Classifications

• • 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
• • 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
  • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
  • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
  • A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
• • 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
  • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
  • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
• • 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
  • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
  • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
  • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
• • 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
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
  • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom 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
  • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
  • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
  • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom 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
  • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
  • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
  • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
  • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
  • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
  • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
  • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

• the present invention relates to heteroaroyl-substituted serine amides of the formula I.
• Het mono- or bicyclic heteroaryl having 5 to 10 ring members containing 1 to 4 heteroatoms from the group nitrogen, oxygen and sulfur, which may be partially or fully halogenated and / or 1 to 3 radicals from the group cyano, nitro, C r C 6 Alkyl, d-Ce-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 1 -C 6 -acoxycarbonyl-C 1 -C 6 -alkoxy, amino, C 1 -C 6 -alkylamino, di (C 1 -C 6 -alkyl) amino, C ⁇ C 6 - Alkylsulfonylamino, dC 6 -haloalkylsulfonylamino, aminocarbonylamino, (d-Ce-alkylamino-carbonylamino, di (C 1 -C 6 -alkyl) -aminocarbonylamino, aryl and aryl (dC 6 -alkyl);
• R 1 , R 2 is hydrogen, hydroxy or C 1 -C 6 -alkoxy
• R 3 is C 1 -C 6 -Alk ⁇ 1 C 1 -C 4 cyanoalkyl or dC 6 -haloalkyl;
• R 4 is hydrogen, 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 , d-Ce-alkylcarbonyl, C 3 -C 6 -cycloalkyl alkylcarbonyl, C 2 -C 6 alkenylcarbonyl, C 2 -C 6 alkynylcarbonyl, CrC nyl -Alkoxycarbo- 6, C 3 -C 6 alkenyloxycarbonyl, Cs Ce alkynyloxycarbonyl, C r C 6 -Alkylaminocar- carbonyl, CRCE-alkenylaminocarbonyl, Cs-Ce alkynylaminocarbonyl, CRCE-alkyl sulfonyla
• R 5 is hydrogen or C 1 -C 6 -alkyl
• R 6 is d-Ce-alkyl, C ⁇ C ⁇ -1-lalogenalkyl or phenyl, where the phenyl radical may be partially or completely halogenated and / or may carry one to three of the following groups: C 1 -C 6 -A ⁇ yI, d-Ce -Haloalkyl or C 1 -C 6 -alkoxy;
• 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.
• Benzoyl-substituted serinamides having pharmaceutical activity which carry a tetrazolyl radical in the ⁇ -position are described inter alia in JP 03/294253. Furthermore, from the literature, for example from WO 03/066576, herbicidally active phenylalanine derivatives which are unsubstituted in the ⁇ -position or optionally carry halogen-substituted alkyl, alkenyl or alkynyl radicals are known.
• heteroaroyl-substituted serine amides of the formula I and de ⁇ ren herbicidal activity were found.
• herbicidal agents were found which contain the compounds I and have a very good herbicidal activity.
• processes for the preparation of these agents 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 der ⁇ those acids 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 C 1 -C 4 -alkyl, hydroxy-Ci-C4-alkyl, -C 4 alkoxy-Ci-C4-alkyl, hydroxy-C 1 -C 4 -alkoxy-Ci-C 4 alkyl, or Phe nyl Benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2- (2-hydroxyeth-1-oxy) eth-1-ylammonium, di- (2-hydroxyeth-1-yl) ammonium, trimethylbenzylammonium , furthermore phosphon
• Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of dC 4 alkanoic acids, preferably formate, acetate, propionate and butyrate ,
• the organic moieties mentioned for the substituents R 1 -R e or as radicals on phenyl, aryl, heteroaryl or heterocyclic rings represent collective terms for individual listings of the individual group members.
• All hydrocarbon chains ie all alkyl, alkylsilyl Alkenyl, alkynyl, cyanoalkyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxy, haloalkoxy, alkoxyalkyl, alkoxyalkoxyalkyl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl , Alkylamino, alkylsulfonylamino, haloalkylsulfonylamino, alkylalkoxycarbonylamino, alkylaminocarbonyl, alkenylaminocarbon
• halogenated substituents preferably carry one to five identical or different halogen atoms.
• the meaning halogen is in each case fluorine, chlorine, bromine or iodine.
• C 1 -C 4 -A ⁇ yI as well as the alkyl moieties of tri-Ci-C4 alkylsilyl, C 1 -C 4 alkylcarbonyloxy, Ci-C4 alkyl -C 4 alkoxycarbonylamino, C 1 -C 6 -Alkyliminooxy C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl and aryl (C r C 4 -alkyl): for example methyl, ethyl, n- Propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl and 1, 1-dimethylethyl;
• alkylcarbonyl for example methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-methyl-ethylcarbonyl, butylcarbonyl, 1-Methylpropylcarbonyl, 2-Methylpropylcarbonyl or
• C 3 -C 6 -cycloalkyl and also the cycloalkyl parts of C 3 -C 6 -cycloalkylcarbonyl monocyclic, saturated hydrocarbon having 3 to 6 ring members, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
• 4-methyl-1-pentynyl 4-methyl-2-pentynyl, 1, 1-dimethyl-2-butynyl, 1, 1-dimethyl-3-butynyl, 1, 2-dimethyl-3-butynyl, 2.2- Dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, i-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2- propynyl;
• - d-Cr-cyanoalkyl e.g. Cyanomethyl, 1-cyanoeth-1-yl, 2-cyanoeth-1-yl, 1-cyano-prop-1-yl, 2-cyanoprop-1-yl, 3-cyanoprop-i-yl, 1-cyanoprop-2-yl 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-propyl 3-yl, 3-cyano-2-methyl-prop-3-yl and 2-cyano-methyl-prop-2-yl;
• - C t -C -haloalkyl a C ⁇ C ⁇ alkyl radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, eg Chlorme ⁇ methyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl , Chloromethyl, dichlorofluoromethyl, chlorodifluoromethyl, bromomethyl, iodomethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-
• C 3 -C 6 -haloalkenyl a C 3 -C 6 -alkenyl radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 2-chloroprop-2-ene 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
• C 3 -C 6 -haloalkynyl a C 3 -C 6 -alkynyl radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, eg 1,1-
• Ci-C 6 haloalkoxy C 1 -C 4 -HaIOgCnBIkOXy as mentioned above, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-Brompentoxy, 5-lodpentoxy, pentoxy Undecafluor-, 6-Fluorhexoxy, 6-Chlorhexoxy, 6 Bromohexoxy, 6-iodohexoxy and tridecafluorohexoxy;
• C 1 -C 6 alkoxy-C 1 -C 4 -alkyl C 1 -C 6 -alkoxy as mentioned above substitutability tes C 1 -C 4 -A ⁇ yI 1 eg methoxymethyl, ethoxymethyl, propoxymethyl, ( 1-
• N (Ci-C 6 alkylamino) imino-C 1 - C ⁇ -alkyl for example, methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino , 1, 1-dimethylethylamino, pentylamino, 1-methylbutylamino, 2-methylbutylamino, 3-methylbutylamino, 2,2-dimethylpropylamino, 1-ethylpropylamino, hexylamino, 1,1-dimethylpropylamino,
• N, N-dipentylamino N, N-dihexylamino, N-methyl-N-pentylamino, N-ethyl-N-pentylamino, N-methyl-N-hexylamino and N-ethyl-N-hexylamino;
• Di (C 1 -C 4 alkyl) aminocarbonylamino for example N, N-dimethylaminocarbonyl, N, N-diethyl-aminocarbonyl, N 1 N-di- (I-methylethyl) aminocarbonyl, N, N-dipropylaminocarbonyl, N, N-Dibutylaminocarbonyl, N 1 N- Di- (1-methylpropyl) aminocarbonyl, N, N-di- (2-methylpropyl) aminocarbonyl, N 1 N -di (1,1-dimethylethylaminocarbonyl, N -ethyl-N-methylaminocarbonyl, N -methyl-N-propylaminocarbonyl , N-methyl-N- (1-methylethyl) aminocarbonyl, N-butyl-N-methylaminocarbonyl, N-methyl-N- (1-methylethyl) aminocarbonyl, N-but
• Di (C 1 -C 6 -alkyl) aminothiocarbonyl eg N, N-dimethylaminothiocarbonyl, N 1 N -diethylaminothiocarbonyl, N, N-di- (1-methylethyl) aminothiocarbonyl, N, N-dipropylaminothiocarbonyl, N, N-dibutylaminothiocarbonyl, N 1 N Di- (1-methylpropyl) -amino-thiocarbonyl, N, N -di-1-methylpropyl- 1 -aminothiocarbonyl, N, N -di (1, 1-dimethyl-ethyl) -aminothiocarbonyl, N-ethyl-N-methylaminothiocarbonyl, N Methyl N-propylaminothiocarbonyl, N-methyl-N- (1-methylethyl) aminothiocarbonyl, N-buty
• N-linked, 5-membered, partially unsaturated rings such as: 2,3-dihydro-1H-pyrrol-1-yl, 2,5-dihydro-1H-pyrrol-1-yl, 4,5-dihydro-1 H-pyrazol-1-yl, 2,5-dihydro-
• C-linked 5-membered aromatic rings such as: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, pyrrol-2-yl, pyrrol-3-yl, pyrazol-3-yl, pyrazole-4 yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-2-yl, imidazole-4 yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, 1, 2,3-oxadiazol-4-yl, 1, 2,3-oxadiazol-5-yl, 1, 2,4-oxadiazole
• N-linked, 5-membered aromatic rings such as: pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl, 1,2,3-triazol-1-yl, 1,2,4- Triazol-i-yl, tetrazol-1-yl;
• C-linked, 6-membered, partially unsaturated rings such as: 2H-3,4-dihydropyran-6-yl, 2H-3,4-dihydropyran-5-yl, 2H-3,4-dihydropyran-4-yl, 2H -3,4-dihydropyran-3-yl, 2H-3,4-dihydropyran-2-yl, 2H-3,4-dihydro-pyran-6-yl, 2H-3,4-dihydrothiopyran-5-yl, 2H-3 , 4-dihydrothiopyran-4-yl, 2H-3,4-dihydropyran
• C-linked, 6-membered, aromatic rings such as: pyridinium-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, Pyrimidin-4-yl, pyrimidin-5-yl, pyrazine-2-yl, 1,3,5-triazin-2-yl, 1, 2,4-triazin-3-yl, 1,2,4-triazine 5-yl, 1, 2,4-triazin-6-yl, 1, 2,4,5-tetrazine-3-yl;
• aryl C r C 4 alkyl: mono- to trinuclear aromatic carbocyclic having 6 to 14 ring members, such as phenyl, naphthyl and anthracenyl;
• 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 one oxygen or sulfur atom: e.g. aromatic 5-membered ring heterocycles linked via a carbon atom, which are adjacent
• Carbon atoms may contain 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. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3 Pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-
• Carbon atoms may contain one to four, preferably one to three, nitrogen atoms as ring members, for example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, Pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1, 3,5-triazin-2-yl and 1, 2,4-triazin-3-yl;
• mono- or bicyclic heteroaryl having 5 to 10 ring members containing 1 to 4 heteroatoms from the group of nitrogen, oxygen and sulfur: mono- or bicyclic aromatic heteroaryl having 5 to 10 ring members, wel ⁇ ches next to carbon atoms 1 to 4 nitrogen atoms, or Contains 1 to 3 nitrogen atoms and one oxygen or one sulfur atom, or an oxygen or sulfur atom, eg Monocycles such as furyl (e.g., 2-furyl, 3-furyl), thienyl (e.g., 2-thienyl, 3-thienyl),
• Pyrrolyl eg pyrrol-2-yl, pyrrol-3-yl
• pyrazolyl eg pyrazol-3-yl, pyrazol-4-yl
• isoxazolyl eg isoxazol-3-yl, isoxazol-4-yl, isoxazole-5 -yl
• isothiazolyl eg isothiazol-3-yl, isothiazol-yl, isothiazol-5-yl
• imidazolyl eg imidazol-2-yl, imidazol-4-yl
• oxazolyl eg oxazol-2-yl, oxazole 4-yl, oxazol-5-yl
• thiazolyl eg thiazol-2-yl, thiazol-4-yl, thiazol-5-yl
• oxadiazolyl eg 1,2,3-oxadiazole
• heteroaroyl-substituted serineamides 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 having one oxygen or sulfur 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;
• heteroaryl may be partially or fully halogenated and / or 1 to 3 radicals selected from cyano, Ci-C 6 alkyl, C 3 -C 6 - cycloalkyl, d-Ce-haloalkyl, C 1 -C 6 -alkoxy , d-Ce-haloalkoxy and C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl; means.
• heteroaryl radicals mentioned may be partially or fully halogenated and / or 1 to 3 radicals from the group cyano, Ci-C ⁇ alkyl, C 3 -C 6 - cycloalkyl, -C 6 haloalkyl, C 1 -C 6 -alkoxy, C r can carry C 6 -haloalkoxy and C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl; means.
• heteroaroyl-substituted serineamides of the formula I in which A is 5- or 6-membered heteroaryl selected from the group consisting of pyrrolyl, thienyl,
• heteroaryl radicals mentioned may be partially or completely halogenated and / or 1 to 3 radicals from the group C 1 -C 6 -AlkVl, C 3 -C 6 -cycloalkyl and d-Ce-haloalkyl may carry;
• heteroaryl selected from the group of thienyl, furyl, pyrazolyl, imidazolyl, thiazolyl and oxazolyl; wherein said heteroaryl may be partially halogenated and / or may carry from 1 to 2 of d-Ce-alkyl and C 1 -C -haloalkyl;
• heteroaryl radicals can be partially halogenated and / or can carry 1 to 2 radicals from the group consisting of C 1 -C 6 -alkyl and dC-r-haloalkyl.
• heteroaroyl-substituted serine amides of the formula I in which A is C-linked 5- or 6-membered heteroaryl selected from the group A1 to A14 with
• R 7 is hydrogen, halogen, C 1 -C 6 -alkyl or C 6 haloalkyl; particularly preferably hydrogen, C 1 -C 4 -alkyl or C 4 haloalkyl; particularly preferably hydrogen or C 1 -C 4 -alkyl; most preferably hydrogen;
• R 8 is halogen, C 1 -C 6 -alkyl, d-Ce-haloalkyl or -C ß haloalkoxy; particularly preferably halogen, C 1 -C 4 -alkyl or -C 4 haloalkyl; especially preferably halogen or C 1 -C 4 -haloalkyl; most preferably CF 3 ;
• R 9 is hydrogen, halogen, C 1 -C 6 alkyl or d-Ce-haloalkyl; particularly preferably hydrogen, halogen or C 1 -C 4 -haloalkyl; especially preferably hydrogen or halogen; most preferably hydrogen; and
• R 10 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 cycloalkyl, C r C 6 haloalkyl or C 1 - C 6 alkoxy C r C 4 alkyl; more preferably CrC 4 alkyl, C 3 -C 6 cycloalkyl, dC 4 haloalkyl or d-OrAlkoxy-dd-alkyl; particularly preferably C 1 -C 4 -alkyl or C 4 haloalkyl; most preferably C 1 -C 4 alkyl; most preferably CH 3 ;
• R 7 to R 9 are defined as mentioned above;
• heteroaroyl-substituted serineamides of the formula I in which Het is mono- or bicyclic heteroaryl having 5 to 10 ring members containing 1 to 4 heteroatoms from the group consisting of nitrogen, oxygen and sulfur, which may be partially or fully halogenated and / or 1 to 3 radicals from the group nitro, C 1 -C 4 alkyl, C r C 4 haloalkyl, hydroxy, C 1 -C 4 alkoxy, ⁇ - haloalkoxy, hydroxycarbonyl , C 1 -C 4 -alkoxycarbonyl, hydroxycarbonyl-C r C 4 -alkoxy, Ci-OrAlkoxycarbonyl-d-cralkoxy, amino, C 1 -C 4 -alkylamino, di (C 1 -C 4 -alkyl) amino, dd-alkylsulfonylamino , C 1 -C 4 -
• heteroaryl selected from the group furyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, quinolinyl and indolyl, where the heteroaryls mentioned may be partially or fully halogenated and / or 1 to 3 radicals from the group comprising nitro, Ci-C 4 alkyl, C 1 -C 4 - haloalkyl, hydroxy, C 1 -C 4 -alkoxy, dC 4 -haloalkoxy, hydroxycarbonyl, dC 4 -alkoxycarbonyl, hydroxycarbonyl-C 1 -C 4 alkoxy, C 1 -C 4 -
• heteroaryls selected from the group of thienyl, thiazolyl, tetrazolyl, pyridyl and indolyl, where said heteroaryls may be partially or completely halogenated and / or 1 to 2 radicals from the group nitro, C 1 -C 4 -AlkVl , C 1 -C 4 -haloalkyl, hydroxy, C 1 -C 4 -alkoxy, C r C 4 -haloalkoxy, hydroxycarbonyl, d-Cr-alkoxycarbonyl, hydroxycarbonyl-C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxycarbonyl-C r C 4 alkoxy, amino, C r C 4 alkylamino, di (C 1 -C 4 alkyl) - amino, Ci-C4 alkylsulfonylamino, C ⁇ CrHalogenalkylsul
• heteroaroyl-substituted serineamides of the formula I 1 in which Het is Het-1 to Het-6,
• R 11 is hydrogen, halogen, C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl; preferably hydrogen, halogen, C 1 -C 4 -alkyl or C r C 4 haloalkyl; especially preferably hydrogen, halogen or C 1 -C 4 -alkyl; particularly preferably hydrogen, fluorine, chlorine or methyl;
• R 12 is hydrogen, halogen, C 1 -C 6 -alkyl or C r C 6 -haloalkyl; preferably hydrogen, halogen, C 1 -C 4 -alkyl or C 1-6 -haloalkyl; especially preferably hydrogen, halogen or C 1 -C 4 -alkyl; particularly preferably hydrogen, fluorine, chlorine or methyl;
• R 13 is hydrogen, halogen or C 1 -C 4 -alkyl; preferably hydrogen, or halogen; especially preferably hydrogen or fluorine;
• heteroaroyl-substituted serine amides are of the formula I 1 wherein R 3 is C 1 -C 6 -alkyl or C r C 6 haloalkyl; particularly preferably C 1 -C 6 -alkyl; especially preferably C 1 -C 4 -alkyl; most preferably CH 3 ; means.
• C ⁇ alkyl where the abovementioned alkyl, cycloalkyl or alkoxy radicals can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, hydroxy, C 3 -C 6 -cycloalkyl, C 1 -C 4 - AIkOXy, C 1 -C 4 -alkylthio, di- (C 1 -C 4 -alkyl) -amino, dC t -alkylcarbonyl, hydroxycarbonyl, C 1 - C 4 -alkoxycarbonyl, aminocarbonyl, C 1 -C 4 -alkylaminocarbonyl, di- (C C 1 -C 4 -alkyl) aminocarbonyl or or SO 2 R 6 ; means. r
• heteroaroyl-substituted serine amides of the formula I 1 in which R 4 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, d-carbonyl Alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, C 1 -C 6 -alkylaminocarbonyl, di- (C 1 -C 6 -alkyl) aminocarbonyl,
• N- (C 1 -C 6 -alkoxy) -N- (C 1 -C 6 -alkyl) -amino-carbonyl where the abovementioned alkyl and alkoxy radicals can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylaminocarbonyl or di (C 1 -C 4 alkyl) -aminocarbonyl; Phenyl-CrCe-alkyl, phenylcarbonyl, phenylcarbonyl-C 1 -C 6 -alkyl, phenylaminocarbonyl, N- (C 1 -C 6 -alkyl) -N- (phenyl) -aminocarbonyl or heterocyclylcarbonyl, where the phenyl and the heterocyclyl radicals of the last mentioned substituents are may be partially or completely
• 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 NEN and / or 1 to 3 radicals from the group CrC 6 alkyl, C 3 -C 6 cycloalkyl and CrC ⁇ -haloalkyl may carry;
• R 4 is hydrogen, d-GrAlkylcarbonyl, dd-alkylaminocarbonyl, di- (dC 4 alkyl) - aminocarbonyl, phenylaminocarbonyl, N- (CI-C4 alkyl) -N- (phenyl) - aminocarbonyl, SO 2 CH 3 or SO 2 (C 6 H 5 ); and R 5 is hydrogen.
• the compounds of the formula I.c. in particular the compounds of the formula I.c.1.1 to I.c.1.192, which differ from the corresponding compounds of the formula I.a.1.1 to I.a.1.192 in that Het is Het-3.
• the compounds of the formula ld1 in particular the compounds of the formula ld1.1 to d.1.192, which differ from the corresponding compounds of the formula Ia1.1 to Ia1.192 in that Het for Het-4 stands.
• the compounds of the formula I.e.1 in particular the compounds of the formulas I.e.1.1 to I.e.1.192, which differ from the corresponding compounds of the formulas Ia.1.1 to Ia.1.192 in that Het is Het-5.
• the compounds of the formula I.f.1 in particular the compounds of the formulas I.f.1.1 to I.f.1.192, which differ from the corresponding compounds of the formulas I.a.1.1 to I.a.1.192 in that Het is Het-6.
• benzoyl-substituted serine amides of the formula I can be obtained in various ways and in the manner of the art, for example by the following processes:
• Serine derivatives of the formula V are first reacted with heteroaryl acid (derivatives) of the formula IV to form corresponding heteroaroyl derivatives of the formula III, which subsequently react with amines of the formula II to give the desired heteroaoyl-substituted serineamides of the formula I:
• L 1 is a nucleophilically displaceable leaving group, for example for hydroxy or C 1 -C 6 - alkoxy.
• L 2 is a nucleophilically displaceable leaving group, for example for hydroxy, halogen, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, Phosphoryl or iso-ureyl.
• the reaction of the serine 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. Bergmann, ED; et al., J Chem Soc 1951, 2673; Zhdankin, VV; et al., Tetrahedron Lett. 2000, 41 (28), 5299-5302; Martin, SF et al., Tetrahedron Lett.
• Suitable activating reagents are condensing agents, e.g. polystyrene-bound dicyclohexylcarbodiimide, diisopropylcarbodiimide, carbonyldiimidazole, chlorocarboxylic acid esters such as methyl chloroformate, ethyl chloroformate, isophoric 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.
• condensing agents e.g. polystyrene-bound dicyclohexylcarbod
• 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) 1 dimethylacetamide (DMA) and N-methylpyrrolidone
• the bases used are generally 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, also 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, trieth
• 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 the usual way, e.g. by mixing with water, separation of 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 Antei ⁇ len. 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 C 5 -C 8 -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.
• aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of C 5 -C 8 -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, diisoprop
• nitriles such as acetonitrile and propionitrile
• ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone
• dimethyl sulfoxide dimethylformamide (DMF), dimethylacetamide (DMA) and N-methylpyrrolidone (NMP) or also in water, particularly preferred are
• Suitable bases are generally inorganic compounds such as alkali metal hydroxides 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, also 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,
• 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.
• serine derivatives of the formula V can be reacted with amines of the formula II first to the corresponding amides in an analogous manner, which then react with heteroaryl acid (derivatives) n of the formula IV to give the desired heteroaroyl-substituted serine amides of the formula I.
• 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 from the corresponding halide analogously to the literature procedure using a Grignard reaction [eg A. Mannschuk et al., Angew , Chem. 100, 299 (1988)].
• Suitable activating reagents are condensing agents, e.g. 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.
• condensing agents e.g. polystyrene-bonded dicyclohexylcarbod
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of C 5 -C 8 -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
• Suitable bases are generally inorganic compounds such as alkali metal hydroxides 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 hydroxides.
• alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate and alkali metal bicarbonates such as sodium bicarbonate
• organic bases for example 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, 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 IM.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of C 5 -C 8 -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.
• aromatic hydrocarbons such as benzene, toluene, o-, m- and p-xylene
• halogenated hydrocarbons such as
• Butyl methyl ketone alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and dimethyl sulfoxide, dimethylformamide (DMF), dimethylacetamide (DM-A) and N-methylpyrrolidone (NMP) or in water, especially preferred are methylene chloride, THF, methanol, ethanol and water.
• the reaction may optionally be carried out in the presence of a base.
• the bases used are generally 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 hydrogencarbonates such as sodium bicarbonate, also organic bases, such as tertiary Ami ⁇ ne 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. Particular preference is given to 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 Il in an excess relative to IM.
• the amines of the formula II required for the preparation of the heteroaroyl-substituted serineamides of the formula I can be purchased.
• Villa VI V with R 4 H
• L 1 represents a nucleophilically 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, Phosphoryl or iso-ureyl.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of C 5 -C 8 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 also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably diethyl ether, dioxane and tetrahydrofuran.
• aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of C 5 -C 8 alkanes
• aromatic hydrocarbons such as toluene, o-, m- and p-xylene
• ethers such as diethyl
• Suitable bases are generally inorganic compounds such as alkali metal and Erdal ⁇ kalimetallhydride such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal azides such as lithium hexamethyldisilazide, organometallic compounds, in particular particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, and alkali metal and alkaline earth metal alkoxides such as sodium, sodium, potassium, potassium tert-butoxide, potassium tert-pentoxide and dimethoxy magnesium, also organic bases, such as tertiary amines such as trimethylamine, triethylamine , Diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyciische amines in Be ⁇ costume. Particularly preferred are sodium hydride, lithium
• the bases are generally employed 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 the heterocyclylcarbonyl compounds VII in an excess based on the glycine derivatives VIII.
• the glycine derivatives of the formula VIII required for the preparation of the compounds I can be purchased, are known in the literature [z. H. Pessoa-Mahana et al., Synth. Comm. 32, 1437 (2002) or can be prepared according to the cited literature.
• 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 C 5 -C 8 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-butyl Butanol and tert-butanol
• the bases used are generally inorganic compounds such as alkali metal hydroxides and alkali earth 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 Li ⁇ thiumcarbonat, potassium carbonate and calcium carbonate and alkali metal hydrogencarbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyl lithium and phenyllithium, alkylmylmesium halides such as methyl magnesium chloride and also alkali metal and alkaline earth metal alcoholates, such as sodium methoxide, sodium ethanol
• tertiary 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.
• Particular preference is given to sodium hydroxide, sodium hydride and triethylamine.
• the bases are generally employed 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 IX in an excess based on III or I.
• the workup and isolation of the products can be carried out in a manner known per se.
• the required compounds of formula VIII can be purchased.
• L is a nucleophilically 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 6 -alkylsulfonyl, phosphoryl or isopropyl.
• L 4 represents a nucleophilically displaceable leaving group, for example for hydroxy or C 1 -C 6 -alkoxy.
• acylation of the aminomalonyl compounds of the formula XI with heteroaryl (derivatives) n of the formula IV to give corresponding N-acylaminomalonyl compounds of the formula X is usually carried out analogously to the reaction of the formula V with heteroaryl acid mentioned under process A. (Derivatives) n of the formula IV to derr corresponding Heteroaroylderivaten of formula III.
• L 4 in the case of the N-acylaminomalonyl compounds of the formula X is C 1 -C 6 -alkoxy, it is advantageous to first prepare L 4 by ester saponification [eg Hellmann, H. et al., Liebigs Ann. Chem. 631, 175-179 (1960)] into a hydroxy group.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of C 5 -C 8 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 also
• the bases used are generally 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 Li ⁇ thiumcarbonat, potassium carbonate and calcium carbonate and alkali metal hydrogencarbonates such as sodium bicarbonate, organometallic compounds, especially alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, Almylmagnesiumhalogenide as Methylmagnesiumchlorid and alkali metal and Erdal- kalimetallalkoholate as sodium methoxide,
• tertiary 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. Particular preference is given to triethylamine and diisopropylethylamine.
• 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 the base in an excess based on X.
• the workup and isolation of the products can be carried out in a manner known per se.
• the required aminomalonyl compounds of the formula XI can be purchased or are known in the literature [z. US 4904674; Hellmann, H. et al., Uebi's Ann. Chem. 631, 175-179 (1960)] or can be prepared according to the cited literature.
• the required heterocyclic compounds of formula VII can be purchased.
• XIII are first acylated with heteroaryl (derivatives) n of the formula IV to give corresponding N-acyl keto compounds of the formula XII and subsequently the keto group is reduced [Girard A, Tetrahedron Lett. 37 (44), 7967-7970 (1996); Nojori R., J. Am. Chem. Soc. 111 (25), 9134-9135 (1989); Schmidt U., Synthesis (12), 1248-1254 (1992); Bolhofer, A .; J. Am. Chem. Soc. 75, 4469 (1953)]:
• L 1 represents a nucleophilically 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 6 -alkylsulfonyl, phosphoryl or isopropyl.
• the acylation of the keto compounds of the formula XIII with heteroaryl acid (derivatives) n of the formula IV to give N-acyl keto compounds of the formula XII is usually carried out analogously to the reaction of the serine derivatives of the formula V mentioned in process A with heteroaryl acid (derivatives) n of the formula IV to the corresponding Heteroaroylderivaten of formula III.
• Chem. 256 (15), 7834-4783 (1981); Vinograd, L et al., Zhurnal Organicheskoi Khimii 16 (12), 2594-2599 (1980); Castro, A. et al., J. Org. Chem. 35 (8), 2815-2816 (1970); JP 02-172956; Suzuki, M. et al., J. Org. Chem. 38 (20), 3571-3575 (1973); Suzuki, M. et al, Synthetic Communications 2 (4), 237-242 (1972)] or can be prepared according to the cited literature.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of C 5 -C 8 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 also
• Suitable reducing agents are, for example, sodium borohydride, zinc borohydride, sodium cyano-borriydride, lithium triethylborohydride (Superhydrid®), lithium tri-sec-butylborohydride (L-Selectrid®), lithium aluminum hydride or borane [cf. eg WO 00/20424; Marchi, C. et al., Tetrahedron 58 (28), 5699 (2002); Blank, S. et al., Liebigs Ann. Chem. (8), 889-896 (1993); Kuwano, R. et al., J. Org. Chem. 63 (10), 3499-3503 (1998); Clariana, J.
• the reduction can also be carried out in the presence of hydrogen and a catalyst.
• Suitable catalysts are, for. B. [Ru (BINAP) CI 2 ] or Pd / C [see. Noyori, R. et al., J. Am. Chem. Soc. 111 (25), 9134-9135 (1989); Bolhofer, A. et al., J. Am. Chem. Soc. 75, 4469 (1953)].
• the reduction can also take place the presence of a microorganism.
• a microorganism e.g. Saccharomyces Rouxii [cf. Soukup, M. et al., HeIv. Chim. Acta 70, 232 (1987)].
• N-acyl keto compounds of the formula XII and the particular reducing agent are generally reacted with one another in equimolar amounts. It may be advantageous to use the reducing agent in an excess relative to XII.
• heteroaroyl derivatives of the formula III in which A is 5- or 6-membered heteroaryl selected from the group consisting of thienyl, furyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl and pyridyl; the mentioned heteroaryl be partially or completely halogen nen and / or 1 to 3 radicals from the group C 1 -C 6 -AlkVl, C 3 -C 6 cycloalkyl, and can carry;
• the heteroaroyl-substituted serine amides of the formula I and their agriculturally useful salts are suitable - both as mixtures of isomers and in the form of pure isomers - as herbicides.
• the herbicidal compositions containing the compounds of the formula I control plant growth on nonculture areas very well, especially at high application rates. In crops such as wheat, rice, maize, soybeans and cotton, they act against weeds and grass weeds, without appreciably damaging crops. This effect occurs especially at low application rates.
• the compounds of the formula I or herbicidal compositions containing them can also be used in a further number of crop plants to eliminate 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 forms of application depend on the intended use; she should ensure in each case as possible the finest 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:
• Medium to high boiling mineral oil fractions 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.
• mineral oil fractions 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 derivative
• Aqueous application forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
• 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.
• concentrates which are active substance, wetting, adhesion, dispersing or emulsifying agent and possibly solvent or oil, which are suitable for dilution with water.
• surface-active substances 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 of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethyl tocylphenol ethers, ethoxylated isooctyl, octyl or nonylphenol, alky
• 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 earths 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, bark, wood and nutshell flour, cellulose powder or other solid carriers.
• mineral earths 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 s
• 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).
• the application of the compounds of the formula I or of the herbicidal compositions can take place in a pre-emergence or postemergence process. If the active ingredients are less compatible for certain crop plants, application techniques can be used in which the herbicidal agents are sprayed with the help of the sprayers so that the leaves of the sensitive crops are not affected if possible, while the active ingredients are applied to the leaves including growing unwanted plants or the uncovered bottom 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).
• 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.
• 1, 2,4-thiadiazoles, 1, 3,4-thiadiazoles, amides, aminophosphoric acid and their derivatives, amides are used as the mixing partners.
• notriazoles anilides, aryloxy / heteroaryloxyalkanoic acids and their derivatives, benzoic acids and derivatives thereof, benzothiadiazinones, 2- (hetaroyl / aroyl) -1, 3-cyclohexanediones, heteroaryl-aryl ketones, benzylisoxazolidinones, meta-CF 3 -phenyl derivatives, Carbamates, quinolinecarboxylic acid and derivatives thereof, chloroacetanilides, cyclohexenone oxime ether derivatives, diazines, dichloropropionic acid and derivatives thereof, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils , Imidazoles, imidazolinones, N-phenyl-3
• the culture vessels used were plastic flower pots with loamy sand with about 3.0% huity as substrate.
• the seeds of the test plants were sown separately by species.
• the active substances 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.
• 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 reared in the same containers or they were first grown separately as seedlings and transplanted into the test vessels a few days before treatment.
• the application rate for postemergence treatment was 1.0 and 0.5 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 reaction to the individual treatments was evaluated.
• a scale of 0 to 100 was used. 100 means no emergence of the plants or complete destruction of at least the above-ground parts and 0 means no damage or normal growth course.
• the plants used in the greenhouse experiments were composed of the following species:
• Compound 3.6 (Table 3) showed a very good action against the undesired plants foxtail, white goosefoot and green bristlecorn in the afterglow.

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