Classifications

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  • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
  • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
  • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole 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
  • C07D277/56—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
  • 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
  • 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

Definitions

• the present invention comprises serine amides of the formula I
• 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 may be partially or fully halogenated and / or 1 to 3 radicals the group cyano, C 1 -C 6 -alkyl, C 3 -Ce- cycloalkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy and C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl;
• R 1 , R 2 are hydrogen, hydroxy or C 1 -C 6 -alkoxy
• R 4 is hydrogen, Ci-C 6 alkyl, C 3 -C 6 -Cycloalky], C 3 -C 6 alkenyl, C 3 -C 6 -AIW nyl, C 3 -C 6 - haloalkenyl, Ca-Ce-haloalkynyl , Formyl, C 1 -C 6 -alkylcarbonyl, C 3 -C 6 -CCCl 10 -alkylcarbonyl, C 2 -C 6 -alkenylcarbonyl, C 2 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, C 2 -C 6 -alkenyloxycarbonyl, C 2 -C 6 -alkyl Alkynioxycarbony !, d-Ce-alkylaminocarbonyl, Ca-C ⁇ -alkenylaminocarbonyl, trCe-alkynylaminocarbonyl,
• R 6 is hydrogen or C 1 -C 6 -alkyl
• R 6 Ci-C 6 -Alky [, C 2 -C 6 -alkyl keny I, C 2 -C 6 alkynyl, CrC 6 -Haiogenalkyl, C 2 -C 6 - haloalkenyl, C2-C6-Ha !, ogenalkiny C 1 -C 6 -cyanoalkyl, C 2 -C 6 -cyanoalkenyl,
• Cydoalkyl, cycloalkenyl or 3- to 6-membered heterocyclyl may be partially or fully halogenated and / or one to three radicals from the group oxo, cyano, 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 -
• Aminocarbonylamino, (Ci-C6-alkylamino) carbonylamino, di- (CrC6-alkyl) - aminocarbonylami ⁇ o, aryl and aryl (CrC6-alky!) Can carry; -C 6 alkoxy-C r C 4 alkyl, C 2 -C 6 alkenyloxy "-C 4 -alkyl> C 2 -C 6 alkynyloxy-CRC4 alkyl, Ci-Ce-haloalkoxy--C 4 -alkyl, C2-C6 -Haloalkenyloxy-CrC 4 -alkyl, C 2 -C 6 -Haioge ⁇ alkinyloxy-Ci-C 4 -alkyl, C r C 6 alkoxy-CrC 4 -alkoxy-Ci-C 4 -alkyl, Cr
• Kenyi phenyl C ⁇ -crhalogenafkinyl, phenyl-C 1 -C 4 -hydroxyalkyl, phenyl-C 2 -C 4 -hydroxyalkenyl, phenyl-C 2 -C 4 -hydroxyalkynyl, phenylcarbonyf-C 1 -C 4 -alkyl, phenylcarbonylamino-C 1 -C 4 -alkyl [, phenylcarbonyloxy -CrC4-alkyl, phenyloxycarbonyl-C 1 -C 4 -alkyl, phenyloxy-Cr
• Halogenoalkylsulfonylamino (C 1 -C 6 -alkylamino) carbonylamino, di (C 1 -C 6 -alkyl) aminocarbonylamino, aryl and aryl (C 1 -C 6 -alkyl);
• R 7 is d-C ⁇ -alkyl.
• the invention relates to processes and intermediates for the preparation of compounds of the forms! I, compositions containing them and the use of these derivatives or agents containing them for controlling harmful plants.
• Fungicidally effective thienyl-substituted amino acid derivatives which carry an alkyl radical in the ⁇ -position which may optionally be substituted by hydroxyl or alkoxy are described inter alia in EP 450 355. Furthermore, from the literature, for example from US 5,346,907, WO 96/012499 and WO 02/069905 serine derivatives with pharmaceutical activity are known, which may carry in ⁇ -position inter alia an alkyl radical which may optionally be substituted by hydroxy or alkoxy.
• 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 enantiomers or diastereomer mixtures.
• the invention provides both the pure enantiomers or diastereomers and mixtures thereof.
• the compounds of the formula I can also be present in the form of their agriculturally useful salts, wherein 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 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 ammonium, where one to four hydrogen atoms are chosen by dC 1 nyl alkyl, hydroxy-C r C 4 alkyl, Ci-C 4 -alkoxy-C r C 4 -alky !, hydroxy-Ci-C ⁇ alkoxy-dC ⁇ alkyl, benzyl or Phe may be replaced, preferably ammonium, Dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2- (2-hydroxyeth-1-oxy) eth-1-yl-ammonium, di- (2-hydroxyeth-1-yl) -ammonium, trimethylbenzylammonium, furthermore phosphonium ions,
• 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 C 1 -C 4 -alkanoic acids, preferably formate, acetate Propionate and butyrate.
• organic moieties mentioned for the substituents R 1 -R 6 or as radicals on phenyl, aryl, heteroaryl or Hetrocyclylringen are collective terms for individual enumerations of the individual group members. All carbon chains hydrocarbons, ie all alkyl, alkylsilyl, alkenyl , Alkynyl, cyanoalkyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxy, haloalkoxy, alkoxyalkyl, alkoxyalkoxyalkyl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyi, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, Alkylamino, alkylsulfonylamino, haloalkylsulfonylamino, alkylalkoxycarbonylamino, alkylaminocarbo ⁇
• halogenated substituents preferably carry one to five identical or different halogen atoms.
• the meaning halogen in each case stands for fluorine, chlorine, bromine or iodine.
• Ci-C4-alkyl as mentioned above, as well as e.g. n-pentyl, 1-methyl-butyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2 Methylpentyl, 3-methylphenyl, 4-methylphenyl, 1,1-dimethylbutyl, 1, 2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl-butyl, 2-ethyl-butoxy !, 1, 1, 2-trimethylpropyl, 1-ethyl-1-methylpropyl! and 1-ethyl-3-methylpropyl;
• C 1 -C 4 -alkylcarbonyl e.g. Methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl, 1-methylpropylcarbonyt, 2-methylpropylcarbonyl or 1, 1-dimethylethylcarbonyl;
• Pentylcarbonyl 1-methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 2,2-dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, hexylcarbonyl, 1, 1-dimethylpropylcarbonyl, 1, 2-dimethylpropylcarbonyl, 1-methylpentylcarbonyl, 2-methylpentylcarbonyl , 3-methylpentylcarbonyi, 4-methylpentylcarbonyl, 1,1-dimethylbutylcarbonyl, 1,2-dimethylbutylcarbonyl, 1,3-dimethylbutylcarbonyl, 2,2-dimethylbutylcarbonyl, 2,3-dimethylbutylcarbonyl, 3,3-dimethylbutylcarbony [ 1-ethylbutylcarbonyl, 2-ethylbutylcarbonyl, 1,1,2-trimethyl [propylcarbonyl, 1,2,2-trimethylphenylcarbony
• C 3 -C 6 cycloalkyicarbonyl monocyclic saturated hydrocarbon having 3 to 6 ring members, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
• C3-Cs-cycloalkenyl eg 1-cyclopropenyl, 2-cyclopropenyl ( 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 1,3-cyclopentadienyl, 1,4-cyclopentadienyl, 2,4- Cyclopentadienyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, 1, 3-cyclohexadienyl, 1, 4-cyclohexadienyl, 2,5-cyclohexadienyl;
• Pentenyl 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl 2-propenyl, 1-ethyl-1-propenyl, i-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-i-pentenyl, 2- methyl-1-pentenyl,
• 3-methyl-1-pentenyl 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentynyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, i-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3 Methyl 4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl -2-buteny [1,2-dimethyl-3-butenyl, 1, 3-dimethyl-1-butenyl, 1, 3-dimethyl-2-butyryl, 1,3-dimethyl-3-butenyl, 2,2- Dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,
• Alkynylaminocarbonyi N- (C 3 -C 12 -alkynyl) -N- (C 1 -C 6 -alkyl) aminocarbonyl, N- (C 3 -C 6 -alkynyl) -N- (C 1 -C 6 -alkoxyaminocarbonyi: for example 1-propynyl, 2- Propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pyridinium, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl 3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexyny
• cyanoalkyl e.g. 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 yl, 2-cyanobut-2-yl, 1-cyanobut-3-yl, 2-cyanobut-3-yl, 1-cya ⁇ o-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;
• Ci-C 4 hydroxyalkyl and the CRD-hydroxyalkyl moieties of phenyl-CrC 4 - hydroxyaikyl, heteroaryl-Ci-C4-hydroxyalkyl: for example hydroxymethyl, 1-hydroxyeth-1-yl,
• 2-hydroxyeth-1-yl 1-hydroxyprop-1-yl, 2-hydroxyprop-i-yl, 3-hydroxyprop-1-yl, 1-hydroxyprop-2-yl, 2-hydroxyprop-2-yl, 1 Hydroxybut-1-yl, 2-hydroxybut-1-yl, 3-hydroxybut-1-yl, 4-hydroxybut-1-yl, 1-hydroxybut-2-yl, 2-hydroxybut-2-yl, 1-hydroxybutyl 3-yl, 2-hydroxybut-3-yl, 1-hydroxy-2-methyl-prop-3-yl, 2-hydroxy-2-methyl-prop-3-yl, 3-hydroxy-2-methyl prop-3-yl and 2-hydroxymethyl-prop-2-yl,
• Ci-C 4 - Hydroxyalkyl Ci-C 4 -Hydroxyalkyl as mentioned above, and for example 1-hydroxy-pent-5-y! : 2-hydroxy-pent-5-yl, 3-hydroxy-pent-5-yl, 4-hydroxy-pent-5-yl, 5-hydroxy-pent-5-yl, i -hydroxypent-4-yl, 2 Hydroxy-4-yl, 3-hydroxypent-4-yl, 4- Hydroxypent-4-yf, 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-yf, 3-hydroxy-2-methyl-but-3-yl, 1-hydroxy-2-methylbut-4-yl, 2-hydroxy-2-methyl but-4-yl, 3-hydroxy-2-methyl-but-4-yl, 4-hydroxy-2-methyl-but-4-yl, 1-hydroxy-3-methylbut-4-yl, 2 Hydroxy-3-methyl-
• -but-4-yl I 1, 2-dihydroxy-pent-5-yl, 2,3-dihydroxy-pent-5-yl, 3,4-dihydroxy-pent-5-yl, 4,5-dihydroxy-pent -5-yl, 1,2-dihydroxypent-4-yl, 2,3-dihydrox ypent-4-yl, 3,4-dihydroxypent-4-yl, 4,5-dihydroxypent-4-yl, 1,2-dihydroxy-pent-3-yl, 2,3-dihydroxy-pent-3-yl, 1,2-dihydroxy-2-methyl-but-3-yl, 2,3-dihydroxy-2-methyl-but-3-yl, 3,4-dihydroxy-2-methyl-but-3-yl, 2 Hydroxy-2-hydroxymethyl-but-3-yl, 1, 2-dihydroxy-2-methyl-but-4-yl, 2,3-dihydroxy-2-methyl-but-4-yl, 3,4-dihydroxy 2-methyl-but-4-yl, 1,
• Ci-C 4 -Ha! Ogenalkyl and the haloalkyl of Heteroaryl-C 1 -C -crhalogenoalkyl 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, chlorofluoromethyl , Dichlorofluoromethyl, chlorodifluoromethyl, bromomethyl, I-odmethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-methyl, 2,2-difluoroethyl, 2,2,2- Trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluor
• C3-C6-haloalkenyl a C3-C6 alkenyl radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, e.g. 2-chloro-prop-2-en-1-yl, 3-chloroprop-2-en-1-yl, 2,3-dichloroprop-2-en-1-yl, 3,3-dichloroprop-2-ene 1-yl, 2,3,3-trichloro-2-en-1-yl, 2,3-dichlorobut-2-en-1-yl, 2-bromoprop-2-en-1-yl, 3-bromopropane 2-en-1-yl, 2,3-dibromoprop-2-en-1-yl, 3,3-dibromoprop-2-en-1-yl, 2,3,3-tribromo-2-ene-1 yl or 2,3-dibromobut-2-en-1-yl;
• C 2 -C 6 -cyanoalkenyl eg 2-cyanovinyl, 2-cyanoailyl, 3-cyanoallyl, 2,3-dicyanoallyl, 3,3-dicyanoallyl, 2,3,3-tricyanoallyl, 2,3-dicyanobut-2 enyl;
• C 3 -C 6 -haloalkynyl a C 3 -C -alkynyl radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, eg 1, 1 -
• C2-C ⁇ -cyanoalkynyl e.g. 1,1-dicyano-prop-2-yn-1-yl, 3-cyano-prop-2-yn-1-y [4-]
• C 1 -C 6 -alkylsulfinyl (C 1 -C 6 -alkyl-S (OO) -) and the C 1 -C 6 -alkylsulfinyl parts of C 1 -C -alkylsulfinyl-C 1 -C 4 -alkyl: for example methylsuifinyl, ethylsulfinyl, propylsulfinyl,
• Ci-C 6 -Alkylsuifinylrest as mentioned above, which partially or completely by fluorine, chlorine, bromine and / or iodine is, for example, fluoromethylsulfinyl, difluoromethylsulfinyl, trifluoromethylsulfinyl, Chlordiflu- ormethylsulfi ⁇ yl, bromodifluoromethylsulfinyl, 2-Fiuorethylsulfinyl, 2-chloroethylsulfinyl, 2-Bromethyisulf ⁇ nyl, 2-iodoethylsulfinyl, 2,2-Dif!
• uorethylsu! finyl 2,2,2-trifluoro ethylsulfinyl, 2,2,2-trichloroethylsulfinyl, 2-chloro-2-fluoroethylsulfinyl, 2-chloro-2,2-di- fluoroethylsulfinyl, 2,2-dichloro-2-fluoroethylsulfinyl, pentafluoroethylsulfinyl, 2-fluoro propylsulfinyl, 3-fluoropropylsulfinyl, 2-chloropropylsulfinyl, 3-chloropropylsulfinyl, 2-
• Ci-Ce-alkylsulfonyi C- ⁇ -C6-alkyl (-S (O) 2 -) and the Ci-Ce-alkylsulfonyl parts of Ci-Cr-alkylsulfonyl-Ci-C4-alkyl, Ci-Cs-alkylsulfonylamino , C 1 -C 6 -alkylsulfonylamino-C 1 -C 4 -alkyl, C 1 -C 6 -alkylsulfonyl- (C 1 -C 6 -alkylarnino) C 1 -C 4 -alkyl: for example methylsulfonyl, ethylsufonyl, propylsulfonyl, 1-methylethyisulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methyl-propylsulfonyl, 2-
• 2,2,2-trichloroethylsulfonyl pentafluoroethylsulfonyl, 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyi, 2-chloro-propylsulfonyl, 3-chloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 2,2-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl, 2, 3-dichloropropylsulfonyl, 3,3,3-trifluoropropylsulfonyl, 3,3,3-trichloropropylsulfonyl, 2,2,3,3,3-pentafluoropropylsulfonyl, heptafluoropropylsulfonyl,
• C 1 -C 4 -alkoxy a C 1 -C 4 -alkoxy radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, eg fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoro - methoxy, 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
• Methylpropoxy) butyl 2- (2-methylpropoxy) butyl, 2 ⁇ (1,1-dimethylethoxy) butyl, 3- (methoxy) butyl, 3- ⁇ ethoxy) butyl, 3- (propoxy) butyl, 3- ( 1-methylethoxy) butyl, 3- (butoxy) -butyl, 3- (1-methylpropoxy) butyl, 3- (2-methylpropoxy) butyl, 3- ⁇ 1,1-dimethylethoxy) butyl, 4 (Methoxy) -butyl, 4- (ethoxy) butyl, 4- (propoxy) butyl, 4- (1-methylethoxy) butyl, 4- (butoxy) butyl [, 4- (1-methylpropoxy) butyl] 4- (2-
• Methylethoxycarbonyl butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl or 1,1-dimethyl [ethoxycarbonyl;
• Ci-C4-Alkoxycarbonony Ci-C4-Alkoxycarbonony!
• Pentoxycarbonyl 1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2,2-dimethylpropoxycarbonyl, 1-ethylpropoxycarbonyl, hexoxycarbonyl, 1,1-dimethylpropoxycarbonyl, 1,2-dimethylpropoxycarbonyl, 1-methylpentoxycarbonyl, 2 Methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4-methylpentoxycarbonyl, 1, 1-dimethylbutoxycarbonyl,
• Methylbutylamino 2,2-dimethylpropylamino, 1-ethylpropylamino, hexylamino, 1,1-dimethylpropylamino, 1,2-dimethylpropylamino, 1-methylpentyiamino, 2-methylpentylamino, 3-methylpentylamino, 4-methylpentylamino, 1, 1-dimethylbutylamino, 1, 2-dimethylbutylamino, 1, 3-dimethylbutylamino, 2,2-dimethylbutylamino, 2,3-dimethylbutylamino, 3,3-dimethylbutylamino, 1
• Ethylbutylamino 2-ethylbutylamino, 1, 1, 2-trimethyl-propylamino, 1, 2,2-trimethyl-propylamino, 1-ethyl-1-methylpropylamino or 1-ethyl-2-methylpropylamino;
• Di (C 1 -C 4 -alkyl) aminocarbonytamino for example N, N-dimethylaminocarbonyl, N, N-diethylaminocarbonyl, N, N-di- (1-methylethyl) aminocarbonyl, N, N-dipropylaminocarbonyl, N, N-dibutylaminocarbonyl, N, N-di (1-methylpropyl) aminocarbonyl, N, N-di- (2-methyl-propyl) ami ⁇ ocarbonyl, N 1 N-di (1, 1-dimethylethyl) aminocarbonyf, N-ethyl-N- methylaminocarbonyl, N Methyl-N-propylaminocarbonyl, N-methyl-N- (1-methylethyl) aminocarbonyl, N-butyl-N-methylaminocarbonyl, N-methyl-N- (1-methyl-propylaminocarbonyl, N
• Dimethylbutylaminocarbonyl 1, 2-dimethylbutylaminocarbonyl, 1, 3-dimethylbutylaminocarbonyl, 2,2-dimethylbutylaminocarbonyl, 2,3-dimethylbutylaminocarbonyl, 3,3-dimethylbutylaminocarbonyl, 1-ethylbutylaminocarbonyl, 2-ethylbutylamino carbonyl, 1, 1, 2-trimethylpropylaminocarbonyl, 1,2,2-trimethyl-propyiaminocarbonyl, 1-ethyl-i-methylpropylaminocarbonyl or 1-ethyl-2-methylpropylaminocarbonyl;
• N-N- (1-ethylpropyl) -aminothiocarbonyl N-methyl-N-hexylaminothiocarbonyl, N-methyl-N- (1, 1-dimethylpropyl ) -aminothiocarbonyl, N-methyl-N- (1, 2-dimethylpropyl) -aminothiocarbonyl, N-methyl-N- (1-methylpentyl) aminothiocarbonyl, N-methyl-N- (2-methylpentyl) -aminothiocarbonyl, N- Methyl-N- (3-methylpentyl) -aminothiocarbonyl, N-methyl-N- (4-methylpentyi) -aminothio-carbonyl, N-methyl-N-
• 3- to 6-membered heterocyclyl as well as the three- to six-membered heterocyclyl parts of three- to six-membered heterocyclyl-C 1 -C 4 -alkyl: monocyclic, saturated or partially unsaturated hydrocarbons having three to six Rssenglie- the mentioned above, which 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, eg
• Monocycles such as Furyi (eg 2-furyl, 3-furyl), thienyl (eg 2-thienyl, 3-thienyl), pyrrolyl (eg pyrrol-2-yl, pyrro-3-yl), pyrazolyl (eg pyrazol-3-yl, pyrazole 4-yl), isoxazolyl (eg, isoxazol-3-yl, isoxazol-1-yl, ⁇ -soxazol-5-yl), isothiazolyl (eg isothiazol-3-yl, isothiazol-yl, isothiazol-5-yl), imidazolyl ( eg imidazo!
• Furyi eg 2-furyl, 3-furyl
• thienyl eg 2-thienyl, 3-thienyl
• pyrrolyl eg pyrrol-2-yl, pyrro-3-yl
• oxazolyl eg oxazol-2-yl, oxazol-4-yl, oxazol-5-yl
• thiazolyl eg thiazol-2-yl, thiazoM-yl, thiazole -5-yl
• oxadiazolyl eg 1,2,3-oxadiazol-4-yl, 1, 2,3-oxadiazol-5-yl, 1,2,4-oxadiazol-3-yl, 1, 2 , 4, -oxadiazol-5-yl, 1, 3,4-oxadiazol-2-yl
• thiadiazolyl eg 1, 2,3-thiadiazol-1-yl, 1, 2,3-thiadiazol-5-yl,
• Tetrazinyl e.g., 1, 2,4,5-tetrazine-3-yl
• Bicyclic compounds such as the benzanellated derivatives of the aforementioned monocycles, e.g. Quinolinyl, isoquinolinyl, indoly, benzthienyl, benzofuranyl, benzoxazolyl, benzothiazolyl, benzisothiazolyl, benzimidazolyl, benzopyrazolyl, benzthiadiazolyl, benzotriazole IyI.
• 5- or 6-g lower 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 1 .
• 5- or 6-g lower 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 1 .
• a C atom linked aromatic 5-membered ring heterocycles which in addition
• 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, eg 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazoly [, 4-isoxazolyl, 5-isoxazolactic, 3-isothiazolyi, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyzole, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyi, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-S-yl, 1, 2,4-thiadiazol-3-yl, 1, 2,4-thiadiazol-5-yl, 1, 2,4-
• heterocyclyl-C 1 -C 6 -alkylcarbonyi are preferably unsubstituted or carry one to three halogen atoms and / or one nitro group, one cyano radical and / or one or two methyl, trifluoromethyl, methoxy or trifluoromethoxy substituents.
• variables of the heteroaroyl-substituted serine amides of the formula I have the following meanings, these considered individually and in combination with one another representing particular embodiments of the compounds of the formula I:
• C 6 alkoxy-Ci-C 4 -alky! can carry; means.
• heteroaroyl-substituted serine amides 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 with one oxygen or sulfur atom; particularly preferably 5-membered heteroaryl selected from the group of thienyl, furyl, pyrazolyl, tmidazoiyl, thiazoiyl and oxazolyl; particularly preferably 5-membered heteroaryl selected from the group
• 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 one oxygen atom; particularly preferably 5-membered heteroaryl selected from the group furyl, pyrazolyl, imidazolyl, thiazoiyl and oxazolyl; Particularly preferably 5-membered heteroaryl selected from the group furyl, pyrazolyl and imidazolyl; where the heteroaryl radicals mentioned may be partially or fully haiogeniert and / or 1 to 3 radicals from the group cyano, -C 6 alkyl, C 3 -C 6 -CyClOaIkVl, C r C 6 haloalkyl, Ci-C 6 alkoxy, C C 1 -C 6 -haloalkoxy and C 1 -C 6 -alkoxy-C 1 -C 4 -alky
• heteroaroyl-substituted serine amides of the formula I in which A is 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 one
• Oxygen or sulfur atom which are substituted by a d-C ⁇ -haloalkyl radical, preferably in the 2-position by a CrC ⁇ -Halogenalkyi radical, and 1 to 3 radicals from the group cyano, dC 6 alkyl, C3-C ⁇ Cycloalkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy and C 1 -C 6 -alkoxy-Cr
• C4 alkyl can carry; means.
• heteroaryl selected from the group of thienyl, furyi, pyrazolyl, imidazolyl, thiazolyl, oxazolyl and pyridyl; wherein said heteroaryl may be partially or fully halogenated and / or may carry from 1 to 3 radicals selected from the group consisting of d-Ce-Aikyl, C3-C6-cycloalkyl and d-Ce-haloalkyl;
• 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 radicals selected from the group consisting of CrC ⁇ -alkyl and d-d-haloalkyl;
• heteroaroyl-substituted serineamides of the formula I in which A is 5- or 6-membered heteroaryl selected from the group consisting of pyrrolyl, furyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, tetrazolyl, pyridyl and pyrimidinyl; where the said heteroaryl radicals can be partially or completely halogenated and / or 1 to 3 radicals from the group cyano, C 1 -C 6 -alkyl,
• heteroaryl selected from the group furyl, pyrazolyl, imidazolyl, thiazoiyl and oxazolyl; wherein said heteroaryl 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 can carry 1 to 2 radicals from the group consisting of C 1 -C 6 -acyl and C 1 -C 4 -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 AU with
• R 8 is hydrogen, halogen, C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl; particularly preferably hydrogen, C 1 -C 4 -alkyl or C 1 -C 3 -haloalkyl; especially preferably hydrogen or C 1 -C 4 -alkyl; most preferably hydrogen;
• R 9 is halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl or C 1 -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 d-Ce-haloalkyl; extremely preferably d-C4-haloalkyl very particularly preferably CF3;
• R 10 is hydrogen, halogen, C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl; particularly preferably hydrogen, halogen or Ci-d-Haiogenalkyl; especially preferably hydrogen or halogen; most preferably hydrogen; and
• R 11 is hydrogen, d-C6 -alkyl, C 3 -C 6 cycloalkyl, -C 6 haloalkyl or Cr C ⁇ -alkoxy-CrC 4 alkyl; particularly preferably C 1 -C 4 -alkyl, C 3 -C 5 -cycloalkyl, C 1 -C 4 -haloalkyl or C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl; especially preferred is CrC 4 -alky! or C r C 4 -Haiogenalkyl; most preferably CiC-rAfkyl; very preferably CH3;
• R e to R 11 are defined as mentioned above;
• heteroaroyi-substituted Ala ⁇ ine of formula I in which R 1 is hydrogen; means.
• heteroaroyi-substituted Ala ⁇ ine the forms! I 1 in the R 2 is hydrogen or hydroxy; particularly preferably hydrogen; means.
• heteroaroyi-substituted serine amides of formula I in which R 3 is d-Ce-alkyl or C r Ce -haloalkyl; particularly preferred Ci-Ce-Aikyl; particularly preferably CrCWMkyl; most preferably CH 3 ; means.
• heteroaroyi-substituted serine amides of the forms! I in which R 4 is hydrogen, CRCE alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, formyl, -C 6 - alkylcarbonyl, C2-C6-alkenylcarbonyl, Ca-Ce-cycloalkylcarbonyl, Ci-Ce - Aikoxycarbonyi, Ci-C ⁇ -Alkylamtnocarbonyl, CrCe-alkylsulfonylaminocarbony], di- (Ci-C3-alky! - aminocarbonyl, N- (CrC ⁇ -alkoxy) -N- (Ci-C6-alkyl) -aminocarbonyl,
• alkyl or alkoxy radicals may be partially or fully halogenated and / or may carry one to three of the following groups: cyano , C 1 -C 4 -alkoxy, C r C 4 alkoxycarbonyl, C r C 4 - alkylaminocarbonyl, di- (CRC-4 alkyl) or -C -aminocarbonyI 4 -
• Phenyl-C 1 -C 6 -alkyl, phenylcarbonyl, phenylcarbonyl-d-C 1 -C 6 -alkyl, phenylsulfonylaminocarbonyl or phenyl-C 1 -C 6 -alkylcarbonyl, where the phenyl ring can be partially or completely halogenated and / or carry one to three of the following groups can: Nitro, Cyano,
• Ci-C 4 -A ky [dd-haloalkyl, -C 4 -alkoxy or C 4 -Halogenoxy; or
• C 1 -C 4 -alkylcarbony ! hydroxycarbonyl, C 1 -C 4 -oxycarbonyl, aminocarbonyl, dd-alkylaminocarbonyl, di- (C 1 -C 4 -alkyl) aminocarbonyl or C 1 -C 4 -alkyicarbonyloxy; or SO 2 R 7 ; means.
• heteroaroyl-substituted are also preferred serine amides of the formula I 1 wherein R 4 is hydrogen, d-Ce-alkyl, C 3 -C 6 -Alkeny [, C 3 -C 6 alkynyl, formyl, CrC 6 - Aikyfcarbony!
• alkyl mentioned and alkoxy radicals may be partially or completely halogenated and / or may carry one to three of the following groups: cyano, d-GrAlkoxy, Ci-C4-alkylaminocarbonyl or di- (d-C4-alkyi) -amänocarbonyl;
• heteroaroyl-substituted serine amides are of the formula I in which R 5 is hydrogen or C r C 4 -AJkyl; preferably hydrogen or CH3; especially preferably hydrogen; means.
• heteroaroyl-substituted serineamides of the formula I in which R 6 is C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 3 -alkynyl, C 1 -C 6 -haloalkyl, C 2 - C 6 -
• Amino-C 1 -C 4 -alkyl di (C 1 -C 6 -alky1-carbonylarnino-d-1-alkyl, di (C 1 -C 6 -acyl) aminocarbonylamino C 1 -C 4 -alkyl, [(d-Ce-alkyl) aminocarbonyl-arnino-C rd-alkyl, [di (C 1 -C 6 -alkyl) aminocarbonyloxy] C 1 -C 4 -alkyl, ⁇ di [di (C 1 -C 6 -alkyl) amino] carbonyloxy ⁇ C 1 -C 4 -alkyl, formylamino-dd-alkyl,
• Phenyl-CrC 4 -alkyl phenyl-C 2 -C 4 -a -alkenyl, phenyl-C 3 -C 4 alkynyl, phenyl-CrC 4 - haloalkyl, phenyl-C 2 -C 4 haloalkenyl, phenyl-CRC4 hydroxyalkyl, loxy phenylene-CrC 4 alkyl, phenylthio--C 4 alkyl, phenylsulfinyl-Ci-C4-alkyl, Phenylsulfo- ny [-CRC 4 alkyl,
• Ci-C 6 -alkenyl particularly preferably d-Ce-alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -haloalkenyl, C 1 -C 6 -hydroxyalkyl, C 1 -C 8 -alkoxy-C 1 -d-alkyl, Hydroxycarbonyl-d-C4-alkyl ; Ci-C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -haloalkenyl, C 1 -C 6 -hydroxyalkyl, C 1 -C 8 -alkoxy-C 1 -d-alkyl, Hydroxycarbonyl-d-C4-alkyl ; Ci-C 6 -alkenyl, C 2 -C 6 -
• C 1 -C 6 -alkyl most preferably C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 1 -C 6 -haloalkyl, C 2 -C 8 -haloalkenyl, C 1 -C 6 -hydroxyalkyl, hydroxycarbonyl-C 1 -C 4 -alkyl, formylamino-d-alkyl, phenyl-d-d alkyl or phenyl-CrC 4 -hydroxyalkyl; means.
• heteroaroyl-substituted are also preferred serine amides of formula I 1 where R 6 is CrC ⁇ -alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Ci-C 6 -Halogenaikyl, C 2 -C 6 -
• Haloalkenyl C 2 -C 6 Halogenal honyl, d-Ce-cyanoalkyl, CrC ⁇ -hydroxyalkyl, C 2 -C ⁇ -hydroxyalkenyl, C 2 -C 6 -Hydroxyalkinyl, C 3 -C 6 -Cycloa [kyl, C 3 -C 6 - Cycloalkenyl, 3- to 6-membered heterocyclyl, where the abovementioned cycloalkyl, cycloalkenyl or 3- to 6-membered heterocyclyl radicals may be partially or completely halogenated and / or one to three radicals from the group consisting of oxo, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 6 -alkoxyalkyl, hydroxycarbonyl and d-Ce-alkoxycarbonyl; , C 1 -C
• C2-C preferably d-C ⁇ -alkyl, ß alkenyl, C 2 -C 6 alkynyl, -C 6 - haloalkyl, CrC ⁇ -hydroxyalkyl, 3- to 6-membered He- terocyclyl, C r C 6 alkoxy CRC4 alkyi, Ci-C 6 alkoxy-Ci-C4-alkoxy-CRC4-alkyl, d- C6-Haloge ⁇ alkoxy-CRC4 a!
• Phenyl-C r -C 4 -alkyl phenyl-C 2 -C 4 alkenyl, phenyl-C 2 -C 4 alkynyl, phenyl-dd- haloalkyl, phenyl-C 2 -C 4 haloalkenyl, phenyl [-CrC4-hydroxyalkyl, loxy phenylene-CrC 4 -alky [, phenylthio--C 4 alkyl, phenyl-sulfinyl--C 4 alkyl or phenyl sulfonyl-d-C4-alkyl, where the phenyl radicals mentioned above may be partially or fully halogenated and halogen- or one to three radicals from the group CrCe- alkyl, CrCe HaiogenalkylCrC ⁇ -alkoxy, hydroxycarbonyl, CrCe-alkoxycarbonyl, d-Ce-al
• CrC ⁇ -alkyl particularly preferably CrC ⁇ -alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, CrCe- haloalkyl, C 2 -C 6 haloalkenyl, d-Ce-hydroxyalkyl, 3- to 6-membered terocyclyi He, C r C e alkoxy-Ci-C4-alky !, -C 6 alkoxy-alkoxy-CRC4 CRC4 -alkyl, hydroxycarbonyl--C 4 alkyl, CRC6-alkoxycarbonyl-CRC4 alkyl, [di (CrCe- alkyOaminocarbonyloxyJCi ⁇ alkyl, formylamino-d-C4-alkyi;
• heteroaroyl-substituted serine amides of the formula I in which R 7 is d-Ce-alkyl, C 1 -C 6 -haloalkyl or phenyl, where the phenyl radical may be partially or partially halogenated and / or may be substituted by C 1 -C 4 -alkyl; particularly preferably dd-alkyl, d-C4-haloalkyl or phenyl; especially preferably methyl, trifluoromethyl or phenyl. means.
• Particularly preferred are the heteroaroyi-substituted serine-amides of the formula I in which
• a 5- or 6-membered heteroaryl selected from the group Thienyi, furyl, PyrazolyJ, imidazolyl, thiazolyl, oxazolyl and pyridyl; wherein said heteroaryl may be partially or completely halogenated and / or 1 to 3 radicals from the group Ci-C ⁇ -alkyl, Cs-Ce-Cycloalky! and can carry C 1 -C 6 -haloalkyl; R 1 and R 2 are hydrogen; R 3 is C 1 -C 4 -alkyl, more preferably CHb; R 4 is hydrogen, formyl, Ci-C ⁇ -alkylaminocarbonyl, di (dC 4 -
• R 5 is hydrogen; and
• R 6 is d-Ce-alkyl, C 2 ⁇ VAIkenyl, C r C 6 -haloalkyl [, C 2 -C 6 -haloalkenyl, CrC 6 -
• heteroaroyl-substituted serine amides of the formula I are obtainable in various ways, for example by the following processes:
• L 1 is a nucleophilically displaceable leaving group, for example for hydroxy or CrCe- atkoxy.
• 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.
• 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-bonded dicyclohexylcarbodiimide, diisopropylcarbodiimide, carbonyldiimidazole, chloroformate such as methyl chloroformate, ethyl chloroformate, isoropyl chloroformate, isobutyl chloroformate, sec-butyl chloroformate or allyl chloroformate, pivatoyl chloride, polyphosphoric acid, propanephosphonic anhydride, bis (2-oxo-3-oxazolidinyl) phosphoryl chloride ( BOPCI) or sulfonyl chlorides such as methanesulfonyl chloride, toluenesulfonyl chloride or benzoisulfonyl chloride.
• condensing agents e.g. polystyrene-bonded dicyclohexylcarbodiimide, diis
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of C 5 -C -Aikanen, aromatic hydrocarbons such as benzene, toluene, o-, m- and p-xylene, halogenated hydrocarbons such as Methyienchlo- 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 Dimethylsuifoxid, dimethylformamide (DMF), dimethylacetamide (DMA) and N-methylpyr
• Suitable bases 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 Caicium 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-
• Particularly preferred are sodium hydroxide, triethylamine and pyridine.
• 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 final products fold 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 trituration.
• the reaction of the serine derivatives of the formula V with heteroaryl acid (derivatives) n of the formula IV, where L 2 is halogen, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, C 1 -C 4 -alkylsulfonyl, phosphoryl or isoureyl, to give heteroaroyl derivatives of the formula III is carried out in the presence of a base usually at temperatures of 0 ° C to the boiling point of the reaction mixture, preferably OX to 100 ° C, more preferably at room temperature in an inert organic solvent [cf.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-C ⁇ -alkanes, aromatic hydrocarbons such as benzene, toluene, o-, n- and p-xylene, halogenated hydrocarbons such as methylene chloride. chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran (THF), nitriles such as acetonitrile!
• aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-C ⁇ -alkanes
• aromatic hydrocarbons such as benzene, toluene, o-, n- and p-xylene
• ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butylmethyiketon, and dimethyl sulfoxide, dimethylformamide (DMF), dimethylacetamide (DMA) and N-methylpyrrolidone (NMP) or in water, particularly preferred are methylene chloride, THF and water.
• DMF dimethylformamide
• DMA dimethylacetamide
• NMP N-methylpyrrolidone
• Suitable bases 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 Caicium hydride, alkali metal and Erdaikalimetall- 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-Methylmorphoiin, and N-methylpiperidine, Pyridi ⁇ , substituted Py ⁇ dine such as collidine, Lutidi ⁇ and 4-dimethylaminopyridine and bicyclic amines into consideration. Particularly preferred
• 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 via a Grignard reaction from the corresponding halide [e.g. A. Mannschuk et al., Angew. Chem. 100, 299 (1988)].
• Suitable activating reagents are condensing agents, e.g. polystyrene bound dicyclohexylcarbodiimide, diisopropylcarbodiimide, carbonyldiimidazole, chlorocarbonic acid esters such as methyl chloroformate, ethyl chloroformate, isophoryl chloroformate, isobutyl chloroformate, sec-butyl chloroformate or allyl chloroformate, pivaloyl chloride, polyphosphoric acid, propanephosphonic anhydride, bis (2-oxo-3-oxazolidinyl) phosphoryichloride (BOPCI) or sulfonyl chlorides such as methanesulfonyl chloride, toluenesulfonyl chloride or benzenesulfonyl chloride.
• condensing agents e.g. polystyrene bound dicyclohexylcarbodiimide
• Suitable solvents are aliphatic hydrocarbons such as penta, 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, A ⁇ isol 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 m
• Butylmethylketo ⁇ alcohols such as methanol, ethanol, n-propanol, isopropanol, ⁇ -butanol and tert-butanol, and dimethyl sulfoxide, dimethylformamide (DMF), dimethylacetamide (DMA) and N-methylpyrrolidone (NMP) or in water, are particularly preferred Methylene chloride, THF, methanol, ethanol and water.
• Bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, Kauumhydroxid and calcium hydroxide, Alkaltmetall- 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, Aikalimetall- 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-
• alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, Kauumhydroxid and calcium hydroxide
• Alkaltmetall- and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and
• Particularly preferred are sodium hydroxide, triethylamine, ethyldiisopropylamine, N-methylmorphotin and pyridine.
• the bases are generally used in catalytic amounts, but they can also be used equimolar, 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 11 in an excess relative to III.
• 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 benzene, toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzoi, ethers such as diethyl ether, Diisopropyl ether, tert-butyl methyl ether, dioxane, aniso!
• aromatic hydrocarbons such as benzene, toluene, o-, m- and p-xylene
• halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzoi
• ethers such as diethyl ether, Diisopropyl ether, tert-butyl methyl ether, dioxane, aniso!
• 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
• dimethyl sulfoxide Dimethylformamide (DMF), dimethylacetamide (DMA) and N-methylpyrrolidone (NMP) or in water, particularly preferred are methylene chloride, THF, methanol, ethanol and water.
• the reaction may optionally be carried out in the presence of a base.
• bases 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, Alkaltmetall- and Erdalkalimetalihydride such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal and Erdalkaümetallcarbonate 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, 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 can be beneficial, I! in an excess, based on III use.
• the amines of the formula II required for the preparation of the heteroaroyl-substituted serine amides of the formula I can be purchased.
• 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 iso-ureyl.
• 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, and dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably diethyl ether, dioxane and tetrahydrofuran.
• 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, diiso
• the bases used 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 nitrides such as lithium diisopropylamide and lithium hexamethyldisilazide, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyl alcohol.
• alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride
• alkali metal nitrides such as lithium diisopropylamide and lithium hexamethyldisilazide
• organometallic compounds in particular alkali metal alkyls such as methyllithium, butyl alcohol.
• alkali metal and Erdaikalimetallalkohoiate such as sodium methoxide, sodium, potassium, potassium tert-butoxide, potassium tert-pentoxide and Dimethoxymagnesium
• 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 bicyclic amines into consideration.
• Particular preference is given to sodium hydride, lithium hexamethyldisilazide and lithium diisopropylamide.
• 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 carbonyl compounds VII in an excess based on the glycine derivatives VII.
• the workup and isolation of the products can be done in a conventional manner.
• 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 d-Ca-alkoxy.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-Cs alkanes, aromatic hydrocarbons such as toluene, o-, n- 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.
• aromatic hydrocarbons such as
• 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, Caici- umoxid and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium, sodium hydride, potassium and Calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and ErdalkaümetaNcarbonate such as lithium carbonate, 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, Almylmagnesiumhalogenide such as methylmagnesium chloride and Aikalimetall- and Alkaline earth metal alcoholates such as sodium methoxide, sodium ethoxide, potassium ethanolate
• 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 IX in an excess based on IEI or I.
• 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, C 1 -C 6 -alkoxycarbonyl, C 1 -C 6 -alkylsulfonyl, phosphoryl or isopropyl.
• L 4 stands for a ⁇ ucleophi! 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 serine derivatives of the formula V with heteroaryl acid (derivatives ) n the forms! IV to the corresponding Heteroaroylderivaten of the forms! III.
• L 4 in the case of the N-acylaminomalonyl compounds of the formula X is C 1 -C 6 -acoxy, it is advantageous to first prepare L 4 by ester hydrolysis [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 Cs-Ca-alkanes, aromatic hydrocarbons such as Toluoi, o-, m- and p-xyiol, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert.-butylmethyl ether, dioxane, aniso!
• aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-Ca-alkanes
• aromatic hydrocarbons such as Toluoi, o-, m- and p-xyiol
• halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene
• ethers such as diethyl
• 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
• dimethylsulfoxide Dimethylformamide and dimethylacetamide, more preferably diethyl ether, dioxane and tetrahydrofuran.
• 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 phenylithium, alkylmagnesium halides such as methylmagnesium chloride and also alkali metal and earth metal halides.
• alkali metal and alkaline earth metal hydroxides such as lithium hydrox
• kalimetallalkoholate such as sodium, sodium, Kaüumethanolat, potassium tert-butoxide, potassium tert-pentoxide and Dimethoxymagnesium
• organic bases eg tertiary amines such as trimethylamine, triethyiamine, Diisopropylethy- lamin and N-methylpiperidine, pyridine, substituted pyridines such as Coüidin, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration.
• Triethyiamine and diisopropylethylamine are particularly preferred.
• 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 done in a conventional manner.
• the required heterozygous compounds of the forms! VII can be purchased.
• L 1 is a nucleophilically displaceable leaving group, for example for hydroxy or C 1 -C 6 -alkoxy.
• L 2 is a nucleophilically displaceable Abga ⁇ gsrios, for example, hydroxy, halogen, d-Ce-alkylcarbonyl, Ci-Ce-alkoxycarbonyl, Ci-Ce-alkylsulfonyl, phosphoryl or Isory- ly.
• the acylation of the keto compounds of the formula XII! with heteroaryl acid (derivatives) n of the formula IV to N-Acy! -Keto compounds of the forms! 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 give the corresponding heteroaroyl derivatives of the formula III.
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-Cs-Alka ⁇ en, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and Chlorbe ⁇ zol, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, aniso!
• aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-Cs-Alka ⁇ en
• aromatic hydrocarbons such as toluene, o-, m- and p-xylene
• halogenated hydrocarbons such as methylene chloride, chloroform and Chlorbe ⁇ zol
• ethers such as diethyl ether
• 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-butanof
• dimethyl sulfoxide, dimethylformamide and dimethylacetamide particularly preferably toluene, methylene chloride or tert-butyl methyl ether.
• Suitable reducing agents are e.g. Sodium borohydride, zinc borohydride, sodium cyanoborohydride, lithium triethylborohydride (Superhydrid®), lithium tri-sec.butylborohydride (L-Sefectrid®), aluminum hydride or borane [cf. e.g. 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. et al., Tetrahedron 55 (23), 7331-7344 (1999)],
• the reduction can also be carried out in the presence of hydrogen and a catalyst.
• Suitable catalysts are z, B. [Ru (BINAP) Cl 2 ] or Pd / C [cf. 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.
• Saccharomyces Rouxii ' see. Soukup, M. et al., HeIv, Chim. Acta 70, 232 (1987)].
• N-acyl-keto compounds of the formula XIi and the respective 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.
• 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.
• R ' is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -hydroxyalkyl, phenyl or C 1 -C 6 -alkoxycarbonyl.
• R " is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -hydroxyalkyl, phenyl or C 1 -C 6 -alkoxycarbonyl.
• This reaction is usually carried out at temperatures from -78 ° C to the boiling point of the reaction mixture, preferably -10 ° C to 120 ° C, particularly preferably 0 ° C to 50 ° C, in an inert organic solvent in optionally in the presence of a reoxidant such as N-methylmorpholine N-oxide (D. Johnson et al., Tetrahedron 2000, 56, 5, 781).
• a reoxidant such as N-methylmorpholine N-oxide (D. Johnson et al., Tetrahedron 2000, 56, 5, 781).
• Suitable solvents are halogenated hydrocarbons, such as methyl chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitrile, 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, as well as dimethylsulfoxide, dimethylformamide, dimethylacetamide and water; particularly preferably acetone or water.
• ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dio
• the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous to use the oxidizing agent in an excess relative to XIV.
• 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 are 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 trituration.
• L 1 is a nucleophilic 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.
• R ' is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -hydroxyalkyl, phenyl or C 1 -C 6 -alkoxycarbonyl.
• R is hydrogen, Ci-C 6 alkyl, d-C ⁇ -Halogenalky], Ci-C ⁇ hydroxyalkyl, phenyl or Ci-Ce-alkoxycarbonyl.
• L 1 is a nucleophilically displaceable leaving group, for example for hydroxy or CrC ⁇ alkoxy.
• R ' represents hydrogen, d-Ce-alkyl, Ci-C 6 haloalkyl, C r C 6 hydroxyalkyl, phenyl- or Ci-C ⁇ -Alkoxycarbo ⁇ yl.
• R " is hydrogen, d-Ce-alkyl, Ci-C 6 -Halogenaikyl, -C 6 hydroxyalkyl, phenyl or Ci-Ce-alkoxycarbonyl.
• Nuc ⁇ M + is, for example thiolates such as sodium thiophenolate, alcoholates such as potassium phenolate, or amides like sodium imidazolate.
• the epoxidation usually takes place at temperatures of from -78 ° C. to the boiling point of the reaction mixture, preferably from -20 ° C. to 50 ° C., particularly preferably from 0 to 30 ° C., in an inert organic solvent [cf. P. Meffre et al., Tetrahedron Lett. 1990, 31, 16, 2291.
• epoxidizing reagents find use peracids and peroxides (eg, Me tachlorperbenzoeklare, peracetic acid, dimethyldioxirane » hydrogen peroxide).
• peracids and peroxides eg, Me tachlorperbenzoeklare, peracetic acid, dimethyldioxirane » hydrogen peroxide.
• Suitable solvents are halogenated hydrocarbons such as methyl chloride, chloroform and chlorobenzene, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and water, more preferably halogenated hydrocarbons and water.
• the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous to use the epoxidizing agent in an excess relative to XIV.
• reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and optionally chromatographi ⁇ che purification of the crude products.
• Some of the intermediates and final products are in the form of viscous oil which, under reduced pressure and at a moderately elevated temperature, has volatiles be freed or cleaned. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or trituration.
• the epoxide opening is usually carried out at temperatures of ⁇ 78 ° C to the boiling point of the reaction mixture, preferably -20 ° C to 100 ° C, more preferably O 0 C to 50'C, in an inert organic solvent! if appropriate in the presence of a catalyst [cf. P. Meffre et al., Tetrahedron Lett. 1990, 31, 16, 2291; M, R. Paleo et al., J. Org. Chem. 2003, 68, 1, 130].
• Suitable solvents are alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert. -Sutanol, and dimethyl sulfoxide, dimethylformamide and dimethylacetamide and water, more preferably methanol and water.
• acidic catalysts are Lewis acids such as boron trifluoride, Aluminiumtrtchloräd, iron-lll-chloride, Zin ⁇ -IV-chloride, titanium-IV-chloride, zinc-II-chloride and Magnesiumperchlo- rat use.
• the catalyst is usually used in a ratio of 1 to 100 mol%, preferably 1 to 10 mo!% Based on the compound XV.
• the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous to use NuC-M + in an excess relative to XV.
• 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.
• Some of the intermediate and end products are in the form of viscous oils, which are freed from volatile constituents under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or digestion. Heteroaroyl derivatives of the forms!
• L 1 is a nucleophilically displaceable leaving group, for example for hydroxy or C 1 -C 8
• L 3 is a nucleophilically displaceable leaving group, for example halogen, hydroxy, or C 1 -C 6 -alkoxy.
• R ' is hydrogen, -C 6 alkyl, d-C ⁇ -haloalkyl, C r C 6 hydroxyalkyl, phenyl or Ci-C ⁇ -alkoxycarbonyl.
• R " is hydrogen, C 1 -C 6 -alkyl, d-Ce-haloalkyl, C r C 3 -hydroxyalky1, phenyl or C 1 -C -alkoxycarbonyl.
• Nuc ⁇ M + is, for example, thiolates such as, for example, sodium thiophenolate, A alcoholates such as potassium phenolate, or amides such as sodium imidazolate.
• R 1 and R 4 , R 5 and R 6 have the meanings given above and L 1 is hydroxy or C 1 -C 6 -alkoxy, are also an object of the present invention.
• a 5- or 6-membered heteroaryl selected from the group of thienyl, furyl, pyrazolyl, imidazolyi, thiazolyl, oxazolyl and pyridyl; wherein said heteroaryl may be partially or completely halogenated and / or 1 to 3 radicals from the group Ci-CB-alkyl, C3-Ce-cycloalkyl, and d-Ce-haloalkyl may carry; R 1 is hydrogen;
• R 4 is hydrogen, formyl, Ci-C4-alkylcarbonyl, dC ⁇ alkylaminocarbonyl, dt (Ci-C 4 - alkyl) aminocarbonyl, phenylaminocarbonyl, N- (CI -C 4 -a ky!) - N- (phenyl ) - aminocarbonyl, SO 2 CH 31 SO 2 CF 3 or SO 2 (C 6 H 5 );
• R 5 is hydrogen; and
• R 6 is Ci-C ⁇ alkyl, C 2 -C 6 alkenyl, Ci-C 6 haloalkyl, C 2 -C @ haloalkenyl, CrC 6 -
• the heteroaroyl-substituted Seri ⁇ -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, 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. emulsions, oil dispersions, pastes, dusts, scattering agents or granules by spraying, atomizing, dusting, scattering or pouring.
• 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 center! contain a herbicidally effective amount of at least one compound of formula I or an agriculturally useful salt of I and for the formulation of pesticides usual auxiliaries.
• Suitable inert auxiliaries are essentially:
• mineral oil fractions such as kerosene and diesel oil, as well as cohyiene oils and vegetable or animal oils, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalenes, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanoi, sutanol 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, as well as cohyiene oils and vegetable or animal oils, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalenes, alkylated naphthalenes and their derivatives, alkylated benzenes and
• 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 of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene noctylphenol ether, ethoxylated.
• aromatic sulfonic acids e.g. Lignin, phenol, naphthalene and dibutyl
• Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.
• Granules, eg, rehydration, impregnation and homogeneous granules can be prepared by binding the active compounds to solid carriers.
• Solid carriers are mineral earths such as silicas, kieselgeie, 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 cornmeal, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
• mineral earths such as silicas, kieselgeie, 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 cornmeal, tree bark, wood and
• Concentrations of compounds of forms! I in the ready-to-use formulations can be varied within a wide range.
• the formulations will contain from about 0.001% to about 98% by weight, preferably from about 0.01% to about 95% by weight, 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 formula I 20 parts by weight of an active compound of 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 Ligninsulfo ⁇ klare 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 the herbicidal agents can be carried out in the pre-emergence or postemergence process. If the active ingredients are less compatible with certain crops, then application techniques may be employed whereby the herbicidal agents are sprayed by the sprayers so as not to hit the leaves of the sensitive crop if possible, while the active ingredients affect the leaves underneath growing undesirable plants or the uncovered floor 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 used with numerous representatives. tern other herbicidal or growth-regulating active ingredient groups are mixed and applied together.
• suitable mixture components are 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and derivatives thereof, aminotriazoles, anilides, aryloxy / heteroaryloxyalkanoic acids and derivatives thereof, benzoic acid and derivatives thereof, benzothiadiazinones, 2- (hetaroyl / Aroyi) -1, 3-cyclohexanediones, heteroaryl-aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinecarboxylic acid and derivatives thereof, chloroacetanilides, cyclohexenone oxime ether derivatives, diazines, dichloroacetanilides, cyclohexenone
• the culture vessels used were plastic flower pots with loamy sand with about 3.0% humus as 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 Testpflanze ⁇ depending on growth form were first grown to a stature height of 3 to 15 cm and only then treated with the suspended in water or eimulg faced thinking 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 the post-emergence treatment was 1.0 kg / ha aS (active substance).
• the plants were kept species-specific at temperatures of 10 to 25 ° C and 20 to 35 ° 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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