁇ -alkoxycarbonyl, aminocarbonyl, (Ci-C6 alkyl) amino carbonyl, di ( C 1 -C 6 -alkyl) aminocarbonyl, N- (C 1 -C 6 -alkoxy) -N- (C 1 -C 6 -alkyl) aminocarbonyl, [(C 1 -C 6 -alkyl) aminocarbonyl (C 1 -C 6 -alkyl) amino] carbonyl or di ( Ci-C6-alkyl) aminothiocarbonyl or SO2R 12 ; and
• R 11 is hydrogen
• benzoyl-substituted alanines of the formula I are obtainable in various ways, for example by the following processes:
• L 1 represents a nucleophilic displaceable leaving group, for example for hydroxy or C 1 -C 6 alkoxy.
• L 2 represents a nucleophilically displaceable leaving group, for example hydroxy, halogen, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, C 1 -C 5 -methylsulfonyl, phosphoryl or iso-ureyl.
• the reaction of the alanine derivatives of the formula V with heteroaryl acid (derivatives) n of the formula IV, where L 2 is hydroxyl, to heteroaroyl derivatives of the formula III is carried out in the presence of an activating reagent and a base usually at temperatures of 0 0 C to the boiling point of the reaction mixture, preferably O 0 C to 11O 0 C, particularly preferably at room temperature, in an inert organic solvent [cf. C. Montalbetti et al., Tetrahedron 2005, 61, 10827 and references cited therein].
• Suitable activating reagents are condensing agents such as, for example, polystyrene-bonded dicyclohexylcarbodiimide, diisopropylcarbodiimide, carbonyldiimidazole, chlorocarbonic acid esters, such as methyl chloroformate, ethyl chloroformate, isophoryl chloroformate, isobutene.
• tyl chloroformate tyl chloroformate, sec-butyl chloroformate or allyl chloroformate, pivaloyl chloride, polyphosphoric acid, propanephosphonic anhydride, bis (2-oxo-3-oxazolidinyl) phosphoryl chloride (BOPCI) or sulphonyl chlorides such as methanesulphonyl chloride, toluenesulphonyl chloride or benzenesulphonyl chloride.
• BOPCI bis (2-oxo-3-oxazolidinyl) phosphoryl chloride
• sulphonyl chlorides such as methanesulphonyl chloride, toluenesulphonyl chloride or benzenesulphonyl chloride.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-C ⁇ alkanes, aromatic hydrocarbons such as benzene, toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, Diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran (THF), nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and dimethyl sulfoxide, dimethylformamide (DMF), dimethylacetamide (DMA) and N-methylpyrrolidone ( NMP
• Bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate and alkali metal hydrogen carbonates such as Nathumhydrogencarbonat, also organic bases, eg tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, N-Methyimorphoiin, and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Particularly preferred are sodium hydroxide,
• the bases are generally used in equimolar amounts. But they can also be used in excess or optionally as a solvent.
• the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous to use IV in an excess relative to V.
• reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and optionally chromatographic purification of the crude products.
• the intermediate and end products fall z. T. in the form of viscous oils, which are freed or purified under reduced pressure and at moderately elevated temperature of volatile fractions. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or digestion.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-Cs alkanes, aromatic hydrocarbons such as benzene, toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, Diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran (THF), nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and dimethyl sulfoxide, dimethylformamide (DMF), dimethylacetamide (DMA ) and N-methylpyrrolidone (N
• Bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate and alkali metal bicarbonates such as sodium bicarbonate, as well as organic bases, eg tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, N-methylmorpholine, and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Particularly preferred are sodium hydroxide, triethy
• the bases are generally used in equimolar amounts. But they can also be used in excess or optionally as a solvent.
• the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous to use IV in an excess relative to V.
• the workup and isolation of the products can be done in a conventional manner.
• heteroaryl acid (derivatives) of the formula IV required for the preparation of the heteroaroyl derivatives of the formula III can be purchased or can be prepared analogously to the procedure known from the literature [e.g. Chang-Ling Liu et al., J. of Fluorine Chem. (2004), 125 (9), 1287-1290; Manfred Schlosser et al., Europ. J. of Org. Chem. (2002), (17), 2913-2920; Hoh-Gyu Hahn et al., Agricult. Chem. And Biotech. (English Edition) (2002), 45 (1), 37-42; Jonatan O Smith et al., J. of Fluorine Chem. (1997), Vol.
• Suitable activating reagents are condensing agents such as, for example, polystyrene-bonded dicyclohexylcarbodiimide, diisopropylcarbodiimide, Carbonyldiimidazole, chlorocarbonic acid esters such as methyl chloroformate, ethyl chloroformate, isoropyl chloroformate, isobutyl chloroformate, sec-butyl chloroformate or allyl chloroformate, pivaloyl chloride, polyphosphoric acid,
• Propanephosphonic anhydride bis (2-oxo-3-oxazolidinyl) phosphoryl chloride (BOPCI) or sulfonyl chlorides such as methanesulfonyl chloride, toluenesulfonyl chloride or benzenesulfonyl chloride.
• BOPCI bis (2-oxo-3-oxazolidinyl) phosphoryl chloride
• sulfonyl chlorides such as methanesulfonyl chloride, toluenesulfonyl chloride or benzenesulfonyl chloride.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-C ⁇ alkanes, aromatic hydrocarbons such as benzene, toluene, o-, m- and p-xylene, halogenated hydrocarbons such as
• ethers such
• Bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate and alkali metal bicarbonates such as sodium bicarbonate, as well as organic bases, eg tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, N-methylmorpholine, and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Particularly preferred are sodium hydroxide, triethy
• the bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as solvent.
• the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous to use II in an excess relative to III.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-Cs alkanes, aromatic hydrocarbons such as benzene, toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, Diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran (THF), nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-
• Bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal hydroxides.
• alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide
• alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide
• alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal hydroxides.
• alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate and alkali metal hydrogencarbonates such as sodium bicarbonate, as well as organic bases, eg tertiary amines such as trimethylamine, thethylamine, diisopropylethylamine, N-methylmorpholine, and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and A-dimethylaminopyridine and bicyclic amines into consideration. Particularly preferred are sodium hydroxide, triethylamine, ethyldiisopropylamine, N-methylmorpholine and pyridine.
• the bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as solvent.
• the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous to use II in an excess relative to III.
• the workup and isolation of the products can be done in a conventional manner.
• the amines of the formula II required for the preparation of the heteroaroyl-substituted alanines of the formula I can be purchased.
• L 1 represents a nucleophilic displaceable leaving group, for example for hydroxy or C 1 -C 6 alkoxy.
• L 2 is a nucleophilically displaceable leaving group, for example hydroxy, halogen, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, C 1 -C 4 -alkylsulfonyl, phosphoryl or iso-ureyl.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-C ⁇ alkanes, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, Anisole and tetrahydrofuran, and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably diethyl ether, dioxane and tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned.
• Suitable bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium isopropylamide and lithium hexamethyldisilazide, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, and alkali metal and alkaline earth metal alkoxides such as sodium methoxide, sodium ethanolate, Potassium ethoxide, potassium tert-butoxide, potassium tert-pentoxide and Dimethoxymagnesium, also organic bases, eg tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bi
• the bases are generally used in equimolar amounts, but they can also be used catalytically, in excess or optionally as a solvent.
• the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous to use the base and / or the imino compounds VII in an excess relative to the glycine derivatives VIII.
• the workup and isolation of the products can be done in a conventional manner.
• L 1 is a nucleophilically displaceable leaving group, for example for hydroxy or C 1 -C 6 -alkoxy.
• L 3 is a nucleophilically displaceable leaving group, for example halogen, hydroxy, or C 1 -C 6 -alkoxy.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-Cs alkanes, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert.-butylmethyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and also di
• Suitable reducing agents are transition metal catalysts (e.g., Pd / C or Raney Ni) in combination with hydrogen.
• the workup and isolation of the products can be done in a conventional manner.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-Cs alkanes, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and Tetrahydrofuran (THF), nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and dimethyl sulfoxide, dimethylformamide and Dimethylacetamide, more preferably toluen
• Suitable reducing agents are transition metal catalysts (eg Pd / C or Reney Ni) in combination with hydrogen.
• the workup and isolation of the product can be carried out in a conventional manner.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-C ⁇ alkanes, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propinonitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert.
• aromatic hydrocarbons such
• Bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate and also alkali metal hydrogencarbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride and also alkali metal and earth metal halides.
• alkali metal and alkaline earth metal hydroxides such as lithium hydro
• kalimetallalkoholate such as sodium, sodium, potassium, potassium tert-butoxide, potassium tert-pentoxide and Dimethoxymagnesium
• organic bases eg te R tiäre amines such as trimethylamine, triethylamine, Diisopropylethy- lamin and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration.
• Particularly preferred are sodium hydroxide, sodium hydride and triethylamine.
• the bases are generally used in equimolar amounts, but they can also be used catalytically, in excess or optionally as a solvent.
• the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous to use the base and / or IX in an excess based on III or I.
• the workup and isolation of the products can be done in a conventional manner.
• R 9 is not H L 1 represents a nucleophilically displaceable leaving group, for example hydroxy or C 1 -C 6 -alkoxy.
• L 2 represents a nucleophilic displaceable leaving group, for example hydroxy, halogen, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, C 1 -C 4 -alkylsulfonyl, phosphoryl or iso-ureyl.
• L 3 represents a nucleophilically displaceable leaving group, for example halogen, hydroxy, or C 1 -C 6 -alkoxy.
• R ⁇ and R z are hydrogen, C 1 -C 6 -alkyl or aryl.
• R w is hydrogen or R 5 .
• R x represents an acyl group such as C 1 -C 6 -alkylcarbonyl (eg methylcarbonyl) or C 1 -C 6 -alkoxycarbonyl (eg methoxycarbonyl).
• the reaction of the glycine derivatives of the formula XII with an allyl alcohol derivative of the formula XI is usually carried out at temperatures from -100 0 C to the boiling point of the reaction mixture, preferably -8O 0 C to 8O 0 C, particularly preferably -2O 0 C to 5O 0 C, in an inert organic solvent in the presence of a transition metal catalyst and a base, and subsequent aqueous-acid work-up.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-Cs alkanes, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and dimethyl
• Palladium, iridium or molybdenum catalysts may preferably be used as catalysts, preferably in the presence of a phosphine ligand such as triphenylphosphine.
• a phosphine ligand such as triphenylphosphine.
• the reaction is also enantioselective (see D. Ikeda et al., Tetrahedron Lett., 2005, 46 (39), 6663; T. Kanayama et al., J. of Org. Chem. 2003, 68 (16), 6197; I. Baldwin et al., Tetrahedron Asym. 1995, 6 (7), 1515; J. Genet et al., Tetrahedron 1988, 44 (17), 5263).
• Bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate, and alkali metal bicarbonates, such as sodium bicarbonate, alkali metal and alkaline earth metal alcoholates, such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butoxide, potassium tert-pentoxide and dimethoxy magnesium; Bases, for example, tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine and N-methylpiperidine, pyridine,
• the subsequent steps 2 and 3 can be carried out analogously to the reaction of alanine derivatives of the formula V described in Method A with heteroaryl acid (derivatives) n of the formula IV to give corresponding heteroaroyl derivatives of the formula III and then reacting the reaction product with amines of the formula II to give the desired heteroaroyl Substituted alanines of the formula I take place.
• the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous to use the base and / or IX in an excess based on III or I.
• the workup and isolation of the products can be done in a conventional manner.
• the required glycine derivatives of the formula XII can be obtained analogously to methods known from the literature (compare Vicky A. Burgess et al., Aust. J. of Chem. (1988), 41 (7), 1063-1070).
• the required allyl alcohol derivatives of the formula XI can be purchased.
• the oxidation of the double bond to the aldehyde is usually carried out at temperatures of -100 0 C to the boiling point of the reaction mixture, preferably -8O 0 C to 40 0 C, particularly preferably -8O 0 C to O 0 C, in an inert organic solvent in in the presence an oxidizing agent.
• the oxidation is carried out with ozone or via the sequential dihydroxylation with osmium catalysts such as Os ⁇ 4 or permanganates such as KMnO 4 and subsequently et al., J. Europ. J. of Org. Chem. 2004, (13), 2905; S. Hanessian et al., J. of Med. Chem. (2001), 44 (19), 3074; J. Sabol et al., Tetrahedron Lett. 1997, 38 (21), 3687; D. Halle et al., J. of Chem. Soc., Chem , (6), 657).
• osmium catalysts such as Os ⁇ 4 or permanganates such as KMnO 4
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-Cs alkanes, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran (THF), nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol,
• the workup and isolation of the product can be carried out in a conventional manner.
• Preferred reducing agents are borohydrides such as NaBH4 (see A. Siebum et al., J. Europ. J. of Org. Chem. 2004, (13), 2905; S. Hanessian et al., J. of Med. Chem. Sabol et al., Tetrahedron Lett. 1997, 38 (21), 3687; D. Halle et al., J. of Chem. Soc., Chem. (6), 657).
• borohydrides such as NaBH4 (see A. Siebum et al., J. Europ. J. of Org. Chem. 2004, (13), 2905; S. Hanessian et al., J. of Med. Chem. Sabol et al., Tetrahedron Lett. 1997, 38 (21), 3687; D. Halle et al., J. of Chem. Soc., Chem. (6), 657).
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-C ⁇ alkanes, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, Anisole and tetrahydrofuran (THF), alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and dimethylformamide and dimethylacetamide, more preferably toluene.THF and dioxane. It is also possible to use mixtures of the solvents mentioned.
• aromatic hydrocarbons such as toluene, o-, m- and p-xylene
• ethers such as diethyl
• the workup and isolation of the product can be carried out in a conventional manner.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-Cs alkanes, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl ethyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably dichloromethane, tert-butyl methyl ether, dioxane and tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned.
• Bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate and alkali metal bicarbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyl lithium, butyl lithium and phenyllithium, alkylmyl- magnesium halides such as methylmagnesium chloride and organic bases, eg tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridine
• Dimethylaminopyridine and bicyclic amines into consideration are particularly preferred.
• Particularly preferred are sodium carbonate, sodium hydride and triethylamine.
• the bases are generally used in equimolar amounts, but they can also be used catalytically, in excess or, if appropriate, as solvent.
• the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous to use the base and / or XIII in an excess based on I.
• R 1 and R 4 , R 5 , R 6 , R 7 and R 8 have the meanings mentioned above and L 1 is a nucleophilically displaceable leaving group, for example, hydroxy or Ci- C ⁇ -alkoxy, are also an object of present invention.
• a 5- or 6-membered heteroaryl selected from the group of thienyl, furyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl and pyridyl; wherein said heteroaryl may be partially or fully halogenated and / or 1 to 3 radicals from the group Ci-C ⁇ -alkyl, Ca-C ⁇ -cycloalkyl and d-C ⁇ -haloalkyl may carry;
• R 1 is hydrogen;
• R 4 is hydrogen;
• R 5 is C ⁇ -C ⁇ -alkenyl, C 1 -C 6 -haloalkyl, 3 to 6-membered heterocyclyl, C 1 -C 6 -alkyl
• Solution A - 60 0 C, 44 g (0.103 mol) of n-butyllithium (15% strength in hexane) was added dropwise to a solution of 10.4 g (0.103 mol) of diisopropylamine in 500 ml THF. It was stirred for 30 min at - 20 0 C and stirred again at - 60 0 C cooled. A solution of 27.5 g (0.103 mol) (Benzhydryliden-amino) -acetic acid ethyl ester in 30 ml THF was added dropwise, and it was 1 h at - 60 0 C stirred.
• Solution B 26 g (0.103 mol) of acetic acid (E) -1,3-diphenylallyl ester (prepared according to J. Chem. So ⁇ , Perkin Trans. 1, 2001, 2588-2594), 5.4 g (0.021 mol) of triphenylphosphine and 1.9 g (0.0052 mol) of [Pd (allyl) Cl] 2 was dissolved in 40 ml of THF. At - 60 0 C solution B was added dropwise to solution A, stirred for 3 h at this temperature and then warmed to room temperature. It was with ges. NH4Cl solution and extracted with MTBE. The combined organic phases were dried over Na ⁇ SCU and the solvent removed in vacuo.
• the heteroaroyl-substituted alanines of the formula I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of pure isomers - as herbicides.
• the compounds of the formula I containing herbicidal agents control plant growth on non-crop areas very well, especially at high application rates. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crops. This effect occurs especially at low application rates.
• the compounds of the formula I or herbicidal compositions containing them can be used in a further number of crop plants for the removal of unwanted plants.
• the following cultures may be considered:
• the compounds of formula I may also be used in cultures tolerant to the action of herbicides by breeding, including genetic engineering.
• the compounds of formula I can also be used in cultures tolerant by breeding including genetic engineering against insect or fungal attack.
• the compounds of the formula I or the herbicidal compositions containing them can be used, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, even high-percentage aqueous, oily or other suspensions or dispersants.
• the forms of application depend on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.
• the herbicidal compositions contain a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of I and auxiliaries customary for the formulation of crop protection agents.
• Suitable inert auxiliaries are essentially:
• Mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strong polar solvents, e.g. Amines such as N-methylpyrrolidone and water.
• Paraffins etrahydronaphthalene
• alkylated naphthalenes and their derivatives alkylated benzenes and their derivatives
• alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol
• ketones such as cyclohexanone
• Aqueous application forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding
• Water to be prepared Water to be prepared.
• the substrates as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agents, tackifiers, dispersants or emulsifiers.
• wetting agents wetting, adhesion, dispersing or emulsifying agent and possibly solvent or oil, which are suitable for dilution with water.
• surfactants are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols and fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethyl noctylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphen
• Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.
• Granules for example coated, impregnated and homogeneous granules, can be prepared by binding the active compounds to solid carriers.
• Solid carriers are mineral soils such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
• mineral soils such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour
• the concentrations of the compounds of the formula I in the ready-to-use formulations can be varied within wide limits.
• the formulations contain from about 0.001 to 98 wt .-%, preferably 0.01 to 95 wt .-%, of at least one active ingredient.
• the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
• an active compound of the formula I 20 parts by weight of an active compound of the formula I are well mixed with 3 parts by weight of the sodium salt of Diisobutylnaphthalinsulfonklare, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill.
• a spray mixture containing 0.1 wt .-% of the active ingredient of the formula I.
• the application of the compounds of the formula I or of the herbicidal compositions can be carried out in the preemergence or postemergence process. If the active ingredients are less compatible with certain crops, application techniques may be used in which the herbicidal agents are sprayed with the help of the sprayers so as not to hit the leaves of the sensitive crops as far as possible, while the active ingredients on the leaves below grow undesirable plants or the uncovered soil surface (post-directed, lay-by).
• the application rates of compound of the formula I are 0.001 to 3.0, preferably 0.01 to 1.0, kg / ha of active substance (see above).
• the heteroaroyl-substituted serine amides of the formula I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups and applied together.
• the culture vessels used were plastic flower pots with loamy sand with about 3.0% humus as the substrate.
• the seeds of the test plants were sown separately by species.
• the active ingredients suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles.
• the jars were lightly rained to promote germination and growth and then covered with clear plastic hoods until the plants had grown. This cover causes a uniform germination of the test plants, if it was not affected by the active ingredients.
• the test plants were grown depending on the growth form only to a stature height of 3 to 15 cm and only then treated with the suspended or emulsified in water agents.
• the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
• the application rate for postemergence treatment was 1.0 kg / ha aS (active substance).
• the plants were kept species-specific at temperatures of 10 to 25 0 C and 20 to 35 0 C.
• the trial period lasted for 2 to 4 weeks. During this time, the plants were cared for, and their response to each treatment was evaluated.
• the rating was based on a scale of 0 to 100. 100 means no emergence of the plants or complete destruction of at least the above-ground parts and 0 no damage or normal growth course.
• the plants used in the greenhouse experiments were composed of the following species:

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• 2007
  • 2007-05-11 JP JP2009510422A patent/JP2009537480A/ja not_active Withdrawn
  • 2007-05-11 EP EP07729014A patent/EP2027095A1/de not_active Withdrawn
  • 2007-05-11 BR BRPI0710930-0A patent/BRPI0710930A2/pt not_active IP Right Cessation
  • 2007-05-11 WO PCT/EP2007/054562 patent/WO2007134984A1/de active Application Filing
  • 2007-05-11 US US12/300,884 patent/US20090186766A1/en not_active Abandoned
  • 2007-05-18 AR ARP070102167A patent/AR061032A1/es not_active Application Discontinuation
• 2008
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