EP1888532A1 - Heteroaroyl-substituted serine amides - Google Patents

Heteroaroyl-substituted serine amides

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Publication number
EP1888532A1
EP1888532A1 EP06725384A EP06725384A EP1888532A1 EP 1888532 A1 EP1888532 A1 EP 1888532A1 EP 06725384 A EP06725384 A EP 06725384A EP 06725384 A EP06725384 A EP 06725384A EP 1888532 A1 EP1888532 A1 EP 1888532A1
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EP
European Patent Office
Prior art keywords
alkyl
alkoxy
phenyl
formula
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP06725384A
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German (de)
French (fr)
Inventor
Matthias Witschel
Cyrill Zagar
Eike Hupe
Toralf KÜHN
William Karl Moberg
Liliana Parra Rapado
Frank Stelzer
Andrea Vescovi
Michael Rack
Robert Reinhard
Bernd Sievernich
Klaus Grossmann
Thomas Ehrhardt
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BASF SE
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BASF SE
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Publication of EP1888532A1 publication Critical patent/EP1888532A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • 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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Abstract

The invention relates to heteroaroyl-substituted serine amides of formula (I), wherein the variables A and R1 to R6 have the meanings indicated in the description, the agriculturally useful salts thereof, methods and intermediate products for the production thereof, and the use of said compounds or agents that contain said compounds and are used for controlling undesired plants.

Description

Heteroaroylsubstituierte Serin-Amide Heteroaroyl substituted serine amides
Beschreibungdescription
Die vorliegende Erfindu uierte Serin-Amide der Formel IThe present invention comprises serine amides of the formula I
in der die Variablen die folgenden Bedeutungen haben:in which the variables have the following meanings:
A 5- oder 6-gliedhges Heteroaryl mit ein bis vier Stickstoffatomen, oder mit ein bis drei Stickstoffatomen und einem Sauerstoff- oder Schwefelatom, oder mit einem Sauerstoff- oder Schwefelatom, welches partiell oder vollständig halogeniert sein kann und/oder 1 bis 3 Reste aus der Gruppe Cyano, CrC6~A!kyl, C3-Ce- Cycloalkyl, d-Ce-Halogenalkyl, CrC6-Alkoxy, CrCe-Halogeπaikoxy und Ci-Ce- Alkoxy-Ci-C4-alkyl tragen kann;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;
R1, R2 Wasserstoff, Hydroxy oder CrC6-Alkoxy;R 1 , R 2 are hydrogen, hydroxy or C 1 -C 6 -alkoxy;
R3 Ci-Ce-Alkyl, CrC4-Cyanoalkyl oder CrC6-Halogenalkyl;R 3 Ci-Ce-alkyl, C r C 4 cyanoalkyl or C r C 6 haloalkyl;
R4 Wasserstoff, Ci-C6-Alkyl, C3-C6-Cycloalky], C3-C6-Alkenyl, C3-C6-AIW nyl, C3-C6- Halogenalkenyl, Ca-Ce-Halogenalkinyl, Formyl, d-Ce-Alkylcarbonyl, C3-C6-CVCI0- alkylcarbonyl, C2-C6-Alkenylcarbonyl, C2-C6-A!kiπylcarbonyl, d-Cβ-Afkoxycarbo- ny!, Cs-Cβ-Alkenyloxycarbonyl, Ca-Cθ-Alkinyioxycarbony!, d-Ce-Alkylaminocar- bonyl, Ca-Cβ-Alkenylaminocarbonyl, drCe-Alkinylaminocarbonyl, Ci-C6-Alkyl- sulfonylaminocarbonyl, DKCi-Cβ-alkyfJ-aminocarbonyl, N-(C3-C6-Alkenyl)-N-(Cr Ce-alkyl)-aminocarbonyl, N-(C3-C6-Aikinyl)-N-(Ci-C6-aJkyl)-aminocarbonyl, N-(Cr Ce-Alkoxy)-N-(Ci-C6-alkyl)-amtno-carbonyl, N-(C3-Ce-Alkeny[)-N-(CrC6-alkoxy)- aminocarbonyl, N-(C3-C6-Alkinyl)-N-(Ci-C6-alkoxy)-aminocarbony1, Di-(CrC6- alkyl)-aminothiocarbonyl, (CrC6-Aikyl)cyanoimino, (Amino)cyanoimino, [(CrCβ-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-Cβ-alkenylaminocarbonyl, trCe-alkynylaminocarbonyl, C 1 -C 6 -alkylsulfonylaminocarbonyl, DKCi-Cβ-alkyl-aminocarbonyl, N- (C 3 -C 6 -alkenyl) -N - (C r Ce-alkyl) aminocarbonyl, N- (C 3 -C 6 Aikinyl) -N- (Ci-C 6 -aJkyl) aminocarbonyl, N- (Cr Ce-alkoxy) -N- (Ci-C 6 alkyl) -amtno-carbonyl, N- (C 3 -Ce-Alkeny [) -N- (-C 6 alkoxy) - aminocarbonyl, N- (C 3 -C 6 alkynyl) -N- (Ci-C6- alkoxy) -aminocarbony1, di- (C 1 -C 6 -alkyl) -aminothiocarbonyl, (C 1 -C 6 -acyl) cyanoimino, (amino) cyanoimino, [(CrCβ-)
Alkyl)amino]cyanoimino, [Di(CrC6-A!kyl)amino]cyanoimino, d-C6-Alkylcarbonyl- Ci-Ce-alkyl, d-Cs-Alkoxyimino-Ci-Ce-alkyl, N-(CrC6-Alkylamino)-imino-Ci-Ce- alkyl, N-(Dt-Ci-C6-alkylamino)-imino-CrC6-alkyl oder Tri-CrC4-alkylsilyl, wobei die genannten Alkyl-, Cycloalkyl- und Alkoxyreste partiell oder voll- ständig halogeniert sein können und/oder eine bis drei der folgenden Gruppen tragen können: Cyano, Hydroxy, Ca-Cβ-Cycloalkyl, CrCe-AIkOXy-CrC4- alkyl, Ci-C^AIkoxy-Ci-C^alkoxy-Ci-C^alkyl, Ci-C4-Alkoxy, CrC4-Alkylthio, Di-(Ci-C4-aikyl)-amino, CrC4-Alky!-CrC4-afkoxycarbonyl-amino, C1-C4- Alkyicarbonyl, Hydroxycarbonyl, CrC^AIkoxycarbonyl, Aminocarbony!, Cr C4-Alkylamino-carbonyl, Di-(CrC4-alkyl)-aminocarbonyl oder CrC4- Alkylcarbonyloxy;Alkyl) amino] cyanoimino, [di (C 1 -C 6 -alkyl) amino] cyanoimino, C 1 -C 6 -alkylcarbonyl-C 1 -C 6 -alkyl, C 1 -C 5 -alkoxyimino-C 1 -C 6 -alkyl, N- (C 1 -C 6 -alkylamino) -imino-Ci-Ce- alkyl, N- (Dt-Ci-C6-alkylamino) -imino-CrC6-alkyl or tri-CrC4-alkylsilyl, said alkyl, cycloalkyl and alkoxy radicals being partially or fully halogenated can and / or carry one to three of the following groups: cyano, hydroxy, C 1 -C 6 -cycloalkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, Ci-C 4 alkoxy, -C 4 alkylthio, di (Ci-C4 -alkyl) -amino, CrC 4 -Alky! -C r C4-afkoxycarbonyl-amino, C1-C4 Alkyicarbonyl, hydroxycarbonyl, CrC ^ alkoxycarbonyl, Aminocarbony !, Cr C 4 alkylamino-carbonyl, di- (C 1 -C 4 -alkyl) aminocarbonyl or C 1 -C 4 -alkylcarbonyloxy;
Phenyl, Phenyl-d-Cβ-alkyl, Phenylcarbonyl, Pheπylcarbonyl-d-Cβ-alkyl, Pheno- xycarbσnyl, Phenylaminocarbonyl, Phenyisulfonylaminocarbonyl, N-(CrCs- A!kyl)-N-(phenyl)-aminocarbonyl, Phenyl-d-Ce-alkylcarbonyi, wobei der Phenylrest partiell oder vollständig halogeniert sein kann und/oder eine bis drei der folgenden Gruppen tragen kann: Nitro, Cyano, CrC4-Alkyl, Ci-C4-Halogenalkyl, C1-C4-AIkGXy oder d-C4-Halogenalkoxy; oder SO2R7;Phenyl, phenyl-C 1 -C 6 -alkyl, phenylcarbonyl, phenylcarbonyl-C 1 -C 6 -alkyl, phenoxycarbonyl, phenylaminocarbonyl, phenylsulfonylaminocarbonyl, N- (C 1 -C 6 -alkyl) -N- (phenyl) -aminocarbonyl, phenyl-d- Ce-alkylcarbonyi, where the phenyl radical may be partially or fully halogenated and / or may carry one to three of the following groups: nitro, cyano, C r C 4 alkyl, Ci-C4-haloalkyl, C 1 -C 4 -AlkGXy or d-C4-haloalkoxy; or SO 2 R 7 ;
R6 Wasserstoff oder Ci-C6-Alkyl;R 6 is hydrogen or C 1 -C 6 -alkyl;
R6 Ci-C6-Alky[, C2-C6-Al keny I, C2-C6-Alkinyl, CrC6-Haiogenalkyl, C2-C6- Halogenalkenyl, C2-C6-Ha!ogenalkiny!, Ci-C6-Cyanoalkyi, C2-C6-Cyanoalkenyl,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,
C2-Cβ-Cyanoalkinyl, d-Ce-Hydroxyalkyl, C2-Ce-Hydroxyalkenyl, C2-C6- Hydroxyalkinyl, C3-C6-Cycloalkyl, C3-C6-Cycloalkenyl, 3- bis 6-gliedriges Hetero- cyclyl, 3- bis 6-gliedriges Heterocyclyl-Ci-C4-alkyl, wobei die voranstehend genannten Cydoalkyl, Cycloalkenyl oder 3- bis 6- giiedrigen Heterocyclylreste partiell oder vollständig halogeniert sein können und/oder ein bis drei Reste aus der Gruppe Oxo, Cyano, Nitro, CrCe- Alkyl, CrCe-Halogenalkyl, Hydroxy, CrCe-Alkoxy, CrCε-Halogenalkoxy, Hydroxycarbonyl, d-Cs-Alkoxycarbonyl, Hydroxycarbonyl-CrC6-alkoxy, Ci-C6-A!koxycarbonyl-CrC6-aikoxy, Amino, d-Ce-Alkylatnino, Di(CrCe- alkyl)amino, Ci-Ce-Alkylsulfonylamino, CrCe-Halogenalkytsuifonylamino,C 2 -C 6 -cycloalkynyl, C 1 -C 6 -hydroxyalkyl, C 2 -C 6 -hydroxyalkenyl, C 2 -C 6 -hydroxyalkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenyl, 3 to 6-membered heterocyclyl, 3 - to 6-membered heterocyclyl-Ci-C 4 -alkyl, wherein the above-mentioned 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 -C 5 -alkoxycarbonyl, hydroxycarbonylCrC 6 -alkoxy, C 1 -C 6 -alkoxycarbonyl-C 1 -C 6 -alkoxy, amino, Ce-alkylatnino, di (C 1 -C 6 -alkyl) amino, C 1 -C 6 -alkylsulfonylamino, C 1 -C 4 -haloalkylsulfonylamino,
Aminocarbonylamino, (Ci-C6-Alkylamino)carbonylamino, Di-(CrC6-alkyl)- aminocarbonylamiπo, Aryl und Aryl(CrC6-alky!) tragen können; CrC6-Alkoxy-CrC4-alkyl, C2-C6-Alkenyloxy"CrC4-alkyl> C2-C6-Alkinyloxy-CrC4- alkyl, Ci-Ce-Halogenalkoxy-CrC4-alkyl, C2-C6-Halogenalkenyloxy-CrC4-alkyi, C2-C6-Haiogeπalkinyloxy-Ci-C4-alkyl, CrC6-Alkoxy-CrC4-alkoxy-Ci-C4-a!kyi, CrAminocarbonylamino, (Ci-C6-alkylamino) carbonylamino, di- (CrC6-alkyl) - aminocarbonylamiπo, 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 -Haiogeπalkinyloxy-Ci-C 4 -alkyl, C r C 6 alkoxy-CrC 4 -alkoxy-Ci-C 4 -alkyl, Cr
C6-Alkylthio-CrC4-aikyl, C2-C6-A!kenylthio-CrC4-alkyl, C2-C6-A(kinylthio-Ci-C4- alkyl, Ci-Ce-Halogenalkyl-Ci^-thioaikyl, C2-C6-Halogenalkenyl'CrC4-thioalkyl, C2-C6-Halogenalkinyl-CrC4-thioalkyl, CrCB-Alkylsuifinyl-CrC4-alkyl, C1-C6- Halogenalkylsulfiny!-CrC4-alky!, CrC6-Alkylsulfonyl-CrC4-alkyl, CrC6- Halogenalkylsulfonyl-CrCA-alkyl, Amino-CrC4-alkyl, CrC6-Alky[amino-CrC4- alkyl, Di(CrC6-Alkyl)amino-CrC4-alkyl, CrC5-Alkylsulfonylamino-CrC4-alkyl, d- Ce-Alkylsulfonyl-(CrC6-a!ky[amino)-CrC4-alkyl, CrCe-Alkylcarbonyi, Hydroxycarbonyl, CrC6-Alkoxycarbonyl, Aminocarbonyl, CrCe-Alkylaminocarbonyl, Di(CrC6-alkyl)aminocarbonyl, CrCe-Alkylcarbonyl-d-Ce-alkyl, Hydroxycarbonyl- CrC4-alkyl, CrC6-Alkoxycarbonyl-CrC4-a!kyl, d-Ce-Halogenalkoxycarbonyl-d-C 6 alkylthio-CrC 4 -alkyl, C2-C 6 -A! Kenylthio CRC4 alkyl, C 2 -C 6 -A (kinylthio-Ci-C4- alkyl, Ci-Ce-haloalkyl-Ci ^ -thioaikyl, C 2 -C 6 Halogenalkenyl'CrC 4 thioalkyl, C 2 -C 6 haloalkynyl -C 4 thioalkyl, CrC B -Alkylsuifinyl CRC4 alkyl, C 1 -C 6 - Halogenalkylsulfiny -CRC 4 -alky !, -C 6 Alkylsulfonyl-C 1 -C 4 -alkyl, C 1 -C 6 -haloalkylsulfonyl-C 1 -C -alkyl, amino-C 1 -C 4 -alkyl, C 1 -C 6 -alkyl [aminoCrC 4 -alkyl, di (C 1 -C 6 -alkyl) aminoCrC 4 -alkyl, C 1 -C 5 -alkylsulfonylamino -CrC4-alkyl, d-C e alkylsulphonyl (CrC 6 -a! ky [amino) -CrC4-alkyl, CRCE-Alkylcarbonyi, hydroxycarbonyl, CRC6-alkoxycarbonyl, aminocarbonyl, CRCE alkylaminocarbonyl, di (CRC6-alkyl) aminocarbonyl , C 1 -C 6 -alkylcarbonyl-C 1 -C 6 -alkyl, hydroxycarbonylCIC 4 -alkyl, C 1 -C 6 -alkoxycarbonyl-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxyalkoxycarbonyl-d
C4-alkyl, CrCΘ-Alkylcarbonyioxy-Ci^-alkyl, Aminocarbonyl-d-C4-alkyl, C1-C6- Alkylaminocarbonyl-Crd-alkyl, Di(CrC6-Alkyl)aminocarbonyl-CrC4-alkyl, C1-Ce- Alkylcarbonylamino-Ci-C4-alkyl, Formylamino-CrC4-alkyl, C1-Ce- Alkoxycarbonylamino-CrC^alkyl, Ct-C6-Alkylcarbonyi-(CrC6~aikylamino)-CrC4- atkyl, [(CrCβ-alkyl)aminocarbonyloxy]-Ci-C4-alkyl, [Di(CrCe- alkyl)aminocarbonyloxy]Ci-C4-alkyl, {Di[di(CrC6-alkyl)amino]carbonyloxy}Ci-C4- alkyf, [(CrCβ-Alkyl)aminocarbonylamino]Ci-C4-alkyl, [Di(CrCe- Alkyl)aminocarbonylamino]-CrC4-a!kyl,C 4 alkyl, C 1 -C 6 -alkylcarbonyloxy C 1 -C 4 alkyl, aminocarbonyl-C 1 -C 4 alkyl, C 1 -C 6 -alkylaminocarbonyl-C 1 -C 4 -alkyl, di (C 1 -C 6 -alkyl) aminocarbonyl-C 1 -C 4 -alkyl, C 1 -Ce Alkylcarbonylamino-C 1 -C 4 -alkyl, formylamino-C 1 -C 4 -alkyl, C 1 -C- Alkoxycarbonylamino-CrC ^ alkyl, Ct-C6-Alkylcarbonyi- (CRC6 ~ aikylamino) -CrC4- atkyl, [(β CrC alkyl) aminocarbonyloxy] -C-C4-alkyl, [di (CrCe- alkyl) aminocarbonyloxy] Ci-C4 alkyl, {di [di (CRC6-alkyl) amino] carbonyloxy} Ci-C4-alkyf, [(β CrC alkyl) aminocarbonylamino] Ci-C4-alkyl, [di (CrCe- alkyl) aminocarbonylamino] -CrC4-a ! kyl,
Phenyl-CrC4-alkyl, Phenyl-C2-C4-alkenyl, Phenyl-C2-C4-alkiny[, Phenyl-CrCr halogenalkyl, Pheny!-C2-C4-ha!ogena!kenyi, Phenyl-C∑-Crhalogenafkinyl, Phe- nyl-CrC4-hydroxyalkyl, Phenyl-C2-C4-hydroxyalkenyl, Phenyl-C2-C4- hydroxyalkinyl, Phenylcarbonyf-CrC4-a!kyl, Phenylcarbonylamino-CrC4-a!ky[, Phenylcarbony!oxy-CrC4-alkyl, Phenyloxycarbonyl-Ci~C4-alkyl, Phenyloxy-CrPhenyl-C r-C4 alkyl, phenyl-C 2 -C 4 alkenyl, phenyl-C 2 -C 4 -alkiny [, phenyl-CrCr haloalkyl, phenyl-C 2 -C 4 -ha! Ogena! Kenyi, phenyl CΣ-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
C4-alkyl, Phenylthio-CrC4-alky[, PhenylsuIfinyl-CrC4-alkyl, Phenylsulfonyl-CrC4- alkyi,C 4 -alkyl, phenylthio-C 1 -C 4 -alkyl [, phenylsulfinyl-C 1 -C 4 -alkyl, phenylsulfonyl-C 1 -C 4 -alkyl,
Heteroaryl-CrC4-alkyi, Heteroaryl-C2-C4-alkenyl, Heteroaryl-C2-C4-alkinyl, Hete- roaryl-CrC4-halogeπalkyl, Heteroaryl-C2-C4-haiogenalkenyl, Heieroaryl-C2-C4- halogenalkinyl, Heteroaryl-CrC4-hydroxyalkyl, Heteroaryl-C2-C4-hydroxyalkenyJ,Heteroaryl CRC4 alkyi, heteroaryl-C2-C4-alkenyl, heteroaryl-C2-C4-alkynyl, heteroaryl-CRC4 halogeπalkyl, heteroaryl-C2-C4-haiogenalkenyl, Heieroaryl-C2 -C4- haloalkynyl, heteroaryl CrC 4 -hydroxyalkyl, heteroaryl-C 2 -C 4 -hydroxyalkylene,
Heteroaryl-C2-C4-hydroxyalkinyl, Heteroarylcarbonyl-Ci-C4-alkyl, Heteroarylcar- bonyloxy-CrC4-alkyl, Heteroaryloxycarbonyl-CrC4-alkyl, Heteroaryloxy-Ci-C4- alkyl, Heteroarylthio-Ci-C4-alkyl, Heteroarylsulfinyl-CrC4-alkyl, Heteroarylsulfo- ny[-Ci-C4-alkyl, wobei die vorstehend genannten Phenyl- und Heteroarylreste partiell oder vollständig halogeniert sein können und/oder ein bis drei Reste aus der Gruppe Cyano, Nitro, Ci-C3-Alkyl, d-Cs-Halogenaikyl, Hydroxy, CrC6- Alkoxy, CrCe-Halogenalkoxy, Hydroxycarbonyl, d-Cβ-Alkoxycarbonyl, Hy- droxycarbonyl-d-Ce-alkoxy, CrCθ-Alkoxycarboπyl-CrCe-alkoxy, Amino, CrCe-Alkylamino, Di(CrC6-alkyl)amino, Ci-Ce-Alkylsulfonylamino, CrC6-Heteroaryl-C 2 -C 4 -hydroxyalkinyl, heteroarylcarbonyl-Ci-C 4 alkyl, Heteroarylcar- bonyloxy CRC4 alkyl, heteroaryloxy-CRC4-alkyl, heteroaryloxy-Ci-C4-alkyl, heteroarylthio-Ci-C4-alkyl, heteroarylsulfinyl -CrC4-alkyl, Heteroarylsulfo- ny [-C-C 4 alkyl, wherein the above-mentioned phenyl and heteroaryl radicals may be partially or fully halogenated and / or one to three radicals from the group cyano, nitro, Ci-C 3 - alkyl, d-Cs-Halogenaikyl, hydroxy, C r C 6 - alkoxy, CRCE -haloalkoxy, hydroxycarbonyl, d-Cβ-alkoxycarbonyl, hydroxycarbonyl-d-Ce-alkoxy, CrCθ-Alkoxycarboπyl-CRCE-alkoxy, amino, CRCE Alkylamino, di (C 1 -C 6 -alkyl) amino, C 1 -C 6 -alkylsulfonylamino, C 1 -C 6 -
Halogenalkylsulfonylamino, (CrCe-AlkylaminoJcarbonylamiπo, Di-(CrCe- aikyl)-aminocarbonylamino, Aryl und Aryl(CrCe-alkyl) tragen können;Halogenoalkylsulfonylamino, (C 1 -C 6 -alkylamino) carbonylamino, di (C 1 -C 6 -alkyl) aminocarbonylamino, aryl and aryl (C 1 -C 6 -alkyl);
R7 d-Cβ-Alkyl. CrC6-Halogeπalkyl oder Phenyi, wobei der Phenyirest partiell oder vollständig halogeniert sein kann und/oder eine bis drei der folgenden Gruppen tragen kann: CrCβ-Alkyl, Cr Cε-Haiogenalkyl oder CrCe-Alkoxy;R 7 is d-Cβ-alkyl. C r C 6 -haloalkyl or phenyl, where the phenyl residue may be partially or completely halogenated and / or may carry one to three of the following groups: C 1 -C 6 -alkyl, C 1 -C 6 -halioalkyl or C 1 -C 6 -alkoxy;
sowie deren landwirtschaftlich brauchbaren Salze.and their agriculturally useful salts.
Außerdem betrifft die Erfindung Verfahren und Zwischenprodukte zur Herstellung von Verbindungen der Forme! I, Mittel welche diese enthalten sowie die Verwendung dieser Derivate oder diese enthaltende Mittel zur Schadpflanzenbekämpfung.Moreover, 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.
Fungizid wirksame thienylsubstituierte Aminosäurederivate, die in α-Position einen Alkylrest tragen, welcher gegebenenfalls durch Hydroxy oder Alkoxy substituiert sein kann, werden u.a. in EP 450 355 beschrieben. Weiterhin sind aus der Literatur, beispielsweise aus US 5,346,907, WO 96/012499 sowie WO 02/069905 Serinderivate mit pharmazeutischer Wirksamkeit bekannt, welche in α-Position unter anderem einen Alkylrest tragen können, der gegebenenfalls durch Hydroxy oder Alkoxy substituiert sein kann.Fungicidally effective thienyl-substituted amino acid derivatives which carry an alkyl radical in the α-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 α-position inter alia an alkyl radical which may optionally be substituted by hydroxy or alkoxy.
Die herbiziden Eigenschaften der bisher bekannten Verbindungen bzw. die Verträglichkeiten gegenüber Kulturpflanzen können jedoch nur bedingt befriedigen.However, the herbicidal properties of the previously known compounds or the tolerances towards crop plants can satisfy only conditionally.
Es lag daher dieser Erfindung die Aufgabe zugrunde, neue, insbesondere herbizid wirksame, Verbindungen mit verbesserten Eigenschaften zu finden.It was therefore an object of the present invention to find novel, in particular herbicidally active, compounds having improved properties.
Demgemäß wurden die heteroaroylsubstituierten Seriπ-Amide der Formel I sowie deren herbizide Wirkung gefunden.Accordingly, the heteroaroyl-substituted Seriπ-amides of formula I and their herbicidal activity were found.
Ferner wurden herbizide Mittel gefunden, welche die Verbindungen I enthalten und eine sehr gute herbizide Wirkung besitzen. Außerdem wurden Verfahren zur Herstellung dieser Mittel und Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs mit den Verbindungen I gefunden.Furthermore, herbicidal agents were found which contain the compounds I and have a very good herbicidal activity. In addition, methods for the preparation of these compositions and methods for controlling undesired plant growth with the compounds I have been found.
Die Verbindungen der Formel I enthalten je nach Substitutioπsmuster zwei oder mehr Chiralitätszentren und liegen dann als Enantiomeren oder Diastereomerengemische vor. Gegenstand der Erfindung sind sowohl die reinen Enantiomeren oder Diastereo- meren als auch deren Gemische.Depending on the substitution pattern, 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.
Die Verbindungen der Formel I können auch in Form ihrer landwirtschaftlich brauchbaren Salze vorliegen, wobei es auf die Art des Salzes in der Regel nicht ankommt. Im allgemeinen kommen die Salze derjenigen Kationen oder die Säureadditionssalze derjenigen Säuren in Betracht, deren Kationen, beziehungsweise Anionen, die herbizide Wirkung der Verbindungen i nicht negativ beeinträchtigen.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. In general, 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.
Es kommen als Kationen insbesondere Ionen der Alkalimetalle, vorzugsweise Lithium, Natrium und Kalium, der Erdalkalimetalle, vorzugsweise Calcium und Magnesium, und der Übergangsmetalle, vorzugsweise Mangan, Kupfer, Zink und Eisen, sowie Ammonium, wobei hier gewünschtenfaüs ein bis vier Wasserstoffatome durch d-C^Alkyl, Hydroxy-CrC4-alkyl, Ci-C4-Alkoxy-CrC4-alky!, Hydroxy-Ci-C^alkoxy-d-C^alkyl, Phe- nyl oder Benzyi ersetzt sein können, vorzugsweise Ammonium, Dimethylammonium, Diisopropylammonium, Tetramethylammonium, Tetrabutylammonium, 2-(2- Hydroxyeth-1-oxy)eth-1-ylarnmonium, Di-(2-hydroxyeth-1-yl)-ammoπium, Tπmethyl- benzylammonium, des weiteren Phosphoniumionen, Sulfoniumioπeπ, vorzugsweise Tri(CrC4-alkyl)sulfonium und Sulfoxoniumionen, vorzugsweise Tri(Ci-C4alky!)- sulfoxonium, in Betracht. Anionen von brauchbaren Säureadditionsaizen sind in erster Linie Chlorid, Bromid, Fluorid, Hydrogensulfat, Sulfat, Dihydrogenphosphat, Hydrogenphosphat, Nitrat, Hydrogencarbonat, Carbonat, Hexafluorosilikat, Hexafluorophosphat, Benzoat sowie die Anionen von Ci-C4-A!kansäuren, vorzugsweise Formiat, Acetat, Propioπat und Butyrat.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, sulfonium compounds, preferably Tri (C 1 -C 4 -alkyl) sulfonium and sulfoxonium ions, preferably tri (C 1 -C 4 -alkyl) sulfoxonium. 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.
Die für die Substituenten R1-R6 oder als Reste an Phenyl-, Aryl-, Heteroaryl- oder Hetrocyclylringen genannten organischen Molekülteile stellen Sammelbegriffe für individuelle Aufzählungen der einzelnen Gruppenmitglieder dar. Sämtliche Kohlenwasser- stoffketten, also alle Alkyl-, Alkylsilyl-, Alkenyl-, Alkinyl-, Cyanoalkyl-, Halogenalkyl-, Halogenalkenyl-, Halogenalkinyl-, Alkoxy-, Halogenalkoxy-, Alkoxyalkyl-, Alkoxyalkoxy- alkyl, Alkylcarbonyl-, Alkenylcarbonyl-, Alkinylcarbonyi-, Alkoxycarbonyl-, Alkenyloxy- carbonyl-, Alkinyloxycarbonyl-, Alkylamino-, Alkylsulfonylamino-, Halogenalkylsulfonyl- amino-, Alkylalkoxycarbonylamino-, Alkylaminocarboπyh Alkenylamiπocarbonyl-, Alki- nylaminocarbonyl-, Alkylsulfonylaminocarbonyl, Dialkylaminocarboπyl-, N-Alkenyi-N- alkylaminocarboπyh N-Alkinyl-N-alkylamino-carbonyl-, N-Alkoxy-N-alkylamiπo- carbonyl-, N-Alkenyl-N-alkoxyaminocarbonyl-, N-Alkinyl-N-alkoxyaminocarbonyi-, Dial- kylaminothiocarbony!-, Aikylcarbonylalkyl-, Alkoximinoalkyl-, N-(Alkylamino)-iminoalkyl, N-(Dialkylamino)-iminoalkyl, Aikylcyanoimino-, Alkylaminocyanoimino-, Dialkylamino- cyanoimino-, Formylaminoalkyl-, Alkoxycarbonylaminoalkyl-, (Alkylami- no)carbonyloxyalkyl-, (Alkylamino)carbonylaminoalkyl-, (Dialkylami- no)carbonylaminoalkyi-, Phenylcarbonylaminoalkyl-, Phenylalkyl-, Phenylcarbonyl- alky!-, N-Alkyl-N-phenylaminocarboπyl-, Phenylalkylcarbonyl-, Arylalkyl-, Hetero- cyclylalky!, Heterocyciylcarbonylalkyl-, N-Alkyl-N-heterocyclylaminocarbonyl-, Hetero- cyclylalkylcarbonyl-, Alkylthio- und Alkylcarbonyloxy-Teile können geradkettig oder verzweigt sein.The 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, alkylaminocarboπyh alkenylaminocarbonyl, alkynylaminocarbonyl, alkylsulfonylaminocarbonyl, dialkylaminocarbonyl, N-alkenyl-N-alkylaminocarbonyl, N-alkynyl-N-alkylamino-carbonyl, N-alkoxy- N-alkylaminocarbonyl, N-alkenyl-N-alkoxyaminocarbonyl, N-alkynyl-N-alkoxyaminocarbonyl, dialkylaminothiocarbonyl, Aikylcarbonylalkyl-, alkoximino alkyl, N- (alkylamino) -iminoalkyl, N- (dialkylamino) -iminoalkyl, aikylcyanoimino, alkylaminocyanoimino, dialkylamino, cyanoimino, formylaminoalkyl, alkoxycarbonylaminoalkyl, (alkylamino) carbonyloxyalkyl, (alkylamino) carbonylaminoalkyl-, (Dialkylamino) carbonylaminoalkyl, phenylcarbonylaminoalkyl, phenylalkyl, phenylcarbonylalkyl, N-alkyl-N-phenylaminocarbonyl, phenylalkylcarbonyl, arylalkyl, heterocyclylalkyl, heterocyclicylcarbonylalkyl, N-alkyl-N-heterocyclylaminocarbonyl -, heterocyclylalkylcarbonyl, alkylthio and alkylcarbonyloxy parts may be straight-chain or branched.
Sofern nicht anders angegeben tragen halogenierte Substituenten vorzugsweise ein bis fünf gleiche oder verschiedene Halogenatome. Die Bedeutung Halogen steht je- weils für Fluor, Chlor, Brom oder lod.Unless otherwise indicated, 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.
Ferner bedeuten beispielsweise:Furthermore, for example:
- Ci-C4-Alkyl sowie die Alkylteile von Ci-C4-Alkylcarboπy!oxy, Ci- C4-aikyl-CrC4-a!koxycarbonylamino, Ci-C6-Alkyliminooxy~Ci-C4-alkyl, Ct-C4- Alkoxy-Ci-C4-alkoxy-C1-C4-a!kyl) Ci-C6-Alkoxy-Ci-C4-aikyl, C2-C6-Alkenyloxy-Ci-C4- alkyl, C2-C6-Alktnyloxy-Ci-C4-alkyl) Ci-C6-Ha!ogenalkoxy-C-ι-C4-alkyl, C2-C6- Halogenalkenyloxy-Ci-C4-alkyl, C2-C6-Halogena[kinyloxy-Ci-C4-alkyl, Ci-Cε-Alkoxy- CrC4-alkoxy-Ci-C4-alkyl, Ci-C6-Alkylthio-Ci-C4-alkylJ C2-C6-Alkenylthio-Ci-C4-alkyl,- Ci-C 4 alkyl and the alkyl moieties of Ci-C4-Alkylcarboπy! Oxy, -C 4 -alkyl-C r C 4 -a Ci! Koxycarbonylamino, Ci-C6-Alkyliminooxy ~ Ci-C4-alkyl, Ct-C4 alkoxy-Ci-C4-alkoxy-C1- C4-a! kyl) Ci-C 6 alkoxy-Ci-C4 -alkyl, C 2 -C 6 alkenyloxy-Ci-C4- alkyl, C2-C6 -Alktnyloxy-Ci-C4 alkyl) Ci ! C6-Ha ogenalkoxy-C-ι-C 4 alkyl, C 2 -C 6 - haloalkenyloxy-Ci-C 4 alkyl, C 2 -C 6 Halogena [kinyloxy-Ci-C4-alkyl, Ci-Cε- alkoxy -C 4 alkoxy-Ci-C4-alkyl, Ci-C6 alkylthio-Ci-C4-alkyl J C 2 -C 6 alkenylthio-Ci-C4-alkyl,
Cz-Ce-Alkinylthio-d-C^alkyl, CrC6-A[kylsu[finyl-Ci-C4-alkyl, CrC6- Halogenalky!sulfinyl-CrC4-alkyl, Ci-C6-Alkylsulfonyl-CrC4-alkyJ, CrC6- HalogenalkylsulfonyhCi-C4-alkyl, Amino-Ci-C4-alkyi, CrCθ-Alkyiamtno-Ci^-alky!, Di(Ci-C6-A]kyl)amino-Ci-C4-alkyl( Formylamino-CrC4-alkyf, CrC6- Alkoxycarbonylamino-Ci-C4-alkyl, CrCe-Alkylsulfonylamino-CrC^alkyi, CrCe- Alky!sulfoπyi-(CrC6-alkylamino)-Ci-C4-alkyl, Hydroxycarbonyl-d-C^alkyl, Ci-Ce- Aikoxycarboπyl-CrC4-alkyl, Ci-Cβ-Halogenalkoxycarbonyl-CrC^alkyf, CrCβ- Alkylcarbonyloxy-Ci-C4-alkyl, Aminσcarbonyl-CrC4-alky[, CrCβ-Alkylaminocarbonyl-Cz-Ce-alkynylthio-dC ^ alkyl, C r C 6 -A [kylsu [finyl-Ci-C4-alkyl, CrC 6 - Halogenalky sulfinyl-C r C 4 alkyl, C 6 -C alkylsulfonyl-4 -alkyJ, C r C 6 - haloalkylsulfonyhCi-C 4 -alkyl, amino-Ci-C4-alkyi, CrCθ-Alkyiamtno-Ci ^ -alky !, Di (Ci-C6-A] alkyl) amino-Ci-C4 alkyl (formylamino -C 4 -alkyf, CrC 6 - alkoxycarbonylamino Ci-C4 alkyl, CRCE-alkylsulfonylamino -C ^ alkyi, CrCe- alky sulfoπyi! - (C 1 -C 6 -alkylamino) C 1 -C 4 -alkyl, hydroxycarbonyl-C 1 -C 4 -alkyl, C 1 -C 6 -alkoxy-carbonyl-C 1 -C 4 -alkyl, C 1 -C 6 -haloalkoxycarbonyl-C 1 -C 4 -alkyl, C 1 -C 6 -alkylcarbonyloxy-C 1 -C 4 -alkyl, aminecarbonyl -CrC4-alky [, CrCβ-alkylaminocarbonyl-
CrC4-alkyl, Di(Ci-C6-Alkyl)aminocarbony!-Ci-C4-alkyl, [(CrC6- alkyl)aminocarbonylamino]-CrC4-a)kyl, [Di(CrCe-alkyl)aminocarbonylamino]-Ci-C4- alkyl, CrCe-AlkylcarbonySamino-Ci^-alkyl, CrCe-AlkylcarbonyKCi-Ce-alkylamino)- Ci-C4-alkyl, [(Ci-C6-A[kyl)aminocarbony!oxy]CrC4-a!kyl, [Di(CrC5- alky[)aminocarbonyloxy]CrC4-alkyt, {Di[di(CrC6-alkyl)amino]carbonyloxy}CrC4- alkyl, Heterocylyl-CrC4-alkyl, Phenyl-CrC4-alkyl, Phenylcarbonylamino~CrC4-a[kyi, Phenyl-CrC4-alky!, Phenylcarbonyi-CrC4-alkyl, Heteroary!carbonyl-CrC4-alkyl, He- teroarylcarbonyloxy-CrC4-alkyl, Heteroaryloxycarbonyi-CrC4-alkyl, Heteroaryloxy- CrC4-alkyl, Heteroarylthio-CrCi-alkyl, Heteroarylsulfinyl-Ci-C4-alky], Heteroarylsul- foπyl-CrC-ralkyl, und Ary!(CrC4-alkyl): z.B. Methyl, Ethyt, n-Propyi, 1-Methylethyl, n-Butyl, 1-Methylpropyl, 2-Methy[propyl und 1,1-Dimethylethyl;-C 4 alkyl, di (Ci-C 6 alkyl) aminocarbony -C-C4-alkyl, [(-C 6 - alkyl) aminocarbonylamino] -CrC4-a) kyl, [di (CRCE-alkyl) aminocarbonylamino] -C -C 4 -alkyl, C 1 -C 6 -alkylcarbony- C 1 -C 4 -alkyl, C 1 -C 6 -alkylcarbonyKCi-C 1 -C 6 -alkylamino) - C 1 -C 4 -alkyl, [(C 1 -C 6 -acyl) aminocarbonyloxy] C 1 -C 4 -alkyl , [Di (C 1 -C 5 -alkyl [) aminocarbonyloxy] C 1 -C 4 -alkyl, {di [di (C 1 -C 6 -alkyl) amino] carbonyloxy} C 1 -C 4 -alkyl, heterocyclylC-C 4 -alkyl, phenyl-C 1 -C 4 -alkyl, phenylcarbonylamino ~CrC 4 -a [kyi, phenyl-CrC 4 -alky !, phenylcarbonyiCrC 4 -alkyl, heteroarylcarbonyl-C 1 -C 4 -alkyl, heteroarylcarbonyloxyCrC 4 -alkyl, heteroaryloxycarbonyiCrC 4 -alkyl, heteroaryloxyCrC 4 -alkyl, Heteroarylthio-C 1 -C 4 -alkyl, heteroarylsulfinyl-C 1 -C 4 -alkyl], heteroarylsulforylCycRalkyl, and aryl (C 1 -C 4 -alkyl): for example methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methyl [propyl and 1,1-dimethylethyl;
- Ci-Ce-Alky! sowie die Alkylteile von Ci-C6-Cyanoalkyl, CrCe-Alkoxycarbonyl-CrCe- alkyl, Cr Ce-Alkylsulfonylamino, CrCβ-Alkylsulfonylaminocarboπyl, N-(C3-Cβ- Alkeny!)-N-(Ci-C6-alkyl)~aminocarbonyi, (Ca-Ce-AlkinyO-N-fd-Ce-aikyl)- amiπocarbonyl, N-(Ci-C6-Alkoxy)~N-(Ci-C6-a(kyl)-aminocarbonyl, Ci-C6- Ci-C6-Alkoxyimino-Ci-C6-alkyl, N-(Ci-C6-Aikylamino)- imiπo-Ci-Ce-alkyl, N~(Di-Ci-C6-alky!-amino)-imino-Ci-C6-afkyl, (CrC6-Alkyl)- cyanoimino, Phenyl-Ci-Cβ-alkyl, Phenylcarbonyl-Ci-Cß-alkyi, N-(Ci-Cs-Alkyl)-N~ phenylaminocarbonyl, Heterocyclyl-Ci-C6-aikyl, Hetrocyclyl-carbonyl-Ci-C6-alkyl und N-(Ci-C6-Alkyl)-N-heterocyclylaminocarbonyl:- Ci-Ce-Alky! and the alkyl moieties of C 1 -C 6 -cyanoalkyl, C 1 -C 6 -alkoxycarbonyl-C 1 -C 6 -alkyl, C 1 -C -alkylsulfonylamino, C 1 -C 6 -alkylsulfonylaminocarbonyl, N- (C 3 -C 6 -alkenyl) -N- (C 1 -C 6 -alkyl) -1 aminocarbonyi, (Ca-Ce-alkyno-N-fd-Ce-aikyl) -aminocarbonyl, N- (Ci-C6-alkoxy) ~ N- (Ci-C6-a (kyl) -aminocarbonyl, Ci-C 6 - C 1 -C 6 -alkoxyimino-C 1 -C 6 -alkyl, N- (C 1 -C 6 -alkylamino) -imino-C 1 -C 6 -alkyl, N - (C 1 -C 6 -alkyl-amino) -imino-Ci -C 6 -afkyl, (CrC 6 -alkyl) - cyanoimino, phenyl-Ci-Cβ-alkyl, phenylcarbonyl-Ci-CSS alkyi, N- (Ci-Cs-alkyl) -N ~ phenylaminocarbonyl, heterocyclyl-Ci-C6 -acyl, Hetrocyclyl-carbonyl-C 1 -C 6 -alkyl and N- (C 1 -C 6 -alkyl) -N-heterocyclylaminocarbonyl:
Ci-C4-Alkyl, wie voranstehend genannt, sowie z.B. n-Pentyl, 1-Methyi-butyl, 2~ Methylbutyl, 3-Methylbutyl, 2,2-Dimethyipropyl, 1-Ethylpropy!, n-Hexyl, 1 ,1- Dimethylpropyl, 1 ,2-Dimethylpropyl, 1-Methylpentyl, 2-Methylpentyl, 3- Methytpentyi, 4-Methylpenty!, 1,1-Dimethylbutyl, 1 ,2-Dimethylbutyl, 1,3-Di- methylbutyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1-Ethyi-butyl, 2-Ethy!buty!, 1 ,1 ,2-Trimethylpropyl, 1-Ethyl-1-methy!propy! und 1-Ethyl-3- methylpropyl;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;
- Ci-C4-Alkylcarbonyl: z.B. Methylcarbonyl, Ethylcarbonyl, Propylcarbonyl, 1-Methyl- ethylcarbonyl, Butylcarbonyl, 1-Methylpropylcarbonyt, 2-Methyipropylcarbonyl oder 1 ,1-Dimethylethylcarbonyl;C 1 -C 4 -alkylcarbonyl: e.g. Methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl, 1-methylpropylcarbonyt, 2-methylpropylcarbonyl or 1, 1-dimethylethylcarbonyl;
- Ci-Ce-Alkylcarbonyl sowie die Alkylcarbonylreste von Ci-Cβ-Alkylcarbonyl-Ci-Ce- alkyl, Ci-Ce-Alkylcarbonyloxy-Ci-Cβ-alkyl, Ci-Ce-Alkylcarbonylamino-Ci^-alkyl,C 1 -C 6 -alkylcarbonyl and the alkylcarbonyl radicals of C 1 -C 6 -alkylcarbonyl-C 1 -C 6 -alkyl, C 1 -C 6 -alkylcarbonyloxy-C 1 -C 6 -alkyl, C 1 -C 6 -alkylcarbonylaminoC 1 -4 -alkyl,
Phenyl-CrCe-alkylcarbonyl und Heterocyclyl-d-Ce-alkylcarbonyl, CrCe- Alky!carbonyl-(CrCB-a[kylamino)-d-C4-a!kyl: Ci-C4-Alkylcarbonyl, wie voranstehend genannt, sowie z,B. Pentylcarbonyl, 1- Methylbutylcarbony!, 2-Methyibutylcarbonyl, 3-Methylbutylcarbonyl, 2,2- Dimethylpropylcarbonyl, 1-Ethylpropylcarbonyl, Hexylcarbonyl, 1 ,1-Dimethyl- propylcarbonyl, 1 ,2-Dimethylpropylcarbonyl, 1-Methylpentylcarbonyl, 2-Methyl- pentylcarbonyl, 3-Methylpentylcarbonyi, 4-Methylpentylcarbonyl, 1 ,1-Dimethyl- butylcarbonyl, 1 ,2-Dimethyibutylcarbonyl, 1,3-Dimethylbutylcarbonyl, 2,2-Di- methylbutylcarbonyl, 2,3-Dimethylbutylcarbonyl, 3,3-Dimethylbutylcarbony[, 1- Ethylbutylcarbonyl, 2-Ethylbutylcarbonyl, 1 ,1 ,2-Trimethy[propylcarbonyl, 1 ,2,2- Trimethyipropylcarbony!, 1-Ethyi-1-methylproρy!carbony[ oder 1-Ethyl-2-methyl- propylcarbonyl;Phenyl-CrCe-alkylcarbonyl and heterocyclyl-d-Ce-alkylcarbonyl, CrCe- alkylcarbonyl- (CrCB-a [kylamino] -d-C4-alkyl) Ci-C4-alkylcarbonyl, as mentioned above, and z, B. 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-trimethylphenylcarbonyl, 1-ethyl-1-methylpropylcarbonyl [or 1-ethyl-2-methylpropylcarbonyl;
- Cϊ-Ce-Cycloalkyl sowie die Cycloalkyiteile von C3-C6-Cycloalkyicarbonyl: monocyc- lischer, gesättigter Kohlenwasserstoff mit 3 bis 6 Ringgliedern, wie Cyclopropyl, Cyclobutyl, Cyclopentyl und Cyclohexyl;- Cϊ-Ce-cycloalkyl and the Cycloalkyiteile of C 3 -C 6 cycloalkyicarbonyl: monocyclic saturated hydrocarbon having 3 to 6 ring members, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
- C3-Cs-Cycloaikenyl: z.B. 1-Cyclopropenyl, 2-Cyclopropenyl( 1-Cyclobutenyl, 2- Cyclobutenyl, 1-Cyc!opentenyl, 2-Cyclopentenyl, 1 ,3-Cyclopentadienyl, 1 ,4- Cyclopentadienyi, 2,4-Cyclopentadienyl, 1-Cyclohexenyl, 2-Cyclohexenyl, 3- Cyclohexenyl, 1 ,3-Cyclohexadienyl, 1 ,4-Cyclohexadienyl, 2,5-Cyc!ohexadienyl;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;
- C3-C6-Aikenyl sowie die Alkenylteüe von C3-C6-Alkenyioxycarbonyl, Cs-Cβ-Alkenyl- aminocarboπyl, N-(C3-C6-Alkenyl)-N-(Ci-C6-alky!)aminocarbonyl und N-(C3-Ce~ Alkenyi)-N-(Ci-C6-afkoxy)aminocarbonyl: z.B. 1-Propenyl, 2-Propenyl, 1-Methyl- ethenyl, 1-Butenyl, 2-Butenyl, 3-Butenyl, 1 -Methyl- 1-propeny I, 2-Methyl-1-propeny), 1-Methy]-2-propenyl, 2-Methyl-2-propenyl, 1-Pentenyl, 2-Pentenyl, 3-Pentenyl, A-- C3-C6-Aikenyl and the Alkenylteüe of C3-C6-Alkenyioxycarbonyl, Cs-Cβ-alkenyl-aminocarboπyl, N- (C 3 -C 6 -alkenyl) -N- (Ci-C6-alky!) Aminocarbonyl and N- (C 3 -C 10 -alkenyl) -N- (C 1 -C 6 -alkoxy) aminocarbonyl: for example 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl- 1-propenyl I, 2-methyl-1-propenyl), 1-methyl] -2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, A-
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-propenyi, 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,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-ρente- nyl, 3-Methyl-2-pentenyl, 4-Methyf-2-pentenyl, i-Methyl-3-pentenyl, 2-Methyl-3- peπtenyl, 3-Methy!-3-pentenyl, 4-Methyl-3-pentenyl, 1-Methyl-4-pentenyi, 2-Methyl- 4-pentenyl, 3-Methyl-4-pentenyl, 4-Methyi-4-pentenyl, 1 ,1-Dtmethyl-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-buteπyl, 1,3-Dimethyl-3-butenyl, 2,2-Dimethyl-3-butenyl, 2,3-Dimethyl-i-butenyl, 2,3-Dirnethyl-2-butenyl, 2,3- Dimethyl-3-butenyl, 3,3-Dimethy!-1-butenyl, 3,3-Dimethyl-2-butenyl, 1 -Ethyl-1- bυtenyl, 1-Ethyl-2-butenyl, 1-Ethyl-3-butenyl, 2-Ethyl-1-butenyl, 2-Ethyl-2-butenyl, 2- Ethyl-3-butenyl, 1 ,1 ,2-Trimethyl-2-propenyl, i -Ethyl-i-methyl-2-propenyl, 1 -Ethyl-2- methyl-1-propenyl und 1Εthyl-2-methyl-2-propenyl; - C2-C6-Atkenyl sowie die Alkenylteile von Cz-Ce-Alkeπyicarbonyl, C2-Ce-Alkenyioxy- Ci-C4-alkyl, C2-C6-Alkenylthio-Ci-C4-aikyl, Phenyl-C2-C4-alkenyi, Heteroary-C2-C4- alkeny!: Ca-Cβ-Alkenyl wie voraπstehend genannt sowie Ethenyl;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, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3.3 -Dimethyl-2-butenyl, 1-ethyl-1-butylen, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl 3-butenyl, 1, 1, 2-trimethyl-2-propenyl, i-ethyl-i-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl ; - C2-C6 -Atkenyl also the alkenyl moieties of Cz-Ce-Alkeπyicarbonyl, C2-Ce-Alkenyioxy- Ci-C4-alkyl, C 2 -C 6 alkenylthio-Ci-C 4 -alkyl, phenyl-C 2 - as voraπstehend called alkeny !: Ca-Cβ-alkenyl and ethenyl - C4 alkenyi, C2-heteroaryl-C 4;
- C3-C6-Alkinyl sowie die Alkinylteile von Ca-Ce-Alkinyloxycarbonyl, C3-Cs-- C3-C6 alkynyl and the alkynyl moieties of Ca-Ce alkynyloxycarbonyl, C3-Cs
Alkinylaminocarbonyi, N-(C3-Ce-Alkinyl)-N-(Ci-C6-alkyl)-aminocarbonyl, N-(C3- C6-Alkinyl)-N-(Ci-C6-alkoxyaminocarbonyi: z.B. 1-Propinyl, 2-Propinyl, 1-Butinyl, 2-Butinyl, 3-Butinyl, 1-Methyl-2-propinyi, 1-Pentinyl, 2-Pentinyl, 3-Peπtiπyl, 4-Pentiny!, 1-Methyl-2-butinyl, 1-Methyl-3-butinyl, 2-Methyl-3-butinyl, 3-Methyl-1- butinyl, 1,1-Dimethyl-2-propinyi, 1-Ethyl-2-propinyl, 1-Hexinyl, 2-Hexinyl, 3-Hexinyl,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-hexynyl .
4-HexinyS, 5-Hexinyl, i-Methyl-2-pentinyl, 1-Methyl-3-pentinyl, 1-Methyl-4-pentinyl, 2-Methyl-3-peπtinyl, 2-Methyl-4-pentinyl, 3-Methyl-1-pentinyi, 3-Methy[-4-ρentiπyl, 4-Methyl-1-peπtinyl, 4-Methyl-2-pentinyi, 1 ,1-Dimethyl-2-butinyl, 1 ,1-Dimethyl-3- butinyl, 1,2-Dimethyl-3-butinyl, 2,2-Dirτiethyl-3-butinyl, 3, 3-Dimethyl-1 -butinyl, 1 -Ethyl-2-butinyl, 1 -Ethyl-3-butiπyl, 2-Ethyl-3-butinyl und 1 -Ethyl-1 -methyl-2- propinyl;4-hexynes, 5-hexynyl, i-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3 Methyl 1-pentynes, 3-methyl [ -4-pyridinium, 4-methyl-1-pyridininyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl , 1,2-dimethyl-3-butynyl, 2,2-diethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butylphenyl, 2-ethyl 3-butynyl and 1-ethyl-1-methyl-2-propynyl;
- C∑-Ce-Alkinyl sowie die Alkinylteüe von Cs-Cε-Alkinylcarbonyl, C2-C2-Alkinyioxy-Ci- 04-alkyl, C2-C6-Alkinylthio-Ci-C4-alky!, Phenyl-C2-C4-alkinyl, Heteroaryl-C2-C4- alkinyl: C3-Ce-A[kinyl wie voranstehend genannt sowie Ethinyi;- CΣ-Ce-alkynyl and the Alkinylteüe of Cs-Cε-alkynylcarbonyl, C2-C2-alkynyloxy-Ci-04-alkyl, C 2 -C6-alkynylthio-Ci-C 4 -alkyl, phenyl-C 2 -C 4 -alkynyl, heteroaryl-C 2 -C 4 alkynyl: C 3 -C 12 A [kinyl as mentioned above and ethynyl;
- Ci-C4-Cyanoalkyl: z.B. Cyanomethyl, 1-Cyanoeth-1-yl, 2-Cyanoeth-1-yl, 1 -Cyano- prop-1-yi, 2-Cyanoprop-1-yl, 3-Cyanoprop-1-yl, 1 -Cyanoprop-2-yl, 2-Cyanoprop-2- yl, 1-Cyanobut-1-yl, 2-Cyanobut-1-yi, 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 -Cyaπo-2-methyl- prop-3-yl, 2-Cyano-2-methyl-prop-3-yl, 3-Cyano-2-methy!-prop-3-yl und 2-Cyano- methyl-prop-2-yl;- C 1 -C 4 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-cyaπo-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-C4-Hydroxyalkyl sowie die Crd-Hydroxyalkyl-Teile von Phenyl-CrC4- hydroxyaikyl, Heteroaryl-Ci-C4-hydroxyalkyl: z.B. Hydroxymethyl, 1-Hydroxyeth-1 -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-yi, 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-Hydroxy but-2-yl, 1- Hydroxybut-3-yl, 2-Hydroxybut-3-yi, 1-Hydroxy -2-methyl-prop-3-y!, 2-Hydroxy -2- methyl-prop-3-yl, 3-Hydroxy -2-methyl-prop-3-yl und 2-Hydroxymethyl-prop-2-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,
1 ,2-Diydroxyethyl, 1 ,2-Dihydroxyprop-3-y[, 2,3-Dihydroxyprop-3-yl, 1 ,2-Dihydroxy- prop-2-y!, 1 ,2-Diydroxybut-4-yl, 2,3-Diydroxybut-4-yl, 3,4-Diydroxybut-4-yl, 1 ,2- Diydroxybut-2-yf, 1 ,2-Diydroxybut-3-yl, 2,3-Diydroxybut-3-yl, 1 ,2-Dihydroxy-2- methyl-prop-3-yi, 2,3-Dihydroxy-2-methyl-prop-3-yl;1, 2-dihydroxyethyl, 1, 2-dihydroxyprop-3-yl, 2,3-dihydroxyprop-3-yl, 1, 2-dihydroxyprop-2-yl, 1, 2-dihydroxybut-4-yl, 2,3-dihydroxybut-4-yl, 3,4-dihydroxybut-4-yl, 1, 2-dihydroxybut-2-yf, 1, 2-dihydroxybut-3-yl, 2,3-dihydroxybut-3-yl, 1, 2-dihydroxy-2-methyl-prop-3-yl, 2,3-dihydroxy-2-methyl-prop-3-yl;
- Ct-Ce-Hydroxyalkyl: Ci-C4-Hydroxyalkyl wie voranstehend genannt, sowie z.B. 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-Hydroxypen-4-tyi, 3-Hydroxypent-4-yl, 4- Hydroxypent-4-yf, 1-Hydroxy-pent-3-yl, 2-Hydroxy-peπt-3-yl, 3-Hydroxy-pent-3-yl, 1- Hydroxy-2-methyl-but-3-yl, 2-Hydroxy-2-methyl-but-3-yf, 3-Hydroxy-2-methyl-but-3- yl, 1 -Hydroxy-2-methyl-but-4-yl, 2-Hydroxy-2-methyl-but-4-yl, 3-Hydroxy-2-methyl- but-4-yt, 4-Hydroxy-2-methyl-but-4-yl, 1-Hydroxy-3-methyl-but-4-yl, 2-Hydroxy-3- methyl-but-4-yl, 3-Hydroxy-3-methyl-but-4-yl, 4-Hydroxy-3-methy!-but-4-yl, 1-- Ct-Ce-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, 3-hydroxy-3-methylbut-4-yl, 4-hydroxy-3-methyl-but-4-yl, 1
Hydroxy-hex-6-yi, 2-Hydroxy-hex-6-yl, 3-Hydroxy-hex-6-yl, 4-Hydroxy-hex-6-yl, 5- Hydroxy-hex-6-yi, 6-Hydroxy-hex-6-yl, 1-Hydroxy-2-methyl-pent-5-yl, 2-Hydroxy-2- methyl-pent-5-yl, 3-Hydroxy-2-methyl-pent-5-yl, 4-Hydroxy-2-methyl-pent-5~yl, 5- Hydroxy-2-methyl-pent-5-yl, 1-Hydroxy-3-methyl-pent-5-yl, 2-Hydroxy-3-methyl- pent-5-yl, 3-Hydroxy-3-methyl-pent-5-yl, 4-Hydroxy-3-methyl-pent-5-yt, 5-Hydroxy-3- methyl-pent-5-yi, 1-Hydroxy-4-methyl-pent-5-yl, 2-Hydroxy-4-methyl-pent-5-yl, 3- Hydroxy-4-methy(-pent-5-yl, 4-Hydroxy-4-methyl-pent-5-yl, 5-Hydroxy-4-methyl- pent-5-yl, 1-Hydroxy-5-methyl-pent-5-yi, 2-Hydroxy-5-methy!-peπt-5-yl, 3-Hydroxy-5- methyl-pent-5-yl, 4-Hydroxy-5-methyl-pent-5-yl, 5-Hydroxy-5-methyl-pent-5-yi, 1- Hydroxy-2,3-dimethyl-but-4-yl, 2-Hydroxy-2,3-dimethy[-but-4-y!, 3-Hydroxy-2,3- dimethyl-but-4-yt, 4-Hydroxy-2,3-dimethy!-but-4-ylI 1 ,2-Dihydroxy-pent-5-yl, 2,3- Dihydroxy-pent-5-yl, 3,4-Dihydroxy-pent-5-yl, 4,5-Dihydroxy-pent-5-yi, 1 ,2- Diydroxypent-4-yl, 2,3-Diydroxypent-4-yl, 3,4-Diydroxypent-4-yl, 4,5-Diydroxypent-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- hdroxymethyl-but-3-yl, 1 ,2-Dihydroxy-2-methyl-but-4-y[, 2,3-Dihydroxy-2-methyl-but- 4-yl, 3,4-Dihydroxy-2-methyl-but-4-yi, 1 ,2-Dihydroxy-3-methyl-but-4-yl, 2,3- Dihydroxy-3-methyl-but-4-yl, 3,4-Dihydroxy-3-methyl-but-4-yl, 3-Hydroxy-3- hydroxymethyl-but-4-yl, 1 ,2-Diydroxy-hex-6-yl, 2,3-Diydroxy-hex-6-yl, 3,4-Diydroxy- hex-6-yl, 4,5-Diydroxy-hex-6-yi, 5,6-Diydroxy-hex-6-yl, 1 ,2-Dihydroxy-2-methyl-pent-Hydroxy-hex-6-yl, 2-hydroxy-hex-6-yl, 3-hydroxy-hex-6-yl, 4-hydroxy-hex-6-yl, 5-hydroxy-hex-6-yl, 6- Hydroxy-hex-6-yl, 1-hydroxy-2-methylpent-5-yl, 2-hydroxy-2-methylpent-5-yl, 3-hydroxy-2-methylpent-5-yl, 4-hydroxy-2-methyl-pent-5-yl, 5-hydroxy-2-methyl-pent-5-yl, 1-hydroxy-3-methyl-pent-5-yl, 2-hydroxy-3-methyl pent-5-yl, 3-hydroxy-3-methylpent-5-yl, 4-hydroxy-3-methylpent-5-yl, 5-hydroxy-3-methylpent-5-yl, 1 Hydroxy-4-methyl-pent-5-yl, 2-hydroxy-4-methyl-pent-5-yl, 3-hydroxy-4-methyl-pent-5-yl, 4-hydroxy-4-methyl-pent 5-yl, 5-hydroxy-4-methyl-pent-5-yl, 1-hydroxy-5-methyl-pent-5-yl, 2-hydroxy-5-methyl-5-yl, 3 Hydroxy-5-methyl-pent-5-yl, 4-hydroxy-5-methylpent-5-yl, 5-hydroxy-5-methylpent-5-yl, 1-hydroxy-2,3-dimethyl but-4-yl, 2-hydroxy-2,3-dimethyl [-but-4-yl, 3-hydroxy-2,3-dimethyl-but-4-yl, 4-hydroxy-2,3-dimethyl! -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, 2-dihydroxy-3-methyl-but-4-yl, 2,3-dihydroxy-3-methyl-but-4-yl, 3,4-dihydroxy-3 -methyl-but-4-yl, 3-hydroxy-3-hydroxymethyl-but-4-yl, 1, 2-dihydroxy-hex-6-yl, 2,3-dihydroxy-hex-6-yl, 3,4 -Dihydroxy-hex-6-yl, 4,5-dihydroxy-hex-6-yl, 5,6-dihydroxy-hex-6-yl, 1, 2-dihydroxy-2-methylpentane
5-yl, 2,3-Dihydroxy-2-methyl-pent-5-yl, 3,4-Dihydroxy-2-methyl-pent-5-yl, 4,5- Dihydroxy-2-methyl-pent-5-yl, 2-Hydroxy-2-hdroxymethyl-pent-5-yl, 1 ,2-Dihydroxy- 3-methyl-pent-5-yl, 2,3-Dihydroxy~3-methyl-pent-5-yl, S^-Dihydroxy-S-methyl-pent- 5-yl, 4,5-Dihydroxy-3-methyl-pent-5-yI, 3-Hydroxy-3-hdroxymethyl-pent-5-yl, 1,2- Dihydroxy-4-methyl-pent-5-yl, 2,3-Dihydroxy-4-methyl-pent-5-yi, 3,4-Dfhydroxy-4- methyl-pent-5-yl, 4,5-Dihydroxy-4-methyl-pent-5-yl, 4-Hydroxy-4-hdroxymethyl-pent- 5~yl, 1,2-Dihydroxy-5-methyl-pent-5-yl, 2,3-Dihydroxy-5-methyl-pent-5-yl, 3,4- Dihydroxy-5-methyl-pent-5-yl, 4,5-Dihydroxy-5-methyf-pent-5-yl, 5-Hydroxy-5- hdroxymethyl-pent-5-yl, 1 ,2-Diydroxy-2,3-dimethy!-bυt-4-yf, 2,3-Diydroxy-2,3- dimethyl-but-4-yl, 3,4-Dihydroxy-2,3-dimethyl-but-4-yl, 2-Hydroxy-2-hydroxymethyl-5-yl, 2,3-dihydroxy-2-methyl-pent-5-yl, 3,4-dihydroxy-2-methyl-pent-5-yl, 4,5-dihydroxy-2-methyl-pent-5 yl, 2-hydroxy-2-hydroxymethyl-pent-5-yl, 1, 2-dihydroxy-3-methyl-pent-5-yl, 2,3-dihydroxy-3-methyl-pent-5-yl, S ^ Dihydroxy-S-methyl-pent-5-yl, 4,5-dihydroxy-3-methyl-pent-5-yl, 3-hydroxy-3-hydroxymethyl-pent-5-yl, 1,2-dihydroxy-4 -methyl-pent-5-yl, 2,3-dihydroxy-4-methylpent-5-yl, 3,4-diphylxy-4-methyl-pent-5-yl, 4,5-dihydroxy-4-methyl -pent-5-yl, 4-hydroxy-4-hydroxymethyl-pent-5-yl, 1,2-dihydroxy-5-methyl-pent-5-yl, 2,3-dihydroxy-5-methyl-pent-5 -yl, 3,4-dihydroxy-5-methyl-pent-5-yl, 4,5-dihydroxy-5-methyl-pent-5-yl, 5-hydroxy-5-hydroxymethyl-pent-5-yl, 1 , 2-dihydroxy-2,3-dimethyl-butyl-4-yf, 2,3-dihydroxy-2,3-dimethyl-but-4-yl, 3,4-dihydroxy-2,3-dimethylbutane 4-yl, 2-hydroxy-2-hydroxymethyl
3-methyl-but-4-yl, 3-Hydroxy-3-hydroxymethyl-2-methyl-but-4-yl;3-methylbut-4-yl, 3-hydroxy-3-hydroxymethyl-2-methylbut-4-yl;
Ci-C4-Ha!ogenalkyl sowie die Halogenalkylteile von Heteroaryl-C-i-Crhalogenalkyl: ein Ci-C4~Alkylrest wie vorstehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder lod substituiert ist, also z.B. Chlormethyl, Dichlormethyl, Trichlormethyi, Fluormethyl, Difluormethyl, Trifiu- ormethyl, Chlorfluormethyl, Dichlorfluormethyl, Chlordifluormethyl, Brommethyl, I- odmethyl, 2-Fluorethyl, 2-Chlorethyl, 2-Bromethyl, 2-todethyl, 2,2-Difluorethyl, 2,2,2- Trifluorethyl, 2-Chlor-2-fIuorethyl, 2-Ch!or-2,2-difluorethyl, 2,2-Dichlor-2-f!uorethyl, 2,2,2-Trichlorethyl, Pentafluorethyl, 2-Fluorpropyl, 3-Fluorpropyl, 2,2-Difluorpropyl, 2,3-Difluorpropyl, 2-Chlorpropyl, 3-Chiorpropyl, 2,3-Dichlorpropyl, 2-Brompropy!, 3- Brompropyl, 3,3,3-Trifluorpropyl, 3,3,3-Trichlorpropyl, 2,2,3,3,3-Pentafluorpropyl, Heptafluorpropyl, 1-(F!uormethyl)-2-fluorethyl, 1-(Chlormethy()-2-chlorethyl, 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-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3 Fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3 Trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl () -2-chloroethyl, 1-
(Brommethyl)-2-bromethyi, 4-Fluorbutyl, 4-Chlorbutyl, 4-Brombutyl, Nonafiuorbutyl, 1 ,1 ,2,2-Tetrafluorethyl und 1-Trifluormethyl-1 ,2,2,2-tetrafluorethyl;(Bromomethyl) -2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, nonafiuorbutyl, 1,1,2,2-tetrafluoroethyl and 1-trifluoromethyl-1,2,2,2-tetrafluoroethyl;
- Ci-C6-Halogenalkyl sowie die Haiogeπalkylteile von CrC6-Halogena!ky!sulfonyl- amiπo, Ci-C6-Halogenalkyl-Ci-C-,-thioa!ky[,: Ci-C4-Halogenalkyl wie voranstehend genannt, sowie z.B. 5-Fluorpentyl, 5-Chlorpentyl, 5-Brompeπtyl, 5-lodpentyl, Un- decafluorpentyl, 6-Fluorhexyl, 6-Chlorhexy[, 6-Bromhexy!, 6-lodhexyl und Tride- cafluorhexyl;C 1 -C 6 -haloalkyl and the haloalkyl parts of C 1 -C 6 -haloalkyl, sulfonylamino, C 1 -C 6 -haloalkyl-C 1 -C 4 -thioalkyl, C 1 -C 4 -haloalkyl as mentioned above, and also for example, 5-fluoropentyl, 5-chloropentyl, 5-bromophenyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexy [, 6-bromohexy !, 6-iodohexyl and tridecafluorohexyl;
- C3-C6-Halogenalkeπyl: ein C3-Ce-Alkenylrest, wie voranstehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder lod substituiert ist, z.B. 2-Chlor- prop-2-en-1-yl, 3-Chlorprop-2-en-1 -yl, 2,3-Dichlorprop-2-en-1-yl, 3,3-Dichlorprop-2- en-1-yl, 2,3,3-Trichlor-2-en-1-yl, 2,3-Dichlorbut-2-en-1-yl, 2-Bromprop-2-en-1-yl, 3- Bromprop-2-en-1-yl, 2,3-Dibromprop-2-en-1-yl, 3,3-Dibromprop-2-en-1-yl, 2,3,3- Tribrom-2-en-1-yl oder 2,3-Dibrombut-2-en-1-yi;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;
- C2-C6-Halogena!kenyl sowie die C2-Ce-Halogenalkenyl-Teile von C2-C6- Halogenalkenyloxy-CrC4-alkyl, C2-C6-Halogenalkenyl-CrC4-thioa!kyl, Phenyl-C2-C4- haJogenaikenyl, Heteroaryl-C2-C4-halogenalkenyl,: ein C2-C6-Alkenylrest, wie voran- stehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder lod substituiert ist, z.B. 2-Chiorvinyl, 2-Chlorallyl, 3-Chlorallyl, 2,3-Dichlorallyl, 3,3- Dichlorallyl, 2,3,3-Trichlorailyl, 2,3-Dich!orbut-2-enylJ 2-Bromvinyl, 2-Bromallyi, 3- Bromallyl, 2,3-Dibromallyl, 3,3-Dibromallyl, 2,3,3-Tribromallyl oder 2,3-Dibrombυt-2- enyl;- C 2 -C 6 -alkenyl and C 2 -Halogena -Ce haloalkenyl moieties of C2-C6- haloalkenyloxy-CRC4-alkyl, C2-C6 haloalkenyl-CrC 4 -thioa alkyl, phenyl-C2-C! 4 -halogenoalkenyl, heteroaryl-C 2 -C 4 -haloalkenyl: a C 2 -C 6 -alkenyl radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 2-chlorovinyl, 2-chloroallyl, 3-chloroallyl, 2,3-dichloroallyl, 3,3-dichloroallyl, 2,3,3-trichloro-lialyl, 2,3-dichloro-2-enyl- J 2-bromovinyl, 2-bromoallyl, 3 Bromallyl, 2,3-dibromallyl, 3,3-dibromallyl, 2,3,3-tribromoallyl or 2,3-dibromobut-2-enyl;
- C2-C6-Cyanoalkenyl: z.B. 2-Cyanovinyl, 2-Cyanoailyl, 3-Cyanoallyl, 2,3-Dicyanoallyl, 3,3-Dicyanoallyl, 2,3,3-Tricyanoallyl, 2,3-Dicyanobut-2-enyl;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;
- C2-C6-Hydroxyalkenyl sowie die Hydroxy-Teile von Phenyl-Ci-C4-hydroxyalkenyl, Heteroaryl-CrC4-hydroxyalkenyl: z.B. 2-Hydroxyvinyl, 2-Hydroxyallyl, 3-- C 2 -C 6 -hydroxyalkenyl -Hydroxyalkenyl and the hydroxyl moieties of phenyl-Ci-C4-hydroxyalkenyl, heteroaryl-CrC 4: for example 2-hydroxyvinyl, 2-hydroxyallyl, 3
Hydroxyallyl, 2,3-Dihydroxyallyl, 3,3-Dihydroxyaliyl, 2,3,3-Trihydroxyallyt, 2,3- Dihydroxybut-2-enyl;Hydroxyallyl, 2,3-dihydroxyallyl, 3,3-dihydroxyaliyl, 2,3,3-trihydroxyallyl, 2,3-dihydroxybut-2-enyl;
- C3-C6-Halogenalkinyl: ein C3-Ce-Alkinylrest, wie voranstehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder lod substituiert ist, z.B. 1 , 1 -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 -
Difluor-prop-2-in-1-yl, 3-lod-prop-2-in-1 -yl, 4-Fluorbut-2-in-1-yl, 4-Chlorbut-2in-1 -yl, 1 ,1-Difluorbut-2-in-1-yl, 4-lodbut-3-in-1-yl, 5-Fluorpent-3-in-1-yl, 5-lodpent-4-in-1-yl, 6-Fluorhex-4-in-1 -yl oder 6-lodhex-5-in-1-yl; - C2-C6-Halogenalkinyl sowie die C2-Ce-Halogenalkinyl-Teile von C2-C6- Halogenalkinyloxy-Ci-C4-alkyl, C∑-Ce-Halogenalkinyl-d-C^thioalkyl, Phenyl-C2-C4- halogeπalkinyl, Heteroaryl-CrC-rhalogenalkinyl: ein C2-C6-Alkinylrest, wie voranste- hend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder lod substituiert ist, z.B. 1 ,1-Difluor-prop-2-in-1-yl, 3-lod-prop-2-in-1-yl, 4-Fluorbut-2-in-1- yl, 4-Chlorbut-2-in-1-yl, 1 ,1 -Difluorbut-2-in-1-yl, 4-lodbut-3-in-1-yl, 5-Fluorpent-3-in- 1-yl, 5-lodpent-4-in-1-yl, 6-Fluorhex-4-in-1-yl oder 6-lodhex-5-in-1-y[;Difluoro-prop-2-yn-1-yl, 3-iodo-prop-2-yn-1-yl, 4-fluorobut-2-yn-1-yl, 4-chlorobut-2in-1-yl, 1, 1-Difluorobut-2-yn-1-yl, 4-iodobut-3-yn-1-yl, 5-fluoropent-3-yn-1-yl, 5-iodopent-4-yn-1-yl, 6 Fluorohex-4-yn-1-yl or 6-iodohex-5-yn-1-yl; - C 2 -C 6 -haloalkynyl and the C 2 -C 6 -haloalkynyl parts of C 2 -C 6 -haloalkynyloxy-C 1 -C 4 -alkyl, C 2 -C 6 -haloalkynyl-C 1 -C 4 -thioalkyl, phenyl-C 2 -C 4 -haloalkynyl, heteroaryl -CrC-haloalkynyl: a C 2 -C 6 -alkynyl radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 1, 1-difluoro-prop-2-yn-1 -yl, 3-iodo-prop-2-yn-1-yl, 4-fluorobut-2-yn-1-yl, 4-chlorobut-2-yn-1-yl, 1,1-difluorobut-2-yne 1-yl, 4-iodobut-3-yn-1-yl, 5-fluoropent-3-yn-1-yl, 5-iodopent-4-yn-1-yl, 6-fluorohex-4-yn-1 -yl or 6-iodohex-5-yn-1-y [;
- C2-Cβ-Cyanoalkinyl: z.B. 1 ,1-Dicyano-prop-2-in-1-yl, 3-Cyano -prop-2-in-1-y[, 4-C2-Cβ-cyanoalkynyl: e.g. 1,1-dicyano-prop-2-yn-1-yl, 3-cyano-prop-2-yn-1-y [4-]
Cyano-but-2-in-1-y!, 1 ,1-Dicyanobut-2-in-1-yl, 4-Cyanobut-3-in-1-y[, 5-Cyanopent-3- in-1-yl, 5-Cyanoρent-4-in-1-yl, 6-Cyanohex-4-in-1-yl oder 6-Cyanohex-5-in-1-yl;Cyano-but-2-yn-1-yl, 1,1-dicyanobut-2-yn-1-yl, 4-cyanobut-3-yn-1-yl, 5-cyanopent-3-yn-1 yl, 5-cyano-p-4-yn-1-yl, 6-cyanohex-4-yn-1-yl or 6-cyanohex-5-yn-1-yl;
- C2-Ce-Hydroxyalkinyl sowie die Hydroxy-Teile von Pheny[-C2-C4-hydroxyalkinyl: z.B. 1 ,1-Dihydrαxy-prop-2-iπ-1-yl, 3-Hydroxy -prop-2-in-1-yl, 4-Hydroxy-but-2-in-1-yl, 1 , 1-C 2 -C 4 -hydroxyalkynyl and also the hydroxy parts of pheny [C 2 -C 4 -hydroxyalkynyl: for example 1,1-dihydroxyprop-2-i-1-yl, 3-hydroxyprop-2-yne 1-yl, 4-hydroxybut-2-yn-1-yl, 1, 1
Dihydroxybut-2-in-1-yl, 4-Hydroxybut-3-in-1-yl, 5-Hydroxypent-3-in-1-yl, 5- Hydroxypent-4-in-1-yl, 6-Hydroxyhex-4-in-1-yl oder 6-Hydroxyhex-5-in-1-yl;Dihydroxybut-2-yn-1-yl, 4-hydroxybut-3-yn-1-yl, 5-hydroxypent-3-yn-1-yl, 5-hydroxypent-4-yn-1-yl, 6-hydroxyhexene 4-yn-1-yl or 6-hydroxyhex-5-yn-1-yl;
- Ci-Ce-Alkylsulfinyl (Ci-C6-Alkyl-S(=O)-) sowie die Ci-C6-Alkylsulfinyl-Teile von Ci-Ce-Alkylsuifinyl-CrOralkyl: z.B. Methylsuifinyl, Ethylsulfinyl, Propylsulfinyl, 1-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,
Methylethylsulfinyl, Butylsulfinyl, 1-Methylpropylsulfinyl, 2-Methylpropyl-sulfinyl, 1,1-Dimethylethylsulfiπyl, Pentylsulfinyl, 1-Methylbutylsulfinyl, 2-Methyl- butyfsulfinyl, 3-Methylbutylsuifinyl, 2,2-Dimethylpropylsulfinyl, 1-Ethylpropyf-sulfinyl, 1,1-Dimethylpropylsulfinyl, 1 ,2-Dimethylpropylsulfinyl, Hexylsulfinyl, 1- Methylpentylsulfinyl, 2-Methylpeπtylsulfinyl, 3-Methylpentylsulfinyl, 4-Methy!penty[- sulfinyl, 1 ,1-Dimethylbutylsulfiπyl, 1 ,2-Dimethylbutylsulfinyl, 1,3-Dimethylbutyl- sulfinyl, 2,2-Dimethylbutylsuifinyl, 2,3-Dimethylbutylsulfinyl, 3,3-Dimethy!bυtyl- sulfinyl, 1— Ethylbutylsulfinyl, 2-Ethylbutylsulfinyl, 1 ,1 ,2-Trimethylpropylsulfinyl, 1 ,2,2-Trimethylpropylsulfinyl, 1— Ethyl— 1— methylpropylsutfinyl und 1— Ethyl— 2— methylpropylsulfinyl;Methylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1,1-dimethylethylsulfinyl, pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, 1, 1-dimethylpropylsulfinyl, 1, 2-dimethylpropylsulfinyl, hexylsulfinyl, 1-methylpentylsulfinyl, 2-methylphenylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1,1-dimethylbutylsulfinyl, 1,2-dimethylbutylsulfinyl, 1,3-dimethylbutyl - sulfinyl, 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3-dimethylsulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1, 1, 2-trimethylpropylsulfinyl, 1, 2,2-trimethylpropylsulfinyl, 1 Ethyl 1-methylpropylsulfinyl and 1-ethyl-2-methylpropylsulfinyl;
- Ci-C6-Haiogenalkylsulfinyl sowie die Ci-Ce-Halogenalkylsulfinyl-Teile von Ci-Cs- Halogenalkylsulfinyl-CrC4-alkyl: Ci-C6-Alkylsuifinylrest wie voranstehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder lod substituiert ist, also z.B. Fluormethylsulfinyl, Difluormethylsulfinyl, Trifluormethylsulfinyl, Chlordiflu- ormethylsulfiπyl, Bromdifluormethylsulfinyl, 2-Fiuorethylsulfinyl, 2-Chlorethylsulfinyl, 2-Bromethyisulfιnyl, 2-lodethylsulfinyl, 2,2-Dif!uorethylsu!finyl, 2,2,2-Trifluor-ethyl- sulfinyl, 2,2,2-Trichlorethylsulfιnyl, 2-Chlor-2-f!uorethylsulfinyl, 2-Chlor-2,2-di- fluorethylsulfinyl, 2,2-Dichlor-2-fluorethylsulfinyl, Pentafluorethylsulfinyl, 2-Fluor- propylsulfinyi, 3-Fluoφropylsulfinyl, 2-Chlorpropylsulfinyl, 3-Chlorpropyl-sulfinyl, 2-- Ci-C6-Haiogenalkylsulfinyl and the Ci-Ce-Halogenalkylsulfinyl parts of Ci-Cs haloalkylsulfinyl-CrC4-alkyl: 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- ormethylsulfiπyl, bromodifluoromethylsulfinyl, 2-Fiuorethylsulfinyl, 2-chloroethylsulfinyl, 2-Bromethyisulfιnyl, 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-
Brompropylsulfiπyl, 3-Brompropylsulfinyl, 2,2-DifEuorpropylsulfinyl, 2,3-Difiuor- propylsulfinyl, 2,3-Dichlorpropylsulfinyl, 3,3,3-Trifluorpropylsutfinyl, 3,3,3-Trichlor- propylsuifinyl, 2,2,3,3,3-Pentafluorpropylsulfinyl, Heptafluorpropylsulfinyl, 1 -(Fluor- methyl)-2-fluorethyisulfinyl, 1-(Ch!ormethyl)-2-chlorethylsulftnyl, i-(Brommethyl)- 2-bromethy!sulfinyl, 4-Fluorbutylsulfiπyl, 4~Chlorbutylsulfinyl, 4-Brombutylsulfinyl, Nonafluorbutylsulfinyl, 5-Fluorpentylsuifinyi, 5-Chlorpentyl-sulfinyI, 5- ßrompentylsuifinyj, 5-lodpentylsulfιnyl, Undecafiuorpentylsulfinyl, 6-Fluorhexyl- sulfinyl, 6-Chlorhexylsulfιnyl, 6-Bromhexylsulfinyl, 6-lodhexylsulfiπyl und Dode- cafluorhexylsulfinyl;Bromopropylsulfinyl, 3-bromopropylsulfinyl, 2,2-difluoropropylsulfinyl, 2,3-difluoropropylsulfinyl, 2,3-dichloropropylsulfinyl, 3,3,3-trifluoropropylsulfinyl, 3,3,3-trichloropropylsulfinyl, 2,2,3, 3,3-pentafluoropropylsulfinyl, heptafluoropropylsulfinyl, 1 - (fluoro- methyl) -2-fluoroethylsulfinyl, 1- (chloromethyl) -2-chloroethylsulfinyl, i- (bromomethyl) -2-bromoethylsulfinyl, 4-fluorobutylsulfinyl, 4-chlorobutylsulfinyl, 4-bromobutylsulfinyl, nonafluorobutylsulfinyl, 5-fluoropentylsulfinyl, 5 -Chlorpentyl-sulfinyI, 5- ßrompentylsuifinyj, 5-iodopentylsulfinyl, undecafluoropentylsulfinyl, 6-fluorohexylsulfinyl, 6-chlorohexylsulfinyl, 6-bromohexylsulfinyl, 6-iodohexylsulfinyl and dodecafluorohexylsulfinyl;
- Ci-Ce-Alkylsulfonyi (C-ι-C6-Alky(-S(O)2-) sowie die Ci-Ce-Alkylsulfonyl-Teile von Ci-Cr-Alkylsulfonyl-Ci-C4-alkyl, Ci-Cs-Alkylsulfonylamino, Ci-C6- Alkylsuifonylamino-CrC^alkyl, Ci-C6-Alkylsulfonyl-(CrC6-alkylarnino}-Ci-C4-alkyl: z.B. Methylsulfonyl, Ethylsuffonyl, Propylsulfonyl, 1-Methylethyisulfonyl, Butyisulfo- nyl, 1-Methylpropylsulfoπyl, 2-Methyl-propylsulfonyl, 1 ,1-Dimethylethy!su[fonyi, Peπtylsulfonyl, 1-Methylbυtyfsulfonyl, 2-Methylbutyisulfonyt, 3-Methylbutylsulfonyl, 1 ,1-Dimethylpropytsulfonyl, 1 ,2-Di-methylpropylsulfonyl, 2,2- Dimethylpropylsulfonyl, 1-Ethylpropy[sulfonyl, Hexylsulfoπyf, 1-- Ci-Ce-alkylsulfonyi (C-ι-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, 1, 1-dimethylethyl, [fonyi, pentylsulfonyl, 1-methylbifluorylsulfonyl, 2-methylbutylisulfonyl, 3-methylbutylsulfonyl, 1, 1-dimethylpropylsulfonyl, 1, 2-dimethylpropylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropyl [sulfonyl, hexylsulfonyl, 1-
Methylpentylsulfonyl, 2-Methylpentylsu[fonyl, 3-Methy[pentylsu!fonyl, 4- Methylpentylsulfonyl, 1,1-Dirnethylbutylsulfonyl, 1,2-Dimethylbutylsulfonyl, 1,3- Dimethylbutylsulfonyl, 2,2-Dimethyibutylsulfonyl, 2,3-Dimethylbutylsulfonyl, 3,3- Dimethylbutylsulfonyl, 1-Ethylbutylsulfonyl, 2-Ethylbutylsuifonyl, 1 ,1,2-Thmethyl- propylsulfonyl, 1 ,2,2-Trimethylpropylsulfonyl, 1-EthyM-methylρropylsulfonyl undMethylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methyl [pentylsulfonyl, 4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,2-dimethylbenzylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1, 1,2-thymethylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1-methylmethylpropylsulfonyl, and
1 -Ethyl-2-methy[propylsulfonyl;1-ethyl-2-methyl [propylsulfonyl;
- Ci-Cβ-Halogenalkylsulfoπyl sowie die Ci-Ce-Ha!ogenalkylsu!fonyl-Teile von Ci-Ce- Hafogenafkylsulfonyl-Ci-C^alkyl, Ci-Ce-Halogenalkyisulfonylamino: einen Ci-Ce- Alkylsulfonylrest wie voranstehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder lod substituiert ist, also z.B. Fiuormethyisulfonyl, Difluor- methylsulfonyl, Trifluormethylsulfonyl, Chlordifluormethylsulfonyl, Bromdifluor- methyisulfonyl, 2-Fiuorethylsulfonyl, 2-Chlorethylsulfonyl, 2-Bromethylsulfonyl, 2- lodethylsulfonyl, 2,2-DifIuorethyl-sulfonyl, 2,2,2-Trifluorethylsulfonyl, 2-Ch!or-2- fluorethylsulfonyi, 2-Chlor-2,2-difluorethylsulfonyl, 2,2-Dichior-2-fluorethylsulfonyl,- Ci-Cβ-Halogenalkylsulfoπyl and the Ci-Ce-Ha! Ogenalkylsu! Fonyl parts of Ci-Ce-Hafogenafkylsulfonyl-Ci-C ^ alkyl, Ci-Ce-Halogenalkyisulfonylamino: a Ci-Ce- Alkylsulfonylrest as mentioned above, the partial or completely substituted by fluorine, chlorine, bromine and / or iodine, eg Fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2-Ch! or-2-fluoroethylsulfonyi, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl,
2,2,2-Trichiorethylsulfonyl, Pentafluorethylsulfonyl, 2-Fluorpropylsulfonyl, 3- Fluorpropylsulfonyi, 2-Chlor-propylsulfonyl, 3-Chlorpropylsulfonyl, 2- Brompropylsulfonyl, 3-Brompropylsulfonyl, 2,2-Difluorpropylsulfonyl, 2,3- Difluorpropylsulfonyl, 2,3-Dichlorpropylsulfonyl, 3,3,3-Trifluorpropylsulfonyl, 3,3,3- Trichlorpropylsulfonyl, 2,2,3,3,3-Pentafluor-propylsulfonyl, Heptafluorpropylsulfony!,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,
1-(Fluormethyl)-2-fluorethylsulfony!, 1-(Chlormethyl)-2-chlorethylsulfonyi, 1 - (Brommethy!)-2-bromethylsulfonyl, 4-Fluorbutylsulfonyl, 4-Chlorbutylsulfonyl, A- Brombutylsulfonyl, Nonafluorbutylsulfonyl, 5-Fluorpentylsulfonyl, 5- Chlorpentylsulfonyl, 5-Brompentylsulfonyl, 5-lod-pentylsulfonyl, 6- Fluorhexylsulfony!, 6-Bromhexylsulfonyl, 6-!odhexylsu!fonyl und Dodecafluorhexyl- sulfonyl; Ci-C4-Alkoxy sowie die Alkoxyteile von Hydroxycarbonyl-CrC4-alkoxy, C1-C4- Alkoxycarbonyl-CrC4-alkoxy, Ci-C4-Alkoxy-Ci-C4-alkoxy-Ci-C4-alkyl und CrC4- alky]-Ci-C4-a!koxycarbonyiamino: z.B. Methoxy, Ethoxy, Propoxy, 1-Methyl-ethoxy, Butoxy, 1-Methylpropoxy, 2-Methyipropoxy und 1 ,1-Dimethylethoxy;1- (fluoromethyl) -2-fluoroethylsulfonyl, 1- (chloromethyl) -2-chloroethylsulfonyi, 1 - (bromomethyl) -2-bromoethylsulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, A-bromobutylsulfonyl, nonafluorobutylsulfonyl, 5-fluoropentylsulfonyl, 5-chloropentylsulfonyl, 5-bromopentylsulfonyl, 5-iodo-pentylsulfonyl, 6-fluorohexylsulfonyloxy, 6-bromohexylsulfonyl, 6'-hexylsulfonyl and dodecafluorohexylsulfonyl; Ci-C 4 -alkoxy and the alkoxy moieties of hydroxycarbonyl -C 4 -alkoxy, C 1 -C 4 - alkoxycarbonyl-CrC 4 alkoxy, Ci-C4-alkoxy-Ci-C4-alkoxy-Ci-C4 alkyl, and -C 4 -alky] -Ci-C 4 -alkoxycarbonyiamino: for example, methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1, 1-dimethylethoxy;
- Ci-Cε-Aikoxy sowie die Alkoxyteile von Hydroxycarbonyl-Ci-C6-alkoxy, C1-Cg- Alkoxycarbonyl-CrCe-aikoxy, N-(Ci-Cβ-Alkoxy)-N-(Ci-C6-aikyl)~aminocarbonyl, N-(C3-C6-Alkenyl)-N-(Ci-Ce-alkoxy)-aminocarbonyl, N-(C3-C6-Alkinyl)-N-(Ci- C6-a!koxy)-aininocarbonyl und Ci-Ce-Alkoxyimino-Cr-Ce-alkyl: Cr-C4-AIkOXy wie voranstehend genannt, sowie z.B. Pentoxy, 1-Methyl-butoxy,- Ci-Cε-Aikoxy and the alkoxy parts of hydroxycarbonyl-Ci-C 6 alkoxy, C 1 -Cg alkoxycarbonyl-CrCe-aikoxy, N- (Ci-Cβ-alkoxy) -N- (Ci-C6-aikyl) ~ aminocarbonyl, N- (C 3 -C 6 -alkenyl) -N- (C 1 -C 6 -alkoxy) -aminocarbonyl, N- (C 3 -C 6 -alkynyl) -N- (C 1 -C 6 -alkoxy) - aininocarbonyl and C 1 -C 6 -alkoxyimino-C 1 -C 6 -alkyl: C 1 -C 4 -alkoxy as mentioned above, and also, for example, pentoxy, 1-methylbutoxy,
2-Methylbutoxy, 3-Methoxylbutoxy, 1 ,1-Dimethyl-propoxy, 1 ,2-Dimethyl-propoxy, 2,2-Dimethylρropoxy, 1 -Ethylpropoxy, Hexoxy, 1 -Methyipentoxy, 2-Methylρentoxy, 3-Methylpentoxy, 4-Methylpentoxy, 1 ,1-Di-methylbutoxy,1 ,2-Dimethyl-butoxy, 1 ,3-Dimethylbutoxy, 2,2-Dimethylbutoxy, 2,3-Dimethylbutoxy, 3,3-Dimethyi-butoxy, 1 -Ethy I butoxy, 2-Ethylbutoxy, 1 ,1,2-Tri-methylpropoxy, 1,2,2-Trirnethyl-propoxy,2-methylbutoxy, 3-methoxybutoxy, 1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4- Methylpentoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 1,2-tri-methylpropoxy, 1,2,2-tri-methyl-propoxy,
1-Ethyl-1-methy(propoxy und 1-Ethyl-2-methylpropoxy;1-ethyl-1-methyl (propoxy and 1-ethyl-2-methylpropoxy;
- Ci-C4-Halogena!koxy: ein Ci-C4-Alkoxyrest wie voranstehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder lod substituiert ist, also z.B. Fluormethoxy, Diffuorm ethoxy, Trifluormethoxy, Chlordifluormethoxy, Bromdifluor- methoxy, 2-FIuorethoxy, 2-Chlorethoxy, 2~Brommethoxy, 2-lodethoxy, 2,2-Difluor- ethoxy, 2,2,2-Trifluorethoxy, 2-Chlor-2-fiuorethoxy, 2-Chlor-2,2-difluorethoxy, 2,2- Dichlor-2-fluorethoxy, 2,2,2-Trichlorethoxy, Pentafluorethoxy, 2-Fluorpropoxy, 3- Fluorpropoxy, 2-Chlorpropoxy, 3-Chlorpropoxy, 2-Brompropoxy, 3-Brompropoxy, 2,2-Difluorpropoxy, 2,3-Difluorpropoxy, 2,3-Dichlorpropoxy, 3,3,3-Trifluorpropoxy,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, 3-bromopropoxy, 2,2 Difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy, 3,3,3-trifluoropropoxy,
3,3,3-Trichlorpropoxy, 2,2,3,3,3-Pentafluorpropoxy, Heptafluorpropoxy, 1- (Fluormethyl)-2-fluorethoxy, 1-(Chlormethyl)-2-chlorethoxy, 1-(Brommethyl)-2- bromethoxy, 4-Fluorbutoxy, 4-Chlorbutoxy, 4-Brombutoxy und Nonafiuorbutoxy;3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1- (fluoromethyl) -2-fluoroethoxy, 1- (chloromethyl) -2-chloroethoxy, 1- (bromomethyl) -2- bromothoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy and nonafiuorbutoxy;
- Ci-Ce-Halogenalkoxy sowie die d-Ce-Halogenalkoxy-Teile von CrCe-Ci-Ce-haloalkoxy and the d-Ce-haloalkoxy parts of CrCe
Halogenalkoxy-CrC4-alkyl, CrC6-Halogenalkoxycarbonyl-CrC4-alkyl: C1-C4- Halogeπalkoxy wie voranstehend genannt, sowie z.B. 5-Fiuorpentoxy, 5- Chlorpentoxy, 5-Brom pentoxy, 5-lodpentoxy, Undecafluorpentoxy, 6-Fluorhexoxy, 6-Chlorhexoxy, 6-Bromhexoxy, 6-lodhexoxy und Dodecafluorhexoxy;Haloalkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -haloalkoxycarbonyl-C 1 -C 4 -alkyl: C 1 -C 4 -haloalkoxy as mentioned above, and also, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6 Chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy and dodecafluorohexoxy;
CrC6-Alkoxy-Ci-C4-alkyl sowie die Ci-C6-Alkoxy-CrC4-alky!-Teile von CrCe- Alkoxy-CrC4-alkoxy-Ci-C4-alkyl I: durch d-Ce-Alkoxy wie vorstehend genannt substituiertes CrC4-Alkyl, also z.B. für Methoxymethyl, Ethoxy methyl, Propoxy- methyl, (I-Methylethoxy)methyi, Butoxymethyl, (I-Methylpropoxy)methyl, (2- Methyl-propoxy)methyl, (1 ,1-Dimethylethoxy)methyl, 2-(Methoxy)ethyl, 2-C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl and the C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl portions of C 1 -C 6 -alkoxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl I: substituted by C 1 -C 6 -alkoxy as mentioned above C 1 -C 4 -alkyl, ie, for example, methoxymethyl, ethoxy-methyl, propoxymethyl, (1-methylethoxy) methyl, butoxymethyl, (1-methylpropoxy) methyl, (2-methylpropoxy) methyl, (1, 1-dimethylethoxy) methyl , 2- (methoxy) ethyl, 2-
(Ethoxy)ethy!, 2-(Propoxy)ethy!, 2-(1-Methyiethoxy)ethyl, 2-(Butoxy)ethyl, 2-(1- Methy!propoxy)-ethyl, 2-(2-Methylpropoxy)ethyl, 2-(1 ,1-Dimethylethoxy)ethyl, 2- (Methoxy)-propyl, 2-{Ethoxy)propyl, 2-(Propoxy)propyl, 2-(1-Methylethoxy)propyl, 2-(Butoxy)propyl, 2-(1-Methylpropoxy)propyl, 2-(2-Methylpropoxy)propy!, 2-(1 ,1- Dimethylethoxy)propyl, 3-{Methoxy)ρropyi, 3-(Ethoxy)-propy!, 3-(Propoxy)propyl, 3-(1-Methyiethoxy)-propyl( 3-{Butoxy)propyl, 3-(1-Methylpropoxy)propyl, 3-(2- Methy!propoxy)propyl, 3-(1 ,1-Dimethylethoxy)propyl, 2-(Methoxy)-butyl, 2- (Ethoxy)butyl, 2-(Propoxy)-butyl, 2-(1-Methylethoxy)butyl, 2-(Butoxy)butyl, 2-(1-(Ethoxy) ethyl, 2- (propoxy) ethyl, 2- (1-methylethoxy) ethyl, 2- (butoxy) ethyl, 2- (1-methylpropoxy) ethyl, 2- (2-methylpropoxy) ethyl , 2- (1,1-dimethylethoxy) ethyl, 2- (methoxy) propyl, 2- {ethoxy) propyl, 2- (propoxy) propyl, 2- (1-methylethoxy) propyl, 2- (butoxy) propyl, 2- (1-methylpropoxy) propyl, 2- (2-methylpropoxy) propyl, 2- (1,1-dimethylethoxy) propyl, 3- {methoxy) ρropyi, 3- (ethoxy) - propyl, 3- (propoxy) propyl, 3- (1-methylethoxy) propyl ( 3- {butoxy) propyl, 3- (1-methylpropoxy) propyl, 3- (2-methylpropoxy) propyl, 3- ( 1, 1-dimethylethoxy) propyl, 2- (methoxy) -butyl, 2- (ethoxy) butyl, 2- (propoxy) -butyl, 2- (1-methylethoxy) butyl, 2- (butoxy) butyl, 2- ( 1-
Methylpropoxy)butyl, 2-(2-Methylpropoxy)butyl, 2~(1 ,1-Dimethylethoxy)butyi, 3- (Methoxy)butyi, 3-{Ethoxy)-butyi, 3-(Propoxy)buty!, 3-(1-Methylethoxy)butyl, 3- (Butoxy)-butyl, 3-(1-Methyl-propoxy)butyl, 3-(2-Methy!propoxy)butyl, 3-{1 ,1- Dimethy!ethoxy)butyl, 4-(Methoxy)-buty!, 4-(Ethoxy)butyl, 4-(Propoxy)butyl, 4-(1- Methylethoxy)butyl, 4-(Butoxy)buty[, 4-(1-Methy!propoxy)butyl, 4-(2-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-
Methylpropoxy)butyl und 4-(1 ,1-Dimethylethoxy)-butyl;Methylpropoxy) butyl and 4- (1,1-dimethylethoxy) butyl;
- Ci-C4-Alkoxycarbonyl sowie die Alkoxycarbonylteile von CrC4-Alkoxycarbonyi-Ci- C4-a!koxy, CrC4-A!koxy-CrC4-alkoxycarbonyl und Dh-(Ci-C4-alkyl)-amino-Ci-C4- alkoxycarbonyl: z.B. Methoxycarbonyi, Ethoxycarboπyl, Propoxycarboπyl, 1-- Ci-C -a 4 -alkoxycarbonyl and -C Alkoxycarbonylteile of 4 -Alkoxycarbonyi-Ci- C 4 -alkoxy, C r C 4 -A koxy alkoxycarbonyl-CrC 4 and DH (Ci-C 4 alkyl)! - amino-C 1 -C 4 -alkoxycarbonyl: for example, methoxycarbonyi, ethoxycarbonyl, propoxycarbonyl, 1
Methylethoxycarbonyl, Butoxycarbonyl, 1-Methylpropoxycarbonyl, 2-Methylprop- oxycarbonyl oder 1,1-Dimethy[ethoxycarbonyl;Methylethoxycarbonyl, butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl or 1,1-dimethyl [ethoxycarbonyl;
- Ci-Ce-Alkoxycarbonyl sowie die Alkoxycarbonylteile von Ci-Ce-Alkoxycarbonyl-Ci- Ce-afkoxy und Ci-Ce-Alkoxycarbonylamino-Ci-C4-alkyl: Ci-C4-Alkoxycarbony!, wie voranstehend genannt, sowie z.B. Pentoxycarbonyl, 1-Methylbutoxycarbonyl, 2- Methyibutoxycarbonyl, 3-Methyl-butoxycarbony!, 2,2-Dimethylpropoxycarbonyl, 1- Ethylpropoxycarbonyl, Hexoxy-carbonyl, 1,1-Dimethyipropoxycarbonyl, 1,2- Dimethylpropoxycarbonyl, 1-Methyl-pentoxycarbonyl, 2-Methylpentoxycarbonyl, 3- Methylpentoxycarbonyl, 4-Methy!-pentoxycarbonyl, 1 ,1-Dimethylbutoxycarbonyl,Ci-Ce-alkoxycarbonyl and the Alkoxycarbonylteile of Ci-Ce-Alkoxycarbonyl-Ce Ce-afkoxy and Ci-Ce-Alkoxycarbonylamino Ci-C4-alkyl: Ci-C4-Alkoxycarbonony! As mentioned before, as well as e.g. 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,
1 ,2-Dimethyibutoxycarbonyl, 1 ,3-Dimethylbutoxycarbonyl, 2,2- Dimethylbutoxycarboπyl, 2,3-Dimethylbutoxycarbonyl, 3,3-Dimethylbutoxycarbonyi, 1-Ethylbutoxycarbonyl, 2-Ethylbutoxycarbonyl, 1,1 ,2-Trimethylpropoxycarbonyl, 1 ,2,2-Trimethylpropoxycarbonyl, 1-Ethy]-1-methy!-propoxycarbony! oder 1-Ethyl-2- methyl-propoxycarbonyi;1, 2-dimethylbenzoxycarbonyl, 1, 3-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl, 2,3-dimethylbutoxycarbonyl, 3,3-dimethylbutoxycarbonyi, 1-ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl, 1,1,2-trimethylpropoxycarbonyl, 1, 2, 2-trimethylpropoxycarbonyl, 1-ethyl] -1-methyl-propoxycarbony! or 1-ethyl-2-methyl-propoxycarbonyl;
- Ci-C4-Alkylthio sowie die CrC4-Alkyithio-Teile von CrC6-Ha!ogena!kyl-C1-C4- thioalkyl, C2-C6-Halogena!kenyl~Ci-C4-thioalkyi, Cz-Cβ-Halogenalkinyl-Ci-Ci- thioalkyl: z.B. Methylthio, Ethylthio, Propylthio, 1-Methy!ethylthio, Butylthio, 1-Methylpropylthio, 2-Methylpropylthio und 1 ,1-Dimethylethylthio;- Ci-C4-alkylthio and C r C 4 -Alkyithio parts of CrC 6 -Ha ogena kyl-C 1 -C 4 -! Thioalkyl, C2-C6-Halogena -alkenyl ~ Ci-C 4 -thioalkyi, Cz-Cβ-haloalkynyl-C 1 -C 10 -thioalkyl: for example methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1, 1-dimethylethylthio;
- Ci-Ce-Alkylthio sowie die Ci-C6-Alkylthio-Teile von Ci~ C4- Alkylthio wie voranstehend genannt, sowie z.B. Pentylthio, 1-Methylbutyithio, 2- Methylbutyithio, 3-Methylbutylthio, 2,2-DimethySpropylthio, 1-Ethylpropyithto, He- xylthio, 1 ,1-Dimethylpropylthio, 1 ,2-Dimethylpropylthio, 1-Methylpentylthio, 2-- Ci-Ce-alkylthio and the Ci-C 6 -alkylthio parts of C 1 -C 4 -alkylthio as mentioned above, and also, for example, pentylthio, 1-methylbutyithio, 2-methylbutyithio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1, 1-dimethylpropylthio, 1, 2 Dimethylpropylthio, 1-methylpentylthio, 2-
Methylpentylthio, 3-Methylpentylthio, 4-Methylpentylthio, 1 , 1 — Dimethylbutylthio, 1 ,2-Dimethylbutylthio, 1 ,3-Dimethylbutylthio, 2,2-Dlmethyibutyl-thio, 2,3- Dimethylbutyϊthio, 3,3-Dimethylbuty!thio, 1-Ethylbutylthio, 2-Ethylbutyl-thio, 1 ,1,2- Trimethyipropylthio, 1,2,2-Trimethylpropylthio, 1-Ethyl-1-methylpropyl-thio und 1- Ethyl~2-methylpropylthio;Methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1, 1-dimethylbutylthio, 1, 2-dimethylbutylthio, 1, 3-dimethylbutylthio, 2,2-dimethylmethylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1, 1,2- Trimethylolpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio and 1-ethyl-2-methylpropylthio;
- Ci-Ce-Alkylamiπo sowie die Ci-Ce-Aikyiaminoreste von N(Ci-Ce-Alkylamino)tmino- Ci-Cs-alkyl, Ci-C6-Alkylsu!fonyl-(Ci-C6-alkylamino)- C-i-C-ralkyl, Ci-C6-Alky!carbony]-(CrC6-alkylarnino}-Ci-C,-alkyl und [(CrC6- Alkyl)amino]cyanoinnino: z.B. Methylamino, Ethylamino, Propylamino, 1- Methyiethylamino, Butylamino, 1-Methyfpropylamino, 2-Methylpropylamino, 1,1- DimethySethylamino, Pentylamino, 1-Methylbutylamino, 2-Methylbutylamino, 3-Ci-Ce-Alkylamiπo and the Ci-Ce-Aikyiaminoreste of N (Ci-Ce-alkylamino) tmino Ci-Cs-alkyl, ! CiC 6 -Alkylsu fonyl- (CiC 6 alkylamino) - CiC-ralkyl, CiC 6 -Alky carbonyl] - (C r C6 alkylarnino} -C-C, alkyl and [(-C 6 -alkyl) amino] cyanoinnino: eg methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1,1-dimethylethylamino, pentylamino, 1-methylbutylamino, 2-methylbutylamino, 3
Methyibutylamino, 2,2-Dimethylpropy[amino, 1-Ethylpropylamino, Hexylamino, 1,1 - Dimethylpropylamino, 1 ,2-Dimethylpropylamino, 1-Methylpentyiamino, 2- Methylpentylamino, 3-Methyl-pentylamino, 4-Methy[pentylamino, 1 ,1- Dimethylbutylamino, 1 ,2-Dimethylbutyl-amino, 1 ,3-Dimethylbutylamino, 2,2- Dimethylbutylamino, 2,3-Dimethylbutylamino, 3,3-Dimethylbutylamino, 1-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 oder 1 -Ethyl-2-methylpropylamino;Ethylbutylamino, 2-ethylbutylamino, 1, 1, 2-trimethyl-propylamino, 1, 2,2-trimethyl-propylamino, 1-ethyl-1-methylpropylamino or 1-ethyl-2-methylpropylamino;
- Di(Ci-C4-a!kyl)amino: z.B. N.N-Dimethylamino, N,N-Diethylamino, N1N- Dipropylamino, N, N-Di-(I -methylethy[)-amino, N.N-Dibutylamino, N1N-Di-(I- methylpropyl)amino, N.N-Di^-methylpropyO-amino, N, N-Di-(1 , 1 -dimethylethyl)- amino, N-Ethy!-N-methylamino, N-Methyl-N-propyiamino, N-Methyl-N-(1- methylethyljamino, N-Butyl-N-methyfamino, N-Methyl-N-(1 -methylpropyl)amino, N- Methyl-N-(2-methylpropyl)amino, N-(1 , 1 -Dimethyl-ethyl)-N-methylamino, N-Ethyl-N- propylamino, N-Ethyl-N-(1-methylethyl)amino, N-Butyl-N-ethylamino, N-Ethyl-N-(1- methylpropyl)amino, N-Ethyl-N-(2-methylpropyl)-amino, N-Ethyl-N-(1 ,1-dimethyi- ethyl)amino, N-(1-Methylethyl)-N-propylamino, N-Butyl-N-propylamino, N-(1- Methylpropyl)-N-propylamino, N-(2-Methylpropyl)-N-propylamino, N-(1 , 1 -Dimethyl- ethyl)-N-propylamino, N-Butyl-N-(1-methylethyl-)amino, N-(1-Methylethyl)-N-(1 - methyipropyl)amino, N-(1 -Methy!ethyl)-N-(2-methyl-propyl)amino, N-(1 ,1-Dimethyl- ethy[)-N-(1-methytethyl)amino, N-Butyl-N-(1-methylpropy!)amino, N-Buty!-N-(2- methylpropy!)amino, N-Butyl-N-(1 ,1-dimethyl-ethyl)amino, N-(1-Methylpropy!)-N-(2- methy]propyl)amino, N-(1 ,1-Dimethylethyf)-N-(1-methylpropyl)amino und N-(1 ,1-Di- methyiethyl)-N-(2-methylpropyl)amino;- di (Ci-C4-a alkyl) amino: for example N, N-dimethylamino, N, N-diethylamino, N 1 N- dipropylamino, N, N-di- (I -methylethy [) - amino, N, N-dibutylamino, N 1 N-di- ( 1 -methylpropyl) amino, N, N -di-methylpropyl-amino, N, N-di- (1, 1-dimethylethyl) -amino, N-ethyl-N-methylamino, N-methyl- N-propylamino, N -methyl-N- (1-methylethylamino, N-butyl-N-methylfamino, N -methyl-N- (1-methylpropyl) amino, N -methyl-N- (2-methylpropyl) amino, N (1, 1-dimethylethyl) -N-methylamino, N-ethyl-N-propylamino, N-ethyl-N- (1-methylethyl) amino, N-butyl-N-ethylamino, N-ethyl-N- (1-methylpropyl) amino, N-ethyl-N- (2-methylpropyl) amino, N-ethyl-N- (1, 1-dimethylethyl) amino, N- (1-methylethyl) -N-propylamino, N-butyl-N-propylamino, N- (1-methylpropyl) -N-propylamino, N- (2-methylpropyl) -N-propylamino, N- (1, 1-dimethyl-ethyl) -N-propylamino, N- Butyl N- (1-methylethyl) amino, N- (1-methylethyl) -N- (1-methylpropyl) amino, N- (1-methylethyl) -N- (2-methylpropyl) amino, N- (1,1-dimethylethyl) -N- (1-methylethyl) amino, N-butyl-N- (1-methylpropyl) am ino, N-butyl! -N- (2-methylpropyl) amino, N-butyl-N- (1, 1-dimethyl-ethyl) -amino, N- (1-methylpropyl) -N- (2-methyl) propyl) amino, N- (1, 1-dimethylethyl) -N- (1-methylpropyl) amino and N- (1, 1-dimethylethyl) -N- (2-methylpropyl) amino;
- Di(Ci-C6-alkyl)amino sowie die Dialkyiaminoreste von N-(Di-Ci-C6-alkylamino)- imino-Ci-C6-alkyl, Di(Ci-C6-alkyl)am!no-Ci-C4-alkyl, [Di(CrC6- alkyl)aminocarbonyioxy]-Ci-C4-alkyl, {Di[di(CrC6-alkyl)amino]carbonyloxy}-CrC4- alkyl und [Di(Ci-C6-a!kyt)amirio]cyanoimino: Di(CrC4-alkyl)amino wie voranstehend genannt sowie: z.B. N,N-Dipentylamiπo, N,N-Dihexylamiπo, N-Methyl-N- pentylamino, N-Ethyl-N-pentylamino, N-Methyl-N-hexylamino und N-Ethyi-N- hexylamino;(Ci-C4-Alkylamino)carbonyl: z.B. Methylaminocarbonyl, Ethylaminocar- bonyl, Propylamiπocarbony!, 1-Methylethyiamiπocarbonyi, Butylaminocarbonyl, 1- Methylpropylaminocarbonyl, 2-Methylpropylaminocarbonyl oder 1 ,1- Dimethylethylamiπocarbonyl;- Di (Ci-C 6 -alkyl) amino and the Dialkyiaminoreste of N- (di-Ci-C6-alkylamino) - imino-Ci-C 6 -alkyl, di (Ci-C 6 -alkyl) am! No-Ci -C4-alkyl, [di (C 1 -C 6 -alkyl) aminocarbonyloxy] -Ci-C 4 -alkyl, {di [di (C 1 -C 6 -alkyl) amino] carbonyloxy} -CrC 4 -alkyl and [di (C 1 -C 6 -alkyl] ) amirio] cyanoimino: di (C 1 -C 4 -alkyl) amino as mentioned above and also: for example N, N-dipentylamino, N, N-dihexylamino, N-methyl-N-pentylamino, N-ethyl-N-pentylamino, N-methyl- N-hexylamino and N-ethyl-N-hexylamino; (C 1 -C 4 -alkylamino) carbonyl: for example methylaminocarbonyl, ethylaminocarbonyl, propylamino-carbonyl, 1-methylethylvinylcarbonyi, butylaminocarbonyl, 1 Methylpropylaminocarbonyl, 2-methylpropylaminocarbonyl or 1, 1-dimethylethylaminocarbonyl;
- (Ci-C4-Afkylamino)carbonyl sowie die (Ci-C4--Alky!amino)carbony!-Teile von (Ci™ C4-Alky!amino)carbonylamino: z.B. Methylaminocarbonyl, Ethylaminocarbonyl, Pro- pylaminocarbonyl, 1-Methylethylaminocarbonyl, Butylaminocarbonyl, 1-Methyl- propylaminocarbonyl, 2-Methylpropylaminocarbonyi oder 1,1-Dimethylethylamino- carbonyl;- (C 1 -C 4 -alkylamino) carbonyl and the (C 1 -C 4 -alkylamino) carbonyl parts of (C 1 -C 4 -alkylamino) carbonylamino: e.g. Methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, 1-methylethylaminocarbonyl, butylaminocarbonyl, 1-methylpropylaminocarbonyl, 2-methylpropylaminocarbonyi or 1,1-dimethylethylaminocarbonyl;
- Di{Ci-C4-alky!)aminocarbonyl sowie die Di(Ci-C4-alkyl)aminocarbonyl-Teile von- Di {Ci-C4-alky!) Aminocarbonyl and the di (Ci-C4-alkyl) aminocarbonyl parts of
Di(Ci-C4-alkyl)aminocarbonytamino: z.B. N.N-Dimethylaminocarbonyl, N,N-Diethyl- aminocarboπyl, N, N-Di-(I -methylethyl)aminocarbonyl, N,N-Dipropylaminocarbonyl, N,N-Dibutyiaminocarbonyl, N,N-Di-(1-methylpropyl)aminocarbonyl, N,N-Di-(2- methy!propyl)amiπocarbonyl, N1N-Di-(1 ,1-dimethylethyl)aminocarbonyf, N-Ethyl-N- methylaminocarbonyl, N-Methyl-N-propylaminocarbonyl, N-Methyl-N-(1-methyl- ethyl)amiπocarbonyl, N-Butyl-N-methylamiπocarbonyl, N-Methyl-N-(1-methyI- propyOaminocarbonyl, N-Methy!-N-(2-methylpropyl)aminocarbonyl, N-(1 , 1 -Dimethyl- ethyi)-N-methylaminocarbonyf, N-Ethyl-N-propylaminocarboπyl, N-Ethyl-N-(1- methylethyl)aminocarbony[, N-Butyi-N-ethylaminocarbonyl, N-Ethy[-N-(1-methyl- propyl)aminocarboπyl, N-Ethyl-N-(2-methyipropyl)aminocarbonyl, N-Ethy!-N-(1 ,1- dimethylethyl)amiπocarbonyl, N-(1-Methylethyl)-N-propylaminocarbonyl, N-Butyl-N- propylaminocarbony!, N-(1 -MethylpropylJ-N-propylaminocarbonyl, N-(2-Methyl- propyl)-N-propylaminocarbonyl, N-(1.i-DimethylethyO-N-propylaminocarbonyl, N- Buty[-N-(1-methylethyl)aminocarbonyl, N-(1-Methy!ethyl)-N-(1-methylpropyl)- aminocarbonyl, N-(1-Methylethyl)-N-(2-methy!propyl)amiπocarbonyl, N-(1 ,1 -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) amiπocarbonyl, 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-methyl-N- (2-methylpropyl) aminocarbonyl, N- (1, 1-dimethylethyl) -N-methylaminocarbonyf, N-ethyl-N-propylaminocarbonyl, N-ethyl-N- (1-methylethyl) aminocarbony [, N-butyl-N ethylaminocarbonyl, N-ethyl [-N- (1-methyl-propyl) -aminocarbonyl, N-ethyl-N- (2-methylpropyl) -aminocarbonyl, N-ethyl-N- (1, 1-dimethylethyl) -aminocarbonyl, N- (1-methylethyl) -N-propylaminocarbonyl, N-butyl-N-propylaminocarbonyl, N- (1-methylpropyl) -N-propylaminocarbonyl, N- (2-methylpropyl) -N-propylaminocarbonyl, N- (1.i -DimethylethyO-N- propylaminocarbonyl, N-butyl [-N- (1-methylethyl) aminocarbonyl, N- (1-methylethyl) -N- (1-methylpropyl) aminocarbonyl, N- (1-methylethyl) -N- (2-methyl ! propyl) aminocarbonyl, N- (1, 1 -
Dimethylethyl)-N-(1 -methylethyl)aminocarbonyl, N-Butyl-N-(1 -methylpropyl)- aminocarbonyl, N-Butyl-N-(2-methylpropyl)aminocarbonyl, N-Butyl-N-(1 , 1-dimethyl- ethy[)aminocarbonyl, N-(1 -Methylpropy!)-N-(2-methylpropyl)aminocarbonyl, N-(1 , 1- Dimethylethyl)-N-(1-methylpropy!)arrιinocarbonyl oder N-(1 ,1-Dimethylethyl)-N-(2- methylpropyl)aminocarbonyj;Dimethylethyl) -N- (1-methylethyl) aminocarbonyl, N-butyl-N- (1-methylpropyl) -aminocarbonyl, N -butyl-N- (2-methylpropyl) aminocarbonyl, N -butyl-N- (1, 1 dimethylethy [) aminocarbonyl, N- (1-methylpropyl) -N- (2-methylpropyl) aminocarbonyl, N- (1, 1-dimethylethyl) -N- (1-methylpropyl) -in-trinocarbonyl or N- (1, 1-dimethylethyl) -N- (2-methylpropyl) aminocarbonyl;
- (Ci-C6-Alkylamino)carbonyl sowie die (Ci-C6-Aikylamino)carbonyl-Tei!e von (Ci- C6-Alkylamino)carbonyfamino, (Ci-Ce-Alkylamino)carbonyloxy-Ci-C4-alkyl( Ci-C6- Alkyiaminocarbony!-Ci-C4-alkyl und [(Ci-C6-Alkyl)aminocarbonylamino]-CrC4-alkyl: (Ci-C4-Alkylamino)carbonyl, wie voranstehend genannt, sowie z.B. Pentyiamino- carbonyl, 1-Methyibutylaminocarbonyl, 2-Methyl-butylaminocarbonyl, 3- Methylbutylaminocarbonyl, 2,2-Dimethylpropylamino-carbonyl, 1-Ethyi- propylaminocarbonyl, Hexylaminocarbonyl, 1 ,1-Dimethylpropyl-aminocarbonyi, 1,2- Dimethylpropylamtnocarbonyl, 1-Methylpentylaminocarbonyl, 2-Methylpentyl- aminocarbonyl, 3-Methylpentylaminocarbonyl, 4-Methylpentylamino-carbonyl, 1 ,1-- (Ci-C 6 -alkylamino) carbonyl and the (Ci-C6-Aikylamino) carbonyl Tei! E of (Ci-C6-alkylamino) carbonylfamino, (Ci-Ce-alkylamino) carbonyloxy-Ci-C4-alkyl ( Ci -C 6 -alkylaminocarbony! -CC-C 4 -alkyl and [(C 1 -C 6 -alkyl) aminocarbonylamino] -CrC 4 -alkyl: (C 1 -C 4 -alkylamino) carbonyl, as mentioned above, and also, for example, pentenoaminocarbonyl, Methylbutylaminocarbonyl, 2-methylbutylaminocarbonyl, 3-methylbutylaminocarbonyl, 2,2-dimethylpropylaminocarbonyl, 1-ethyl-propylaminocarbonyl, hexylaminocarbonyl, 1,1-dimethylpropyl-aminocarbonyi, 1,2-dimethylpropylamtnocarbonyl, 1-methylpentylaminocarbonyl, 2-methylpentyl- aminocarbonyl, 3-methylpentylaminocarbonyl, 4-methylpentylaminocarbonyl, 1, 1
Dimethylbutylaminocarbonyl, 1 ,2-Dimethylbutylaminocarbonyl, 1 ,3-Dimethylbutyl- aminocarbonyl, 2,2-Dimethylbutylaminocarbonyl, 2,3-Dimethylbutyl-aminocarbonyl, 3,3-Dimethylbutylaminocarbonyl, 1-Ethylbutylaminocarbonyl, 2-Ethylbutylamino- carbonyl, 1 ,1 ,2-Trimethylpropylaminocarbonyl, 1,2,2-Trimethyl- propyiaminocarbonyl, 1-Ethyl-i-methyIpropylaιninocarbonyl oder 1-Ethy!-2- methylpropylaminocarboπyl;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;
Di(Ci-C6-alkyl)aminocarboπyi sowie die Di(Ci-C6-aikyl)aminocarbony!-Teile von Di(C1-C6-alkyl)aminocarbonylanπiπo, Di(Ci-C6-a!kyl)aminocarbonyl-Ci-C4-alkyl und [Di(CrC6-atkyl)aminocarbonylarπino]-Ci-C4-alkyi: Di(Ci-C4-a!kyl)aminocarbonyl, wie voranstehend genannt, sowie z.B. N-Methyl-Nl-pentylaminocarbonyl, N-Methyi-N- (i-methylbutyl)-aminocarbonyl, N-Methyl-N-{2-methylbutyl)-aminocarbonyl, N- Methyl-N-(3-methylbutyl)-aminocarbonyl, N-Methyl-N-(2,2-dimethylpropyl)- aminocarbonyl, N-Methy!-N-(1-ethy!propyl)-aminocarbonyl, N-Methyl-N- hexylaminocarbonyl, N-Methyl-N-(1 ,1-dimethylpropyl)-aminocarbonyl, N-Methyl- N-(1 ,2-dimethylpropyl)-aminocarbonyl, N-Methyl-N-(1 -methylpentyl)- aminocarbonyl, N~Methyl-N-(2-rnethyipentyl)-arninocarbonyi, N-Methyl-N-(3- methy!pentyl)-aminocarbonyl, N-Methyl~N~(4-methylpeπtyl)-aminocarbonyl, N-Di (Ci-C 6 -alkyl) aminocarboπyi and the di (Ci-C6-aikyl) aminocarbony! Parts of di (C 1 -C 6 -alkyl) aminocarbonylanπiπo, di (Ci-C 6 -a! Kyl) aminocarbonyl- C 1 -C 4 -alkyl and [di (C 1 -C 6 -alkyl) aminocarbonylarinyl] C 1 -C 4 -alkyl: di (C 1 -C 4 -alkyl) aminocarbonyl, as mentioned above, and also, for example, N-methyl-N 1 -pentylaminocarbonyl, N Methyl-N- (i-methyl-butyl) -aminocarbonyl, N-methyl-N- {2-methyl-butyl) -aminocarbonyl, N-methyl-N- (3-methyl-butyl) -aminocarbonyl, N-methyl-N- (2, 2-dimethylpropyl) -aminocarbonyl, N-methyl-N- (1-ethyl-propyl) -aminocarbonyl, N-methyl-N-hexylaminocarbonyl, N-methyl-N- (1, 1-dimethylpropyl) -aminocarbonyl, N- Methyl N- (1, 2-dimethylpropyl) aminocarbonyl, N-methyl-N- (1-methylpentyl) aminocarbonyl, N-methyl-N- (2-methylpentyl) -arninocarbonyi, N-methyl-N- (3 methyl-pentyl) -aminocarbonyl, N-methyl-N- (4-methyl-pentyl) -aminocarbonyl, N-
Methy[-N-(1 ,1-dimethylbutyl)-aιrιinocarbonyl, N-Methyl-N-(1 ,2-dimethylbutyl)- aminocarbonyl, N-Methyl-N-(1 ,3-dimethylbutyl)-aminocarbonyi, N-Methy]~N-(2,2- dimethylbutyl)-aminocarbonyl, N-Methyl-N-(2,3-dimethylbutyl)~ amino-carboπyl, N- Methyl-N-(3,3-dimethylbutyl)-aminocarbonyl, N-Methyl-N-(i-ethyl-butyi)- aminocarbonyl, N-Methyt-N-(2-ethylbuty[)-aminocarbony!, N-Methyl-N-( 1 ,1 ,2- trimethylpropyl)-amiπocarboπyl, N-Methyl-N-(1 ,2,2-triιnethylpropyl)-amino- carbonyl, N-Methyl-N-(1-ethyl-1-methylpropy!)-aminocarbonyl, N-Methyl-N-(1- ethyl-2-tnethylpropyl)-aminocarbonyl, N-Ethyl-N-pentylaminocarbonyi, N-Ethyl-N- (1 -methylbutyl)-aminocarbonyl, N-Ethyl-N-(2-methylbutyl)-aminocarbonyl, N- Ethyl-N-(3-methylbutyl)-aminocarbonyl, N-Ethy[-N-(2,2-dimethylpropyl)- aminocarbonyl, N-Ethyl-N-(1-ethy[propyl)-aminocarbonyl, N-Ethyt-N- hexylaminocarbonyl, N-Ethyl-N~(1 ,1-dimethylpropy!)-aminocarbonyl, N-Ethy!-N- (1 ,2-dimethylpropyl)-aminocarbony[, N-Ethyl-N-(1 -methylpentyl)-aminocarbonyl, N-Ethyl-N-(2-methy!pentyl)-aminocarbonyi, N-Ethyl-N-(3~methylpentyl)- aminocarbonyl, N-Ethy[-N-(4-methy!pentyl)-amiπocarbonyl, N— Ethyi— N— (1 ,1— dimethylbutyf)-aminocarbonyl, N-Ethyl-N-(1 ,2-dirnethylbutyi)-aminocarbony[, N- Ethyl-N— (1 ,3-dimethylbutyl)-aminocarbonyl, N-Ethyl-N-{2,2-dimethylbutyl)- aminocarbonyl, N-Ethyl-N-(2,3-dimethytbutyl)-aminocarbonyl, N-Ethyl-N-(3,3- dimethylbutyO-aminocarbonyl, N-Ethyl-N-(1 -ethylbutyl)-amino-carbonyl, N-Ethy[- N-(2-ethylbuty!)-aminocarbony!, N-Ethyl-N-(1 , 1 ,2-trimethyl-propyl)"aminocarbonyl,Methy [-N- (1, 1-dimethylbutyl) -αιrιinocarbonyl, N-methyl-N- (1, 2-dimethylbutyl) - aminocarbonyl, N-methyl-N- (1, 3-dimethylbutyl) aminocarbonyi, N-methyl ] N- (2,2-dimethylbutyl) aminocarbonyl, N-methyl-N- (2,3-dimethylbutyl) amino-carbamoyl, N-methyl-N- (3,3-dimethylbutyl) -aminocarbonyl, N- Methyl-N- (i-ethylbutyl) -aminocarbonyl, N-methyl-N- (2-ethyl-butyl) -aminocarbonyl, N-methyl-N- (1, 1, 2-trimethyl-propyl) -aminocarbonyl, N- Methyl-N- (1,2,2-tri-methylpropyl) -aminocarbonyl, N-methyl-N- (1-ethyl-1-methylpropyl) -aminocarbonyl, N-methyl-N- (1-ethyl-2-) ethyl-propyl) -aminocarbonyl, N-ethyl-N-pentylaminocarbonyl, N-ethyl-N- (1-methyl-butyl) -aminocarbonyl, N-ethyl-N- (2-methyl-butyl) -aminocarbonyl, N-ethyl-N- (3 methylbutyl) -aminocarbonyl, N-ethyl [-N- (2,2-dimethylpropyl) -aminocarbonyl, N-ethyl-N- (1-ethyl-propyl) -aminocarbonyl, N-ethyl-N-hexylaminocarbonyl, N-ethyl- N ~ (1, 1-dimethylpropyl) -aminocarbonyl, N-ethyl-N- (1, 2-dimethylpropyl) aminocarbony [, N-ethyl-N- (1-methylpentyl) -aminocarbonyl, N-ethyl-N- (2-methylpentyl) -aminocarbonyl, N-ethyl-N- (3-methylpentyl) -aminocarbonyl, N-ethyl [-N- (4-methylpentyl) -aminocarbonyl, N-ethyl N- (1, 1-dimethylbutyl) -aminocarbonyl, N-ethyl-N- (1, 2-dimethylbutyl) -aminocarbonyl, N-ethyl-N- (1,3-dimethylbutyl) -aminocarbonyl, N-ethyl- N- {2,2-dimethylbutyl) -aminocarbonyl, N-ethyl-N- (2,3-dimethyl-butyl) -aminocarbonyl, N-ethyl-N- (3,3-dimethylbutyl-aminocarbonyl, N-ethyl-N- ( 1-ethylbutyl) -aminocarbonyl, N-ethyl [- N- (2-ethylbuty!) -Aminocarbony !, N-ethyl-N- (1, 1, 2-trimethyl-propyl) -aminocarbonyl,
N~Ethyl-N-(1 ,2,2-trimethylpropyl)-aminocarbonyl, N-Ethyl-N- (1-ethyi-1- methylpropyi)-aminocarbonyi, N-Ethyl-N-(1-ethyl-2-methy[propyl)-aminocarbonyl, N-Propyl-N-pentylaminocarbonyl, N-Butyl-N-pentylaminocarbonyl, N1N- Dipentylaminocarbonyl, N-Propyl-N-hexyl-aminocarbonyl, N-Butyl-N- hexySaminocarbonyl, N-Pentyl-N-hexy!aminocarbonyl oder N,N-Dihexylamino- carbonyi; Di(Ci-C6-alkyl)aminothiocarboπyl: z.B. N.N-Dimethylaminothiocarbonyl, N1N- Diethylaminothiocarbonyl, N1N-Di-(I -methy]ethyl)aminothiocarbonyl, N,N-Dipropyl- aminothiocarbonyl, NjN-Dibutylaminothiocarbonyl, N, N-Di-(I -methylpropyi)-amino- thiocarbonyl, N,N-Di-(2-methylpropyi)-aminothiocarbonyl, N1N-Di-(1 ,1-dimethyl- ethy!)-aminothiocarbonyl, N-Ethyl-N-methylaminothiocarbonyl, N-Methyl-N-propyl- amiπothiocarbonyl, N-Methyl-N-(1 -methylethyl)-aminothiocarbony(, N-Butyl-N- methylaminothiocarbonyi, N-Methyl-N-(1-methy!propyi)-aminothiocarbony!, N- Methyi-N-(2-methylpropyl)aminothiocarbonyl, N-( 1 ,1 -Dimethylethy I)-N- methylaminothiocarbonyl, N-Ethyl-N-propylaminothiocarbonyl, N~Ethyl-N-{1 - methy!ethyl)-aminothiocarbonyl, N-Butyl-N-ethylaminothiocarboπyl, N-Ethyl-N-(1- methylpropyl)-amiπothiocarbonyl, N-Ethy[-N-(2-methylpropyl)-aminothiocarboπy|, N-Ethyl-N-(1 ,1-dimethylethyl)-aminothiocarbony[, N-(1-Methylethyl)-N- propylaminothiocarbonyl, N-Butyl-N-propylaminothiocarbony[, N-(1-Methylpropyl)-N- propylaminothiocarbonyl, N-(2-Methylpropyl)-N-propylatnino-thiocarbonyl, N-(1 , 1- Dimethylethyl)-N-propylaminothiocarbonyl, N-Butyl-N-(i-methyiethyl)- aminothiocarbony!, N-(1-Methylethyl)-N-(1-methylpropyl)-aminothiocarbonyl, N-(1- Methy[ethy[)-N-(2-methylpropyl)-aminothiocarbonyJ, N-(1 ,1-Dimethylethyl)-N-(1- methylethyl)~aminothiocarbonyl, N-Butyl-N-(1 -methylpropyl)-aminothiocarbonyl, N- Butyl-N-(2-methylpropyl)-arτiinothiocarbonyi, N-Butyl-N-(1 ,1-dimethylethyl)- aminothiocarbony!, N-(1-Methylpropyl)-N-(2-methylpropyl)-amiπothiocarbonyl, N-N ~ ethyl N- (1, 2,2-trimethylpropyl) aminocarbonyl, N-ethyl-N- (1-ethyl-1-methylpropyl) -aminocarbonyi, N-ethyl-N- (1-ethyl-2-methyl [propyl) aminocarbonyl, N-propyl-N-pentylaminocarbonyl, N-butyl-N-pentylaminocarbonyl, N 1 N- Dipentylaminocarbonyl, N-propyl-N-hexyl-aminocarbonyl, N-butyl-N- hexySaminocarbonyl, N-pentyl N-hexy! Aminocarbonyl or N, N-dihexylaminocarbonyl; Di (Ci-C6 alkyl) aminothiocarboπyl: for example, NN-Dimethylaminothiocarbonyl, N 1 N- Diethylaminothiocarbonyl, N 1 N-di- (I -methyl] ethyl) aminothiocarbonyl, N, N-dipropyl aminothiocarbonyl, NJN-Dibutylaminothiocarbonyl, N, N-di- (I -methylpropyi) amino thiocarbonyl, N, N-di- (2-methylpropyi) aminothiocarbonyl, N 1 N-di- (1, 1-dimethyl-ethyl) - aminothiocarbonyl, N-ethyl N-methylaminothiocarbonyl, N-methyl-N-propylaminothiocarbonyl, N-methyl-N- (1-methylethyl) aminothiocarbonyl (, N-butyl-N-methylaminothiocarbonyi, N-methyl-N- (1-methylpropyl) ) -aminothiocarbonyl, N-methyl-N- (2-methylpropyl) aminothiocarbonyl, N- (1, 1-dimethylethyl) -N-methylaminothiocarbonyl, N-ethyl-N-propylaminothiocarbonyl, N-ethyl-N- {1 - ethyl) -aminothiocarbonyl, N-butyl-N-ethylaminothiocarbonyl, N-ethyl-N- (1-methylpropyl) -amiπothiocarbonyl, N-ethyl [-N- (2-methylpropyl) -aminothiocarbony], N-ethyl-N - (1, 1-dimethylethyl) aminothiocarbony [, N- (1-methylethyl) -N-propylaminothiocarbonyl, N-butyl-N-propylaminothiocarbony [, N- ( 1-methylpropyl) -N-propylaminothiocarbonyl, N- (2-methylpropyl) -N-propylatino-thiocarbonyl, N- (1, 1-dimethylethyl) -N-propylaminothiocarbonyl, N-butyl-N- (i-methylethyl) -aminothiocarbony !, N- (1-methylethyl) -N- (1-methylpropyl) -aminothiocarbonyl, N- (1-methyl-ethyl) -N- (2-methylpropyl) aminothiocarbonyl, N- (1, 1-dimethylethyl) N- (1-methylethyl) aminothiocarbonyl, N-butyl-N- (1-methylpropyl) -aminothiocarbonyl, N-butyl-N- (2-methylpropyl) -arothenothiocarbonyi, N-butyl-N- (1, 1) dimethylethyl) - aminothiocarbony !, N- (1-methylpropyl) -N- (2-methylpropyl) -amiπothiocarbonyl, N-
(1 ,1 -Dimethylethyl)-N-(1 -methylpropyl)-aminothiocarbonyl, N-(1 , 1 -Dimethylethyl)-N- (2-methylpropyl)-aminothiocarbonyl, N-Methyl-N-pentylaminothiocarbonyl, N- Methyl-N-fi-methylbutylJ-amiπothio-carbonyl, N-Methyf-N-(2-methylbutyl)- aminothiocarboπyt, N-Methy[-N-(3-methylbutyl)-aminothiocarbonyl, N-Methy!-N- (2,2-dimethy[propyl)~atninothio-carbonyi, N-Methy!-N-(1 -ethylpropy!)- aminothiocarbonyl, N-Methyl-N-hexyl-aminothiocarbonyl, N-Methyl-N- (1 ,1- dimethy!propyl)-aminothiocarboπyl, N-Methyt-N-(1 ,2-dimethylpropyl)- aminothiocarbonyl, N-Methyl-N-(1 -methylpentyl)-aminothiocarboπyl, N-Methyl-N- (2-methylpentyl)-aminothiocarbonyl, N-Methyl-N-(3-methylpentyl)- aminothiocarbonyl, N~Methyl-N-(4-methy!pentyi)-aminothio-carbonyl, N-Methyl-N-(1,1-dimethylethyl) -N- (1-methylpropyl) -aminothiocarbonyl, N- (1,1-dimethylethyl) -N- (2-methylpropyl) -aminothiocarbonyl, N-methyl-N-pentylaminothiocarbonyl, N-methyl- N-fi-methylbutyl-1-aminothiocarbonyl, N-methyl-N- (2-methyl-butyl) -aminothiocarbonate, N-methyl [-N- (3-methyl-butyl) -aminothiocarbonyl, N-methyl-N- (2,2 -dimethyl [propyl] acrylothio-carbonyl, N-methyl! -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-
(1 ,1 -dimethylbutyl)-aminothiocarbonyi, N-Methyl-N-(1 ,2-dimethylbυtyl)- aminothiocarbony!, N~Methyl-N-(1 ,3-dimethylbutyl)-aminothiocarbonyl, N-Methyl- N-(2,2-dimethyfbutyi)- aminothiocarbonyl, N-Methy!-N-(2,3-dimethylbutyS)- aminothiocarbonyl, N~Methyl-N-(3,3-dimethylbυtyl)-aminothiocarbonyl, N-Methyl- N~(1 -ethyibutyl)-aminothiocarbonyl, N-Methyl-N-(2-ethylbutyl)-aminothiocarbonyl,(1, 1-dimethylbutyl) aminothiocarbonyi, N-methyl-N- (1, 2-dimethylbuthyl) aminothiocarbonyl, N-methyl-N- (1, 3-dimethylbutyl) -aminothiocarbonyl, N-methyl-N- ( 2,2-dimethybutyl) -aminothiocarbonyl, N-methyl-N- (2,3-dimethylbutyl) -aminothiocarbonyl, N-methyl-N- (3,3-dimethylbuthyl) -aminothiocarbonyl, N-methyl-N-1 (1 -ethyibutyl) -aminothiocarbonyl, N-methyl-N- (2-ethylbutyl) -aminothiocarbonyl,
N-Methyl-N-ethyl-N-(1 ,1 ,2-trimethylpropyl)-aminothiocarbonyl, N-Methyl-N- (i^^-trimethylpropyO-aminothiocarbonyl, N-Methy(-N-(1-ethyl-1-methy!propyt)- aminothiocarbonyl, N-Methyl-N^I-ethyl^-methylpropyl^aminothiocarbonyl, N- Ethyl~N-pentyl-aminothiocarbony!, N-Ethyl-N-(1-methylbutyl)-aminothiocarbonyl, N-Ethyl-N-(2-methylbuty!)-aminothiocarbonyl, N-Ethyl-N-(3-methylbutyl)- aminothiocarbonyl, N-Ethyl-N-(2,2-dimethyipropyl)~amtnothiocarbonyl, N-Ethyl-N-(1- ethylpropyl)-aminothiocarbonyl, N-Ethyl-N-hexylaminothiocarbonyl, N-Ethyl-N- (1 ,1 -dimethyl-propyO-aminothiocarbonyi, N-Ethyl-N-(1 ,2-dimethylpropyl)- ami- nothiocarbonyl, N-Ethyl-N-(1-methylρentyl)-aminothiocarbonyl, N-Ethyl~N-{2- rnethy!pentyl)-arninothiocarbonyl, N-Ethyl-N-(3-methylpentyl)-aminothiocarbonyl, N-Eihyl-N-(4-rneihylpentyl)-aminothiocarbonyl, N-Ethyi-N-(1 , 1-dimethyibutyl)- amino-thiocarbonyl, N-Ethyl-N-(1 ,2-dimethy!butyl)- aminothiocarbonyi, N-Ethyi- N-(1 ,3-dimethylbutyi)-aminothiocarbonyl, N-Ethy!-N-(2,2-dimethylbutyl)-aminothio- carboπyl, N-Ethy!-N-(2,3-dimethylbυtyl)-aminothiocarbonyl, N-Ethyl-N-{3,3- dimethylbutyl)-aminothiocarbonyl, N-Ethyl-N-(1-ethy!butyl)-aminothiocarbonyl, N- Ethyl-N-(2-ethylbutyl)-aminothiocarbonyl, N-Ethyl-N-(1 ,1 ,2-trimethylpropyl)- aminothiocarbonyl, N-Ethyl-N-(1 ,2,2-trirnethylpropyi)-arninothiocarbonyl, N-Ethyl- N-(1-ethyl-1-methylpropy!)-aminothiocarbonyl, N-Ethyl-N-(1-ethyl-2-methylpropyl)- aminothiocarbonyl, N-Propyi-N-pentylaminothiocarbonyl, N-Butyl-N- pentylaminothiocarbonyl, N,N-Dipentylaminothiocarbonyl, N-Propyl-N-hexyl- aminothiocarbonyl, N-Butyl-N-hexylaminothiocarbonyl, N-Pentyi-N-hexyl- aminothiocarbonyl oder N(N-Dihexylaminothiocarbonyi;N-methyl-N-ethyl-N- (1, 1, 2-trimethyl-propyl) -aminothiocarbonyl, N-methyl-N- (1) -trimethyl-propyl-aminothiocarbonyl, N-methyl (-N- (1-ethyl-1 -methylpropyt) -aminothiocarbonyl, N-methyl-N, N-ethyl-methylpropyl-aminothiocarbonyl, N-ethyl-N-pentyl-aminothiocarbonyl, N-ethyl-N- (1-methylbutyl) -aminothiocarbonyl, N- Ethyl N- (2-methylbuty!) -Aminothiocarbonyl, N-ethyl-N- (3-methylbutyl) -aminothiocarbonyl, N-ethyl-N- (2,2-dimethylpropyl) -ethylthiocarbonyl, N-ethyl-N- ( 1-ethylpropyl) aminothiocarbonyl, N-ethyl-N-hexylaminothiocarbonyl, N-ethyl-N- (1, 1-dimethyl-propoxy-aminothiocarbonyl, N-ethyl-N- (1, 2-dimethylpropyl) -amino nothiocarbonyl, N-ethyl-N- (1-methylpentyl) -aminothiocarbonyl, N-ethyl-N- (2-methylpentyl) -arninothiocarbonyl, N-ethyl-N- (3-methylpentyl) -aminothiocarbonyl, N-ethylbenzyl N- (4-trimethylpentyl) -aminothiocarbonyl, N-ethyl-N- (1, 1-dimethyl-butyl) -amino-thiocarbonyl, N-ethyl-N- (1, 2-dimethylbutyl) -aminothiocarbonyi, N-ethyl- N- (1,3-dimethylbutyl) -aminothiocarbonyl, N-ethyl-N- (2,2-dimethylbutyl) aminothiocarbonyne, N-ethyl-N- (2,3-dimethylbuthyl) aminothiocarbonyl, N- Ethyl N- {3,3-dimethylbutyl) -aminothiocarbonyl, N-ethyl-N- (1-ethyl-butyl) -aminothiocarbonyl, N-ethyl-N- (2-ethylbutyl) -aminothiocarbonyl, N-ethyl-N- (1,1,2-trimethyl-propyl) -aminothiocarbonyl, N-ethyl-N- (1,2-tri-methyl-propyl) -arninothiocarbonyl, N-ethyl-N- (1-ethyl-1-methylpropyl) -aminothiocarbonyl, N Ethyl N- (1-ethyl-2-methylpropyl) -aminothiocarbonyl, N-propyl-N-pentylaminothiocarbonyl, N-butyl-N-pentylaminothiocarbonyl, N, N-dipentylaminothiocarbonyl, N-propyl-N-hexylaminothiocarbonyl, N Butyl-N-hexylaminothiocarbonyl, NP entyi-N-hexylaminothiocarbonyl or N ( N-dihexylaminothiocarbonyi;
drei- bis sechsgliedriges Heterocyclyl sowie die drei- bis sechsgliedrigen Heterocyc- tyl-Teile von drei- bis sechsgliedriges Heterocyc!yl-Ci-C4-alkyl: monocyclische, gesättigte oder partiell ungesättigte Kohlenwasserstoffe mit drei bis sechs Rängglie- dem wie voranstehend genannt, welche neben Kohlenstoffatomen ein bis vier Stickstoffatome, oder ein bis drei Stickstoffatome und ein Sauerstoff- oder Schwefelatom, oder ein bis drei Sauerstoffatome, oder ein bis drei Schwefelatome enthalten können, und welche über ein C-Atom oder ein N-Atom verknüpft sein können, z.B.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 Rängglie- 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
z.B. 2-Oxrianyl, 2-Oxetany!, 3-Oxetanyl, 2-Aziridinyl, 3-Thiethany!, 1-Azetidinyl, 2-e.g. 2-oxrianyl, 2-oxetany !, 3-oxetanyl, 2-aziridinyl, 3-thiethany !, 1-azetidinyl, 2-
Azetidinyl,azetidinyl,
z.B. 2-Tetrahydrofuranyl, 3-Tetrahydrofuranyl, 2-Tetrahydrothienyl, 3-Tetra- hydrothienyl, 2-Pyrroiidinyl, 3-Pyrroüdinyl, 3-lsoxazolidinyl, 4-lsoxazolidiny!, 5- isoxazolidinyl, 3-lsothiazolidinyl, 4-fsothiazolidiπyl, 5-lsothiazolidinyl, 3-Pyrazolidinyl,e.g. 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl !, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl , 3-pyrazolidinyl,
4-Pyrazolidinyl, 5-Pyrazolidinyl, 2-Oxazolidinyl, 4-Oxazolidinyl, 5-Oxazolidinyl, 2- Thiazolidiny!, 4-Thiazolidinyl, 5-Thiazo!idinyl, 2-lmidazolidinyl, 4-!midazo!idinyl, 1 ,2,4-Oxadiazolidiπ-3-yl, 1 ,2,4-Oxadiazo!idin-5-yl, 1 ,2,4-Thiadiazolidin-3-yl, 1 ,2,4- Thiadiazolidin-5-yl, 1 ,2,4-Triazolidin-3-yl, 1 ,3,4-Oxadiazolidin-2-yl, 1 ,3,4-Thia- diazo!idin-2-yl, 1 ,3,4-Triazolidin-2-y(, 1 ,2,3,4-Tetrazo!idin-5-yl;4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolinyl, 2-imidazolidinyl, 4-midazolinyl, 1, 2, 4-oxadiazolidin-3-yl, 1,2,4-oxadiazolipin-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2, 4-triazolidin-3-yl, 1, 3,4-oxadiazolidin-2-yl, 1, 3,4-thiadiazolidin-2-yl, 1, 3,4-triazolidin-2-y (1 !, 2,3,4-tetrazo idin-5-yl;
z.B. 1-Pyrrolidinyl, 2-lsothiazolidinyl, 2-lsothiazolidinyl, 1-Pyrazolϊdinyl, 3-OxazolS- dinyl, 3-Thiazolidinyl, 1-lmidazolidinyl, 1 ,2,4-Triazolidin-i-yS, 1 ,2,4-Oxadiazoiidin-2- yl, 1 ,2,4-Oxadiazolidin-4-yl, 1 ,2,4-Thiadiazolidin-2-yl, 1 ,2,4-Thiadiazolidin-4-yl, 1 ,2,3,4-Tetrazolidin-1-yl,e.g. 1-Pyrrolidinyl, 2-isothiazolidinyl, 2-isothiazolidinyl, 1-pyrazolodinyl, 3-oxazol-5-dinyl, 3-thiazolidinyl, 1-imidazolidinyl, 1, 2,4-triazolidin-i-yS, 1, 2,4-oxadiazoiidine 2-yl, 1, 2,4-oxadiazolidin-4-yl, 1, 2,4-thiadiazolidin-2-yl, 1, 2,4-thiadiazolidin-4-yl, 1, 2,3,4-tetrazolidine 1-yl,
z.B. 2,3-Dihydrofur-2-yi, 2,3-Dihydrofur-3-yl, 2,4-Dihydrofur-2-yl, 2,4-Dihydrofur-3-yl, 2,3-Dihydrothäen-2-yl, 2,3-Dihydrothien-3-yl, 2,4-Dihydrothien-2-yl, 2,4-Dihydrothien- 3-yt, 4,5-Dihydropyrrol-2-yl, 4,5-Dihydropyrrol-3-yl, 2,5-Dihydropyrrol-2-yl, 2,5- Dihydropyrrol-3-y!, 4,5-Dihydroisoxazol-3-yl, 2,5-Dihydroisoxazol-3-yl, 2,3-Di- hydroisoxazol-3-yl, 4,5-Dihydroisoxazol-4-yl, 2,5-Dihydroisoxazol-4-yi, 2,3-Dihydro- isoxazol-4-yi, 4,5-Dihydroisoxazol-5-yl, 2,5-Dihydroisoxazol-5-y!, 2,3-Dihydro- isoxazol-5-yl, 4,5-Dihydroisothiazol-3-yl, 2,5-Dihydroisothiazol-3-yl, 2,3-Dihydro- isothiazoi-3-yl, 4]5-Dihydroisothiazol-4-yl, 2,5-Dihydroisothiazol-4-y!, 2,3-Dihydro- isothiazol-4-yl, 4,5-Dihydroisothiazol-5-yl, 2,5-Dihydroisothiazol-5-yl, 2,3-Dihydro- isothiazol -5-yl, 2,3-Dihydropyrazol-2-yl, 2,3-Dihydropyrazol-3-yl, 2,3-Dihydro- pyrazol-4-yl, 2,3-Dihydropyrazol-5-yl, 3,4-Dihydropyrazol-3-yl, 3,4-Dihydropyrazol-4- yl, 3,4-Dihydropyrazol-5-yl, 4,5-Dihydropyrazol-3-yl, 4,5-Dihydropyrazol-4-yl, 4,5-for example, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothaene-2-yl , 2,3-dihydro-thien-3-yl, 2,4-dihydro-2-yl, 2,4-dihydro-thienyl 3-yt, 4,5-dihydropyrrol-2-yl, 4,5-dihydropyrrol-3-yl, 2,5-dihydropyrrol-2-yl, 2,5-dihydropyrrol-3-yl, 4,5-dihydroisoxazole 3-yl, 2,5-dihydroisoxazol-3-yl, 2,3-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl, 2,5-dihydroisoxazol-4-yl, 2,3 Dihydroisoxazol-4-yl, 4,5-dihydroisoxazol-5-yl, 2,5-dihydroisoxazol-5-yl, 2,3-dihydroisoxazol-5-yl, 4,5-dihydroisothiazole-3 yl, 2,5-dihydroisothiazol-3-yl, 2,3-dihydroisothiazoi-3-yl, 4 ] 5-dihydroisothiazol-4-yl, 2,5-dihydroisothiazol-4-yl, 2,3-dihydro isothiazol-4-yl, 4,5-dihydroisothiazol-5-yl, 2,5-dihydroisothiazol-5-yl, 2,3-dihydroisothiazol-5-yl, 2,3-dihydropyrazol-2-yl, 2 , 3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl , 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-
Dihydropyrazol-5-yl, 2,3-Dihydroimidazol-2-yl, 2,3-Dihydroimidazol-3-yl ,2,3-Di- hydroimidazol-4-yl, 2,3-Dihydroimidazol-5-yl, 4,5-Dihydroimidazol-2-yl, 4,5-Di- hydroimidazol-4-yl, 4,5-Dihydroimidazot-5-yl, 2,5-Dihydroimidazol-2-yl, 2,5-Di- hydroimidazol-4-yl, 2,5-Dihydroimidazol-5-yl, 2,3-Dihydrooxazol-3-yl, 2,3-Dihydro- oxazol-4-yl, 2,3-Dihydrooxazol-5-yl, 3,4-Dihydrooχazol-3-yl, 3,4-Dihydrooxazol-4-yl,Dihydropyrazol-5-yl, 2,3-dihydroimidazol-2-yl, 2,3-dihydroimidazol-3-yl, 2,3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl, 4, 5-Dihydroimidazol-2-yl, 4,5-dihydroimidazol-4-yl, 4,5-dihydroimidazot-5-yl, 2,5-dihydroimidazol-2-yl, 2,5-dihydroimidazole-4 yl, 2,5-dihydroimidazol-5-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooazazole 3-yl, 3,4-dihydrooxazol-4-yl,
3,4-Dihydrooxazol-5-yl, 2,3-Dihydrothiazol-3-yl, 2)3-Dihydrothiazol-4-yl, 2,3-Di- hydrothiazol-5-yl, 3,4-Dihydrothiazol-3-yl, 3,4-Dihydrothiazol-4-yl, 3,4-Dihydro- thiazol-5-yl, 3,4-Dihydrothiazol-2-yi, 3,4-Dihydrothiazol-3-yl, 3,4-Dihydrothiazol-4-yl,3,4-dihydrooxazol-5-yl, 2,3-dihydrothiazol-3-yl, 2 ) 3-dihydrothiazol-4-yl, 2,3-di-hydrothiazol-5-yl, 3,4-dihydrothiazole-3 yl, 3,4-dihydrothiazol-4-yl, 3,4-dihydro-thiazol-5-yl, 3,4-dihydrothiazol-2-yl, 3,4-dihydrothiazol-3-yl, 3,4-dihydrothiazole 4-yl,
z.B. 4,5-Dihydropyrrol-1-y!, 2,5-DihydropyrroM-yl, 4,5-Dihydroisoxazol-2-yl) 2,3-eg 4,5-dihydropyrrol-1-yl, 2,5-dihydropyrromol-yl, 4,5-dihydroisoxazol-2-yl ) 2,3-
Dihydroisoxazol-1-yl, 4,5-Dihydroisothtazol-1-yl, 2,3-Dihydroisothiazol-1-yl, 2,3-Di- hydropyrazol-1 -yl, 4,5-Dihydropyrazol-1-yl, 3,4-Dihydropyrazol-i-yl, 2,3-Dihydro- imidazol-1 -yl, 4,5-Dihydroimidazol-1-yl, 2,5-Dihydroimidazol-1-yl, 2,3-Dthydrooxazol- 2-yi, 3,4-Dihydrooxazol-2-yl, 2,3-Dihydrothiazol-2-yl, 3,4-Dihydrothiazol-2-yl;Dihydroisoxazol-1-yl, 4,5-dihydroisothtazol-1-yl, 2,3-dihydroisothiazol-1-yl, 2,3-dihydropyrazol-1-yl, 4,5-dihydropyrazol-1-yl, 3, 4-dihydropyrazol-1-yl, 2,3-dihydroimidazol-1-yl, 4,5-dihydroimidazol-1-yl, 2,5-dihydroimidazol-1-yl, 2,3-dithydrooxazol-2-yl, 3,4-dihydrooxazol-2-yl, 2,3-dihydrothiazol-2-yl, 3,4-dihydrothiazol-2-yl;
z.B. 2-Piperidinyl, 3-Piperidinyl, 4-Piperidinyl, 1,3-Dioxan-2-yI, 1 ,3-Dioxan-4-yl, 1 ,3- Dioxan-S-yl, 1 ,4-Dioxan-2-yl, 1,3-Dithian-2-yl, 1 ,3-Dithian-3-yl, 1 ,3-Dithian-4-yl, 1 ,4- Dithian-2-yl, 1,3-Dithian-5-yl, 2-Tetrahydropyranyi, 3-Tetrahydropyraπyl, 4- Tetrahydropyraπyl, 2-Tetrahydrothiopyranyl, 3-Tetrahydrothiopyranyl, A- Tetrahydrothiopyranyl, 3-Hexahydropyridazinyl, 4-Hexahydropyridazinyl, 2-e.g. 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-dioxan-2-yl, 1, 3-dioxan-4-yl, 1, 3-dioxane-S-yl, 1, 4-dioxane-2 yl, 1,3-dithian-2-yl, 1, 3-dithian-3-yl, 1, 3-dithian-4-yl, 1, 4-dithian-2-yl, 1,3-dithiane-5 yl, 2-tetrahydropyranyi, 3-tetrahydropyraπyl, 4-tetrahydropyraπyl, 2-tetrahydrothiopyranyl, 3-tetrahydrothiopyranyl, A-tetrahydrothiopyranyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-
Hexahydropyrimidinyl, 4-Hexahydropyrimidinyl, 5-Hexahydropyrirπidinyl, 2- Piperazinyl, 1 ,3,5-Hexahydrotriazin-2-yl, 1 ,2,4-Hexahydrotriazin-3-yl, Tetrahydro- 1 ,3-oxazin-2-yl, Tetrahydro-1 ,3-oxazin-6-yl, 2-Morpholinyl, 3-Morpholinyl, 1 ,3,5- Trioxan-2-yl;Hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrirπidinyl, 2-piperazinyl, 1, 3,5-hexahydrotriazin-2-yl, 1, 2,4-hexahydrotriazin-3-yl, tetrahydro-1,3-oxazin-2-yl, Tetrahydro-1,3-oxazin-6-yl, 2-morpholinyl, 3-morpholinyl, 1, 3,5-trioxan-2-yl;
z.B. 1-Piperidinyl, 1-Hexahydropyridazinyl, 1-Hexahydropyrimidinyt, 1-Piperazinyl, 1 ,3,5-Hexahydrotriazin-i-yl, 1 ,2,4-Hexahydrotriazin-1-y!, Tetrahydro-1 ,3-oxazin-1-yl, 1-Morpholinyl;e.g. 1-piperidinyl, 1-hexahydropyridazinyl, 1-hexahydropyrimidinylt, 1-piperazinyl, 1, 3,5-hexahydrotriazin-i-yl, 1, 2,4-hexahydrotriazin-1-yl, tetrahydro-1,3-oxazine-1 -yl, 1-morpholinyl;
z.B. 2H-Pyran-2-yl, 2H-Pyran-3-yl, 2H-Pyran-4-yl, 2H-Pyran-5-yl, 2H-Pyraπ-6-yl,e.g. 2H-pyran-2-yl, 2H-pyran-3-yl, 2H-pyran-4-yl, 2H-pyran-5-yl, 2H-pyra-6-yl,
3,6-Dihydro-2H-pyran-2-yl, 3,6-Dihydro-2H-pyran-3-yl, 3,6-Dihydro-2H-pyran-4-yl, 3,6-Dihydro-2H-pyran-5-yi, 3,6-Dihydro-2H-pyran-6-yl, 3,4-Dihydro-2H-pyran-3-yl, 3,4-Dihydro-2H-pyran-4-yl, 3,4-Dihydro-2H-pyran-6-y!, 2H-Thiopyran-2-yl, 2H- Thiopyran-3-yl, 2H-Thiopyraπ-4-yl, 2H-Thiopyran-5-yl, 2H-Thiopyran-6-yl, 5,6- Dihydro-4H-1 ,3-oxazin-2-yl3,6-dihydro-2H-pyran-2-yl, 3,6-dihydro-2H-pyran-3-yl, 3,6-dihydro-2H-pyran-4-yl, 3,6-dihydro-2H- pyran-5-yl, 3,6-dihydro-2H-pyran-6-yl, 3,4-dihydro-2H-pyran-3-yl, 3,4-dihydro-2H-pyran-4-yl, 3, 4-Dihydro-2H-pyran-6-yl, 2H-thiopyran-2-yl, 2H- Thiopyran-3-yl, 2H-thiopyra-4-yl, 2H-thiopyran-5-yl, 2H-thiopyran-6-yl, 5,6-dihydro-4H-1,3-oxazin-2-yl
- Aryl sowie der Arylteil von Aryl(Ci-C4-alkyl): ein- bis dreikerniger aromatischer Car- bocyctus mit 6 bis 14 Ringgliedern, wie z.B. Phenyl, Naphthyl und Anthracenyl;Aryl and the aryl part of aryl (C 1 -C 4 -alkyl): mono- to trinuclear aromatic carboxylate having 6 to 14 ring members, such as e.g. Phenyl, naphthyl and anthracenyl;
- Heteroaryl sowie die Heteroarylreste in Heteroaryl-Ci-C4- alkyl, Heteroaryi-C2-C4-aikenyl, Heteroaryl-C2-C4-alkinyi, Heteroaryl-C-ι-C4- halogenalkyl, Heteroaryl-C2-C4-halogenalkenyf, Heteroaryl-C2-C4-halogenalkinyl, Heteroaryl-Ci-C4-hydroxyalkyl, Heteroaryl-Ca-C4-hydroxyalkenyl, Heteroaryl-C2-C4- hydroxyaikiπyl, Heteroarylcarbonyl-Ci-C4-alky[, Heteroarylcarbony!oxy-Ci-C4-alkyt, HeteroarySoxycarbonyl-Ci-C4-alkyl, Heteroaryloxy-Ci-C4-alkyl, Heteroarylthio-d-C4- alkyl, Heteroarylsulfinyl-Ci-C4-alkyl, Heteroaryisulfonyf-Ci-C4-alkyf : mono- oder bicyclisches aromatisches Heteroaryl mit 5 bis 10 Ringgliedern, wei- ches neben Kohlenstoffatomen 1 bis 4 Stickstoffatome, oder 1 bis 3 Stickstoffatome und ein Sauerstoff- oder ein Schwefelatom, oder ein Sauerstoff- oder ein Schwefelatom enthält, z.B.- heteroaryl and the heteroaryl radicals in Heteroaryl-C 1 -C 4 -alkyl, heteroaryl-C 2 -C 4 -alkenyl, heteroaryl-C 2 -C 4 -alkynyl, heteroaryl-C 1 -C 4 -haloalkyl, heteroaryl-C 2 -C 4 -haloalkenyl, heteroaryl-C 2 -C 4 -haloalkynyl, Heteroaryl-C 1 -C 4 -hydroxyalkyl, heteroarylCa-C 4 -hydroxyalkenyl, heteroarylC 2 -C 4 -hydroxyalkyl, heteroarylcarbonyl-C 1 -C 4 -alkyl [, heteroarylcarbonyloxy-C 1 -C 4 -alkyl, heteroaryloxycarbonyl-C 1 -C 4 -alkyl , Heteroaryloxy-C 1 -C 4 -alkyl, heteroarylthio-C 1 -C 4 -alkyl, heteroarylsulfinyl-C 1 -C 4 -alkyl, heteroaryisulfonyl-C 1 -C 4 -alkyl: mono- or bicyclic aromatic heteroaryl having 5 to 10 ring members, and more besides carbon atoms Contains 1 to 4 nitrogen atoms, or 1 to 3 nitrogen atoms and an oxygen or a sulfur atom, or an oxygen or a sulfur atom, for example
Monocyclen wie Furyi (z.B. 2-Furyl, 3-Furyl), Thienyl (z.B. 2-Thienyl, 3-Thienyl), Pyrrolyl (z.B. Pyrrol-2-yl, Pyrrok3-yl), Pyrazolyl (z.B. Pyrazol-3-yl, Pyrazol-4-yl), isoxazolyl (z.B. lsoxazol-3-yl, Isoxazol^-yl, !soxazol-5-yl), Isothiazolyl (z.B. lsothiazoi-3-yl, IsothiazoM-yl, isothiazol-5-yl), imidazolyl (z.B. lmidazo!-2-y[, ImidazoM— yl), Oxazolyl (z.B. Oxazol-2-yl, Oxazol-4-yl, Oxazol-5-yl), Thiazolyl (z.B. Thiazol-2-yl, ThiazoM-yl, Thiazol-5-yl), Oxadiazolyl (z.B. 1,2,3-Oxadiazol- 4-yl, 1 ,2,3-Oxadiazo!-5-yl, 1,2,4-Oxadiazo!-3-yl, 1 ,2,4,-Oxadiazol-5-yl, 1 ,3,4- Oxadiazol-2-yl), Thiadiazolyl (z.B. 1 ,2,3-Thiadiazol^-yl, 1 ,2,3-Thiadiazol-5-yl,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, β-soxazol-5-yl), isothiazolyl (eg isothiazol-3-yl, isothiazol-yl, isothiazol-5-yl), imidazolyl ( eg imidazo! -2-y [, imidazoM-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,
1 ,2,4-Thiadiazol-3-yl, 1 ,2,4-Thiadiazol-5-yi, 1 ,3,4-Thiadiazoiy!-2-yl), Triazolyl (z.B. 1 ,2,3-Triazol-4-yl, 1 ^Λ-Triazol-S-yl), Tetrazol-5-yl, Pyridyl (z.B. Pyridin-2- yl, Pyridin-3-yl, Pyridin-4-yl), Pyrazinyl (z.B. Pyridazin-3-yl, Pyridazin^-yl), Pyri- midinyi (z.B. Pyrimidin-2-yl, Pyrimidin^- yl, Pyrimidin-5-yl), Pyrazin-2-yl, Triazϊnyl (z.B. 1,3,5-Triazin-2-yl, 1 ,2,4-Triazin-3-yl, 1 ,2,4-Triazin-5-yl, 1 ,2,4-Triazin-6-yl),1, 2,4-thiadiazol-3-yl, 1, 2,4-thiadiazol-5-yl, 1, 3,4-thiadiazolyl-2-yl), triazolyl (eg, 1, 2,3-triazole-4 -yl, 1 ^ Λ-triazol-S-yl), tetrazol-5-yl, pyridyl (eg, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl), pyrazinyl (eg, pyridazin-3-yl , Pyridazin ^ -yl), pyrimidines (eg pyrimidin-2-yl, pyrimidin-1-yl, pyrimidin-5-yl), pyrazine-2-yl, triazolnyl (eg 1,3,5-triazin-2-yl , 1, 2,4-triazin-3-yl, 1, 2,4-triazin-5-yl, 1, 2,4-triazin-6-yl),
Tetrazinyl (z.B. 1 ,2,4,5-Tetrazin-3-yl); sowieTetrazinyl (e.g., 1, 2,4,5-tetrazine-3-yl); such as
Bicyclen wie die benzanellierten Derivate der vorgenannten Monocyclen, z.B. Chi- πoliπyl, Isochinolinyi, Indolyi, Benzthienyl, Benzofuranyl, Benzoxazolyl, Benzthiazo- IyI, Benzisothiazolyl, Benzimidazolyl, Benzopyrazolyl, Benzthiadiazolyl, Benzotriazo- IyI.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- oder 6-g!iedriges Heteroaryl mit ein bis vier Stickstoffatomen, oder ein bis drei Stickstoffatomen und einem Sauerstoff- oder Schwefelatom, oder mit einem Sauerstoff- oder Schwefelatom1. z.B. über ein C-Atom verknüpfte aromatische 5-Ring-Heterocyclen, welche neben5- 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 . for example, via a C atom linked aromatic 5-membered ring heterocycles, which in addition
Kohlenstoffatomen ein bis vier Stickstoffatome, oder ein bis drei Stickstoffatome und ein Schwefel- oder Sauerstoffatom, oder ein Schwefel- oder Sauerstoffatom als Ringglieder enthalten können, z.B. 2-Furyl, 3-Furyl, 2-Thienyl, 3-Thienyl, 2-Pyrrolyl, 3-Pyrrolyl, 3-lsoxazoly[, 4-lsoxazolyl, 5-lsoxazoly!, 3-lsothiazolyi, 4-lsothiazolyl, 5- Isothiazolyl, 3-Pyrazolyt, 4-Pyrazolyl, 5-Pyrazolyl, 2-Oxazolyl, 4-Oxazolyi, 5- Oxazolyl, 2-Thiazolyl, 4-Thiazolyl, 5-Thiazolyl, 2-lmidazolyl, 4-lmidazolyl, 1 ,2,4- Oxadiazol-3-yl, 1,2,4-Oxadiazol-S-yl, 1 ,2,4-Thiadiazol-3-yl, 1 ,2,4-Thiadiazol-5-yi, 1 ,2,4-Triazol-3-yl, 1 ,3,4-Oxadiazol-2-yl, 1 ,3,4-Thiadiazol-2-yl und 1 ,3,4-Triazol-2-yl;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-triazol-3-yl, 1, 3,4-oxadiazol-2-yl, 1, 3, 4-thiadiazol-2-yl and 1, 3,4-triazol-2-yl;
z.B. über ein C-Atom verknüpfte aromatische 6-Ring Heterocyclen, weiche neben Kohlenstoffatomen ein bis vier, vorzugsweise ein bis drei Stickstoffatome als Ring- güeder enthalten können, z.B. 2-Pyridinyl, 3-Pyridinyl, 4-Pyridinyl, 3-Pyridazinyl, A- Pyridazinyl, 2-Pyrimidinyl, 4-Pyrimidinyi, 5-PyrimidinyS, 2-Pyrazinyl, 1 ,3,5-Triazin-2-yl und 1 ,2,4-Triazin-3-yl;e.g. aromatic 6-membered ring heterocycles linked via a carbon atom, which besides carbon atoms may contain one to four, preferably one to three, nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, A-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1, 3,5-triazin-2-yl and 1, 2,4-triazine-3-yl;
Alle Phenyl- und Arylringe bzw. Heterocyclyl- und Heteroarylreste sowie alle Phenyl- komponenten in Phenyl-Ci-Ce-alky!, Phenylcarbonyl, Phenylcarbonyl-Ci-Ce-aikyi, Phenylcarbonylamino-CrC^alkyl, Phenoxycarbonyl, Phenylaminocarbonyl, Phenylsul- fonylaminocarbonyl, N-(Ci-C6-Alkyl)-N-phenylaminocarbonyl und Phenyl-d-C6- alkylcarbonyl, alle Arylkomponenten in Aryl(Ci-C4-alkyl), alle Heteroarylkomponenten in mono- oder bicyclischem Heteroaryi und alle Heterocyclylkomponenten in Heterocylyl, Heterocyclyl-Ci-Cfr-alkyl, Heterocyclylcarbonyl, Heterocyciylcarbonyl-Ci-Ce-alkyl, Heterocyclyloxycarbonyl, Heterocyclylaminocarbonyl, Heterocyclylsulfoπylaminocarbo- nyl, N-(Ci-Ce-Alkyl)-N-heterocyclylaminocarbony! und Heterocyclyl-CrC6- alkylcarbonyi sind, soweit nicht anders angegeben, vorzugsweise unsubstituiert oder tragen ein bis drei Halogenatome und/oder eine Nitrogruppe, einen Cyanorest und/oder einen oder zwei Methyl-, Trifluormethyl-, Methoxy- oder Trifluormethoxy- substituenten.All phenyl and aryl rings or heterocyclyl and heteroaryl radicals and all phenyl components in phenyl-C 1 -C 6 -alkyl, phenylcarbonyl, phenylcarbonyl-C 1 -C 6 -alkyl, phenylcarbonylaminoC-C 1 -C 4 -alkyl, phenoxycarbonyl, phenylaminocarbonyl, phenylsulfonylaminocarbonyl, N- (C 1 -C 6 -alkyl) -N-phenylaminocarbonyl and phenyl-C 1 -C 6 -alkylcarbonyl, all aryl components in aryl (C 1 -C 4 -alkyl), all heteroaryl components in mono- or bicyclic heteroaryl and all heterocyclyl components in heterocyclyl, heterocyclyl -C-C f r-alkyl, heterocyclylcarbonyl, Heterocyciylcarbonyl-Ci-Ce-alkyl, heterocyclyloxycarbonyl, Heterocyclylaminocarbonyl, Heterocyclylsulfoπylaminocarbo- nyl, N- (Ci-Ce-alkyl) -N-heterocyclylaminocarbony! and unless otherwise specified, 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.
In einer besonderen Ausführungsform haben die Variablen der heteroaroylsubstituier- ten Serin-Amide der Formel I folgende Bedeutungen, wobei diese für sich allein betrachtet als auch in Kombination miteinander besondere Ausgestaltungen der Verbindungen der Formel I darstellen:In a particular embodiment, the 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:
Bevorzugt sind die heteroaroyl-substituierten Serin-Amide der Formel I1 in der A 5-gliedriges Heteroaryi mit ein bis vier Stickstoffatomen, oder ein bis drei Stickstoffatomen und einem Sauerstoff- oder Schwefelatom, oder mit einem Sauerstoff oder Schwefelatom; besonders bevorzugt 5-gliedriges Heteroaryi ausgewählt aus der Gruppe ThJe- nyl, Furyl, Pyrazolyl, Imidazolyl, Thiazolyl und Oxazolyl; insbesonders bevorzugt 5-gliedriges Heteroaryi ausgewählt aus der Gruppe Thienyl, Furyl, Pyrazolyl und Imidazolyl; wobei die genannten Heteroarylreste durch einen CrCβ-Halogeπalkyl- Rest, bevorzugt in 2-Position durch einen C-i-Ce-Halogenalkyl-Rest substituiert sind, und 1 bis 3 Reste aus der Gruppe Halogen, Cyano, Cr Ce-Alkyl, C3-C6-Cyc]oalkyl, Ci-C6-Alkoxy, d-Ce-Halogenalkoxy und Ci-Preferably, the heteroaroyl-substituted serine amides of the formula I 1 in the A 5-membered heteroaryl having one to four nitrogen atoms, or one to three nitrogen atoms and one oxygen or sulfur atom, or with an oxygen or sulfur atom; particularly preferred 5-membered heteroaryl selected from the group ThJe- nyl, furyl, pyrazolyl, imidazolyl, thiazolyl and oxazolyl; especially preferred 5-membered heteroaryl selected from the group thienyl, furyl, pyrazolyl and imidazolyl; wherein the heteroaryl radicals mentioned are substituted by a C 1 -C 6 -haloalkyl radical, preferably in the 2-position by a C 1 -C 6 -haloalkyl radical, and 1 to 3 radicals from the group halogen, cyano, C 1 -C 6 -alkyl, C 3 -C 6 -Cyc] oalkyl, Ci-C 6 alkoxy, d-Ce-haloalkoxy and ci
C6-Alkoxy-Ci-C4-alky! tragen können; bedeutet.C 6 alkoxy-Ci-C 4 -alky! can carry; means.
Ebenso bevorzugt sind die heteroaroyl-substituierteπ Serin-Amide der Formel !, in der A 5-gliedriges Heteroaryl mit ein bis vier Stickstoffatomen, oder ein bis drei Stickstoffatomen und einem Sauerstoff- oder Schwefelatom, oder mit einem Sauerstoff oder Schwefelatom; besonders bevorzugt 5-gliedriges Heteroaryl ausgewählt aus der Gruppe Thie- nyl, Furyl, Pyrazolyl, tmidazoiyl, Thiazoiyl und Oxazolyl; insbesondere bevorzugt 5-gliedriges Heteroaryl ausgewählt aus der GruppeLikewise preferred are the 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
Thienyl, Furyl, Pyrazolyl und [midazoiyl; wobei die genannten Heteroarylreste partiell oder vollständig haiogeniert sein können und/oder 1 bis 3 Reste aus der Gruppe Cyano, C-i-Cg-Alkyl, C3-C6-Cycloalkyl, Ci-C6-Halogenalkyl, Ci-C6-Alkoxy, CrC6- Halogenalkoxy und Ci-C6-Alkoxy-CrC4-alkyl tragen können; bedeutet.Thienyl, furyl, pyrazolyl and [midazoyl; where the heteroaryl radicals mentioned may be partially or fully haiogeniert and / or 1 to 3 radicals from the group cyano, Ci-Cg-alkyl, C 3 -C 6 cycloalkyl, Ci-C 6 haloalkyl, Ci-C 6 alkoxy, Can carry CrC 6 - haloalkoxy and Ci-C6-alkoxy-CrC 4 -alkyl; means.
Ebenso bevorzugt sind die heteroaroyl-substituierten Serin-Amide der Formel I, in der A 5-gliedriges Heteroaryl mit ein bis vier Stickstoffatomen, oder ein bis drei Stick- stoffatomeπ und einem Sauerstoff- oder Schwefelatom, oder mit einem Sauerstoffatom; besonders bevorzugt 5-gliedriges Heteroaryl ausgewählt aus der Gruppe Furyl, Pyrazolyl, Imidazolyl, Thiazoiyl und Oxazolyl; insbesoπders bevorzugt 5-gliedriges Heteroaryl ausgewählt aus der Gruppe Fu- ryl, Pyrazolyl und Imidazolyl; wobei die genannten Heteroarylreste partiell oder vollständig haiogeniert sein können und/oder 1 bis 3 Reste aus der Gruppe Cyano, CrC6-Alkyl, C3-C6-CyClOaIkVl, CrC6-Halogenalkyl, Ci-C6-Alkoxy, C1-C6- Halogenalkoxy und CrC6-A!koxy-Ci-C4-alkyl tragen können; bedeutet.Likewise preferred are the 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 -alkyl; means.
Ebenso bevorzugt sind die heteroaroyl-substituierten Serin-Amide der Formel I, in der A 6-gliedriges Heteroaryl mit ein bis vier Stickstoffatomen; besonders bevorzugt Pyridyl oder PyrimidyL insbesondere bevorzugt Pyrimidyl; wobei die genannten Heteroarylreste partiell oder vollständig halogeniert sein können und/oder 1 bis 3 Reste aus der Gruppe Cyano, d-Ce-Alkyl, C3-C6-Cycloalkyl, CrC6-Halogenalkyl, Ci-C6-Alkoxy, CrC6- Halogenalkoxy und CrC6-Alkoxy-Ci-C4-alkyl tragen können; bedeutet.Likewise preferred are the heteroaroyl-substituted serine amides of the formula I in which A is 6-membered heteroaryl having one to four nitrogen atoms; particularly preferably pyridyl or pyrimidyl, particularly preferably pyrimidyl; where the heteroaryl radicals mentioned may be partially or fully halogenated and / or 1 to 3 radicals from the group cyano, d-Ce-alkyl, C 3 -C 6 cycloalkyl, C r C 6 haloalkyl, Ci-C 6 alkoxy, Can carry CrC 6 - haloalkoxy and CrC6-alkoxy-Ci-C4-alkyl; means.
Ebenso bevorzugt sind die heterαaroylsubstituierten Serin-Amide der Formel I, in der A 5- oder 6-giiedriges Heteroaryl mit ein bis vier Stickstoffatomen, oder mit ein bis drei Stickstoffatomen und einem Sauerstoff- oder Schwefelatom, oder mit einemLikewise preferred are the 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
Sauerstoff- oder Schwefelatom, welches durch einen d-Cβ-Halogenalkyl-Rest, bevorzugt in 2-Position durch einen CrCβ-Halogenalkyi-Rest, substituiert sind, und 1 bis 3 Reste aus der Gruppe Cyano, d-C6-Alkyl, C3-Cβ-Cycloalkyl, CrCβ- Halogenalkyl, Ci-Ce-Alkoxy, d-C6-Halogenalkoxy und CrCβ-Alkoxy-CrOxygen or sulfur atom, which are substituted by a d-Cβ-haloalkyl radical, preferably in the 2-position by a CrCβ-Halogenalkyi radical, and 1 to 3 radicals from the group cyano, dC 6 alkyl, C3-Cβ 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 tragen kann; bedeutet.C4 alkyl can carry; means.
Ebenso bevorzugt sind die heteroaroylsubstituierten Serän-Amide der Formel I1 in der A 5- oder 6-gliedriges Heteroaryl ausgewählt aus der Gruppe Pyrrolyl, Thienyl,Likewise preferred are the heteroaroyl-substituted serane amides of the formula I 1 in the A 5 or 6-membered heteroaryl selected from the group pyrrolyl, thienyl,
Furyl, Pyrazolyl, Imidazolyl, Thiazolyl, Oxazolyl, Tetrazolyl, Pyridy! und Pyrimidi- nyl; wobei die genannten Heteroarylreste partiell oder vollständig halogeniert sein können und/oder 1 bis 3 Reste aus der Gruppe Cyano, d-Cβ-Alkyl, Ca-Ce-Cycloalkyl, d-C6-Halogenalkyl, d-Ca-Alkoxy, CrC6-Furyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, tetrazolyl, pyridy! and pyrimidinyl; where the heteroaryl radicals mentioned may be partially or fully halogenated and / or 1 to 3 radicals from the group cyano, d-Cβ-alkyl, Ca-Ce-cycloalkyl, dC 6 -haloalkyl, d-Ca-alkoxy, CrC 6 -
Halogenalkoxy und Ci-C6-Alkoxy-CrC4-a!kyl tragen können;Halogenoalkoxy and C 1 -C 6 alkoxy-C 1 -C 4 -alkyl;
besonders bevorzugt 5- oder 6-gliedriges Heteroaryl ausgewählt aus der Gruppe Thienyl, Furyi, Pyrazolyl, Imidazolyl, Thiazolyl, Oxazolyl und Pyridyl; wobei die genannten Heteroarylreste partiell oder vollständig halogeniert sein können und/oder 1 bis 3 Reste aus der Gruppe d-Ce-Aikyl, C3-C6- Cycloalkyl und d-Ce-Halogenalkyi tragen können;particularly preferably 5- or 6-membered 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;
insbesondere bevorzugt 5-gliedriges Heteroaryl ausgewählt aus der Gruppe Thienyl, Furyl, Pyrazolyl, imidazolyl, Thiazolyl und Oxazolyl; wobei die genannten Heteroarylreste partiell halogeniert sein können und/oder 1 bis 2 Reste aus der Gruppe CrCβ-Alkyl und d-d- Halogenalkyl tragen können;particularly preferably 5-membered 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 CrCβ-alkyl and d-d-haloalkyl;
außerordentlich bevorzugt 5-gliedriges Heteroaryi ausgewählt aus der Gruppemost preferably 5-membered heteroaryl selected from the group
Thienyl, Fury!, Pyrazolyl und Imidazolyl; wobei die genannten Heteroarylreste partiell halogeniert sein können und/oder 1 bis 2 Reste aus der Gruppe Ci~C6-A[kyl und C1-C4- Haiogenalkyf tragen können. bedeutet.Thienyl, Fury !, pyrazolyl and imidazolyl; wherein said heteroaryl may be partially halogenated and / or 1 to 2 radicals from the group Ci ~ C6-A [Kyl and C1-C4 Haiogenalkyf can carry. means.
Ebenso bevorzugt sind die heteroaroylsubstituierten Serin-Amide der Formel I, in der A 5- oder 6-gliedriges Heteroaryl ausgewählt aus der Gruppe Pyrrolyl, Furyl, Pyra- zolyl, Imidazolyl, Thiazolyl, Oxazolyl, Tetrazolyl, Pyridyl und Pyrimidinyl; wobei die genannten Heteroarylreste partiell oder vollständig halogeniert sein können und/oder 1 bis 3 Reste aus der Gruppe Cyano, Ci-C6-A!kyl,Likewise preferred are the 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,
C3-Cβ-Cycloalkyl, d-Cβ-Halogenalkyl, Ci-C3-Alkoxy, CrC6- Halogenalkoxy und tragen können;C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 6 haloalkoxy and can carry;
besonders bevorzugt 5- oder 6-giiedriges Heteroaryl ausgewählt aus der Gruppeparticularly preferably 5- or 6-membered heteroaryl selected from the group
Furyl, Pyrazolyl, Imidazolyl, Thiazolyl, Oxazolyi und Pyridyl; wobei die genannten Heteroarylreste partiell oder vollständig halogeniert sein können und/oder 1 bis 3 Reste aus der Gruppe d-Ce-Alkyl, C3-C6- Cycloalkyl und d-Cβ-Halogenalkyl tragen können;Furyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyi 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 C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl and C 1 -C 6 haloalkyl;
insbesondere bevorzugt 5-gliedriges Heteroaryl ausgewählt aus der Gruppe Furyl, Pyrazolyl, Imidazolyl, Thiazoiyl und Oxazolyl; wobei die genannten Heteroarylreste partiell halogeniert sein können und/oder 1 bis 2 Reste aus der Gruppe Ci-Ce-Alkyl und C1-C4- Halogenalkyl tragen können;particularly preferably 5-membered 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;
außerordentlich bevorzugt 5-gliedriges Heteroaryl ausgewählt aus der Gruppe Furyl, Pyrazolyl und Imidazolyl; wobei die genannten Heteroarylreste partiell halogeniert sein können und/oder 1 bis 2 Reste aus der Gruppe Ci-Cδ-Aikyl und CrC4- Halogenalkyl tragen können, bedeutet.most preferably 5-membered heteroaryl selected from the group furyl, pyrazolyl and imidazolyl; where the said 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.
Ebenso bevorzugt sind die heteroaroyl-substituierten Serin-Amide der Formel I, in der A C-verknüpftes 5-oder 6-gliedriges Heteroaryl ausgewählt aus der Gruppe A1 bis AU mitLikewise preferred are the 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
A12 A13 A14 wobei der Pfeil die Verknüpfungspositioπ anzeigt undA12 A13 A14 where the arrow indicates the link position and
R8 Wasserstoff, Halogen, CrC6-Alkyl oder Ci-Cβ-Halogenatkyl; besonders bevorzugt Wasserstoff, CrC4-Alkyl oder CrdrHalogenalkyl; insbesondere bevorzugt Wasserstoff oder Ci-C4-Alky!; außerordentlich bevorzugt Wasserstoff;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;
R9 Halogen, d-Cβ-Alkyl, Ci-C6-Halogenalkyl oder d-Ce-Halogenalkoxy; besonders bevorzugt Halogen, Ci-C4-Alkyl oder Ci-Cβ-Halogenalkyl; insbesondere bevorzugt Halogen oder d-Cβ-Halogenalkyl; sehr bevorzugt d-Ce-Halogenalkyl; außerordentlich bevorzugt d-C4-Halogenalkyl sehr außerordentlich bevorzugt CF3;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;
R10 Wasserstoff, Halogen, d-Cβ-Alkyl oder Ci-Ce-Halogenalkyl; besonders bevorzugt Wasserstoff, Halogen oder Ci-d-Haiogenalkyl; insbesondere bevorzugt Wasserstoff oder Halogen; außerordentlich bevorzugt Wasserstoff; undR 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
R11 Wasserstoff, d -C6-Al kyl, C3-C6-Cycloalkyl, CrC6-Halogenalkyl oder Cr Cβ-Alkoxy-CrC4-alkyl; besonders bevorzugt CrC4-Alkyl, C3-Cs-Cycloa!kyl, CrC4-Halogenalkyl oder Ci-C4-Alkoxy-CrC4-alkyl; insbesondere bevorzugt CrC4-Alky! oder CrC4-Haiogenalkyl; außerordentlich bevorzugt C-i-C-rAfkyl; sehr außerordentlich bevorzugt CH3;R 11 is hydrogen, d-C6 -alkyl, C 3 -C 6 cycloalkyl, -C 6 haloalkyl or Cr Cβ-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;
bedeuten;mean;
besonders bevorzugt A1, A2, A3, A4, A5, A6, Aδ oder A9; wobei Re bis R11 wie voranstehend genannt definiert werden;particularly preferably A1, A2, A3, A4, A5, A6, Aδ or A9; wherein R e to R 11 are defined as mentioned above;
außerordentlich bevorzugt A1 , A2, A5 oder A6; wobei R8 bis R11 wie voranstehend genannt definiert werden; bedeutet.most preferably A1, A2, A5 or A6; wherein R 8 to R 11 are defined as mentioned above; means.
Ebenso bevorzugt sind die heteroaroyi-substituierten Alaπine der Formel I, in der R1 Wasserstoff; bedeutet.Also preferred are the heteroaroyi-substituted Alaπine of formula I, in which R 1 is hydrogen; means.
Ebenso bevorzugt sind die heteroaroyi-substituierten Alaπine der Forme! I1 in der R2 Wasserstoff oder Hydroxy; besonders bevorzugt Wasserstoff; bedeutet.Also preferred are the heteroaroyi-substituted Alaπine the forms! I 1 in the R 2 is hydrogen or hydroxy; particularly preferably hydrogen; means.
Ebenso bevorzugt sind die heteroaroyi-substituierten Serin-Amide der Formel I, in der R1 Wasserstoff; und R2 Wasserstoff oder Hydroxy; besonders bevorzugt Wasserstoff; bedeuten.Likewise preferred are the heteroaroyi-substituted serine amides of the formula I in which R 1 is hydrogen; and R 2 is hydrogen or hydroxy; particularly preferably hydrogen; mean.
Ebenso bevorzugt sind die heteroaroyi-substituierten Serin-Amide der Formel I, in der R3 d-Ce-Alkyl oder CrCe-Halogenalkyl; besonders bevorzugt Ci-Ce-Aikyl; insbesondere bevorzugt CrCWMkyl; außerordentlich bevorzugt CH3; bedeutet.Also preferred are the 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.
Ebenso bevorzugt sind die heteroaroyi-substituierten Serin-Amide der Forme! I, in der R4 Wasserstoff, CrCe-Alkyl, C3-C6-Alkenyl, C3-C6-Alkinyl, Formyl, CrC6- Alkylcarbonyl, C2-C6-Alkenylcarbonyl, Ca-Ce-Cycloalkylcarbonyl, Ci-Ce- Aikoxycarbonyi, C-i-Cβ-Alkylamtnocarbonyl, CrCe-Alkylsulfonylaminocarbony], Di-(Ci-C3-alky!)-aminocarbonyl, N-(CrCβ-Alkoxy)-N-(Ci-C6-alkyl)-aminocarbonyl,Equally preferred are the 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-Cβ-Alkylamtnocarbonyl, CrCe-alkylsulfonylaminocarbony], di- (Ci-C3-alky!) - aminocarbonyl, N- (CrCβ-alkoxy) -N- (Ci-C6-alkyl) -aminocarbonyl,
Di-{Ci-C6-alkyl)-aminothicarbonyl, CrCθ-Alkoxyimino-Ci-Cβ-aikyl, wobei die genannten Alkyl, Cycloalkyl- und Alkoxyreste partiell oder vollständig haiogeniert sein können und/oder eine bis drei der folgenden Grup- pen tragen können: Cyano, Hydroxy, C3-C6-Cycloa!kyl, d-d-Alkoxy, C1-C4- Alkylthio, Di-(Ci-C4-alky!)-amino, Ci-C4-Alkylcarbonyl, Hydroxycarbonyl, Cr C4-Alkoxycarbonyl, Amiπocarbonyf, CrC4-Alkylaminocarbony!, Di-(CrC4- alkyl)-aminocarbonyl, oder Crd-Alkylcarbonyloxy; Phenyl, Phenyl-d-Cθ-alkyl, Phenylcarbonyl, Phenylcarbonyl-d-Ce-alkyl, Phenyl- sulfonylaminocarbonyl oder Pheπyi-Ci-Cs-alkylcarbonyl, wobei der Phenytring partiell oder vollständig halogeniert sein kann und/oder eine bis drei der folgenden Gruppen tragen kann: Nitro, Cyano, Ci-C4-Alkyl, Ci-C4-Halogenalkyl, Ci-C4-Alkoxy oder CrC4-Halogenalkoxy; oderDi (C 1 -C 6 -alkyl) -aminotharbonyl, C 1 -C 6 -alkoxyimino-C 1 -C 6 -alkyl, where the said alkyl, cycloalkyl and alkoxy radicals may be partially or completely halogenated and / or one to three of the following groups: cyano, hydroxy, C 3 -C 6 -cycloalkyl, dd-alkoxy, C 1 -C 4 -alkylthio, di- (C 1 -C 4 -alkyl) -amino, C 1 -C 4 -alkylcarbonyl, hydroxycarbonyl, C 1 -C 4 alkoxycarbonyl, Amiπocarbonyf, CrC 4 -Alkylaminocarbony !, di- (CrC 4 - alkyl) aminocarbonyl, or Crd-alkylcarbonyloxy; Phenyl, phenyl-C 1 -C 6 -alkyl, phenylcarbonyl, phenylcarbonyl-C 1 -C 6 -alkyl, phenylsulfonylaminocarbonyl or phenylalkyl-C 1 -C 5 -alkylcarbonyl, where the phenyl ring may be partially or completely halogenated and / or one to three of the following groups can carry: nitro, cyano, Ci-C 4 alkyl, Ci-C4-haloalkyl, Ci-C 4 alkoxy or -C 4 -haloalkoxy; or
SO2R7;SO 2 R 7 ;
besonders bevorzugt Wasserstoff, d-Ce-Alkyl, Cs-Ce-Alkenyl, C3-C6-Alkinyl,particularly preferably hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl,
Formyl, d-Ce-Alkytcarbony!, C2-C6-Alkenylcarbonyl, d-Ce-Alkoxycarbonyl, d- Cθ-AIkylsuifonylaminocarbonyl, Di-(CrC6-alkyl)-aminocarbonyl, N-(CrCe-Formyl, d-Ce-alkylcarbonyloxy, C 2 -C 6 -alkenylcarbonyl, d-Ce-alkoxycarbonyl, C 1 -C 6 -alkylsulfonylaminocarbonyl, di- (C 1 -C 6 -alkyl) aminocarbonyl, N- (C 1 -C 6 -alkylcarbonyloxy)
Alkoxy)-N-(d-C6-alky!)-aminocarbonyl oder DKd-Ce-alkyO-aminothiocarbonyl, wobei die genannten Alkyl- oder Alkoxyreste partiell oder vollständig halogeniert sein können und/oder eine bis drei der folgenden Gruppen tragen können: Cyano, C1-C4-AIkOXy, CrC4-Alkoxycarbonyl, CrC4- Alkylaminocarbonyl, Di-(CrC4-alkyl)-aminocarbonyI oder CrC4-Alkoxy) -N- (d-C6-alky!) - Aminocarbonyl or DKd-Ce-alkyO-aminothiocarbonyl, said 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 -
Alkylcarbonyloxy;alkylcarbonyloxy;
Phenyl-d-Cβ-alky!, Phenylcarbonyl, Phenylcarbonyl-d-Ce-alkyl, Phenylsulfoπyl- aminocarbonyl oder Phenyl-d-Ce-alkylcarbonyl, wobei der Phenylring partiell oder vollständig halogeniert sein kann und/oder eine bis drei der folgenden Gruppen tragen kann: Nitro, Cyano,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-C4-A!ky[, d-d-Halogenalkyl, CrC4-AIkOXy oder Ci-C4-Halogenoxy; oder! Ci-C 4 -A ky [dd-haloalkyl, -C 4 -alkoxy or C 4 -Halogenoxy; or
SO2R7;SO 2 R 7 ;
insbesondere bevorzugt Wasserstoff, CrCβ-Alkyl, Ca-Ce-Alkenyl, C3-C6-Alkinyl, Formyl, d-C6-Alkyl-carbonyl, CrCβ-Alkenylcarbonyl, d-Cβ-Aikoxycarbonyl, Di-particularly preferably hydrogen, C 1 -C 6 -alkyl, C 1 -C -alkenyl, C 3 -C 6 -alkynyl, formyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkenylcarbonyl, C 1 -C 6 -alkoxycarbonyl, di-
(CrC6-alkyl)-amino-carbonyl, N-(CrC6-Atkoxy)-N-(Ci-C6-alkyl)-aminocarbonyl, Di-fCrCe-alkyO-aminothiocarbonyl, Phenyl-d-Ce-alkyl, Phenylcarbonyl, Phenyl- carbonyl-d-Ce-alkyl oder Phenyl-Ci-Ce-aikylcarbony] wobei der Phenylring partiell oder vollständig halogeniert sein kann und/oder eine bis drei der folgenden Gruppen tragen kann: Nitro, Cyano,(C 1 -C 6 -alkyl) amino carbonyl, N- (C 1 -C 6 -alkoxy) -N- (C 1 -C 6 -alkyl) aminocarbonyl, C 1 -C 4 -C 4 -alkyl-amino-thiocarbonyl, phenyl-C 1 -C 6 -alkyl, phenylcarbonyl, phenyl carbonyl-d-Ce-alkyl or phenyl-Ci-Ce-aikylcarbony] where the phenyl ring may be partially or fully halogenated and / or may carry one to three of the following groups: nitro, cyano,
CrC4-Alkyl, d-C4-Halogenalkyl, Ci-C4-Alkoxy oder CrC4-Halogen-alkoxy; oder SO2R7; bedeutet.-C 4 alkyl, dC 4 haloalkyl, Ci-C 4 alkoxy or -C 4 -halogen-alkoxy; or SO 2 R 7 ; means.
Ebenso bevorzugt sind die heteroaroyl-substituierten Serin-Amide der Formel I, in der R4 Wasserstoff, Ci-Ce-Alkyl, C3-C6-Alkenyl, Ca-Ce-Alkinyl, Formyl, CrCe- Alkylcarbonyl, C2-C6-Alkenylcarbonyl, C^-Ce-Cycloalkylcarbonyl, CrC6- Alkoxycarbonyl, CrCβ-Alkylaminocarbonyl, Di-(Ci-Cβ-alkyl)-aminocarbonyl, N- (Ci-Ce-Alkoxy)-N-(Ci-C6-alkyl)-aminocarbonyl, Di-<CrC6-alkyl)- aminothiocarbonyl, Ci-Ce-Alkoxyimino-Ci-Ce-alkyl, wobei die genannten Alkyl-, Cycioalkyl- oder Alkoxyreste partiell oder voll- ständig halogeπiert sein können und/oder eine bis drei der folgenden Gruppen tragen können: Cyano, Hydroxy, Cs-Cθ-Cycloalkyl, Ci-C4-Alkoxy, CrC4- Alkylthio, Di-(Ci-C4-alkyl)-amino! CrC4-Alkylcarbony!, Hydroxycarbonyl, Cr C4-Aikoxycarbonyl, Aminocarbonyl, d-d-Alkylaminocarbonyl, Di-(CrC4- alkyl)-aminocarbonyl oder CrC4-Alkyicarbonyloxy; oder SO2R7; bedeutet.Likewise preferred are the heteroaroyl-substituted serineamides of the formula I in which R 4 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 1 -C -alkynyl, formyl, C 1 -C 6 -alkylcarbonyl, C 2 -C 6- alkenylcarbonyl, C 1 -C 6 -cycloalkylcarbonyl, CrC 6 - Alkoxycarbonyl, CrCβ-alkylaminocarbonyl, di- (Ci-Cβ-alkyl) aminocarbonyl, N- (Ci-C e alkoxy) -N- (Ci-C 6 alkyl) aminocarbonyl, di <C r C 6 - alkyl) - aminothiocarbonyl, Ci-Ce-alkoxyimino-Ci-Ce-alkyl, wherein said alkyl, cycioalkyl or alkoxy radicals may be partially or completely halogeπiert and / or carry one to three of the following groups: cyano, hydroxy , Cs-Cθ-cycloalkyl, Ci-C4-alkoxy, CrC 4 - alkylthio, di- (Ci-C 4 alkyl) amino! 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.
Ebenso bevorzugt sind die heteroaroyl-substituierten Serin-Amide der Formel I1 in der R4 Wasserstoff, d-Ce-Alkyl, C3-C6-Alkeny[, C3-C6-Alkinyl, Formyl, CrC6- Aikyfcarbony!, CrC6-Alkoxycarbonyl, d-Ce-Alkylamiπocarbonyl, Di-(CrCe-alkyl)- aminocarbonyl, N-(CrC6-Alkoxy)-N-(Ci-C6-alkyl)-amino-carbonyl, wobei die genannten Alkyl-,und Alkoxyreste partiell oder vollständig halo- geniert sein können und/oder eine bis drei der folgenden Gruppen tragen können: Cyano, d-GrAlkoxy, Ci-C4-Alkylaminocarbonyl oder Di-(d-C4- alkyi)-amänocarbonyl;The 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! , -C 6 alkoxycarbonyl, d-Ce-Alkylamiπocarbonyl, di- (CRCE-alkyl) - aminocarbonyl, N- (CrC 6 alkoxy) -N- (Ci-C 6 alkyl) amino-carbonyl, wherein the 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;
Phenyl-CrCβ-alkyl, Phenylcarbonyf, Phenylcarbonyl-d-Ce-alkyl, Phenylamino- carbonyl, oder N-(CrC6-Alkyl)-N-(pheπyl)-aminocarbonyl, wobei der Phenylring partiell oder vollständig halogeniert sein kann und/oder eine bis drei der folgenden Gruppen tragen kann: Cyano, C1-C4- Alkyl oder Ci-C4-Ha!ogenalky!; oderPhenyl-CrCβ-alkyl, phenylcarbonyf, phenylcarbonyl-d-Ce-alkyl, phenylaminocarbonyl, or N- (C 1 -C 6 -alkyl) -N- (phenyl) -aminocarbonyl, where the phenyl ring can be partially or fully halogenated and / or a can carry up to three of the following groups: cyano, C 1 -C 4 -alkyl or C 1 -C 4 -halogenalky !; or
SO2R7;SO 2 R 7 ;
besonders bevorzugt Wasserstoff, Formyl, d-d-Alkylcarbonyl, d-d- Alkylaminocarbonyl, Di-(CrC4-alkyl)-aminocarbonyl, Phenytaminocarbonyl, N- (CrC4-Alkyl)-N-(phenyl)-aminocarbonyl, SO2CH3, SO2CF3 oder SO2(C6H5); bedeutet.particularly preferably hydrogen, formyl, dd-alkylcarbonyl, dd-alkylaminocarbonyl, di- (C 1 -C 4 -alkyl) aminocarbonyl, phenytaminocarbonyl, N- (C 1 -C 4 -alkyl) -N- (phenyl) -aminocarbonyl, SO 2 CH 3 , SO 2 CF 3 or SO 2 (C 6 H 5 ); means.
Ebenso bevorzugt sind die heteroaroyl-substituierten Serin-Amide der Formel I, in der R5 Wasserstoff oder CrC4-AJkyl; bevorzugt Wasserstoff oder CH3; insbesondere bevorzugt Wasserstoff; bedeutet.Also preferred are the 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.
Ebenso bevorzugt sind die heteroaroyl-substituierten Serin-Amide der Formel I, in der R6 d-Ce-Alkyl, C2-C6-Alkenyl, C2-C3-Alkinyl, d-Ce-Halogenalky!, C2-C6-Equally preferred are the 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 -
Halogenalkenyl, C2-C6-Halogenalkinyl, d-Cs-Cyanoalkyl, CrC6-Hydroxyalkyl, Ca-Ce-Hydroxyalkenyl, Cz-Cg-Hydroxyalkinyl, Cß-Cβ-Cycloalkyl, C3-Ce- Cycloalkenyl, 3- bis 6-gliedriges Heterocyclyl-d-d-alkyl, wobei die voranstehen genannten Cycloalkyl, Cycloalkenyl oder 3- bis 6- giiedrigen Heterocyclylreste partiell oder vollständig halogeniert sein können und/oder einen bis drei Rest aus der Gruppe Oxo, d-Cβ-Alkyl, Ci-Ce- Halogenalkyi, Hydroxycarbonyi und Ci-C6-Alkoxycarboπyi tragen können, Ci-C6-Alkoxy-Ci-C4-aikyl, CrC6-Halogenalkoxy-CrC4-alkyl, CrCθ-Aikoxy-Ci-C4- alkoxy-Ci-C4-alkyi, CrCe-Alkyithio-d-d-alkyl, Ci-C6-A!kylsulfonylamino-Ci-C4- alkyl, Hydroxycarbonyi, CrC6-Alkoxycarbonyl, Hydroxycarbonyl-d-d-alkyl, d- Cβ-Alkoxycarbonyl-Crd-alky!, CrCe-Halogenalkoxycarbonyl-CrC4-a!kyl, Ci-Ce- Alkylcarbonyloxy-CrC4-alkyl, CrC6-Alkylcarbony!amino-CrC4-alkyl, Di(CrCe- Alky^carbonylarnino-d-d-alkyl, Di(CrC6-aikyl)aminocarbonyl-amino-CrC4- alkyl, [(d-Ce-alky^aminocarbonyllarnino-Crd-alkyl, [Di(CrCo- a!kyl)aminocarbonyloxy]CrC4-alkyl, {Di[di(CrC6-alkyl)amino]carbonyloxy}CrC4- alkyl, Formylamino-d-d-alkyl,Haloalkenyl, C 2 -C 6 -haloalkynyl, C 1 -C 8 -cycloalkyl, C 1 -C 6 -hydroxyalkyl, C 1 -C -hydroxyalkenyl, C 1 -C 8 -hydroxyalkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenyl, 3 to 6 heterocyclyl-dd-alkyl, wherein the above-mentioned 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 -haloalkyl, hydroxycarbonyi and C 1 -C 4 can carry 6 -Alkoxycarboπyi, Ci-C 6 alkoxy-Ci-C 4 -alkyl, -C 6 haloalkoxy--C 4 -alkyl, CrC θ -alkoxy-Ci-C 4 - alkoxy-Ci-C4-alkyi, CrCe- Alkyithio-dd-alkyl, C 1 -C 6 -alkylsulfonylamino-C 1 -C 4 -alkyl, hydroxycarbonyi, C 1 -C 6 -alkoxycarbonyl, hydroxycarbonyl-d-d-alkyl, C 1 -C 6 -alkoxycarbonyl-C 1 -C -alkyl, C 1 -C 6 -haloalkoxycarbonyl- C 1 -C 4 -alkyl, C 1 -C 6 -alkylcarbonyloxy-C 1 -C 4 -alkyl, C 1 -C 6 -alkylcarbony! 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-CrC4-alkyl, Phenyl-C2-C4-a!kenyl, Phenyl-C3-C4-alkinyl, Phenyl-CrC4- halogenalkyl, Phenyl-C2-C4-halogenalkenyl, Phenyl-CrC4-hydroxyalkyl, Pheny- loxy-CrC4-alkyl, Phenylthio-CrC4-alkyl, Phenylsulfinyl-Ci-C4-alkyl, Phenylsulfo- ny[-CrC4-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,
Heteroaryl-CrC4-alkyl, Heteroaryl-CrC4-hydroxyalkyl, Heteroaryloxy-d-Ci-alkyl, Heteroarylthio-CrC4-alky!, Heteroaryisulfinyl-CrC4-alkyl oder Heteroarylsulfonyl- Ci-C4-alkyl, wobei die vorstehend genannten Phenyl- und Heteroarylreste partiell oder vollständig halogeniert sein können und/oder ein bis drei Reste aus der Gruppe Cyano, Nitro, CrC6-Alkyl, d-Ce-Halogenalkyl, Hydroxy, Ci-Ce- Alkoxy, CrCe-Halogenalkoxy, Hydroxycarbonyi, d-C6-Alkoxycarbonyl, Hydroxycarbonyl-Ci-Ce-alkoxy, d-Ce-Alkylsulfonyiamino und CrCe-Heteroaryl -C 4 alkyl, heteroaryl-CrC 4 hydroxyalkyl, heteroaryloxy-Ci-d-alkyl, heteroarylthio--C 4 -alky !, Heteroaryisulfinyl--C 4 alkyl or heteroarylsulfonyl Ci-C4 alkyl, where the abovementioned Phenyl and heteroaryl may be partially or completely halogenated and / or one to three radicals from the group cyano, nitro, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, hydroxy, C 1 -C 6 -alkoxy, C 1 -C 4 -haloalkoxy, hydroxycarbonyi, d -C6-alkoxycarbonyl, hydroxycarbonyl-Ci-Ce-alkoxy, d-Ce-Alkylsulfonyiamino and CrCe-
Halogenalkylsulfonylamino tragen können;Can carry halogenoalkylsulfonylamino;
besonders bevorzugt d-Ce-Alkyl, C2-C6-Alkenyl, C2-Ce-Alkinyl, d-Ce- Halogenalkyl, CrCβ-Halogenalkenyl, CrCe-Hydroxyalkyl, Ci-Cs-Alkoxy-Ci-d- alkyl, Hydroxycarbonyl-d-C4-alkyl; Ci-C6-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 -
Alkoxycarbonyl-Ci-C4-alkyl, Ci-Cβ-Alkylcarbonyloxy-Ci^-alkyl, CrCe- Alkylcarbonylamino-CrC4-alkyl, [Di(Ci-C6-alkyl)aminocarbonyloxy]CrC4-alkyl, {Di[di(CrC6-alkyl)amino]carbonyloxy}d-C4-alkyl, Formylamino-CrC4-alkyl; Pheny[-CrC4-alkyl, Phenyi-C2-C4-a[kenyl, Phenyl-C2-C4-alkinyl, Phenyl-Ci-C4- halogenalkyi, Phenyl-C2-C4-halogenalkenyl, Phenyl-CrC4-hydroxyalkyi, Pheny-Alkoxycarbonyl-C 1 -C 4 -alkyl, C 1 -C 6 -alkylcarbonyloxy-C 1 -C 4 -alkyl, C 1 -C 6 -alkylcarbonylamino-C 1 -C 4 -alkyl, [di (C 1 -C 6 -alkyl) aminocarbonyloxy] C 1 -C 4 -alkyl, {di [di (C 1 -C 6 -cycloalkyl) alkyl) amino] carbonyloxy} C 1 -C 4 alkyl, formylamino-C 1 -C 4 alkyl; Phenyl [-C r C 4 alkyl, phenyl-C2-C 4 -a [-alkenyl, phenyl-C 2 -C 4 -alkynyl, phenyl-Ci-C 4 - halogenalkyi, phenyl-C 2 -C 4 haloalkenyl, phenyl -CrC 4 -hydroxyalkyi, phenyl
Joxy-CrC4-alky!, Phenylthio-CrC4-alkyl, Phenylsulfinyi-Ci-C4-alkyl oder Phenyl- sulfonyl-CrC4-aikyl, wobei die vorstehend genannten Phenylreste partiell oder vollständig halogeniert sein können und/oder ein bis drei Reste aus der Gruppe CrCs- Alkyl, CrC6-Ha!ogenalkylCrC6-Alkoxy, Hydroxycarbonyi, d-Cβ-Alkoxy- carbonyl, d-Ce-Alkylsulfonylamino und CrCe-Halogeπalkylsulfonylamino tragen können; insbesondere bevorzugt d-Cβ-Alkyl, C2-C6-Alkeny!, C∑-Ce-Alkinyi, CrC6- Halogenalkyl, C2-C6-HalogenalkenylJ Ci-C6-Hydroxyalkyl, Hydroxycarbonyl-d- C4-alkyl, Ci-C3-Alkoxycarbonyl-Ci-C4-alky!, [Di(d-C6-alkyl)aminocarbonyloxy]d- d-alkyl, {Di[di(CrC6-alky])amino]carbonyloxy}Ci-C4-alkyi, Formylamino-CrC4- alkyt;Joxy-C r C 4 -alkyl, phenylthio-C 1 -C 4 -alkyl, phenylsulfinyl-C 1 -C 4 -alkyl or phenylsulfonyl-C 1 -C 4 -acyl, where the abovementioned phenyl radicals may be partially or fully halogenated and / or a one to three radicals from the group CRCS alkyl, CrC 6 -Ha ogenalkylCrC 6 alkoxy, Hydroxycarbonyi may bear d-Cβ-alkoxy carbonyl, d-Ce-alkylsulfonylamino and CRCE-Halogeπalkylsulfonylamino,!; more preferably d-Cβ-alkyl, C2-C6 -Alkeny !, CΣ-Ce-Alkinyi, -C 6 - haloalkyl, C 2 -C 6 haloalkenyl J Ci-C 6 hydroxyalkyl, hydroxycarbonyl-d-C 4 - alkyl, C 1 -C 3 -alkoxycarbonyl-C 1 -C 4 -alkyl, [di (C 1 -C 6 -alkyl) aminocarbonyloxy] d-d-alkyl, {di [di (C 1 -C 6 -alkyl)] amino] carbonyloxy} C 1 -C 4 -alkyi, formylamino-C r C4-alkyl;
Phenyl-d-C4-alkyl, Pheny!-C2-C4-alkenyl, Phenyl-Ci-C4-hydroxyalkyl oder Phe- nylthio-Ci-d-alkyl;Phenyl-C 1 -C 4 -alkyl, phenyl-C 2 -C 4 -alkenyl, phenyl-C 1 -C 4 -hydroxyalkyl or phenylthio-C 1 -d-alkyl;
außerordentlich bevorzugt d-C6-Alkyl, C2-C6-Alkenyl, d-Cβ-Halogenalkyl, C2-Cs- Halogenalkenyl, d-Cβ-Hydroxyalkyl, Hydroxycarbonyl-d-C4-alkyl, Formylamino- d-d-alkyl, Phenyi-d-d-alkyl oder Pheπyl-CrC4-hydroxyalkyl; bedeutet.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.
Ebenso bevorzugt sind die heteroaroyl-substituierten Serin-Amide der Formel I1 in der R6 CrCβ-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Ci-C6-Halogenaikyl, C2-C6-The heteroaroyl-substituted are also preferred serine amides of formula I 1 where R 6 is CrCβ-alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Ci-C 6 -Halogenaikyl, C 2 -C 6 -
Halogenalkenyl, C2-C6-Halogenalkänyl, d-Ce-Cyanoalkyl, CrCβ-Hydroxyalkyl, C2-Cβ-Hydroxyalkenyl, C2-C6-Hydroxyalkinyl, C3-C6-Cycloa[kyl, C3-C6- Cycloalkenyl, 3- bis 6-gliedriges Heterocyclyl, wobei die voranstehend genannten Cycloalkyl, Cycloalkenyl oder 3- bis 6- gliedrigen Heterocyclyl reste partieil oder vollständig halogeniert sein können und/oder einen bis drei Rest aus der Gruppe Oxo, d-C6-Alkyl, CrCe- Halogenalkyl, Hydroxycarbonyl und d-Ce-Alkoxycarbonyl tragen können, C 1 -Cβ-Alkoxy-C 1 -C4- al ky! , C 1 -C6-H a logenal koxy-Cr C4-a I ky I , C 1 -C6-Al koxy-Ci -C4- alkoxy-Ci-C4-alkyl, Ci-Cs-Alkylsulfonylamino-Ci-C4- alkyl, Hydroxycarbonyl, Ci-Ce-Alkoxycarbonyl, Hydroxycarbonyl-CrC4-alkyl, d- C6-Alkoxycarbonyl-d-d-alkyl, CrC6-Halogenalkoxycarbonyl-CrC4-alkyl, CrCe- Alkylcarbonyloxy-CrC4-alkyl, CrC6-Alkylcarbonylamino-Ci-C4-a!kyl, Di(CrCe- Alkyl)carbonylamino-CrC4-alkyl, Di(CrC6-alkyl)aminocarbonyiamino-CrC4-alkyl, [(CrC6-alkyl)aminocarbonyl]amino-Ci-C4-alkyi, [Di(CrCe- alkyl)amiπocarbonyloxy]CrC4-alky!, Formylamino-CrC4-alkyl, Phenyl-CrC4-a!kyl, Phenyl-C2-C4-a!kenyl, Phenyl-C2-C4-alkiny!, Phenyl-d-C4- halogenalkyl, Pheny!-C2-C4-halogenalkenyl, Pheny!-d-C4-hydroxyalkyl, Pheny- loxy-Ci-C4-alkyi, Phenylthio-CrC4-alkyl, Pheπyisulfinyl-CrC4-alky!, PhenySsulfo- nyl-d-d-alkyl,Haloalkenyl, C 2 -C 6 Halogenalkänyl, d-Ce-cyanoalkyl, CrCβ-hydroxyalkyl, C 2 -Cβ-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 6 -H a logenal koxy-C r C 4 -a I ky I, C 1 -C 6 Al koxy-Ci -C 4 - alkoxy-Ci-C 4 alkyl, Ci-Cs-alkylsulfonylamino-Ci-C 4 - alkyl, hydroxycarbonyl, Ci-Ce-alkoxycarbonyl, hydroxycarbonyl-CRC4-alkyl, d- C6-alkoxycarbonyl-dd-alkyl, halo-alkoxycarbonyl-CRC6 -C 4 alkyl, alkylcarbonyloxy CrCe- C 1 -C 4 -alkyl, C 1 -C 6 -alkylcarbonylamino-C 1 -C 4 -alkyl, di (C 1 -C 6 -alkyl) carbonylamino-C 1 -C 4 -alkyl, di (C 1 -C 6 -alkyl) aminocarbonyiamino-C 1 -C 4 -alkyl, [(C 1 -C 6 -alkyl) aminocarbonyl] amino-Ci-C 4 -alkyi, [di (CrCe- alkyl) amiπocarbonyloxy] CRC-4 alky !, formylamino-CRC4-alkyl, phenyl-CrC 4 -a! kyl, phenyl-C 2 -C 4 -a! -alkenyl, phenyl-C 2 -C 4 -alkiny !, phenyl-dC 4 - haloalkyl, phenyl-C2-C4 haloalkenyl, phenyl-d-C4-hydroxyalkyl, phenylethyl loxy-Ci-C 4 -alkyi, phenylthio! -C 4 alkyl, -C 4 -alky !, Pheπyisulfinyl-PhenySsulfo- nyl-dd-alkyl,
Heteroaryl-CrC4-alkyl, Heteroaryl-CrC4-hydroxyalkyl, Heteroaryloxy-CrC4-alkyl, Heteroarylthio-CrC4-alkyl, Heteroarylsulfinyl-CrCraiky! oder Heteroaryisulfonyl- CrC4-alkyl, wobei die vorstehend genannten Phenyl- und Heteroarylreste partiell oder vollständig halogeniert sein können und/oder ein bis drei Reste aus derHeteroaryl -C 4 alkyl, heteroaryl -C 4 hydroxyalkyl, heteroaryloxy--C 4 alkyl, heteroarylthio -C 4 alkyl, heteroarylsulfinyl-CrCraiky! or Heteroaryisulfonyl- CrC 4 alkyl, wherein the above-mentioned phenyl and heteroaryl may be partially or fully halogenated and / or one to three radicals from the
Gruppe Cyano, Nitro, d-Ce-Alkyl, d-Ce-Halogenalkyl, Hydroxy, CrC6- Alkoxy, d-Cβ-Halogenalkoxy, Hydroxycarbonyl, CrCe-Alkoxycarbonyl, Hydroxycarbonyl-Ci-Cβ-alkoxy, CrC6-A!kylsu!foπylamino und CrC6- Halogenalkylsulfonylamino tragen können;Cyano, nitro, d-Ce-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 -alkylsulfinylamino and C 1 -C 6 -haloalkylsulfonylamino;
besonders bevorzugt d-Cβ-Alkyl, C2-Cß-Alkenyl, C2-C6-Alkinyl, CrC6- Halogenalkyl, CrCβ-Hydroxyalkyl, 3- bis 6-gliedriges He- terocyclyl, CrC6-Alkoxy-CrC4-alkyi, Ci-C6-Alkoxy-Ci-C4-alkoxy-CrC4-alkyl, d- C6-Halogeπalkoxy-CrC4-a!kyi, Hydroxycarbonyl-d-C^alkyl, CrCe- Alkoxycarbonyi-CrC4-alky!, d-Ce-Alkylcarbonyloxy-C-t-C^alkyl, d-Cε- Alkylcarbonylamino-CrC^aikyl, [Di(CrCe-alkyl)amsnocarbony!oxy]CrC4-alkyl, Formylamino-Ci-C4-alkyl;especially C2-C preferably d-Cβ-alkyl, ß alkenyl, C 2 -C 6 alkynyl, -C 6 - haloalkyl, CrCβ-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-Halogeπalkoxy-CRC4 a! kyi, hydroxycarbonyl-dC ^ alkyl, CrCe- alkoxycarbonyl-CrC 4 -alky !, d-Ce-alkylcarbonyloxy-CtC ^ alkyl, C 1 -C 6 -alkylcarbonylamino-C 1 -C 6 -alkyl, [di (C 1 -C 6 -alkyl) amsnocarbonyloxy ] C 1 -C 4 -alkyl, formylamino-C 1 -C 4 -alkyl;
Pheny!-CrC4-alkyl, Phenyl-C2-C4-alkenyl, Phenyl-C2-C4-alkinyl, Phenyl-d-d- halogenalkyl, Phenyl-C2-C4-halogenalkenyl, Pheny[-CrC4-hydroxyalkyl, Pheny- loxy-CrC4-alky[, Phenyithio-CrC4-alkyl, Pheny!sulfinyl-CrC4-alkyl oder Phenyl- sulfonyl-d-C4-alkyl, wobei die vorstehend genannten Phenylreste partiell oder vollständig halo- geniert sein können und/oder ein bis drei Reste aus der Gruppe CrCe- Alkyl, CrCe-HaiogenalkylCrCβ-Alkoxy, Hydroxycarbonyl, CrCe-Alkoxy- carbonyl, d-Ce-Alkylsulfonylamino und CrCe-Halogenalkylsulfonylamino tragen können;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 HaiogenalkylCrCβ-alkoxy, hydroxycarbonyl, CrCe-alkoxycarbonyl, d-Ce-alkylsulfonylamino and CrCe-Halogenalkylsulfonylamino can carry;
insbesondere bevorzugt CrCβ-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, CrCe- Halogenalkyl, C2-C6-Halogenalkenyl, d-Ce-Hydroxyalkyl, 3- bis 6-gliedriges He- terocyclyi, CrCe-Alkoxy-Ci-C4-alky!, CrC6-Alkoxy-CrC4-alkoxy-CrC4-aikyl, Hydroxycarbonyl-CrC4-alkyl, CrC6-Aikoxycarbonyl-CrC4-alkyl, [Di(CrCe- alkyOaminocarbonyloxyJCi^-alkyl, Formylamino-d-C4-alkyi;particularly preferably CrCβ-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;
Phenyl-CrC4-alkyl, Phenyl-C2-C4-alkenyl, Phenyl-CrC4-hydroxyalkyl oder Phe- nylthio-CrC4-alkyl;Phenyl-CrC 4 -alkyl, phenyl-C 2 -C 4 alkenyl, phenyl-CrC 4 hydroxyalkyl or Phe-nylthio -C 4 alkyl;
außerordentlich bevorzugt d-Cβ-Alkyl, C2-C6-Alkenyl, CrC6-Halogena!kyl, C2-C6- Halogenalkenyl, CrCe-Hydroxyalkyl, 3- bis 6-gliedriges Heterocyclyl, CrCβ-very preferably d-Cβ-alkyl, C 2 -C 6 -alkenyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -haloalkenyl, C 1 -C 6 -hydroxyalkyl, 3 to 6-membered heterocyclyl, C 1 -C 6 -alkylene
Alkoxy-CrC4-alkyl, CrC6-Alkoxy-CrC4-alkoxy-CrC4-alkyl, Hydroxycarbonyl-d- d-alkyl, Formylamino-d-C4-alkyl, Phenyl-CrC4-a!kyl oder Phenyl-CrC4- hydroxyalkyl; bedeutet.Alkoxy-CrC 4 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, hydroxycarbonyl-d-d-alkyl, formylamino-C 1 -C 4 -alkyl, phenyl-C 1 -C 4 -alkyl or phenyl-C 1 -C 4 -hydroxyalkyl; means.
Ebenso bevorzugt sind die heteroaroyl-substituierten Serin-Amide der Formel !, in der R7 d-Ce-Alkyl, CrCe-Halogenalkyi oder Pheπyl, wobei der Phenylrest partiell oder teilweise haiogeniert sein kann und/oder durch CrC4-Aikyl substituiert sein kann; besonders bevorzugt d-d-Alky!, d-C4-Halogenalkyl oder Phenyl; insbesondere bevorzugt Methyl, Trifluormethyl oder Phenyl. bedeutet. Besonders bevorzugt sind die heteroaroyi-substituierten Serin-Arnide der Formel I, in derEqually preferred are the 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- oder 6-gliedriges Heteroaryl ausgewählt aus der Gruppe Thienyi, Furyl, Pyra- zolyJ, Imidazolyl, Thiazolyl, Oxazolyl und Pyridyl; wobei die genannten Heteroarylreste partiell oder vollständig halogeniert sein können und/oder 1 bis 3 Reste aus der Gruppe Ci-Cβ-Alkyl, Cs-Ce-Cycloalky! und d-Cε-Halogenalkyl tragen können; R1 und R2 Wasserstoff; R3 C1-C4-AIRyI, besonders bevorzugt CHb; R4 Wasserstoff, Formyl, Ci-Cψ-Alkylaminocarbonyl, Di-(d-C4-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-Cβ-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-Cψ-alkylaminocarbonyl, di (dC 4 -
Alkyl)-aminocarbonyl, Phenylaminocarbonyl, N-(C1-C4-alkyl)-N-(phenyl)- aminocarbonyl, SO2CH3, SO2CF3 oder SO2(C6H5); R5 Wasserstoff; und R6 d-Ce-Alkyl, C2<VAIkenyl, CrC6-Halogenalky[, C2-C6-Halogenalkenyl, CrC6-Alkyl) -aminocarbonyl, phenylaminocarbonyl, N- (C 1 -C 4 -alkyl) -N- (phenyl) -aminocarbonyl, SO 2 CH 3 , SO 2 CF 3 or SO 2 (C 6 H 5 ); 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 -
Hydroxyalkyl, CrC6-Alkoxy-Ci-C4-alkyl, C1-C6-Alkoxy-Ci-C4-alkoxy-Ci-C4-alkyl,Hydroxyalkyl, C r C6-alkoxy-Ci-C4-alkyl, C 1 -C 6 alkoxy-Ci-C4-alkoxy-Ci-C4-alkyl,
3- bis 6-gliedriges Heterocyclyl, Hydroxycarboπyl-CrC4-alkyl, Phenyl-CrC4-alkyl oder Phenyl-CrC4-hydroxyalkyl bedeuten.3- to 6-membered heterocyclyl, hydroxycarboπyl-CrC4-alkyl, phenyl-C r C4-alkyl or phenyl-CrC 4 -hydroxyalkyl.
Außerordentlich bevorzugt sind die Verbindungen der Formel La (entspricht Formel I mit A = A-1 mit R8 = H, R9 = CF3, R1, R2 und R5 = H; R3 = CH3), insbesondere die Verbindungen der Formel l.a.1 bis l.a.138 der Tabelle 1 , wobei die Definitionen der Variablen A und R1 bis R6 nicht nur in Kombination miteinander, sondern auch jeweils für sich allein betrachtet für die erfindungsgemäßen Verbindungen eine besondere Rolle spielen.Very particular preference is given to the compounds of the formula La (corresponds to formula I where A = A-1 where R 8 = H, R 9 = CF 3 , R 1 , R 2 and R 5 = H; R 3 = CH 3 ), in particular the Compounds of the formulas Ia1 to Ia138 of Table 1, where the definitions of the variables A and R 1 to R 6, not only in combination with one another but also individually considered, play a particular role for the compounds according to the invention.
Tabelle 1Table 1
6 061128 6 061128
3737
Ebenso außerordentlich bevorzugt sind die Verbindungen der Formel l.b, insbesondere die Verbindungen der Formel l.b.1 bis l.b. 138, die sich von den entsprechenden Verbindungen der Formel l.a.1 bis l.a.138 dadurch unterscheiden, daß A für A1 mit R8 = CH3 und R9 = CF3 steht:Equally extraordinarily preferred are the compounds of the formula Ib, in particular the compounds of the formulas Ib 1 to Ib 138, which differ from the corresponding compounds of the formulas Ia1 to Ia138 in that A is Al with R 8 = CH 3 and R 9 = CF 3 stands:
Ebenso außerordentlich bevorzugt sind die Verbindungen der Formel l.c, insbesondere die Verbindungen der Formel I.e.1 bis I.e.138, die sich von den entsprechenden Verbindungen der Formel l.a.1 bis l.a.138 dadurch unterscheiden, daß A für A2 mit R8 = H und R9 =CF3steht:Equally exceptionally preferred are the compounds of the formula Ic, in particular the compounds of the formulas Ie1 to Ie138, which differ from the corresponding compounds of the formulas Ia1 to Ia138 in that A is A2 where R 8 = H and R 9 = CF 3 :
Ebenso außerordentlich bevorzugt sind die Verbindungen der Formel l.d, insbesondere die Verbindungen der Forme! l.d.1 bis l.d.138, die sich von den entsprechenden Verbindungen der Formel l.a.1 bis Ka.138 dadurch unterscheiden, daß A für A3 mit R3 = H und R9 = CF3 steht: Equally extraordinarily preferred are the compounds of formula ld, in particular the compounds of the forms! ld1 to ld138, which differ from the corresponding compounds of the formula Ia1 to Ka.138 in that A is A3 with R 3 = H and R 9 = CF 3 :
Ebenso außerordentlich bevorzugt sind die Verbindungen der Formel Le, insbesondere die Verbindungen der Formel l.e.1 bis I.e.138, die sich von den entsprechenden Verbindungen der Formel La.1 bis i.a.138 dadurch unterscheiden, daß A für A3 mit R8 = CH3 und R9 = CF3 steht:Equally exceptionally preferred are the compounds of the formula Le, in particular the compounds of the formula Ie1 to Ie138, which differ from the corresponding compounds of the formula Ia1 to Ia138 in that A is A3 in which R 8 = CH 3 and R 9 = CF 3 stands:
Ebenso außerordentlich bevorzugt sind die Verbindungen der Formel l.f, insbesondere die Verbindungen der Formel !.f.1 bis I. f.138, die sich von den entsprechenden Verbindungen der Formel La.1 bis l,a.138 dadurch unterscheiden, daß A für A4 mit Ra = H und Rθ = CF3 steht:Equally extraordinarily preferred are the compounds of the formula If, in particular the compounds of the formula I! F.1 to I.138, which differ from the corresponding compounds of the formula Ia.1 to I, a.138 in that A is A4 with R a = H and R θ = CF 3 is:
Ebenso außerordentlich bevorzugt sind die Verbindungen der Formel l.g, insbesondere die Verbindungen der Formel l.g.1 bis l.g.138, die sich von den entsprechenden Verbindungen der Formel La.1 bis l.a.138 dadurch unterscheiden, daß A für A5 mit R11 = H, R9 = CF3 und R10 = H steht:Equally extraordinarily preferred are the compounds of the formula Ig, in particular the compounds of the formula Ig1 to Ig138, which differ from the corresponding compounds of the formula Ia1 to Ia138 in that A is A5 with R 11 = H, R 9 = CF 3 and R 10 = H is:
Ebenso außerordentlich bevorzugt sind die Verbindungen der Formel l.h, insbesondere die Verbindungen der Formel l.h.1 bis l.h.138, die sich von den entsprechenden Verbindungen der Formel l.a.1 bis !.a.138 dadurch unterscheiden, daß A für A5 mit R11 = CH3, R9 = CF3 und R10 = H steht: Equally extremely preferred are the compounds of the formula Ih, in particular the compounds of the formula Ih1 to Ih138, which differ from the corresponding compounds of the formula Ia1 to Ia.138 in that A is A5 where R 11 = CH 3 , R 9 = CF 3 and R 10 = H is:
Ebenso außerordentlich bevorzugt sind die Verbindungen der Formel l.j, insbesondere die Verbindungen der Formel Ij.1 bis !.j.138, die sich von den entsprechenden Verbindungen der Formel l.a.1 bis l.a.138 dadurch unterscheiden, daß A für A8 mit R8 = H und R9 = CF3 steht:Equally extraordinarily preferred are the compounds of the formula Ij, in particular the compounds of the formula Ij.1 to!. J.138, which differ from the corresponding compounds of the formula Ia1 to Ia138 in that A for A8 with R 8 = H and R 9 = CF 3 is:
Ebenso außerordentlich bevorzugt sind die Verbindungen der Formel l.k, insbesondere die Verbindungen der Formel l.k.1 bis l.k.138, die sich von den entsprechenden Verbindungen der Formel l.a.1 bis La.138 dadurch unterscheiden, daß A für A8 mit R8 = CH3 und R9 = CF3 steht:Equally extraordinarily preferred are the compounds of the formula Ik, in particular the compounds of the formula IK1 to IK138, which differ from the corresponding compounds of the formula Ia1 to La.138 in that A is A8 where R 8 = CH 3 and R 9 = CF 3 stands:
Die heteroaroyl-substituierten Serin-Amide der Formel I sind auf verschiedene Art und Weise erhältlich, beispielsweise nach folgenden Verfahren:The heteroaroyl-substituted serine amides of the formula I are obtainable in various ways, for example by the following processes:
Verfahren A Serinderivate der Formel V werden zunächst mit Heteroarylsäure(derivate)n der Formel IV zu entsprechenden Heteroaroylderivaten der Formel III umgesetzt, welche anschließend mit Aminen der Formel Il zu den gewünschten heteroaroyl-substituierten Seπn-Amiden der Formet I reagieren: Process A Serine derivatives of the formula V are first reacted with heteroaryl acid (derivatives) n of the formula IV to give corresponding heteroaroyl derivatives of the formula III, which subsequently react with amines of the formula II to give the desired heteroaroyl-substituted selenium amides of the formula I:
L1 steht für eine nucleophil verdrängbare Abgangsgruppe, z.B. für Hydroxy oder CrCe- Atkoxy.L 1 is a nucleophilically displaceable leaving group, for example for hydroxy or CrCe- atkoxy.
L2 steht für eine nucleophil verdrängbare Abgangsgruppe, z.B. für Hydroxy, Halogen, Ci-Ce-Alkylcarbonyl, CrC6-Alkoxycarbonyl, Ci-C4-Alkylsulfonyl, Phosphoryl oder Iso- ureyl.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.
Die Umsetzung der Serinderivate der Formel V mit Heteroarylsäure(derivate)n der Formel IV, wobei L2 für Hydroxy steht, zu Heteroaroylderivaten der Formel III erfolgt in Gegenwart eines Aktivierungsreagenz und einer Base üblicherweise bei Temperaturen von 0 0C bis zum Siedepunkt des Reaktionsgemisches, vorzugsweise O0C bis 11O0C, besonders bevorzugt bei Raumtemperatur, in einem inerten organischen Lösungsmittel [vgl. Bergmann, E. D.; et al., J Chem Soc 1951 , 2673; Zhdankin, V. V.; et a!., Tetrahedron Lett. 2000, 41 (28), 5299-5302; Martin, S. F. et al., Tetrahedron Lett.1998, 39 (12), 1517-1520; Jursic, B. S. et al., Synth Commun 2001 , 31 (4), 555-564; Albrecht, M. et al., Synthesis 2001 , (3), 468-472; Yadav, L. D. S. et al., lndian J. Chem B. 41 (3),593-595(2002); Clark, J. E. et al., Sythesls (10),891-894 (1991)].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. 1998, 39 (12), 1517-1520; Jursic, BS et al., Synth Commun 2001, 31 (4), 555-564; Albrecht, M. et al., Synthesis 2001, (3), 468-472; Yadav, LDS et al., Indian J. Chem B. 41 (3), 593-595 (2002); Clark, JE et al., Sythesls (10), 891-894 (1991)].
Geeignete Aktivieruπgsreagenzien sind Kondensationsmittel wie z.B. poiystyrolgebun- denes Dicyclohexylcarbodiimid, Diisopropylcarbodiimid, Carbonyldiimidazol, Chlorkohlensäureester wie Methylchloroformiat, Ethylchloroformiat, Isoropylchloroformiat, Isobu- tylchloroformiat, sec-Butylchloroformiat oder Allylchloroformiat, Pivatoylchlorid, PoIy- phosphorsäure, Propanphosphonsäureanhydrid, Bis(2-oxo-3-oxazo!idinyl)- phosphorylchlorid (BOPCI) oder Sulfonylchloride wie Methansulfonylchlorid, Toluolsul- fonylchlorid oder Benzoisulfonylchlorid.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.
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Gemische von C5-C&-Aikanen, aromatische Kohlenwasserstoffe wie Benzol, Toluol, o-, m- und p-Xylol, halogenierte Kohlenwasserstoffe wie Methyienchlo- rid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert- Butylmethylether, Dioxan, Anisoi und Tetrahydrofuran (THF), Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert- Butylmethylketon, sowie Dimethylsuifoxid, Dimethylformamid (DMF), Dimethylacetamid (DMA) und N-Methylpyrrolidon (NMP) oder auch in Wasser, besonders bevorzugt sind Methylenchlorid, THF und Wasser. Es können auch Gemische der genannten Lösungsmittel verwendet werden.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-methylpyrrolidone (NMP) or in water, particularly preferred are methylene chloride, THF and water. It is also possible to use mixtures of the solvents mentioned.
Als Basen kommen allgemein anorganische Verbindungen wie Aikalimetall- und Erdal- kalimetallhydroxide wie Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid und Calci- umhydroxid, Alkalimetall- und Erdalkalimetalloxide wie Lithiumoxid, Natriumoxid, Calci- umoxid und Magnesiumoxid, Alkalimetall- und Erdalkalimetallhydride wie Lithiumhydrid, Natriumhydrid, Kaliumhydrid und Caiciumhydrid, Alkalimetall- und Erdalkalimetall- carbonate wie Lithiumcarbonat, Kaliumcarbonat und Calciumcarbonat sowie Alkalime- tallhydrogencarbonate wie Natriumhydrogencarbonat, außerdem organische Basen, z.B. tertiäre Amine wie Trimethylamin, Triethylamin, Diisopropylethylamin, N-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-
Methylmorpholin, und N-Methy!piperidin, Pyridin, substituierte Pyridine wie Cotüdin, Lutidin und 4-Dimethylaminopyridin sowie bicyclische Amine in Betracht. Besonders bevorzugt werden Natriumhydroxid, Triethylamin und Pyridin.Methylmorpholine, and N-methylpiperidine, pyridine, substituted pyridines such as Cotüdin, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Particularly preferred are sodium hydroxide, triethylamine and pyridine.
Die Basen werden im allgemeinen in äquimolar Mengen eingesetzt. Sie können aber auch im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden.The bases are generally used in equimolar amounts. But they can also be used in excess or optionally as a solvent.
Die Edukte werden im allgemeinen in äquimolaren Mengen miteinander umgesetzt. Es kann vorteilhaft sein, IV in einem Überschuß bezogen auf V einzusetzen.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.
Die Reaktionsgemische werden in üblicher Weise aufgearbeitet, z.B. durch Mischen mit Wasser, Trennung der Phasen und gegebenenfalls chromatographische Reinigung der Rohprodukte, Die Zwischen- und Endprodukte falten z. T. in Form zäher Öle an, die unter vermindertem Druck und bei mäßig erhöhter Temperatur von flüchtigen Antei- len befreit oder gereinigt werden. Sofern die Zwischen- und Endprodukte als Feststoffe erhalten werden, kann die Reinigung auch durch Umkristallisieren oder Digerieren erfolgen.The 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.
Die Umsetzung der Serinderivate der Formel V mit Heteroarylsäure(derivate)n der Formel IV, wobei L2 für Halogen, Ci-C6-Alkylcarbonyl, CrC6-Alkoxycarbonyl, Ci-C4- Alkylsulfonyl, Phosphoryl oder Isoureyl steht, zu Heteroaroylderivaten der Formel III erfolgt in Gegenwart einer Base üblicherweise bei Temperaturen von 0°C bis zum Siedepunkt des Reaktionsgemisches, vorzugsweise OX bis 100°C, besonders bevorzugt bei Raumtemperatur in einem inerten organischen Lösungsmittel [vgl. Bergmann, E. D.; et al., J Chem Soc 1951 , 2673; Zhdankin, V. V.; et al., Tetrahedron Lett. 2000, 41 (28), 5299-5302; Martin, S. F. et al., Tetrahedron Lett.1998, 39 (12), 1517-1520; Jursic, B. S. et al., Synth Commun 2001 , 31 (4), 555-564; Albrecht, M. et al., Synthesis 2001 , (3), 468-472; Yadav, L. D. S. et al., lndian J. Chem B. 41(3),593-595(2002); Clark, J. E. et al., Synthesis (10),891-894 (1991)].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. 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. 1998, 39 (12), 1517-1520; Jursic, BS et al., Synth Commun 2001, 31 (4), 555-564; Albrecht, M. et al., Synthesis 2001, (3), 468-472; Yadav, LDS et al., Indian J. Chem B. 41 (3), 593-595 (2002); Clark, JE et al., Synthesis (10), 891-894 (1991)].
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyciohexan und Gemische von Cs-Cβ-Alkanen, aromatische Kohlenwasserstoffe wie Benzol, Toluol, o-, n> und p-Xylol, halogenierte Kohlenwasserstoffe wie Methyienchlo- rid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert- Butylmethylether, Dioxan, Anisol und Tetrahydrofuran (THF), Nitrile wie Acetonitri! und Propionitril, Ketone wie Aceton, Methyiθthylketon, Diethylketon und tert- Butylmethyiketon, sowie Dimethylsulfoxid, Dimethylformamid (DMF), Dimethylacetamid (DMA) und N-Methylpyrrolidon (NMP) oder auch in Wasser, besonders bevorzugt sind Methylenchlorid, THF und Wasser.Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-Cβ-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! and propionitrile, 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.
Es können auch Gemische der genannten Lösungsmittel verwendet werden.It is also possible to use mixtures of the solvents mentioned.
Als Basen kommen allgemein anorganische Verbindungen wie Alkalimetafl- und Erdalkalimetallhydroxide wie Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid und Calci- umhydroxid, Alkalimetall- und Erdalkalimetalloxide wie Lithiumoxid, Natriumoxid, Calci- umoxid und Magnesiumoxid, Alkalimetall- und Erdalkalimetallhydride wie Lithiumhyd- rid, Natriumhydrid, Kaliumhydrid und Caiciumhydrid, Alkalimetall- und Erdaikalimetall- carbonate wie Lithiumcarbonat, Kaliumcarbonat und Calciumcarbonat sowie Alkalime- tallhydrogencarbonate wie Natriumhydrogencarbonat, außerdem organische Basen, z.B. tertiäre Amine wie Trimethylamin, Triethylamin, Diisopropylethylamin, N- Methylmorphoiin, und N-Methylpiperidin, Pyridiπ, substituierte Pyπdine wie Collidin, Lutidiπ und 4-Dimethylaminopyridin sowie bicyclische Amine in Betracht. Besonders bevorzugt werden Natriumhydroxid, Triethylamin und Pyridin.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, Pyridiπ, substituted Pyπdine such as collidine, Lutidiπ and 4-dimethylaminopyridine and bicyclic amines into consideration. Particularly preferred are sodium hydroxide, triethylamine and pyridine.
Die Basen werden im allgemeinen in äquimolar Mengen eingesetzt. Sie können aber auch im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden.The bases are generally used in equimolar amounts. But they can also be used in excess or optionally as a solvent.
Die Edukte werden im allgemeinen in äquimolaren Mengen miteinander umgesetzt. Es kann vorteilhaft sein, IV in einem Überschuß bezogen auf V einzusetzen.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.
Die Aufarbeitung und Isolierung der Produkte kann in an sich bekannter Weise erfolgen.The workup and isolation of the products can be done in a conventional manner.
Natürlich können auch in analoger Weise zunächst die Seriπderivate der Formel V mit Aminen der Formel Il zu den entsprechenden Amideπ umgesetzt werden, welche dann mit Heteroarylsäure(derivate)π der Formel IV zu den gewünschten heteroaroyl- substituierten Serin-Amiden der Formel I reagieren.Of course, the Seriπderivate of formula V can be reacted with amines of formula II to the corresponding Amideπ also in an analogous manner, which then react with heteroaryl (derivatives) π of the formula IV to the desired heteroaroyl-substituted serine amides of the formula I.
Die für die Hersteilung der Heteroaroylderivate der Formel III benötigten Serinderivate der Formel V (z.B. mit L1 = Hydroxy oder Ci-Ce-Alkoxy) sind, auch in enantiomeren- und diastereomerenreiner Form, in der Literatur bekannt oder können gemäß der zitierten Literatur hergestellt werden:The serine derivatives of the formula V required for the preparation of the heteroaroyl derivatives of the formula III (for example with L 1 = hydroxy or C 1 -C 6 -alkoxy) are known in the literature, even in enantiomerically and diastereomerically pure form, or can be prepared according to the cited literature :
- durch Kondensation von Glycinenolat-Equivalenten mit Aldehyden oder Ketonen [Blaser, D. et al., Liebigs Ann. Chem. 10, 1067-1078 (1991); Seethaler, T. et al., Liebigs Ann. Chem. 1 , 11-17 (1991); Welteπauer, G. et al., Gazz. Chim. Ital. 81 , 162 (1951 ); Dal!a Croce, P. et al., Heterocycles 52(3), 1337-1344 (2000); Van der Werf, A. W. et al., J. Chern. Soc. Chem. Commuπ. 100, 682-683 (1991); Caddick, S. et al., Tetrahedron 57 (30), 6615-6626 (2001); Owa, T. et al., Chem. Lett. 1 , 83-86 (1988); Alker, D. et al., Tetrahedron 54 (22), 6089-6098 (1998); Rousseau, J. F. et al., J. Org. Chem. 63 (8), 2731-2737 (1998); Saeed, A. et al., Tetrahedron 48 (12),by condensation of glycinenolate equivalents with aldehydes or ketones [Blaser, D. et al., Liebigs Ann. Chem. 10, 1067-1078 (1991); Seethaler, T. et al., Liebigs Ann. Chem. 1, 11-17 (1991); Welteπauer, G. et al., Gazz. Chim. Ital. 81, 162 (1951); Dalia Croce, P. et al., Heterocycles 52 (3), 1337-1344 (2000); Van der Werf, AW et al., J. Chern. Soc. Chem. Commuπ. 100, 682-683 (1991); Caddick, S. et al., Tetrahedron 57 (30), 6615-6626 (2001); Owa, T. et al., Chem. Lett. 1, 83-86 (1988); Alker, D. et al., Tetrahedron 54 (22), 6089-6098 (1998); Rousseau, JF et al., J. Org. Chem. 63 (8), 2731-2737 (1998); Saeed, A. et al., Tetrahedron 48 (12),
2507-2514 (1992); Dong, L et al., J. Org. Chem. 67 (14), 4759-4770 (2002)].2507-2514 (1992); Dong, L et al., J. Org. Chem. 67 (14), 4759-4770 (2002)].
- durch Aminohydroxylierung von Acrylsäure-Derivaten [Zhang, H. X. et al., Tetrahedron Asymmetr. 11(16), 3439-3447 (2000); Fokin, V. V. et al., Angew. Chem. Int, Edit. 40(18), 3455 (2001); Sugiyama, H. et al., Tetrahedron Lett. 43(19), 3489-3492by aminohydroxylation of acrylic acid derivatives [Zhang, H.X. et al., Tetrahedron Asymmetr. 11 (16), 3439-3447 (2000); Fokin, V.V. et al., Angew. Chem. Int. Edit. 40 (18), 3455 (2001); Sugiyama, H. et al., Tetrahedron Lett. 43 (19), 3489-3492
(2002); Bushey, M. L. et al., J. Org. Chem. 64(9), 2984-2985 (1999); Raatz, D. et al., Syniett (12), 1907-1910 (1999)].(2002); Bushey, M.L. et al., J. Org. Chem. 64 (9), 2984-2985 (1999); Raatz, D. et al., Syniett (12), 1907-1910 (1999)].
- durch nukleophile Substitution von Abgangsgruppen in 2-Position von 3-Hydroxy- Propionsäurederivaten [Owa, T. et al., Chem. Lett. (1 1), 1873-1874 (1988); Boger,by nucleophilic substitution of leaving groups in the 2-position of 3-hydroxypropionic acid derivatives [Owa, T. et al., Chem. Lett. (11), 1873-1874 (1988); Boger,
D. L. et al., J. Org. Chem. 57(16), 4331-4333 (1992); Alcaide, B. et al., Tetrahedron Lett. 36(30), 5417-5420 (1995)].D.L. et al., J. Org. Chem. 57 (16), 4331-4333 (1992); Alcaide, B. et al., Tetrahedron Lett. 36 (30), 5417-5420 (1995)].
- durch Kondensation von Aldehyden mit Nukleophilen unter Ausbildung von Oxazo- linen sowie anschließender Hydrolyse [Evans, D. A. et al., Angew. Chem. Int. Edit.- by condensation of aldehydes with nucleophiles to form oxazolines and subsequent hydrolysis [Evans, D.A. et al., Angew. Chem. Int. Edit.
40(10), 1884-1888 (2001); Ito, Y. et al., Tetrahedron Lett. 26(47), 5781 -5784 (1985); Togni, A. et al., J. Organomet. Chem. 381(1), C21 -5 (1990); Longmire, J. M. et al., Organometallics 17(20), 4374-4379 (1998); Suga, H. et al., J. Org. Chem. 58(26), 7397-7405 (1993)].40 (10), 1884-1888 (2001); Ito, Y. et al., Tetrahedron Lett. 26 (47), 5781-5784 (1985); Togni, A. et al., J. Organomet. Chem. 381 (1), C21 -5 (1990); Longmire, J.M. et al., Organometallics 17 (20), 4374-4379 (1998); Suga, H. et al., J. Org. Chem. 58 (26), 7397-7405 (1993)].
- durch oxidative Cyclisierung von 2-Acylamino-Propionsäuredehvaten zu Oxazolinen sowie anschließende Hydrolyse (JP10101655).- By oxidative cyclization of 2-acylamino-Propionsäuredehvaten to oxazolines and subsequent hydrolysis (JP10101655).
- durch Die!s-Alder-Reaktion von Vinyliminen mit Aldehyden zu Oxazinen und an- schließende Hydrolyse [Bongini, A. et al., Tetrahedron Asym. 12(3), 439-454- by the! s-Alder reaction of vinylimines with aldehydes to oxazines and subsequent hydrolysis [Bongini, A. et al., Tetrahedron Asym. 12 (3), 439-454
(2001)].(2001)].
Die für die Herstellung der Heteroaroylderivate der Formel III benötigten Heteroaryl- säure(derivate) der Formel IV können käuflich erworben werden oder können analog zu literaturbekannten Vorschrift über eine Grignard-Reaktion aus dem entsprechenden Halogenid hergestellt werden [z.B. A. Mannschuk et al., Angew. Chem. 100, 299 (1988)].The 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)].
Die Umsetzung der Heteroaroylderivate der Formel Hl mit L1 = Hydroxy bzw. deren Salze mit Aminen der Formel Il zu den gewünschten heteroaroyl-substituierten Seriπ- Amiden der Forme! I erfolgt in Gegenwart eines Aktivierungsreagenz und gegebenenfalls in Gegenwart einer Base üblicherweise bei Temperaturen von O0C bis zum Siede- punkt des Reaktionsgemisches, vorzugsweise 0°C bis 100°C, besonders bevorzugt bei Raumtemperatur in einem inerten organischen Lösungsmittel, [vgl. Perich, J. W., Johns, R. B., J. Org. Chem. 53 (17), 4103-4105 (1988); Somlai, C. et al., Syπthesis (3), 285-287 (1992) ; Gupta, A. et al., J. Chem. Soc. Perkin Trans. 2, 1911 (1990); Guan et al., J. Comb. Chem. 2, 297 (2000)].The reaction of the heteroaroyl derivatives of the formula III with L 1 = hydroxy or their salts with amines of the formula II to give the desired heteroaroyl-substituted Seriπ- amides of the forms! I is carried out in the presence of an activating reagent and optionally in the presence of a base, usually at temperatures of from 0 ° C. to boiling point. point of the reaction mixture, preferably 0 ° C to 100 ° C, more preferably at room temperature in an inert organic solvent, [cf. Perich, JW, Johns, RB, J. Org. Chem. 53 (17), 4103-4105 (1988); Somlai, C. et al., Syllesis (3), 285-287 (1992); Gupta, A. et al., J. Chem. Soc. Perkin Trans. 2, 1911 (1990); Guan et al., J. Comb. Chem. 2, 297 (2000)].
Geeignete Aktivieruπgsreagenzien sind Kondensationsmittel wie z.B. polystyrolgebun- deπes Dicyclohexylcarbodiimid, Diisopropylcarbodiimid, Carbonyldiimidazo!, Chlorko- hleπsäureester wie Methylchloroformiat, Ethylchioroformiat, Isoropylchloroformiat, Iso- butyichloroformiat, sec-Butylchloroforrniat oder Allylchloroformiat, Pivaloylchlorid, PoIy- phosphorsäure, Propanphosphonsäureanhydrid, Bis(2-oxo-3-oxazolidinyl)- phosphoryichlorid (BOPCI) oder Sulfonylchloride wie Methansulfonylchlorid, Toluolsul- fonylchlorid oder Benzolsulfonylchlorid.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.
Geeignete Lösungsmittel sind aiiphatische Kohlenwasserstoffe wie Pentaπ, Hexan, Cyclohexan und Gemische von Cs-Cs-Alkanen, aromatische Kohlenwasserstoffe wie Benzol, Toluol, o-, m- und p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlo- rid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert- Butylmethylether, Dioxan, Aπisol und Tetrahydrofuran (THF), Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert.-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, Aπisol and tetrahydrofuran (THF), nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert.
Butylmethylketoπ, Alkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, π-Butanol und tert.-Butanol, sowie Dimethylsulfoxid, Dimethylformamid (DMF), Dimethylacetamid (DMA) und N-Methylpyrrolidon (NMP) oder auch in Wasser, besonders bevorzugt sind Methylenchlorid, THF, Methanol, Ethanol und Wasser.Butylmethylketoπ, alcohols such as methanol, ethanol, n-propanol, isopropanol, π-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.
Es können auch Gemische der genannten Lösungsmittel verwendet werden.It is also possible to use mixtures of the solvents mentioned.
Als Basen kommen allgemein anorganische Verbindungen wie Alkalimetall- und Erdalkalimetallhydroxide wie Lithiumhydroxid, Natriumhydroxid, Kaüumhydroxid und Calci- umhydroxid, Alkaltmetall- und Erdalkalimetalloxide wie Lithiumoxid, Natriumoxid, Calci- umoxid und Magnesiumoxid, Alkalimetall- und Erdalkalimetallhydride wie Lithiumhydrid, Natriumhydrid, Kaliumhydrid und Calciumhydrid, Aikalimetall- und Erdalkalimetall- carbonate wie Lithiumcarbonat, Kaliumcarbonat und Calciumcarbonat sowie Atkalime- tallhydrogencarbonate wie Natriumhydrogencarbonat, außerdem organische Basen, z.B. tertiäre Amine wie Trimethylamin, Triethylamin, Diisopropylethylamin, N-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-
Methylmorpholin, und N-Methylpiperidin, Pyridin, substituierte Pyridine wie Collidin, Lutidin und 4-Dimethylaminopyridin sowie bicydische Amine in Betracht. Besonders bevorzugt werden Natriumhydroxid, Triethylamin, Ethyldiisopropylamin, N- methylmorphotin und Pyridin.Methylmorpholine, and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicydric amines into consideration. Particularly preferred are sodium hydroxide, triethylamine, ethyldiisopropylamine, N-methylmorphotin and pyridine.
Die Basen werden im allgemeinen in katalytischen Mengen eingesetzt, sie können aber auch äquimolar, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden. Die Edukte werden im allgemeinen in äquimolaren Mengen miteinander umgesetzt. Es kann vorteilhaft sein 11 in einem Überschuß bezogen auf III einzusetzen.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.
Die Aufarbeitung und Isolierung der Produkte kann in an sich bekannter Weise erfolgen.The workup and isolation of the products can be done in a conventional manner.
Die Umsetzung der Heteroaroyϊderivate der Formel III mit L1 = CrCε-Alkoxy mit Ami- nen der Forme! Il zu den gewünschten heteroaroyl-substituierten Serin-Amiden der Forme! I erfolgt üblicherweise bei Temperaturen von O0C bis zum Siedepunkt des Reaktionsgemisches, vorzugsweise 0°C bis 100°C, besonders bevorzugt bei Raumtemperatur in einem inerten organischen Lösungsmittel gegebenenfalls in Gegenwart einer Base [vgl. Kawahata, N1 H. et al., Tetrahedron Lett. 43 (40), 7221-7223 (2002); Taka- hashi, K. et al., J. Org. Chem. 50 (18), 3414-3415 (1985); Lee, Y. et al., J. Am. Chem. Soc. 121 (36), 8407-8408 (1999)].The reaction of the heteroaroy derivatives of the formula III with L 1 = C 1 -C 6 -alkoxy with amines of the forms! II to the desired heteroaroyl-substituted serine amides of the forms! I is usually carried out at temperatures of from 0 ° C to the boiling point of the reaction mixture, preferably 0 ° C to 100 ° C, particularly preferably at room temperature in an inert organic solvent optionally in the presence of a base [cp. Kawahata, N 1 H. et al., Tetrahedron Lett. 43 (40), 7221-7223 (2002); Takahashi, K. et al., J. Org. Chem. 50 (18), 3414-3415 (1985); Lee, Y. et al., J. Am. Chem. Soc. 121 (36), 8407-8408 (1999)].
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Gemische von Cs-Cs-AIkanen, aromatische Kohlenwasserstoffe wie Benzol, Toluol, o-, m- und p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzoi, Ether wie Diethylether, Diisopropylether, tert- Butylmethylether, Dioxan, Aniso! und Tetra hydrofu ran (THF), Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert,- Butylmethylketon, Alkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol und tert.-Butanol, sowie Dimethylsulfoxid, Dimethylformamid (DMF), Dimethylacetamid (DMA) und N-Methylpyrrolidon (NMP) oder auch in Wasser, besonders bevorzugt sind Methylenchlorid, THF, Methanol, Ethanol und Wasser.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! and tetrahydrofuran (THF), nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and dimethyl sulfoxide , Dimethylformamide (DMF), dimethylacetamide (DMA) and N-methylpyrrolidone (NMP) or in water, particularly preferred are methylene chloride, THF, methanol, ethanol and water.
Es können auch Gemische der genannten Lösungsmittel verwendet werden.It is also possible to use mixtures of the solvents mentioned.
Die Umsetzung kann gegebenenfalls in Gegenwart einer Base erfolgen. Als Basen kommen allgemein anorganische Verbindungen wie Alkalimetall- und Erdalkalimetallhydroxide wie Lithiumhydroxid, Natriumhydroxid, Kaiiumhydroxid und Calciumhydroxid, Alkalimetall- und Erdalkalimetalloxide wie Lithiumoxid, Natriumoxid, Calciumoxid und Magnesiumoxid, Alkaltmetall- und Erdalkalimetalihydride wie Lithiumhydrid, Natriumhydrid, Kaliumhydrid und Calciumhydrid, Alkalimetall- und Erdalkaümetallcarbonate wie Lithiumcarbonat, Kaliumcarbonat und Calciumcarbonat sowie Alkalimetallhydrogencar- bonate wie Natriumhydrogencarbonat, außerdem organische Basen, z.B. tertiäre Amine wie Trimethylamin, Triethylamin, Diisopropylethylamin, N-Methylmorpholin, und N- Methylpiperidin, Pyridin, substituierte Pyridine wie Collidin, Lutidin und 4-The reaction may optionally be carried out in the presence of a base. As 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-
Dimethylaminopyridin sowie bicyclische Amine in Betracht. Besonders bevorzugt werden Natriumhydroxid, Triethylamin, Ethyldiisopropylamin, N-methylmorpholin und Pyridin. Die Basen werden im allgemeinen in katalytischen Mengen eingesetzt, sie können a- ber auch äquimolar, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden.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.
Die Edukte werden im allgemeinen in äquimolaren Mengen miteinander umgesetzt. Es kann vorteilhaft sein, I! in einem Überschuß, bezogen auf III einzusetzen.The starting materials are generally reacted with one another in equimolar amounts. It can be beneficial, I! in an excess, based on III use.
Die Aufarbeitung und Isolierung der Produkte kann in an sich bekannter Weise erfol- gen.The workup and isolation of the products can take place in a manner known per se.
Die für die Herstellung der heteroaroyl-substituierten Serin-Amide der Formel I benötigten Amine der Formel Il können käuflich erworben werden.The amines of the formula II required for the preparation of the heteroaroyl-substituted serine amides of the formula I can be purchased.
Verfahren BMethod B
Heteroaroylderivate der Formel IiI mit R4 = Wasserstoff können auch erhalten werden, indem acylierte Glycin-Derivate der Formel VIII, wobei die Acylgruppe eine abspaltbare Schutzgruppe wie Benzyloxycarboπyl (vgl. Villa mit Σ = Benzyl) oder tert-Heteroaroyl derivatives of the formula II with R 4 = hydrogen can also be obtained by reacting acylated glycine derivatives of the formula VIII where the acyl group is a removable protecting group such as benzyloxycarbonyl (compare Villa with Σ = benzyl) or tert-butyl.
Butyloxycarbonyl (vgl. Villa mit ∑ = tert-Butyl) sein kann, mit Carbonylverbindungen VI! zu entsprechenden Aldolprodukten VI kondensiert werden. Anschließend wird die Schutzgruppe abgespaften und das so entstandene Serinderivat der Formel V mit R4 = Wasserstoff mit Heteroarylsäurederivateπ der Formel IV acyliert.Butyloxycarbonyl (see Villa with Σ = tert-butyl) may be, with carbonyl compounds VI! be condensed to corresponding aldol VI. The protecting group is then removed and the resulting serine derivative of the formula V is acylated with R 4 = hydrogen with heteroaryl acid derivatives of the formula IV.
Analog kann auch ein acyliertes Glycin-Derivat der Formel VIII, wobei die Acylgruppe ein substituierter Heteroarolyrest (vgl. VIMb) ist, unter Baseneinfluß mit einer Carboπyl- verbindung VlI zum Heteroaroylderivat III mit R4 = Wasserstoff umgesetzt werden: Analogously, an acylated glycine derivative of the formula VIII where the acyl group is a substituted heteroarol radical (cf., VIMb) can also be reacted under base influence with a carbamoyl compound VI to give the heteroaroyl derivative III with R 4 = hydrogen:
Villa VI V mit R4 = HVilla VI V with R 4 = H
VIIIb II! mit R4 = HVIIIb II! with R 4 = H
L1 steht für eine nucleophil verdrängbare Abgangsgruppe, z.B. für Hydroxy oder CrCe- Alkoxy.L 1 represents a nucleophilically displaceable leaving group, for example for hydroxy or C 1 -C 6 -alkoxy.
L2 steht für eine nucieophil verdrängbare Abgangsgruppe, z.B. für Hydroxy, Halogen, CrCβ-Alkylcarbonyl, Ci-Cε-Alkoxycarbonyl, d-GrAlkylsulfonyl, Phosphoryl oder Iso- ureyl.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.
Die Umsetzung der Glycinderivate VIlI mit Carbonylverbindungen VII zum entspre- chenden Aldolprodukt Vl bzw. Heteroaroylderivat Ml mit R4 = Wasserstoff erfolgt üblicherweise bei Temperaturen von -100°C bis zum Siedepunkt der Reaktionsmischung, bevorzugt -80°C bis 20°C, insbesondere bevorzugt -80°C bis -20°C, in einem inerten organischen Lösungsmittel in Gegenwart einer Base [vgl. J. -F. Rousseau et al., J. Org. Chem. 63, 2731-2737 (1998)].The reaction of the glycine derivatives VIlI with carbonyl compounds VII to the corresponding aldol product Vl or heteroaroyl derivative Ml with R 4 = hydrogen is usually carried out at temperatures from -100 ° C to the boiling point of the reaction mixture, preferably -80 ° C to 20 ° C, particularly preferably -80 ° C to -20 ° C, in an inert organic solvent in the presence of a base [cf. J. -F. Rousseau et al., J. Org. Chem. 63, 2731-2737 (1998)].
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Gemische von Cs-Cs-Alkanen, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p-Xylol, Ether wie Diethylether, Diisopropylether, tert.- Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, sowie Dimethylsulfoxid, Di- methylformamid und Dimethylacetamid, besonders bevorzugt Diethylether, Dioxan und Tetrahydrofuran.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.
Es können auch Gemische der genannten Lösungsmittel verwendet werden.It is also possible to use mixtures of the solvents mentioned.
Als Basen kommen allgemein anorganische Verbindungen wie Alkalimetall- und Erdal- kaümetallhydride wie Lithiumhydrid, Natriumhydrid, Kaliumhydrid und Calciumhydrid, Alkalirnetallamide wie Lithiumdiisopropylamid und Lithiumhexarnethyldisilazid, metallorganische Verbindungen, insbesondere AlkalimetailaJkyle wie Methyllithium, Butylii- thium und Pheπylfithium, sowie Alkalimetall- und Erdaikalimetallalkohoiate wie Natrium- methanolat, Natriumethanolat, Kaliumethanolat, Kalium- tert.-Butanolat, Kalium-tert- Pentanolat und Dimethoxymagnesium, außerdem organische Basen, z.B. tertiäre Amine wie Trimethylamin, Triethylamin, Diisopropylethylamin und N-Methylpiperidin, Pyri- din, substituierte Pyridine wie Collidin, Lutidin und 4-Dimethylaminopyridin sowie bicyc- lische Amine in Betracht. Besonders bevorzugt werden Natriumhydrid, Lithiumhexa- methyldisilazid und Lithiumdiisopropylamid.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. thium and Pheπylfithium, and alkali metal and Erdaikalimetallalkohoiate such as sodium methoxide, sodium, potassium, potassium tert-butoxide, potassium tert-pentoxide and Dimethoxymagnesium, 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 bicyclic amines into consideration. Particular preference is given to sodium hydride, lithium hexamethyldisilazide and lithium diisopropylamide.
Die Basen werden im allgemeinen in äquimolaren Mengen eingesetzt, sie können aber auch katalytisch, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden.The bases are generally used in equimolar amounts, but they can also be used catalytically, in excess or optionally as a solvent.
Die Edukte werden im allgemeinen in äquimoiaren Mengen miteinander umgesetzt. Es kann vorteilhaft sein, die Base und/oder die Carbonylverbindungen VII in einem Über- schuß bezogen auf die Glycinderivate VlIl einzusetzen.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.
Die Aufarbeitung und Isolierung der Produkte kann in an sich bekannter Weise erfolgen.The workup and isolation of the products can be done in a conventional manner.
Die für die Herstellung der Verbindungen I benötigten Glycinderivate der Formel VIII können käuflich erworben werden, sind in der Literatur bekannt [z. B. H. Pessoa- Mahana et al., Synth. Comm. 32, 1437 (2002] oder können gemäß der zitierten Literatur hergestellt werden.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.
Die Abspaltung der Schutzgruppe zu Serinderivaten der Formel V mit R4 = Wasserstoff erfolgt nach literaturbekannten Methoden [vgl. J, -F. Rousseau et al., J. Org. Chem. 63, 2731-2737 (1998) ); J. M. Andres, Tetrahedron 56, 1523 (2000)]; im Fall von Σ = Beπ- zyl durch Hydrogenolyse, bevorzugt durch Wasserstoff und Pd/C in Methanol; im Fall von Σ = tert.-Butyi durch Säure, bevorzugt Salzsäure in Dioxan.The cleavage of the protective group to form serine derivatives of the formula V where R 4 = hydrogen is carried out by methods known from the literature [cf. J, -F. Rousseau et al., J. Org. Chem. 63, 2731-2737 (1998)); JM Andres, Tetrahedron 56, 1523 (2000)]; in the case of Σ = benzyl by hydrogenolysis, preferably by hydrogen and Pd / C in methanol; in the case of Σ = tert-butyl with acid, preferably hydrochloric acid in dioxane.
Die Umsetzung der Serinderivate V mit R4= Wasserstoff mit Heteroarylsäure(derivate)n IV zu Heteroaroylderivaten IiI mit R4 = Wasserstoff erfolgt üblicherweise analog der unter Verfahren A genannten Umsetzung der Serinderivate der Formel V mit Heteroa- rylsaure(derivate)n der Formel III zu Heteroaroylderivaten III.The reaction of the serine derivatives V with R 4 = hydrogen with heteroaryl acid (derivatives) n IV to heteroaroyl derivatives IiI with R 4 = hydrogen is usually carried out analogously to the reaction of the serine derivatives of formula V with heteroaryl acid (derivatives) n of the formula III mentioned under process A. to heteroaroyl derivatives III.
Die Heteroaroylderivate der Formel III mit R4 = Wasserstoff lassen sich anschließend mit Aminen der Forme! Il analog zu Verfahren A zu den gewünschten heteroaroyl- substituierten Serin-Amiden der Formel I mit R4 = Wasserstoff umsetzen, welche dann mit Verbindungen der Formel IX zu heteroaroyl-substituierteπ Serin-Amiden der Formel I derivatisiert werden können [vgl. z.B. Yokokawa, F. et aL, Tetrahedron Lett. 42 (34), 5903-5908 (2001); Arrault, A. et al., Tetrahedron Lett. 43( 22), 4041-4044 (2002)]. Ebenso können die Heteroaroylderivate der Formel III mit R4 = Wasserstoff zunächst mit Verbindungen der Formel IX zu weiteren Heteroaroylderivaten der Forme! III deri- vatisiert werden [vgl. z.B. Troast, D. et al., Org. Lett. 4 (6), 991-994 (2002); Ewing W. et al., Tetrahedron Lett., 30 (29), 3757-3760 (1989); Paulsen, H. et al., Liebigs Ann. Chem. 565 (1987)] und anschließend analog zu Verfahren A mit Aminen der Forme! Il zu den gewünschten heteroaroyl-substituierten Serin-Amiden der Formel I umgesetzt werden:The heteroaroyl derivatives of the formula III where R 4 = hydrogen can then be reacted with amines of the forms! II analogously to process A to the desired heteroaroyl-substituted serine amides of the formula I with R 4 = react hydrogen, which can then be derivatized with compounds of formula IX to heteroaroyl-substituted Serin amides of the formula I [vgl. eg Yokokawa, F. et al., Tetrahedron Lett. 42 (34), 5903-5908 (2001); Arrault, A. et al., Tetrahedron Lett. 43 (22), 4041-4044 (2002)]. Likewise, the heteroaroyl derivatives of formula III with R 4 = hydrogen, first with compounds of formula IX to further Heteroaroylderivaten the forms! III be privatized [cf. eg Troast, D. et al., Org. Lett. 4 (6), 991-994 (2002); Ewing W. et al., Tetrahedron Lett., 30 (29), 3757-3760 (1989); Paulsen, H. et al., Liebigs Ann. Chem. 565 (1987)] and then analogously to process A with amines of the forms! II are converted to the desired heteroaroyl-substituted serine amides of the formula I:
III I mit R4 = H mit R4 = HIII I with R 4 = H with R 4 = H
R4-L3 IX R4-L3 IXR 4 -L 3 IX R 4 -L 3 IX
II
L1 steht für eine nucleophil verdrängbare Abgangsgruppe, z.B. für Hydroxy oder Ci-Cß- Alkoxy.L 1 is a nucleophilically displaceable leaving group, for example for hydroxy or C 1 -C 6 -alkoxy.
L3 steht für eine nucleophil verdräπgbare Abgangsgruppe, z.B. für Halogen, Hydroxy, oder d-Ca-Alkoxy.L 3 is a nucleophilically displaceable leaving group, for example, halogen, hydroxy, or d-Ca-alkoxy.
Die Umsetzung der Heteroaroylderivate der Formel III (gegebenenfalls mit R4 = Wasserstoff) mit Aminen der Formel Il zu heteroaroyi-substituierten Serin-Amiden der Formel I (gegebenenfalls mit R4 = Wasserstoff) erfolgt üblicherweise analog der unter Ver- fahren A geschilderten Umsetzung der Heteroaroylderivate der Formel III mit Aminen der Formel II.The reaction of the heteroaroyl derivatives of the formula III (where appropriate with R 4 = hydrogen) with amines of the formula II to heteroaroyi-substituted serine amides of the formula I (where appropriate with R 4 = hydrogen) is usually carried out analogously to the reaction of the formula A described under process A. Heteroaroyl derivatives of the formula III with amines of the formula II.
Die Umsetzung der Heteroaroylderivate der Formel III mit R4 = Wasserstoff bzw. der heteroaroyl-substituierten Serin-Amide der Formel I mit R4 = Wasserstoff mit Verbin- düngen der Formel IX zu Heteroaroyiderivaten der Forme! III bzw. heteroaroyl- substituierten Serin-Amiden der Forme! I erfolgt üblicherweise bei Temperaturen von 00C bis 100°C, vorzugsweise 10"C bis 50°C, in einem inerten organischen Lösungsmitte! in Gegenwart einer Base [vgl. z.B. Troast, D. et al., Org. Lett. 4 (6), 991-994 (2002); Ewing W. et al., Tetrahedron Lett., 30 (29), 3757-3760 (1989); Paulsen, H. et al., Lie- bigs Ann. Chem. 565 (1987)].The reaction of the heteroaroyl derivatives of the formula III where R 4 = hydrogen or the heteroaroyl-substituted serineamides of the formula I where R 4 = hydrogen with compound of the formula IX to heteroaroyiderivates of the forms! III or heteroaroyl-substituted serine amides of the forms! I is usually carried out at temperatures of 0 0 C to 100 ° C, preferably in the presence of a base 10 "C to 50 ° C, in an inert organic solvent! [See. Eg Troast, D. et al., Org. Lett. 4 (6), 991-994 (2002); Ewing W. et al., Tetrahedron Lett., 30 (29), 3757-3760 (1989); Paulsen, H. et al., Lieutens Ann. Chem. 565 (1987)].
Geeignete Lösungsmittel sind aliphatäsche Kohlenwasserstoffe wie Pentan, Hexan, Cyciohexan und Gemische von Cs-Cs-Alkanen, aromatische Kohlenwasserstoffe wie Toluol, o-, n> und p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Düsopropylether, tert- Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propi- onitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert.-Butyimethylketon, Alkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol und tert.-Butaπol, sowie Dimethylsulfoxid, Dimethylformamid und DimethySacetamid, besonders bevorzugt Dichlormethan, tert.-Butylmethylether, Dioxan und Tetrahydrofuran.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. Butaπol, and dimethyl sulfoxide, dimethylformamide and DimethySacetamid, more preferably dichloromethane, tert-butyl methyl ether, dioxane and tetrahydrofuran.
Es können auch Gemische der genannten Lösungsmittel verwendet werden.It is also possible to use mixtures of the solvents mentioned.
Als Basen kommen allgemein anorganische Verbindungen wie Alkalimetali- und Erdalkalimetallhydroxide wie Lithiumhydroxid, Natriumhydroxid, Kaiiumhydroxid und Calci- umhydroxid, Alkalimetall- und Erdalkalimetalloxide wie Lithiumoxid, Natriumoxid, Caici- umoxid und Magnesiumoxid, Alkalimetall- und Erdalkalimetallhydride wie Lithiumhyd- rid, Natriumhydrid, Kaliumhydrid und Calciumhydrid, Alkalimetallamide wie Lithiuma- mid, Natriumamid und Kaliumamid, Alkalimetall- und ErdalkaümetaNcarbonate wie Lithiumcarbonat, Kaliumcarbonat und Calciumcarbonat sowie Alkalimetall- hydrogencarbonate wie Natriumhydrogencarbonat, metallorganische Verbindungen, insbesondere Alkalimetallalkyle wie Methyllithium, Butyllithium und Phenyllithium, Al- kylmagnesiumhalogenide wie Methylmagnesiumchlorid sowie Aikalimetall- und Erdal- kalimetallalkoholate wie Natriummethanolat, Natriumethanolat, Kaliumethanolat, Kalium- tert.-Butanolat, Kalium-tert.-Pentanolat und Dimethoxymagnesium, außerdem organische Basen, z.B. tertiäre Amine wie Trimethylamin, Triethylamin, Diisopropylethy- lamin und N-Methylpiperidin, Pyridin, substituierte Pyridine wie Coilidin, Lutidin und 4- Dimethylaminopyridin sowie bicyclische Amine in Betracht. Besonders bevorzugt werden Natriumhydroxid, Natriumhydrid und Triethylamin.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, potassium tert-butoxide, potassium tert-pentoxide and dimethoxy magnesium, as well as organic bases, eg tertiary amines such as trimethylamine, triethylamine, Diisopropylethy- lamin and N-methylpiperidine, pyridine, substituted pyridines such as Coilidin, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Particularly preferred are sodium hydroxide, sodium hydride and triethylamine.
Die Basen werden im allgemeinen in äquimoiaren Mengen eingesetzt, sie können aber auchkatalytisch, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet wer- den.The bases are generally used in equimolar amounts, but they can also be used catalytically, in excess or, if appropriate, as solvent.
Die Edukte werden im allgemeinen in äquimoiaren Mengen miteinander umgesetzt. Es kann vorteilhaft sein, die Base und/oder IX in einem Überschuß bezogen auf IEI bzw. I einzusetzen.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.
Die Aufarbeitung und Isolierung der Produkte kann in an sich bekannter Weise erfolgen. Die benötigten Verbindungen der Formel VIII können käuflich erworben werden.The workup and isolation of the products can be done in a conventional manner. The required compounds of formula VIII can be purchased.
Verfahren CMethod C
Heteroaroylderivate der Formet III mit R4 = Wasserstoff können auch erhalten werden, indem Aminomalonyl-Verbindungen der Formel Xt zunächst mit Heteroarylsäu- re(derivate)n der Forme! IV zu entsprechenden N-Acyl-Arninomalonyl-Verbindungen der Formel X acyliert werden und anschließend mit einer Carbonylverbindung der For- mel VII unter Decarboxylierung kondensiert werden:Heteroaroyl derivatives of the formula III with R 4 = hydrogen can also be obtained by first aminomalonyl compounds of the formula Xt with heteroaryl (derivatives) n of the forms! IV are acylated to corresponding N-acyl-Arninomalonyl compounds of formula X and then condensed with a carbonyl compound of the formula VII with decarboxylation:
mit R4 = H with R 4 = H
L1 steht für eine nucleophil verdrängbare Abgangsgruppe, z.B. für Hydroxy oder CrCe- Alkoxy.L 1 represents a nucleophilically displaceable leaving group, for example for hydroxy or C 1 -C 6 -alkoxy.
L2 steht für eine nucleophil verdrängbare Abgangsgruppe, z.B. für Hydroxy, Halogen, Ci-Cβ-Alkylcarbonyl, Ci-Cβ-Alkoxycarbonyl, CrCe-Alkylsuifonyl, Phosphoryl oder Isou- reyl.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.
L4 steht für eine πucleophi! verdrängbare Abgangsgruppe, z.B. für Hydroxy oder d-Cß- Alkoxy.L 4 stands for a πucleophi! displaceable leaving group, for example for hydroxy or C 1 -C 6 -alkoxy.
Die Acylierung der Aminomalonyl-Verbindungen der Formel Xl mit Heteroaryisäu- re(derivate)n der Formel IV zu entsprechenden N-Acyl-Aminomalonyl-Verbindungen der Formel X erfolgt üblicherweise analog der unter Verfahren A genannten Umsetzung der Serinderivate der Formel V mit Heteroarylsäure(derivate)n der Forme! IV zu den entsprechenden Heteroaroylderivaten der Forme! III.The 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.
Die Umsetzung der N-Acyl-Aminoma!ony!-Verbindungen der Formel X mit Carbonyl- verbindungen der Formel VII zu Heteroaroylderivaten der Formel III mit R4 = Wasserstoff erfolgt üblicherweise bei Temperaturen von 0°C bis 1004C, vorzugsweise 10°C bis 50°C, in einem inerten organischen Lösungsmittel in Gegenwart einer Base [vgl. z.B. US 4904674; Heümann, H. et al., üebigs Ann. Chem. 631 , 175-179 (1960)]. Falls L4 bei den N-Acyi-Aminomalonyl-Verbindungen der Formel X für CrCε-Akoxy steht, ist es von Vorteil, L4 zunächst durch Esterverseifung [z.B. Hellmann, H. et al., Liebigs Ann. Chem. 631 , 175-179 (1960)] in eine Hydroxygruppe zu überführen.The reaction of the N-acyl-Aminoma! Ony! Compounds of the formula X with carbonyl compounds of formula VII to Heteroaroylderivaten of formula III with R 4 = hydrogen is usually carried out at temperatures from 0 ° C to 100 4 C, preferably 10 ° C. to 50 ° C, in an inert organic solvent in the presence of a base [see. eg US 4904674; Heümann, H. et al., Ann. Chem. 631, 175-179 (1960)]. If 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.
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Gemische von Cs-Ca-Alkanen, aromatische Kohlenwasserstoffe wie Toluoi, o-, m- und p-Xyiol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert.-Butylmethyl- ether, Dioxan, Aniso! und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, Keto- ne wie Aceton, Methylethylketon, Diethylketon und tert.-Butyimethylketon, Alkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol und tert.-Butanol, sowie Di- methylsulfoxid, Dimethylformamid und Dimethylacetamid, besonders bevorzugt Diethylether, Dioxan und Tetrahydrofuran.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! 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 dimethylsulfoxide, Dimethylformamide and dimethylacetamide, more preferably diethyl ether, dioxane and tetrahydrofuran.
Es können auch Gemische der genannten Lösungsmittel verwendet werden.It is also possible to use mixtures of the solvents mentioned.
Als Basen kommen allgemein anorganische Verbindungen wie Alkalimetall- und Erdalkalimetallhydroxide wie Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid und Calci- umhydroxid, Alkalimetall- und Erdalkalimetalloxide wie Lithiumoxid, Natriumoxid, Calci- umoxid und Magnesiumoxid, Alkalimetall- und Erdalkalimetallhydride wie Lithiumhydrid, Natriumhydrid, Kaliumhydrid und Calciumhydrid, Alkalimetallamide wie Lithiuma- mid, Natriumamid und Kaliumamid, Alkalimetall- und Erdalkalimetallcarbonate wie Lithiumcarbonat, Kaüumcarbonat und Calciumcarbonat sowie Alkalimetall- hydrogencarbonate wie Natriumhydrogencarbonat, metallorganische Verbindungen, insbesondere Alkalimetallalkyle wie Methyllithium, Butyllithium und Phenyliithium, Al- kylmagnesiumhalogenide wie Methylmagnesiumchlorid sowie Alkalimetall- und Erdal- kalimetallalkoholate wie Natriummethanolat, Natriumethanolat, Kaüumethanolat, Kalium- tert.-Butanolat, Kalium-tert.-Pentanolat und Dimethoxymagnesium, außerdem organische Basen, z.B. tertiäre Amine wie Trimethylamin, Triethyiamin, Diisopropylethy- lamin und N-Methylpiperidin, Pyridin, substituierte Pyridine wie Coüidin, Lutidin und 4- Dimethylaminopyridin sowie bicyclische Amine in Betracht. Besonders bevorzugt werden Triethyiamin und Diisopropylethylamin.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. kalimetallalkoholate such as sodium, sodium, Kaüumethanolat, potassium tert-butoxide, potassium tert-pentoxide and Dimethoxymagnesium, also 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.
Die Basen werden im allgemeinen in katalytischen Mengen eingesetzt, sie können a- ber auch äquimolar, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden.The bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as solvent.
Die Edukte werden im allgemeinen in äquimolaren Mengen miteinander umgesetzt. Es kann vorteilhaft sein, die Base in einem Überschuß bezogen auf X einzusetzen.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.
Die Aufarbeitung und Isolierung der Produkte kann in an sich bekannter Weise erfolgen. Die so erhaltenen Heteroaroylderivate der Formel IM mit R4 = Wasserstoff können anschließend gemäß den voranstehend genannten Verfahren A bzw. B zu den gewünschten heteroaroyl-substituierteπ Serϊn-Amiden der Formel I umgesetzt werden.The workup and isolation of the products can be done in a conventional manner. The heteroaroyl of the formula III thus obtained with R can be the above-mentioned method A or B converted to the desired heteroaroyl-substituierteπ Serϊn-amides of the formula I 4 = hydrogen subsequently to the invention.
Die benötigten Aminomalonyl-Verbindungen der Forme! Xl können käuflich erworben werden bzw. sind in der Literatur bekannt [z. B. US 4904674; Hellmann, H. et al„ Ue- bigs Ann. Chem. 631 , 175-179 (1960)] oder können gemäß der zitierten Literatur hergestellt werden.The required aminomalonyl compounds of the forms! XI can be purchased or are known in the literature [eg. US 4904674; Hellmann, H. et al., "U- bigs Ann. Chem. 631, 175-179 (1960)] or can be prepared according to the cited literature.
Die benötigten heteroycüschen Verbindungen der Forme! VII können käuflich erworben werden.The required heterozygous compounds of the forms! VII can be purchased.
Verfahren DMethod D
Heteroaroylderivate der Formel HI mit R4 und R5 = Wasserstoff können auch erhalten werden, indem Ketoverbindungen der Formel XIlI zunächst mit Heteroaryisäu- re(derivate)n der Formel IV zu entsprechenden N-Acyt-Ketoverbindungen der Formel XlI acyliert werden und anschließend die Ketogruppe reduziert wird [Girard A, Tetrahedron Lett. 37(44),7967-7970(1996); Nojori R., J. Am. Chem. Soc. 11 1(25),9134- 9135(1989); Schmidt U., Synthesis (12),1248-1254 (1992); Bolhofer, A.; J. Am. Chem.Heteroaroyl derivatives of the formula III with R 4 and R 5 = hydrogen can also be obtained by first keto compounds of the formula XIII being 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. 11 1 (25), 9134-9135 (1989); Schmidt U., Synthesis (12), 1248-1254 (1992); Bolhofer, A .; J. Am. Chem.
mit R4, R5 = H with R 4 , R 5 = H
L1 steht für eine nucleophil verdrängbare Abgangsgruppe, z.B. für Hydroxy oder CrCε- Alkoxy.L 1 is a nucleophilically displaceable leaving group, for example for hydroxy or C 1 -C 6 -alkoxy.
L2 steht für eine nucleophil verdrängbare Abgaπgsgruppe, z.B. für Hydroxy, Halogen, d-Ce-Alkylcarbonyl, Ci-Ce-Alkoxycarbonyl, C-i-Ce-Alkylsulfonyl, Phosphoryl oder Isou- reyt.L 2 is a nucleophilically displaceable Abgaπgsgruppe, for example, hydroxy, halogen, d-Ce-alkylcarbonyl, Ci-Ce-alkoxycarbonyl, Ci-Ce-alkylsulfonyl, phosphoryl or Isory- ly.
Die Acylierung der Ketoverbindungen der Formel XII! mit Heteroarylsäure(derivate)n der Formel IV zu N-Acy!-Ketoverbindungen der Forme! XII erfolgt üblicherweise analog der unter Verfahren A genannten Umsetzung der Serinderivate der Formel V mit Hete- roary!säure(derivate)n der Formel IV zu den entsprechenden Heteroaroylderivaten der Formel III. Die für die Herstellung der Heteroaroyidθrivate der Formel III mit R4 und Rs = Wasserstoff benötigten Ketoverbindungen der Formel XiII sind in der Literatur bekannt [WO 02/083111; Boto, A. et al., Tetrahedron Letters 39 (44), 8167-8170 (1988); von Geldern, T. et al., J. of Med. Chem. 39(4), 957-967 (1996); Singh, J. et al., Tetrahe- dronLetters 34 (2), 211 -214 (1993); ES 2021557; Maeda, S: et al., Chem. & Pharm. Bull. 32 (7), 2536-2543 (1984); Ito, S. et al., J. of Biol. 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)] oder können gemäß der zitierten Literatur hergestellt werden.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. The keto compounds of the formula XiII required for the preparation of the heteroarloyide derivatives of the formula III where R 4 and R s = hydrogen are known in the literature [WO 02/083111; Boto, A. et al., Tetrahedron Letters 39 (44), 8167-8170 (1988); von Geldern, T. et al., J. of Med. Chem. 39 (4), 957-967 (1996); Singh, J. et al., Tetrahedral Letters 34 (2), 211-214 (1993); ES 2021557; Maeda, S: et al., Chem. & Pharm. Bull. 32 (7), 2536-2543 (1984); Ito, S. et al., J. of Biol. 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.
Die Reduktion der N-Acyl-Ketoverbindungen der Formel XII zu Heteroaroyiderivaten der Formel III mit R4 und R5 = Wasserstoff erfolgt üblicherweise bei Temperaturen von 0°C bis 100°C, vorzugsweise 20°C bis 80"C, in einem inerten organischen Lösungsmittel in Gegenwart eines Reduktionsmittels.The reduction of the N-acyl keto compounds of the formula XII to heteroaryl derivatives of the formula III with R 4 and R 5 = hydrogen is usually carried out at temperatures of 0 ° C to 100 ° C, preferably 20 ° C to 80 "C, in an inert organic Solvent in the presence of a reducing agent.
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Gemische von Cs-Cs-Alkaπen, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbeπzol, Ether wie Diethylether, Diisopropylether, tert.-Butyl- methylether, Dioxan, Aniso! und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert.-Butylmethylketon, Alkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol und tert.-Butanof, sowie Dimethylsulfoxid, Dimethylformamid und Dimethylacetamid, besonders bevorzugt Toluol, Methylenchlorid oder tert.-Butylmethylether.Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-Cs-Alkaπen, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and Chlorbeπzol, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, aniso! 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-butanof, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably toluene, methylene chloride or tert-butyl methyl ether.
Es können auch Gemische der genannten Lösungsmittel verwendet werden.It is also possible to use mixtures of the solvents mentioned.
Als Reduktionsmittel eignen sich z.B. Natriumborhydrid, Zinkborhydrid, Natriumcyano- borhydrid, Litium-triethylborhydrid (Superhydrid®), Litium-tri-sec.butylborhydrid (L- Sefectrid®), Utiumaluminiumhydrid oder Boran [vgl. z.B. 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)],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)],
Weiterhin kann die Reduktion auch in Gegenwart von Wasserstoff und eines Katalysa- tor erfolgen. Als Katalysatoren eignen sich z, B. [Ru(BINAP)CI2] oder Pd/C [vgl. Noyori, R. et al., J. Am. Chem. Soc. 111 (25), 9134-9135 (1989); Bolhofer, A. et al., J. Am. Chem. Soc. 75, 4469 (1953)]. Daneben kann die Reduktion auch Gegenwart eines Mikroorganismus erfolgen. Als Mikroorganismus eignet sich z.B. Saccharomyces Rouxii '[vgl. Soukup, M. et al., HeIv, Chim. Acta 70, 232 (1987)].Furthermore, 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)]. In addition, the reduction can also take place the presence of a microorganism. As a microorganism, for example, Saccharomyces Rouxii ' [see. Soukup, M. et al., HeIv, Chim. Acta 70, 232 (1987)].
Die N-Acyl-Ketoverbindungen der Formel XIi und das jeweilige Reduktionsmittel werden im allgemeinen in äquimolaren Mengen miteinander umgesetzt. Es kann vorteilhaft sein, das Reduktionsmittel in einem Überschuß bezogen auf XII einzusetzen.The 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.
Die Aufarbeitung und Isolierung der Produkte kann in an sich bekannter Weise erfolgen.The workup and isolation of the products can be done in a conventional manner.
Die so erhaltenen Heteroaroylderivate der Formel IiI mit R4 und R5 = Wasserstoff können anschließend gemäß den voranstehend genannten Verfahren A und B zu den gewünschten heteroaroyl-substituierten Serin-Amiden der Formel I umgesetzt werden.The heteroaroyl derivatives of the formula IiI with R 4 and R 5 = hydrogen thus obtained can then be reacted according to the abovementioned processes A and B to give the desired heteroaroyl-substituted serineamides of the formula I.
Verfahren EMethod E
Heteroaroylderivate der Forme! III mit R4 = Wasserstoff und R6 = -C(OH)R1R" können auch erhalten werden, indem Vinylglycine der Formel XIV mit einem Oxidationsmittel wie Osmiumtetroxid oder Permanganat dihydroxyliert werden:Heteroaroyl derivatives of the forms! III with R 4 = hydrogen and R 6 = -C (OH) R 1 R "can also be obtained by dihydroxylating vinylglycines of formula XIV with an oxidizing agent such as osmium tetroxide or permanganate:
XIV mit R4 = H und R^ = -C(OH)R1R"XIV with R 4 = H and R ^ = -C (OH) R 1 R "
L1 steht für eine nucleophil verdrängbare Abgangsgruppe, z.B. für Hydroxy oder Ci-Ce- Alkoxy.L 1 is a nucleophilically displaceable leaving group, for example for hydroxy or C 1 -C 6 -alkoxy.
R' steht für Wasserstoff, Ci-Cβ-Alkyl, d-Ce-Halogenalkyl, CrCβ-Hydroxyalkyl, Phenyl oder CrCö-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.
R" steht für Wasserstoff, Ci-C6-Alkyl, d-Ce-Halogenalkyl, Ci-C6-Hydroxyalkyl, Phenyl oder d-Ce-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.
Diese Umsetzung erfolgt üblicherweise bei Temperaturen von -78°C bis zum Siedepunkt der Reaktionsmischung, bevorzugt -10°C bis 120°C, insbesondere bevorzugt 0°C bis 50°C, in einem inerten organischen Lösungsmittel in gegebenenfalls in Gegenwart eines Reoxidationsmittels wie z.B. N-Methylmorpholin-N-oxid (D. Johnson et al., Tetrahedron 2000, 56, 5, 781). Geeignete Lösungsmittel sind halogenierte Kohlenwasserstoffe wie Methyleπchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert- Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrilβ wie Acetonitril und Propi- onitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert.-Butyimethylketon, Alkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol und tert.-Butanol, sowie Dimethylsulfoxid, Dimethylformamid, Dimethylacetamid und Wasser; besonders bevorzugt Aceton oder Wasser.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). 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.
Es können auch Gemische der genannten Lösungsmittel verwendet werden.It is also possible to use mixtures of the solvents mentioned.
Die Edukte werden im allgemeinen in äquimolaren Mengen miteinander umgesetzt. Es kann vorteilhaft sein, das Oxidationsmittel in einem Überschuß bezogen auf XIV einzusetzen.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.
Die Reaktionsgemische werden in üblicher weise aufgearbeitet, z.B. durch Mischen mit Wasser, Trennung der Phasen und gegebenenfalls chromatographische Reinigung der Rohprodukte. Die Zwischen- und Endprodukte fallen z.T. in Form zäher Öle an, die unter vermindertem Druck und bei mäßig erhöhter Temperatur von flüchtigen Anteilen befreit oder gereinigt werden. Sofern die Zwischen- und Endprodukte als Feststoffe erhalten werden, kann die Reinigung auch durch Umkristallisieren oder Digerieren erfolgen.The 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.
Die für die Herstellung der Heteroaroylderivate der Formel III mit R4 = Wasserstoff und R6 = -C(OH)R1R" benötigten Vinylglycine der Formel XIV sind in der Literatur bekannt [ D. B. Berkowitz et al., J. Org. Chem. 2000, 65, 10, 2907; M. Koen et al., J. Chem. Soc. Perkin I 1997, 4, 487] oder können gemäß der zitierten Literatur hergestellt werden.The vinylglycines of the formula XIV required for the preparation of the heteroaroyl derivatives of the formula III where R 4 = hydrogen and R 6 = -C (OH) R 1 R "are known in the literature [DB Berkowitz et al., J. Org. Chem. 2000, 65, 10, 2907, M. Koen et al., J. Chem. Soc. Perkin I 1997, 4, 487] or can be prepared according to the cited literature.
Die Heteroaroylderivate der Formel IH mit R4 = Wasserstoff und R6 = -C(OH)R1R" lassen sich anschließend mit Aminen der Formel Il analog zu Verfahren A zu den gewünschten heteroaroyl-substituierten Serin-Amiden der Formel I mit R4 = Wasserstoff und R6 = -C(OH)R1R" umsetzen, welche dann mit Verbindungen der Forme! IX zu hete- roaroylsubstituierten Serin-Amiden der Formel I mit Rs = -C(OR4)R'R" derivatisiert wer- den können [vgl. z.B. Yokokawa, F. et al., Tetrahedron Lett. 42 (34), 5903-5908 (2001); Arrault, A. et al., Tetrahedron Lett. 43( 22), 4041-4044 (2002)];The heteroaroyl derivatives of the formula IH where R 4 = hydrogen and R 6 = -C (OH) R 1 R "can then be reacted with amines of the formula II analogously to process A to give the desired heteroaroyl-substituted serineamides of the formula I with R 4 = Hydrogen and R 6 = -C (OH) R 1 R "react, which then with compounds of the forms! IX can be derivatized to heteroaroyl-substituted serine amides of the formula I with R s = -C (OR 4 ) R'R "[cf., for example, Yokokawa, F. et al., Tetrahedron Lett., 42 (34), 5903-5908 (2001); Arrault, A. et al., Tetrahedron Lett. 43 (22), 4041-4044 (2002)];
ebenso können die Heteroaroylderivate der Formei IH mit R4 = Wasserstoff zunächst mit Verbindungen der Formel IX zu weiteren Heteroaroyiderivaten der Formel III mit Rs = -C(OR4)R'R" analog Verfahren B derivatisiert werden [vgl. z.B. Troast, D. et al., Org. Lett. 4 (6), 991-994 (2002); Ewing W. et al., Tetrahedron Lett., 30 (29), 3757-3760 (1989); Paulsen, H. et al., Liebigs Ann. Chem. 565 (1987)] und anschließend analog zu Verfahren A mit Aminen der Formel Il zu den gewünschten heteroaroylsubstituierten Serin-Amideπ der Formel I mit R6 = -C(OR4)R'R" umgesetzt werden:likewise, the heteroaroyl derivatives of the formula IH with R 4 = hydrogen can first be derivatized with compounds of the formula IX to form further heteroarloyer derivatives of the formula III where R s = -C (OR 4 ) R'R "analogously to process B [cf., for example, Troast, D. et al., Org. Lett 4 (6), 991-994 (2002); Ewing W. et al., Tetrahedron Lett., 30 (29), 3757-3760 (1989); Paulsen, H. et al ., Liebigs Ann. Chem. 565 (1987)] and then analogously to Process A with amines of the formula II to the desired heteroaroyl-substituted serine Amideπ of the formula I with R 6 = -C (OR 4 ) R'R "be implemented:
III I mit R4 = H und R6 = -C(OH)R1R" mit R4 = H und R6 = -C(OH)R1R"III I with R 4 = H and R 6 = -C (OH) R 1 R "with R 4 = H and R 6 = -C (OH) R 1 R"
I mit R6 = -C{0R4)R'R" mit R6 = -C(OR4)R'R"I with R 6 = -C {0R4) R'R "with R 6 = -C (OR 4 ) R'R"
L1 steht für eine nucleophtl verdrängbare Abgangsgruppe, z.B. für Hydroxy oder Ci-Ce- Alkoxy.L 1 is a nucleophilic displaceable leaving group, for example for hydroxy or C 1 -C 6 -alkoxy.
L3 steht für eine nucleophil verdrängbare Abgangsgruppe, z.B. für Halogen, Hydroxy, oder Ci-Cδ-Alkoxy.L 3 is a nucleophilically displaceable leaving group, for example halogen, hydroxy, or C 1 -C 6 -alkoxy.
R' steht für Wasserstoff, d-Cβ-Aikyl, d-C6-Halogenalkyl, Ci-Ce-Hydroxyalkyl, Phenyl oder C 1 -Ce-Al koxycarboπyl .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" steht für Wasserstoff, Ci-C6-Alkyl, d-Cβ-Halogenalky], Ci-Cβ-Hydroxyalkyl, Phenyl oder Ci-Ce-Alkoxycarbonyl.R "is hydrogen, Ci-C 6 alkyl, d-Cβ-Halogenalky], Ci-C β hydroxyalkyl, phenyl or Ci-Ce-alkoxycarbonyl.
Verfahren FMethod F
Heteroaroylderivate der Formel III mit R4 = Wasserstoff und R6 = -C(Nuc)R'R" können auch erhalten werden, indem Vinylglycine der Formel XIV mit einem Epoxidierungs- reagenz zu Epoxyglycinen der Formel XV epoxydiert werden und anschließend eine nucleophile Epoxidöffnung erfolgt: Heteroaroyl derivatives of the formula III where R 4 = hydrogen and R 6 = -C (Nuc) R'R "can also be obtained by epoxydating vinylglycines of the formula XIV with an epoxidation reagent to form epoxyglycines of the formula XV, followed by nucleophilic epoxide opening :
XiV XV mit R4 = H und R6 = -C(Nuc)R'R"XiV XV with R 4 = H and R 6 = -C (Nuc) R'R "
L1 steht für eine nucleophil verdrängbare Abgangsgruppe, z.B. für Hydroxy oder CrCβ- Alkoxy.L 1 is a nucleophilically displaceable leaving group, for example for hydroxy or CrCβ alkoxy.
R' steht für Wasserstoff, d-Ce-Alkyl, Ci-C6-Halogenalkyl, CrC6-Hydroxyalkyl, Pheny! oder Ci-Cβ-Alkoxycarboπyl.R 'represents hydrogen, d-Ce-alkyl, Ci-C 6 haloalkyl, C r C 6 hydroxyalkyl, phenyl- or Ci-Cβ-Alkoxycarboπyl.
R" steht für Wasserstoff, d-Ce-Alkyl, Ci-C6-Halogenaikyl, CrC6-Hydroxyalkyl, Phenyl oder Ci-Ce-Alkoxycarbonyl. Nuc~M+ steht beispielsweise für Thiolate wie z.B. Natriumthiophenolat, Alkoholate wie Kaliumphenolat, oder Amide wie Natriumimidazolat.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.
Die Epoxidierung erfoigt üblicherweise bei Temperaturen von -78°C bis zum Siede- punkt der Reaktionsmischung, bevorzugt -20°C bis 50°C, insbesondere bevorzugt O'C bis 30°C, in einem inerten organischen Lösungsmittel [vgl. P. Meffre et ai., Tetrahedron Lett. 1990, 31 , 16, 2291.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.
Als Epoxidierungsreagenzien finden Verwendung Persäuren und Peroxide (z.B. Me- tachlorperbenzoesäure, Peressigsäure, Dimethyldioxiran» Wasserstoffperoxid).As epoxidizing reagents find use peracids and peroxides (eg, Me tachlorperbenzoesäure, peracetic acid, dimethyldioxirane » hydrogen peroxide).
Geeignete Lösungsmittel sind halogenierte Kohlenwasserstoffe wie Methyienchlorid, Chloroform und Chlorbenzol, Alkohole wie Methanol, Ethanol, n-Propano!, Isopropanol, n-Butanol und tert.-Butanol, sowie Wasser, besonders bevorzugt halogenierte Kohlenwasserstoffe und Wasser.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.
Es können auch Gemische der genannten Lösungsmittel verwendet werden.It is also possible to use mixtures of the solvents mentioned.
Die Edukte werden im allgemeinen in äquimolaren Mengen miteinander umgesetzt. Es kann vorteilhaft sein, das Epoxidierungsmittel in einem Überschuß bezogen auf XIV einzusetzen.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.
Die Reaktionsgemische werden in üblicher Weise aufgearbeitet, z.B. durch Mischen mit Wasser, Trennung der Phasen und gegebenenfalls chromatographiεche Reinigung der Rohprodukte. Die Zwischen- und Endprodukte fallen z.T. in Form zäher Öie an, die unter vermindertem Druck und bei mäßig erhöhter Temperatur von flüchtigen Anteilen befreit oder gereinigt werden. Sofern die Zwischen- und Endprodukte als Feststoffe erhalten werden, kann die Reinigung auch durch Umkristallisieren oder Digerieren erfolgen.The reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and optionally chromatographiεche 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.
Die für die Herstellung der Heteroaroylderivate der Formel ill mit R4 = Wasserstoff und R6 = -C(OH)R1R" benötigten Vinylglycine der Formel XIV sind in der Literatur bekannt [ D. B. Berkowitz et al., J. Org. Chem. 2000, 65, 10, 2907; M. Koen et al., J. Chem. Soc. Perkin I 1997, 4, 487] oder können gemäß der zitierten Literatur hergestellt werden.The vinylglycines of the formula XIV required for the preparation of the heteroaroyl derivatives of the formula III where R 4 = hydrogen and R 6 = -C (OH) R 1 R "are known in the literature [DB Berkowitz et al., J. Org. Chem. 2000, 65, 10, 2907, M. Koen et al., J. Chem. Soc. Perkin I 1997, 4, 487] or can be prepared according to the cited literature.
Die Epoxidöffnung erfolgt üblicherweise bei Temperaturen von ~78°C bis zum Siedepunkt der Reaktionsmischung, bevorzugt -20°C bis 100°C, insbesondere bevorzugt O0C bis 50'C, in einem inerten organischen Lösungsmitte! gegebenenfalls in Gegenwart eines Katalysators [ vgl. P. Meffre et al., Tetrahedron Lett. 1990, 31 , 16, 2291; M, R. Paleo et al., J. Org. Chem. 2003, 68, 1 , 130].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].
Geeignete Lösungsmittel sind Alkohole wie Methanol, Ethanol, n-Propanol, Isopropa- nol, n-Butanol und tert. -Sutanol, sowie Dimethylsulfoxid, Dimethylformamid und Di- methylacetamid und Wasser, besonders bevorzugt Methanol und Wasser.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.
Es können auch Gemische der genannten Lösungsmittel verwendet werden.It is also possible to use mixtures of the solvents mentioned.
Als saure Katalysatoren finden Lewis-Säuren wie Bortrifluorid, Aluminiumtrtchloräd, Ei- sen-lll-chlorid, Zinπ-IV-chlorid, Titan-IV-chlorid, Zink-ll-chlorid und Magnesiumperchlo- rat Verwendung.As acidic catalysts are Lewis acids such as boron trifluoride, Aluminiumtrtchloräd, iron-lll-chloride, Zinπ-IV-chloride, titanium-IV-chloride, zinc-II-chloride and Magnesiumperchlo- rat use.
Der Katalysator wird üblicher weise in einem Mengenverhältnis von 1 bis 100 mol%, bevorzugt 1 bis 10 mo!% bezogen auf die Verbindung XV eingesetzt.The catalyst is usually used in a ratio of 1 to 100 mol%, preferably 1 to 10 mo!% Based on the compound XV.
Die Edukte werden im allgemeinen in äquimolaren Mengen miteinander umgesetzt. Es kann vorteilhaft sein, NuC-M+ in einem Überschuß bezogen auf XV einzusetzen.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.
Die Reaktionsgemische werden in üblicher weise aufgearbeitet, z.B. durch Mischen mit Wasser, Trennung der Phasen und gegebenenfalls chromatographische Reinigung der Rohprodukte. Die Zwischen- und Endprodukte fallen z.T. in Form zäher Öle an, die unter vermindertem Druck und bei mäßig erhöhter Temperatur von flüchtigen Anteilen befreit oder gereinigt werden. Sofern die Zwischen- und Endprodukte als Feststoffe erhalten werden, kann die Reinigung auch durch Umkristallisieren oder Digerieren er- folgen. Die Heteroaroylderivate der Forme! i Il mit R4 = Wasserstoff und R6 = -C(Nuc)R'R" lassen sich anschließend mit Aminen der Formel Il analog zu Verfahren A zu den gewünschten benzσylsubstituierten Serin-Amiden der Formel I mit R4 = Wasserstoff und R6 = -C(Nuc)R'R" umsetzen, weiche dann mit Verbindungen der Formel IX zu heteroa- royl-substituierten Serin-Amiden der Formel I mit R6 = -C(Nuc)R'R" derivatisiert werden können [vgl. z.B. Yokokawa, F. et al., Tetrahedron Lett. 42 (34), 5903-5908 (2001); Arrault, A. et al., Tetrahedron Lett. 43( 22), 4041 ^044 (2002)];The 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! i II with R 4 = hydrogen and R 6 = -C (Nuc) R'R "can then be reacted with amines of the formula II analogously to process A to give the desired benzσylsubstituierten serine amides of formula I with R 4 = hydrogen and R 6 = -C (Nuc) R'R ", which can then be derivatized with compounds of the formula IX to heteroaroyl-substituted serine amides of the formula I with R 6 = -C (Nuc) R'R" [cf. For example, Yokokawa, F. et al., Tetrahedron Lett., 42 (34), 5903-5908 (2001), Arrault, A. et al., Tetrahedron Lett., 43 (22), 4041-4044 (2002)];
ebenso können die Heteroaroylderivate der Forme! III mit R4 = Wasserstoff zunächst mit Verbindungen der Forme! IX zu weiteren Benzoylderivaten der Formel \\\ mit R6 = -C(Nuc)R'R" analog Verfahren B derivatisiert werden [vgl. z.B. Troast, D. et al., Org. Lett. 4 (6), 991 -994 (2002); Ewing W. et al., Tetrahedron Lett., 30 (29), 3757-3760 (1989); Paulsen, H. et al., Liebigs Ann. Chem. 565 (1987)] und anschließend analog zu Verfahren A mit Aminen der Formel I! zu den gewünschten heteroaroylsubstituierten Serin-Ami umgesetzt werden:likewise, the heteroaroyl derivatives of the forms! III with R 4 = hydrogen first with compounds of the forms! IX to give further benzoyl derivatives of the formula I with R 6 = -C (Nuc) R'R "analogously to process B [cf., for example, Troast, D. et al., Org. Lett. 4 (6), 991] 994 (2002); Ewing W. et al., Tetrahedron Lett., 30 (29), 3757-3760 (1989); Paulsen, H. et al., Liebigs Ann. Chem. 565 (1987)] and then analogously to Process A with amines of the formula I! To give the desired heteroaroyl-substituted serine amines:
mit R4 = H und R6 = -C(Nuc)R'R" mit R4 = H und R6 = -C(Nuc)R'R"with R 4 = H and R 6 = -C (Nuc) R'R "with R 4 = H and R 6 = -C (Nuc) R'R"
R4-L3 IX R4-L3 iXR 4 -L 3 IX R 4 -L 3 iX
III I mit R6 = -C(NUC)R1R" mit R6 = -C(Nuc)R'R"III I with R 6 = -C (NUC) R 1 R "with R 6 = -C (Nuc) R'R"
L1 steht für eine nucleophil verdrängbare Abgangsgruppe, z.B. für Hydroxy oder Ci-Cε-L 1 is a nucleophilically displaceable leaving group, for example for hydroxy or C 1 -C 8
Alkoxy. L3 steht für eine nucleophil verdräπgbare Abgangsgruppe, z.B. für Halogen, Hydroxy, oder Ci-Ce-Alkoxy.Alkoxy. L 3 is a nucleophilically displaceable leaving group, for example halogen, hydroxy, or C 1 -C 6 -alkoxy.
R' steht für Wasserstoff, CrC6-Alkyl, d-Cβ-Halogenalkyl, CrC6-Hydroxyalkyl, Phenyi oder Ci-Cβ-Alkoxycarbonyl.R 'is hydrogen, -C 6 alkyl, d-Cβ-haloalkyl, C r C 6 hydroxyalkyl, phenyl or Ci-Cβ-alkoxycarbonyl.
R" steht für Wasserstoff, C1-C6-AIkVl, d-Ce-Halogenalkyf, CrC3-Hydroxyalky1, Phenyi oder d-Cs-Alkoxycarbonyl. Nuc~M+ steht beispielsweise für Thiolate wie z.B. Natriumthiophenolat, AJkoholate wie Kaliumphenolat, oder Amide wie Natriumimidazolat.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.
Heteroaroyiderivate der Formel IIIHeteroaroyido derivatives of the formula III
wobei A, R1 sowie R4, R5 und R6 die voanstehend genannten Bedeutungen haben und L1 für Hydroxy oder CrCe-Alkoxy steht, sind ebenfalls ein Gegenstand der vorliegenden Erfindung.where A, 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.
Die besonders bevorzugten Ausfϋhrungsformen der Zwischenprodukte in Bezug auf die Variablen entsprechen denen der Reste A, R1 sowie R4 bis R6 der Formel i.The particularly preferred embodiments of the intermediates with respect to the variables correspond to those of the radicals A, R 1 and R 4 to R 6 of the formula i.
Besonders bevorzugt werden Heteroaroyiderivate der Forme! III, in derParticularly preferred are heteroaroyido derivatives of the forms! III, in the
A 5- oder 6-gliedriges Heteroaryl ausgewählt aus der Gruppe Thienyl, Furyl, Pyra- zolyl, Imidazolyi, Thiazolyl, Oxazolyl und Pyridyl; wobei die genannten Heteroarylreste partiell oder vollständig halogeniert sein können und/oder 1 bis 3 Reste aus der Gruppe Ci-CB-Alkyl, C3-Ce-Cycloalkyl, und d-Ce-Halogenalkyl tragen können; R1 Wasserstoff;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;
R4 Wasserstoff, Formyl, Ci-C4-Alkylcarbonyl, d-C^Alkylaminocarbonyl, Dt-(Ci-C4,- Alkyl)-aminocarbonyl, Phenylaminocarbonyl, N-(CI -C4-a!ky!)-N-(phenyl)- aminocarbonyl, SO2CH31 SO2CF3 oder SO2(C6H5); R5 Wasserstoff; und R6 Ci-Cβ-Alkyl, C2-C6-Alkenyl, Ci-C6-Halogenalkyl, C2-C@-Halogenalkenyl, CrC6-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-Cβ alkyl, C 2 -C 6 alkenyl, Ci-C 6 haloalkyl, C 2 -C @ haloalkenyl, CrC 6 -
Hydroxyalkyl, Phenyl-CrC4-alkyl oder Pheny!-Ci- C4-hydroxyalkyl; bedeuten.hydroxyalkyl, ! Phenyl-C r C 4 alkyl or Phenyl -ci- C 4 hydroxyalkyl; mean.
Die folgenden Beispiele dienen der Erläuterung der Erfindung. HerstθllungsbeispieleThe following examples serve to illustrate the invention. Herstθllungsbeispiele
Beispiel 1example 1
Essigsäure-i-fmethylcarbamoyl-^i-methyl-S-trifluoromethyl-IH-pyrazoM-carbonyl)- amino]-methyl}-allylester (Tab. 3 Nr. 3.10)Acetic acid-i-methylcarbamoyl-1-methyl-S-trifluoromethyl-1H-pyrazole-1-carbonyl) -amino] -methyl} -allyl-ester (Tab. 3 No. 3.10)
1.1) [(1-Methyi-3-trifluoromethyi-1 H-pyrazole-4-carbonyl)-amino]-essigsäureethyiester1.1) [(1-Methyi-3-trifluoromethyl-1H-pyrazole-4-carbonyl) -amino] -acetic acid ethyl ester
3.63 g (25.8 mmol) Glycinethylester Hydrochlorid wurde in CH2CI2 gelöst und bei RT THF, 5.00 g (25.8 mmol) 1 -Methy!-3-trifluorrnethy-4-Carbonsäure und 7.82 g Triethy- lamin (77.3 mmol), sowie bei 00C 6.56 g (25.8 mmol) Bis-(2-oxo)-3-oxazolidinyl)- phosphonsäurechlorid zugegeben. Es wurde 3 h bei 00C und anschließend 16 h bei RT gerührt. Danach wuden die Lösungsmittel entfernt, der Rückstand mit Essigester aufgenommen, gewaschen, getrocknet und das Lösungsmittel entfernt. Man erhielt 3.88 g (54 % der Theorie) der Titelverbindung als rotes Öl.3.63 g (25.8 mmol) of glycine ethyl ester hydrochloride were dissolved in CH 2 Cl 2 and at RT THF, 5.00 g (25.8 mmol) of 1-methyl-3-trifluoromethyl-4-carboxylic acid and 7.82 g of triethylamine (77.3 mmol), and at 0 0 C 6.56 g (25.8 mmol) of bis (2-oxo) -3-oxazolidinyl) - phosphonic added. The mixture was stirred at 0 ° C. for 3 h and then at RT for 16 h. Thereafter, the solvents were removed, the residue was taken up in ethyl acetate, washed, dried and the solvent was removed. This gave 3.88 g (54% of theory) of the title compound as a red oil.
1H-NMR (DMSO): δ - 1.20 (t,3H); 3.95 (s, 6H); 4.15 (q, 2H); 8.35 (s, 1 H); 8.65 (t, 1 H). 1 H NMR (DMSO): δ - 1.20 (t, 3H); 3.95 (s, 6H); 4.15 (q, 2H); 8.35 (s, 1H); 8.65 (t, 1H).
1.2) 3-Hydroxy-2-[(1-rnethyl-3-trifluoromethy!-1 H-pyrazole-4-carbonyl)-amino]-pent-4- ensäureethylester (Tab. 2, Nr. 2.2)1.2) 3-Hydroxy-2 - [(1-methyl-3-trifluoromethyl-1H-pyrazole-4-carbonyl) amino] pent-4-enoic acid ethyl ester (Table 2, No. 2.2)
H. H.
Bei -500C wurden 3.45g (12.4 mmol) [(1-Methyf-3-trifluoromethyl-1 H-pyrazole-4- carbonyl)-amino]-essigsäureethylester gelöst in THF zu 18.5 ml (37.0 mmol) 2M Lithi- umdi-iso-propoylamid-Lösung in THF/Heptan/Ethylbenzol getropft. Nach 1.5 h Rühren bei -5O0C wurde auf -78°C gekühlt und 0.83 g (14.8 mmol) Acrolein gelöst in THF zu- getropft. Nach 2 h Rühren bei -780C wurde mit ges. NH4Cl~Lösung hydrolyiert und auf RT erwärmt. Nah Trennung der Phasen wurde die organische Phase getrocknet und das Lösungsmittel entfernt. Der Rückstand wurde chromatographisch gereinigt (SiO2, Cyclohexan/Essigester). Man erhielt 1.65 g (40 % der Theorie) der Titelverbindung als farblosen Feststoff (ca. 1 :1 Diastereomerenmischung), die ohne weitere Reinigung eingesetzt wurde. 1.3) 1-Methyi-3-trif!uoromethyl-1 H-pyrazole-4-carbonsäure-(2-hydroxy-1- methylcarfaarrioyl-but-3-eπyl)-amid (Tab. 3, Nr. 3.4)At -50 0 C 3.45g (12.4 mmol) of [(1-Methyf-3-trifluoromethyl-1H-pyrazole-4-carbonyl) -amino] -acetic acid ethyl ester was dissolved in THF to 18.5 ml (37.0 mmol) of 2M lithium umdi -iso-propoylamide solution in THF / heptane / ethylbenzene added dropwise. After 1.5 h stirring at -5O 0 C was cooled to -78 ° C and 0.83 g (14.8 mmol) of acrolein dissolved in THF added dropwise. After 2 h stirring at -78 0 C was washed with sat. NH4Cl solution hydrolyzed and warmed to RT. Close separation of the phases, the organic phase was dried and the solvent removed. The residue was purified by chromatography (SiO 2 , cyclohexane / ethyl acetate). This gave 1.65 g (40% of theory) of the title compound as a colorless solid (about 1: 1 diastereomeric mixture), which was used without further purification. 1.3) 1-Methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (2-hydroxy-1-methylcarfaarrioyl-but-3-enyl) -amide (Tab. 3, No. 3.4)
1.65 g (4.92 mmol) 3-Hydroxy-2-[(1-methyl~3-trifluorornethyl-1 H-pyrazole-4-carbonyl)- amino]-pent-4-eπsäureethylester wurden in Methanol gelöst. Man leitete 1 h bei O0C Methylamingas ein. Nach 16 h Rühren bei RT wurde das Lösungsmittel entfernt und der Rückstand aus Aceton umkristallisiert. Der Niederschlag ergab 0.65 g Erythro- Titelverbindung als farbloses Pulver, das Filtrat enthielt 0.75 g Isomerenmischung. Man erhielt daher insgesamt 1.40 g (89 % der Theorie). 1H-NMR (DMSO) (Erythro-isomer): δ = 2.55 (d, 3H); 4.95 (s, 3H); 4.25 (m, 1 H); 4.35 (t, 1 H); 5.10 (d, 1H); 5.25 (d, 1H); 5.35 (d, 1 H); 5,80 (m, 1 H); 7.95 (d, 1 H); 8.10 (d, 1 H); 8.45 (s, 1 H).1.65 g (4.92 mmol) of 3-hydroxy-2 - [(1-methyl-3-trifluoro-ethyl-1-H-pyrazole-4-carbonyl) -amino] -pent-4-hydroxyethyl ester were dissolved in methanol. The mixture was introduced at 0 ° C. for 1 h. After stirring at RT for 16 h, the solvent was removed and the residue was recrystallized from acetone. The precipitate gave 0.65 g of erythro-title compound as a colorless powder, the filtrate containing 0.75 g of isomer mixture. Therefore, a total of 1.40 g (89% of theory) was obtained. 1 H NMR (DMSO) (erythro isomer): δ = 2.55 (d, 3H); 4.95 (s, 3H); 4.25 (m, 1H); 4.35 (t, 1H); 5.10 (d, 1H); 5.25 (d, 1H); 5.35 (d, 1H); 5.80 (m, 1H); 7.95 (d, 1H); 8.10 (d, 1H); 8.45 (s, 1H).
1.4) Essigsäure-1 -{methylcarbamoyl-[(1-methyl-3-trifluoromethyl-1 H-pyra2θi-4- carbonyl)-amino]-methyl}-ailylester (Tab. 3 Nr. 3.10)1.4) acetic acid 1 - {methylcarbamoyl - [(1-methyl-3-trifluoromethyl-1H-pyra-2-methyl-4-carbonyl) -amino] -methyl} -ailyl ester (Tab. 3 No. 3.10)
134 mg (0.42 mmol) 1-Methyl-3-trifluoromethyl-1H-pyrazole-4-carbonsäure-(2-hydroxy- 1-methylcarbamoyl-but-3-enyl)-amid, 28 mg (0.46mmol) Essigsäure und 20 mg (0.17 mmol) Dimethylaminopyridin wurden in CH2CI2 gelöst. Man gab bei 00C 88 mg (0.46 mmol) 1-(3-Dimethylamiπopropyl)-3-(ethylcarbodiimid)-Hydrochlorid zugegeben. Nach 16 h Rühren bei RT wurde die Reaktionslösung gewaschen und das Lösungsmittel entfernt. Man erhielt 0.10 g (66 % der Theorie) der Titelverbindung als farbloses Pulver (M+ (m/z)=362).134 mg (0.42 mmol) of 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (2-hydroxy-1-methylcarbamoyl-but-3-enyl) -amide, 28 mg (0.46 mmol) of acetic acid and 20 mg (0.17 mmol) dimethylaminopyridine were dissolved in CH 2 Cl 2 . Was added at 0 0 C 88 mg (0:46 mmol) of 1- (3-Dimethylamiπopropyl) -3- (ethylcarbodiimide) hydrochloride. After stirring at RT for 16 h, the reaction solution was washed and the solvent was removed. This gave 0.10 g (66% of theory) of the title compound as a colorless powder (M + (m / z) = 362).
In den nachfolgenden Tabellen 2 und 3 werden neben den voranstehenden Verbindungen noch weitere Heteroaroylderivate der Formel III sowie heteroaroyl-substituierte Serin-Amide der Formel I aufgeführt, die in analoger Weise nach den voranstehend beschriebenen Verfahren hergestellt wurden oder herstellbar sind. In the following Tables 2 and 3, other heteroaroyl derivatives of the formula III and heteroaroyl-substituted serine amides of the formula I are listed in addition to the above compounds, which were prepared in an analogous manner by the methods described above or can be prepared.
Tabelle 2Table 2
Tabelle 3Table 3
Biotogische WirksamkeitBiotogical efficacy
Die heteroaroylsubstituierten Seriπ-Amide der Formel I und deren landwirtschaftlich brauchbaren Salze eignen sich - sowohl als Isomerengemische als auch in Form der reinen Isomeren - als Herbizide. Die Verbindungen der Formel I enthaltenden herbizi- den Mittel bekämpfen Pflanzenwuchs auf Nichtkulturflächen sehr gut, besonders bei hohen Aufwandmengen. In Kulturen wie Weizen, Reis, Mais, Soja und Baumwolle wirken sie gegen Unkräuter und Schadgräser, ohne die Kulturpflanzen nennenswert zu schädigen. Dieser Effekt tritt vor allem bei niedrigen Aufwandmengen auf.The heteroaroyl-substituted Seriπ-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.
In Abhängigkeit von der jeweiligen Applikationsmethode können die Verbindungen der Formel I bzw. sie enthaltenden herbiziden Mittel noch in einer weiteren Zahl von Kulturpflanzen zur Beseitigung unerwünschter Pflanzen eingesetzt werden. In Betracht kommen beispielsweise folgende Kulturen:Depending on the particular application method, 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. For example, the following cultures may be considered:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. aftissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tiπctori- us, Carya illinoiπensis, Citrus lirnon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucuimis sativus, Cynodon dactylon, Daucus carota, Elaeis guineen- sis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossy- pium herbaceurn, Gossypium vitifolium), Helianthus anπuus, Hevea brasiliensis, Hor- deum vulgäre, Humuius lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec, Manihot esculenta, Medicago sativa, Musa spec, Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa , Pha- seolus iunatus, Phaseolus vulgaris, Picea abies, Pinus spec, Pisum sativum, Prunus avium, Prunus persica, Pyrus cσmmunis, Ribes sylvestre, Ricinus communis, Saccha- rum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgäre), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera und Zea mays.Allium cepa, pineapple comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. aftissima, Beta vulgaris spec. rapese, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tiπctori- us, Carya illinoiπensis, Citrus lirnon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucuimis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceurn, Gossypium vitifolium), Helianthus anuuus, Hevea brasiliensis, Hordeum vulgare, Humuius lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phasolus iunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus cmmmmunis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (see vulgaris), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.
Darüber hinaus können die Verbindungen der Formel I auch in Kulturen, die durch Züchtung einschließlich gentechnischer Methoden gegen die Wirkung von Herbiziden tolerant sind, verwandt werden.In addition, the compounds of formula I may also be used in cultures tolerant to the action of herbicides by breeding, including genetic engineering.
Darüber hinaus können die Verbindungen der Formel I auch in Kulturen, die durch Züchtung einschließlich gentechnischer Methoden gegen Insekten- oder Pilzbefall tolerant sind, verwandt werden.In addition, the compounds of formula I can also be used in cultures tolerant by breeding including genetic engineering against insect or fungal attack.
Die Verbindungen der Formel I bzw. die sie enthaltenden herbiziden Mittel können beispielsweise in Form von direkt versprühbaren wäßrigen Lösungen, Pulvern, Suspensionen, auch hochprozentigen wäßrigen, öligen oder sonstigen Suspensionen oder Dis- persionen, Emulsionen, Öldispersionen, Pasten, Stäubemittelπ, Streumitteln oder Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gießen angewendet werden. Die Anwendungsformen richten sich nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfindungsgemäßen Wirkstoffe gewährleisten.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.
Die herbiziden Mitte! enthalten eine herbizid wirksame Menge mindestens einer Verbindung der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I und für die Formulierung von Pflanzenschutzmitteln übliche Hilfsmittel.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.
Als inerte Hilfsstoffe kommen im Wesentlichen in Betracht:Suitable inert auxiliaries are essentially:
Mineralölfraktionen von mittlerem bis hohem Siedepunkt wie Kerosin und Dieselöl, ferner Kohienteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyc- lische und aromatische Kohlenwasserstoffe, z.B. Paraffine, Tetrahydronaphthaün, alky- lierte Naphthaline und deren Derivate, alkylierte Benzole und deren Derivate, Alkohole wie Methanol, Ethanol, Propanoi, Sutanol und Cyclohexanol, Ketone wie Cyciohexa- non, stark polare Lösungsmittel, z.B. Amine wie N-Methylpyrrolidon und Wasser.Medium to high boiling point 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.
Wäßrige Anwendungsformen können aus Emulsionskonzentraten, Suspensionen, Pas- ten, netzbaren Pulvern oder wasserdispergierbaren Granulaten durch Zusatz vonAqueous application forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding
Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder Öldispersionen können die Substrate als solche oder in einem Öl oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emulgiermittel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz, Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder Öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind.Water to be prepared. To prepare emulsions, pastes or oil dispersions, 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. However, it is also possible to prepare concentrates consisting of active substance, wetting, adhesion, dispersing or emulsifying agent and possibly solvent or oil, which are suitable for dilution with water.
Als oberflächenaktive Stoffe (Adjuvantien) kommen die Alkali-, Erdalkali-, Ammoniumsalze von aromatischen Sulfonsäuren, z.B. Lignin-, Phenol-, Naphthalin- und Dibutyl- naphthalinsulfonsäure, sowie von Fettsäuren, Alkyi- und Alkylarylsulfonaten, Alkyl-, Laurylether- und Fettalkoholsulfaten, sowie Salze sulfatierter Hexa-, Hepta- und Octa- decanolen sowie von Fettalkoholglykolether, Kondensationsprodukte von sulfoπiertem Naphthalin und seiner Derivate mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphthalinsulfonsäureπ mit Phenol und Formaldehyd, Polyoxyethyle- noctylphenolether, ethoxyiiert.es Isooctyl-, Octyl- oder Nonylphenol, Alkylphenyl-, Tribu- tylphenylpolyglykoleiher, Alkylarylpolyetheralkohole, Isotridecylalkohol, Fettalkoholethy- lenoxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylen- oder PoSyoxypropylenal- kylether, Laurylalkohoipolyglykoletheracetat, Sorbitester, Ligniπ-Sulfitablaugen oder Methylcelluiose in Betracht.As surfactants (adjuvants) 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. isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol-ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene or PoSyoxypropylenal- kylether, Laurylalkohoipolyglykoletheracetat, sorbitol esters, Ligniπ-Sulfitablaugen or Methylcelluiose into consideration.
Pulver-, Streu- und Stäubemittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden. Granulate, z.B. Umhüüungs-, Imprägnierungs- und Homogengranulate können durch Bindung der Wirkstoffe an feste Trägerstoffe hergestellt werden. Feste Trägerstoffe sind Mineralerden wie Kieselsäuren, Kieselgeie, Silikate, Talkum, Kaolin, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie Ammoniumsulfat, Ammoniumphosphat, Ammonium πitrat, Harnstoffe und pflanzliche Produkte wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver oder andere feste Trägerstoffe.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.
Die Konzentrationen der Verbindungen der Forme! I in den anwendungsfertigen Zubereitungen können in weiten Bereichen variiert werden. Im allgemeinen enthaften die Formulierungen etwa von 0,001 bis 98 Gew.-%, vorzugsweise 0,01 bis 95 Gew.-%, mindestens eines Wirkstoffs. Die Wirkstoffe werden dabei in einer Reinheit von 90% bis 100%, vorzugsweise 95% bis 100% (nach NMR-Spektrum) eingesetzt.Concentrations of compounds of forms! I in the ready-to-use formulations can be varied within a wide range. In general, 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).
Die folgenden Formulierungsbeispiele verdeutlichen die Herstellung solcher Zubereitungen:The following formulation examples illustrate the preparation of such preparations:
I. 20 Gewichtsteile eines Wirkstoffs der Formel I werden in einer Mischung gelöst, die aus 80 Gewichtsteilen alkyliertem Benzol, 10 Gewichtsteilen des Anlagerungsproduktes von 8 bis 10 Mol Ethylenoxid an 1 Mol Ölsäure-N- monoethanolamid, 5 Gewichtsteileπ Calciumsalz der Dodecylbeπzolsulfonsäure und 5 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Rizinusöl besteht. Durch Ausgießen und feines Verteilen der Lösung inI. 20 parts by weight of an active compound of the formula I are dissolved in a mixture of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic N-monoethanolamide, 5 parts by weight calcium dodecylbenzenesulfonic acid and 5 parts by weight of Addition product of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in
100000 Gewichtsteälen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew.-% des Wirkstoffs der Formel I enthält.100,000 weight parts of water gives an aqueous dispersion containing 0.02 wt .-% of the active ingredient of the formula I.
II. 20 Gewichtsteile eines Wirkstoffs der Forme! I werden in einer Mischung gelöst, die aus 40 Gewichtsteilen Cyclohexanon, 30 Gewichtsteileπ Isobutanol, 20 Gewichtsteilen des Anlagerungsproduktes von 7 Mol Ethylenoxid an 1 Mol Isooc- tylphenol und 10 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Rizinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew.-% des Wirkstoffs der Forme! I enthält.II. 20 parts by weight of an active substance of the forms! I are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of iso-tocylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water to obtain an aqueous dispersion containing 0.02 wt .-% of the active ingredient of the forms! I contains.
Hl. 20 Gewichtsteile eines Wirkstoffs der Formel I werden in einer Mischung gelöst, die aus 25 Gewichtsteilen Cyclohexanon, 65 Gewichtsteilen einer Mineralölfraktion vom Siedepunkt 210 bis 28O0C und 10 Gewichtsteilen des Anlagerungspro- duktes von 40 Mol Ethylenoxid an 1 Mol Ricinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100000 Gewichtsteileπ Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew.-% des Wirkstoffs der Formel I enthält. IV. 20 Gewichtsteile eines Wirkstoffs der Formel I werden mit 3 Gewichtsteilen des Natriumsalzes der Diisobutylnaphthalinsulfonsäure, 17 Gewichtsteilen des Natriumsalzes einer Ligninsulfoπsäure aus einer Sulfit-Ablauge und 60 Gewichtsteilen pulverförmigem Kieselsäuregel gut vermischt und in einer Hammermühle vermählen. Durch feines Verteilen der Mischung in 20000 Gewichtsteilen Wasser erhält man eine Spritzbrühe, die 0,1 Gew.-% des Wirkstoffs der Formel I enthält.Hl. 20 parts by weight of an active ingredient of formula I are dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction boiling from 210 to 28O 0 C and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and finely distributing the solution in 100,000 parts by weight of water, an aqueous dispersion containing 0.02% by weight of the active ingredient of the formula I is obtained. IV. 20 parts by weight of an active compound of formula I are well mixed with 3 parts by weight of the sodium salt of Diisobutylnaphthalinsulfonsäure, 17 parts by weight of the sodium salt of a Ligninsulfoπsäure from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water to obtain a spray mixture containing 0.1 wt .-% of the active ingredient of the formula I.
V. 3 Gewichtsteile eines Wirkstoffs der Formel I werden mit 97 Gewichtsteilen fein- teiligem Kaolin vermischt. Man erhält auf diese Weise ein Stäubemittel, das 3V. 3 parts by weight of an active compound of the formula I are mixed with 97 parts by weight of finely divided kaolin. Obtained in this way a dust, the 3rd
Gew.-% des Wirkstoffs der Formel I enthält.Wt .-% of the active ingredient of the formula I.
VI. 20 Gewichtsteile eines Wirkstoffs der Formel I werden mit 2 Gewichtsteilen CaI- ciumsalz der Dodecylbenzolsulfonsäure, 8 Gewichtsteilen Fettalkoholpolyglykol- ether, 2 Gewichtsteilen Natriυmsalz eines Phenol-Harnstoff-Formaldehyd-VI. 20 parts by weight of an active compound of the formula I are mixed with 2 parts by weight of cesium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde
Kondensates und 68 Gewichtsteilen eines paraffinischeπ Mineralöls innig vermischt. Man erhält eine stabile ölige Dispersion.Condensates and 68 parts by weight of a paraffinischeπ mineral oil intimately mixed. This gives a stable oily dispersion.
VII. 1 Gewichtsteil eines Wirkstoffs der Formel I wird in einer Mischung gelöst, die aus 70 Gewichtsteilen Cyclohexanon, 20 Gewichtsteilen ethoxyüertem Isooc- tylphenol und 10 Gewichtsteilen ethoxyliertem Rizinusöl besteht. Man erhält ein stabiles Emulsionskonzentrat.VII. 1 part by weight of an active compound of the formula I is dissolved in a mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isoacylphenol and 10 parts by weight of ethoxylated castor oil. A stable emulsion concentrate is obtained.
ViII. 1 Gewichtsteil eines Wirkstoffs der Formel I wird in einer Mischung gelöst, die aus 80 Gewichtsteilen Cyclohexanon und 20 Gewichtsteilen WettolR EM 31 (= nichtionischer Emulgator auf der Basis von ethoxyliertem Rizinusöl) besteht. Man erhält ein stabiles Emulsionskonzentrat.VIII. 1 part by weight of an active compound of the formula I is dissolved in a mixture consisting of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol R EM 31 (= nonionic emulsifier based on ethoxylated castor oil). A stable emulsion concentrate is obtained.
Die Applikation der Verbindungen der Formel I bzw. der herbiziden Mittel kann im Vor- auflauf- oder im Nachauflaufverfahren erfolgen. Sind die Wirkstoffe für gewisse Kulturpflanzen weniger verträglich, so können Ausbringungstechniken angewandt werden, bei welchen die herbiziden Mittel mit Hilfe der Spritzgeräte so gespritzt werden, daß die Blätter der empfindlichen Kulturpflanzen nach Möglichkeit nicht getroffen werden, während die Wirkstoffe auf die Blätter darunter wachsender unerwünschter Pflanzen oder die unbedeckte Bodenfläche gelangen (post-directed, lay-by).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).
Die Aufwandmengen an Verbindung der Formel I betragen je nach Bekämpfungsziel, Jahreszeit, Zielpflanzen und Wachstumsstadium 0,001 bis 3,0, vorzugsweise 0,01 bis 1 ,0 kg/ha aktive Substanz (a. S.).Depending on the control target, season, target plants and growth stage, 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).
Zur Verbreiterung des Wirkungsspektrums und zur Erzielung synergistischer Effekte können die heteroaroylsubstituierten Serin-Amide der Formel I mit zahlreichen Vertre- tern anderer herbizider oder wachstumsregulierender Wirkstoffgruppen gemischt und gemeinsam ausgebracht werden. Beispielsweise kommen als Mischuπgspartner 1 ,2,4- Thiadiazole, 1 ,3,4-Thiadiazole, Amide, Aminophosphorsäure und deren Derivate, Ami- notriazole, Anilide, Aryloxy-/Heteroaryloχyalkansäuren und deren Derivate, Benzoesäu- re und deren Derivate, Benzothiadiazinone, 2-(Hetaroyl/Aroyi)-1 ,3- cyclohexandione, Heteroaryl-Aryl-Ketone, Benzylisoxazolidinone, meta-CF3-Phenylderivate, Carbamate, Chinolincarbonsäure und deren Derivate, Chloracetanilide, Cyclohexenonoximetherde- rivate, Diazine, Dichlorpropionsäure und deren Derivate, Dihydrobenzofurane, Dihydro- furan-3-one, Dinitroaniüne, Diπitrophenole, Diphenylether, Dipyridyle, Haiogencarbon- säuren und deren Derivate, Harnstoffe, 3-Phenyluracile, Imidazole, Imidazolinone, N- Phenyl-3,4,5,6-tetrahydrophthalimide, Oxadiazole, Oxirane, Phenole, Aryloxy- und He- teroaryloxyphenoxypropionsäureester, Phenylessigsäure und deren Derivate, 2- Phenylpropionsäure und deren Derivate, Pyrazole, Phenylpyrazole, Pyridazine, Pyri- dincarbonsäure und deren Derivate, Pyrimidylether, Sulfonamide, Sulfonylharnstoffe, Triazine, Triazinone, Triazolinone, Triazolcarboxamide und Uracile in Betracht.To broaden the spectrum of action and to achieve synergistic effects, the 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. Examples of 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, dichloropropionic acid and derivatives thereof, dihydrobenzofurans, Dihydrofuran-3-ones, dinitroani- thes, diπitrophenols, diphenyl ethers, dipyridyls, halocarbonic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes , Phenols, aryloxy- and heteroaryloxyphenoxypropionic acid esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and derivatives thereof, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and their derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.
Außerdem kann es von Nutzen sein, die Verbindungen der Formel I aliein oder in Kombination mit anderen Herbiziden auch noch mit weiteren Pflanzenschutzmitteln gemischt, gemeinsam auszubringen, beispielsweise mit Mitteln zur Bekämpfung von Schädlingen oder phytopathogenen Pilzen bzw. Bakterien. Von Interesse ist ferner die Mischbarkeit mit Miπeralsaiziösungen, welche zur Behebung von Ernährungs- und Spurenelementmängeln eingesetzt werden. Es können auch nichtphytotoxische Öle und Ölkonzentrate zugesetzt werden.In addition, it may be useful to mix the compounds of formula I aliein or in combination with other herbicides also mixed with other crop protection agents, together, for example, with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with Miπeralsaiziösungen, which are used for the elimination of nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.
Anwendungsbeispieleapplications
Die herbizide Wirkung der heteroaroylsubstituierteπ Serin-Amide der Formel I ließ sich durch die folgenden Gewächshausversuche zeigen:The herbicidal action of the heteroaroyl-substituted serine amides of the formula I was demonstrated by the following greenhouse experiments:
Als Kulturgefäße dienten Plastikblumentöpfe mit lehmigem Sand mit etwa 3,0 % Humus als Substrat. Die Samen der Testpflanzen wurden nach Arten getrennt eingesät.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.
Bei Vorauflaufbehandlung wurden die in Wasser suspendierten oder emuigierten Wirkstoffe direkt nach Einsaat mittels fein verteilender Düsen aufgebracht. Die Gefäße wurden leicht beregnet, um Keimung und Wachstum zu fördern, und anschließend mit durchsichtigen Plastikhauben abgedeckt, bis die Pflanzen angewachsen waren. Diese Abdeckung bewirkt ein gleichmäßiges Keimen der Testpflanzen, sofern dies nicht durch die Wirkstoffe beeinträchtigt wurde. Zum Zweck der Nachaufiaufbehandlung wurden die Testpflanzeπ je nach Wuchsform erst bis zu einer Wuchshöhe von 3 bis 15 cm angezogen und erst dann mit den in Wasser suspendierten oder eimulgierten Wirkstoffen behandelt. Die Testpfianzen wurden dafür entweder direkt gesät und in den gleichen Gefäßen aufgezogen oder sie wurden erst als Keimpflanzen getrennt angezogen und einige Tage vor der Behandlung in die Versuchsgefäße verpflanzt. Die Aufwandmenge für die Nachauflaufbehand- iung betrug 1 ,0 kg/ha a.S. (aktive Substanz).In the pre-emergence treatment, 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. For the purpose of Nachaufiaufbehandlung the Testpflanzeπ 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 eimulgierten agents. For this purpose, 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).
Die Pflanzen wurden artenspezifisch bei Temperaturen von 10 bis 25°C bzw. 20 bis 35°C gehalten. Die Versuchsperiode erstreckte sich über 2 bis 4 Wochen. Während dieser Zeit wurden die Pflanzen gepflegt, und ihre Reaktion auf die einzelnen Behandlungen wurde ausgewertet.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.
Bewertet wurde nach einer Skala von 0 bis 100. Dabei bedeutet 100 kein Aufgang der Pflanzen bzw. völlige Zerstörung zumindest der oberirdischen Teile und 0 keine Schädigung oder normaler Wachstumsverlauf.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.
Die in den Gewächshausversuchen verwendeten Pflanzen setzten sich aus folgenden Arten zusammen:The plants used in the greenhouse experiments were composed of the following species:
Bei Aufwandmengen von 1 kg/ha zeigte die Verbindung 3.7 (Tabelle 3) im Nachauflauf eine sehr gute Wirkung gegen die unerwünschten Pflanzen Amaranthus retroflexus und Chenopodium album.At application rates of 1 kg / ha, Compound 3.7 (Table 3) postemergence showed a very good action against the unwanted plants Amaranthus retroflexus and Chenopodium album.
Weiterhin bekämpfte Verbindung 3.12 (Tabelle 3) im Nachauflauf bei Aufwandmengen von 1 kg/ha die Schadpflanzen Amaranthus retroflexus, Chenopodium album und Polygonum convolvulus sehr gut. Furthermore, compound 3.12 (Table 3) postemergence at application rates of 1 kg / ha fought the weeds Amaranthus retroflexus, Chenopodium album and Polygonum convolvulus very well.

Claims

Patentansprüche: claims:
1. Heteroaroyisubstituierte Serin-Amide der Formel I1. Heteroaroyisubstituted serine amides of the formula I
in der die Variablen die folgenden Bedeutungen haben: in which the variables have the following meanings:
A 5- oder 6-gliedriges Heteroaryl mit ein bis vier Stickstoffatomen, oder mit ein bis drei Stickstoffatomen und einem Sauerstoff- oder Schwefeiatom, oder mit einem Sauerstoff- oder Schwefelatom, welches partiell oder vollständig halogeniert sein kann und/oder 1 bis 3 Reste aus der Gruppe Cyano, CrC6- Alkyl, C3-C6-CyClOaIkVl, CrC6-Halogenalkyl, d-Ce-Alkoxy, CrC6- Halogenalkoxy und CrC6-Alkoxy-CrC4-alky! tragen kann;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 completely halogenated and / or 1 to 3 radicals the group consisting of cyano, CrC 6 - alkyl, C 3 -C 6 -CyClOaIkVl, C r C 6 haloalkyl, d-Ce-alkoxy, CrC 6 - haloalkoxy and CRC6-alkoxy-CRC4 alky! can carry;
R1, R2 Wasserstoff, Hydroxy oder d-Ce-Alkoxy;R 1 , R 2 are hydrogen, hydroxy or d-Ce-alkoxy;
R3 CrCβ-Alkyl, d-d-Cyanoaikyl oder d-Cβ-Halogenalkyl;R 3 is C 1 -C 6 -alkyl, dd-cyanoalkyl or C 1 -C 6 -haloalkyl;
R4 Wasserstoff, d-Cβ-Alkyl, C3-Ce-Cycloa!kyl, C3-C6-Alkenyl, C3-C6-Alkinyl, C3-C6-Halogeπalkeny!, Cs-Ce-Halogenalkinyl, Formyl, d-Ce-Alkylcarbonyl,R 4 is hydrogen, d-Cβ-alkyl, C 3 -C e -Cycloa! Kyl, C 3 -C 6 alkenyl, C 3 C 6 alkynyl, C 3 -C 6 -Halogeπalkeny !, Cs-Ce-haloalkynyl, Formyl, d-Ce-alkylcarbonyl,
Ca-Cβ-Cycloalkylcarbonyl, C2-C6-Alkenylcarbonyi, Cz-Cβ-AJkinylcarbonyl, Cr Cβ-Alkoxycarbonyl, Ca-Cβ-Alkenyloxycarbonyl, Ca-Cβ-Alkinyloxycarbonyl, Cr Cβ-Alkylaminocarbonyl, Ca-Ce-Alkenylaminocarbonyl, C3-C6-Alkinylamino- carbonyl, CrCβ-Alkylsulfonylaminocarbonyl, Dä-(Ci-C6-alkyl)-aminocarbonyl, N-(C3-Cβ-Alkenyl)-N-(Ci-Cβ-alkyl)-aminocarbonyl, Ca-Cβ-cycloalkylcarbonyl, C 2 -C 6 -alkenylcarbonyi, Cz-Cβ-AJkinylcarbonyl, Cr Cβ-alkoxycarbonyl, Ca-Cβ-alkenyloxycarbonyl, Ca-Cβ-alkynyloxycarbonyl, Cr Cβ-alkylaminocarbonyl, Ca-Ce-alkenylaminocarbonyl, C 3 -C 6 Alkynylaminocarbonyl, CrCβ-alkylsulfonylaminocarbonyl, di (C 1 -C 6 -alkyl) aminocarbonyl, N- (C 3 -C 6 -alkenyl) -N- (C 1 -C 6 -alkyl) aminocarbonyl,
Cβ-alkylJ-aminocarbonyl, N-(CrCβ-Alkoxy)-N-(Ci-C6-alkyl)-amino-carboπyl, N-(C3-C6-Alkenyi)-N-(CrC6-alkoxy)-aminocarboπyl, N-(C3-C6-Alkinyl)-N-(Cr Ce-alkoxyJ-aminocarbonyl, Di'(CrC6-alky!)-aminothiocarbonyt, (CrC6- Alky!)cyanoimino, (Amino)cyanoimino, [(CrC6-Alkyl)amino]cyanoimino, [Di(CrC6-alkyl)amino]cyanoimino, CrCe-Alkylcarbonyl-CrCβ-alkyl, CrC6-Cβ-alkyl-1-aminocarbonyl, N- (C 1 -C 6 -alkoxy) -N- (C 1 -C 6 -alkyl) -amino-carbonyl, N- (C 3 -C 6 -alkenyl) -N- (C 1 -C 6 -alkoxy) -aminocarbonyl, N- (C 3 -C 6 -alkynyl) -N- (C 1 -C 6 -alkoxy-aminocarbonyl, di '(C 1 -C 6 -alkyl) -aminothiocarbonyt, (C 1 -C 6 -alky!) Cyanoimino, (amino) cyanoimino, [(C 1 -C 6) Alkyl) amino] cyanoimino, [di (C 1 -C 6 -alkyl) amino] cyanoimino, C 1 -C 6 -alkylcarbonyl-C 1 -C 6 -alkyl, C 1 -C 6 -
Alkoxyimino-CrCe-alkyl, N-(CrCs-Alkylamino)-imino-Ci-C6-alkyl, N-(Di-Cr C6~alkyiamino)-imino-CrC6-aikyl oder Tri-CrC4-alkylsilyl, wobei die genannten Alkyl-, Cycloalkyl- und Alkoxyreste partiell oder vollständig halogeniert sein können und/oder eine bis drei der folgen- den Gruppen tragen können: Cyano, Hydroxy, C3-C6-Cycloalkyl, d-AlkoxyiminoCrCe-alkyl, N- (C 1 -C 6 -alkylamino) -imino-C 1 -C 6 -alkyl, N- (C 1 -C 6 -cycloalkylamino) -imino-C 1 -C 6 -alkyl or tri-C 1 -C 4 -alkylsilyl, where the said alkyl , Cycloalkyl and 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, d-
Ce-Alkoxy-Crd-alkyl, Ci-C4-Alkoxy-CrC4-alkoxy-CrC4-alkyl, CrC4- Alkoxy, CrC-rAlkylthio, Di-(CrC4-alkyl)-amino, Ci-C4-Alkyl-CrC6- alkoxycarboπylamino, CrC4-Afkylcarbonyl, Hydroxycarboπyl, CrC4- Alkoxycarbonyl, Arninocarbonyl, d-C^Alkylaminocarbonyl, Di-(Ci -C4- alky!)-aminocarbonyl oder d-C4-Alky!carbonyloxy; Phenyl, Phenyl-d-Cβ-alkyl, Pheπyicarbonyi, Phenylcarbonyl-d-Ce-alkyl, Phenoxycarbonyl, Pheπylaminocarbonyi, Phenylsulfonylaminocarbonyl, N- (CrC6-Alkyl)-N-(phenyl)-aminocarbonylJ Phenyl-d-Ce-alkylcarboπyl, wobei der Phenylrest partiell oder vollständig halogeniert sein kann und/oder eine bis drei der folgenden Gruppen tragen kann: Nitro, Cy- ano, Ci-C4-Alkyl, CrC4-Halogenalkyl, Ci-C4-AIkOXy oder CrC4- Halogenalkoxy; oder SO2R7;Ce-alkoxy-Crd-alkyl, Ci-C4-alkoxy-CRC4-alkoxy-CrC 4 alkyl, -C 4 - alkoxy, CrC rAlkylthio, di- (CrC 4 alkyl) amino, Ci-C 4 alkyl CrC 6 -alkoxycarbonylamino, CrC 4 -alkylcarbonyl, hydroxycarbonyl, CrC 4 - Alkoxycarbonyl, Arninocarbonyl, dC ^ alkylaminocarbonyl, di- (! Ci -C 4 - alky) - aminocarbonyl or C 4 -Alky carbonyloxy;! Phenyl, phenyl-C 1 -C 6 -alkyl, phenylcyclo-d-C 1 -C 6 -alkyl, phenoxycarbonyl, phenylaminocarbonyi, phenylsulfonylaminocarbonyl, N- (C 1 -C 6 -alkyl) -N- (phenyl) -aminocarbonyl, J phenyl-d-C 1 -C 6 -alkylcarbamoyl , where the phenyl radical may be partially or fully halogenated and / or may carry one to three of the following groups: nitro, Cy ano, Ci-C 4 alkyl, C r C 4 haloalkyl, Ci-C 4 -alkoxy or CrC 4 - haloalkoxy; or SO 2 R 7 ;
R5 Wasserstoff oder d-Ce-Alkyl;R 5 is hydrogen or d-Ce-alkyl;
R6 Ci-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Al kiηyl, d-Ce-Halogenalkyl, C2-C6- Ha- logenalkenyl, C2-C6-Halogenalkinyl, CrCβ-Cyanoalkyl, C2-C6-Cyanoa!kenyl,R 6 is C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkyl, d-Ce-haloalkyl, C 2 -C 6 -halogenoalkenyl, C 2 -C 6 -haloalkynyl, C 1 -C 6 -cycloalkyl, C 2 -C 6 -cyanoalkenyl,
C2-C6-Cyanoalkiny!t d-Ce-Hydroxyalkyl, C2-Cβ-Hydroxyalkenyl, C2-Ce- Hydroxyalkinyl, C3-C6-Cycloalkyl, Ca-Ce-Cycloalkenyl, 3- bis 6-gliedriges He- terocyclyl, 3- bis 6-gliedriges Heterocyclyl-d-d-alkyl, wobei die voranstehen genannten Cycloalkyl, Cycloalkenyl oder 3- bis 6- gliedrigen Heterocyclylreste partiell oder vollständig halogeniert sein können und/oder ein bis drei Reste aus der Gruppe Oxo, Cyano, Nitro, CrCe- Alkyl, d-Cβ-Halogenalkyl, Hydroxy, d-Cθ-Alkoxy, d-Ce-Halogenalkoxy, Hydroxycarbonyl, CrCe-Alkoxycarbonyl, Hydroxycarbonyl-CrC6-alkoxy, CrCe-Alkoxycarbonyl-Ci-Cβ-alkoxy, Amino, d-Ce-Alkylamino, Di(CrCe- alkyl)amino, d-Ce-Alkylsulfonylamino, CrCs-Halogenalkylsuifonylamino, C2-C6 -Cyanoalkiny! t is C 1 -C 6 -hydroxyalkyl, C 2 -C 6 -hydroxyalkenyl, C 2 -C 6 -hydroxyalkynyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -cycloalkenyl, 3 to 6-membered heterocyclyl, 3 to 6-membered heterocyclyl -dd-alkyl, 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, cyano, nitro, C 1 -C 6 -alkyl, C 1 -C 6 -cycloalkyl 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 -alkoxycarbonyl-C 1 -C 6 -alkoxy, amino, C 1 -C 6 -alkylamino, di (CrCe alkyl) amino, d-Ce-alkylsulfonylamino, C 1 -C -haloalkylsulfonylamino,
Aminocarbonylamino, (Ci-C6-Alkylamino)carbony!amino, Di-(Ci-Ce-alkyl)- aminocarbonylamino, Aryl und Aryl(CrC6-alkyl) tragen können; CrC6-A]koxy-Ci-C4-alkyl, C2-C6-AiW nyloxy- CrC4-alkyl, CrCe-Halogenaikoxy-CrCralkyl, C2-C6-Halogenalkenyloxy-Cr C4-alkyl, Ca-Ce-Halogeπalkinyloxy-CrC^alkyl, Ci-C6-Alkoxy-d-C4-alkoxy-Aminocarbonylamino, (C 1 -C 6 -alkylamino) carbonylamino, di- (C 1 -C 6 -alkyl) aminocarbonylamino, aryl and aryl (C 1 -C 6 -alkyl); C 1 -C 6 -alkoxy-C 1 -C 4 -alkyl, C 2 -C 6 -AiW nyloxy- -C 4 alkyl, CRCE-Halogenaikoxy-CrCralkyl, C2-C6 haloalkenyloxy-Cr C4-alkyl, Ca-Ce-Halogeπalkinyloxy-CrC ^ alkyl, Ci-C 6 alkoxy dC 4 alkoxy
Ci-C4-alkyl, Ci-C6-Alkylthio-CrC4-alkyl, CrCe-Alkenyithio-d-C^alkyl, C2- C6-Alkinylthio-CrC4-alkyi, Ci-Ce-Halogenalkyl-d-C^thioalkyl, C2-C6- Halogenalkenyl-Ci-C4-thioalkyl, C2-Cβ-Halogenalkinyf-CrC4-thioalkyl, d-Cβ- Alkylsulfinyl-CrC4-alkyl, CrC6-Halogenalkylsu!finyl-CrC4-alkyl, C1-C6- Alkylsulfonyl-CrC4-alkyi, Ci-C6-Halogenalkylsulfony!-Ci-C4-alkyt, Amino-Ci-C 1 -C 4 -alkyl, C 1 -C 6 -alkylthio-C 1 -C 4 -alkyl, C 1 -C 6 -alkenylthio-C 1 -C 4 -alkyl, C 2 -C 6 -alkynylthio-C 1 -C 4 -alkyi, C 1 -C 4 -haloalkyl-C 1 -C 4 -thioalkyl, C 2 -C 6 - haloalkenyl-Ci-C4-thioalkyl, C2-Cβ-Halogenalkinyf CRC4 thioalkyl, d-Cβ- alkylsulfinyl-C r C 4 alkyl, -C 6 -Halogenalkylsu finyl--C 4 alkyl, C! C 1 -C 6 -alkylsulfonyl-C 1 -C 4 -alkyl, C 1 -C 6 -haloalkylsulfony! -Ci-C 4 -alkyl, amino-ci
C4-alkyl, CrCβ-Alkylamino-CrC4-alkyl, Di(CrC6-Alkyl)amino-CrC4-alkyi, CrC6-Alkylsu!fonylamino-CrC4-alkyl, CrC3-Alkylsulfonyl-(CrC6-alkyl)- amino-CrC4-alkyl, d-Cs-Alkylcarbonyl, Hydroxycarbonyl, CrCe- Alkoxycarboπyl, Arninocarbonyl, CrCβ-Alkylaminocarbonyl, Di(Cr Ce- alkyl)aminocarbonyl, d-Cβ-Alkylcarbonyl-CrCe-alkyl, Hydroxycarbonyl-d-! C 4 alkyl, CrCβ-alkylamino-CRC4 alkyl, di (CRC6-alkyl) amino-CrC 4 -alkyi, CrC 6 -Alkylsu fonylamino--C 4 alkyl, -C 3 alkylsulfonyl (-C 6 alkyl) - amino-C 1 -C 4 -alkyl, C 1 -C 6 -alkylcarbonyl, hydroxycarbonyl, C 1 -C 6 -alkoxycarbonyl, arninocarbonyl, C 1 -C 6 -alkylaminocarbonyl, di (C 1 -C 6 -alkyl) aminocarbonyl, C 1 -C 6 -alkylcarbonyl-C 1 -C 6 -alkyl, hydroxycarbonyl-d
C4-alkyl, CrC6-Alkoxycarbony!-CrC4-alkyl, d-Ce-Halogenalkoxycarbonyl- CrC4-alkyl, CrC6-A[ky!carbonyloxy-d-C4-alkyl, Aminocarbonyl-CrC4-alky!, Ci-C6-Alkylaminocarboπyl-Ci-C4-alkyl, Di(d-C6-Alkyl)anπinocarbonyl-CrC4- alkyl, Formylamino-CrC4-alkyl, Ci-C6-Alkoxycarbonylaminσ-Ci-C4-alkyt, d- Cs-AlkylcarbonylaiΥiino-CrC4-a]kyl, CrCβ-Alkylcarbonyl-{Ci-C6-alkylarniπo)- CrCή-alkyl, [(Ci-C6-alkyt)aminocarbonyloxy]-Ci-C4-alkyl, [Di(CrC6- alkyl)aminocarbonyloxy]Ci-C4-a]kyl, {Di[di(CrC6-alkyl)amino]carbonyloxy}-C 4 -alkyl, C 1 -C 6 -alkoxy carbonyl, C 1 -C 4 -alkyl, C 1 -C 6 -haloalkoxycarbonylCyc4-alkyl, C 1 -C 6 -alkyloxy-C 1 -C 4 -alkyl, aminocarbonyl-C 1 -C 4 -alkyl, Ci-C6-Alkylaminocarboπyl-Ci-C4-alkyl, di (dC 6 -alkyl) anπinocarbonyl-CrC4- alkyl, formylamino-CrC 4 -alkyl, Ci-C6-Alkoxycarbonylaminσ-Ci-C 4 -alkyt, d- Cs-AlkylcarbonylaiΥiino -CrC4-a] kyl, CrCβ-alkylcarbonyl {Ci-C6-alkylarniπo) -CrCή-alkyl, [(Ci-C 6 -alkyt) aminocarbonyloxy] -Ci-C4-alkyl, [di (CrC 6 -alkyl) aminocarbonyloxy ] C 1 -C 4 -alkyl], [di [di (C 1 -C 6 -alkyl) amino] carbonyloxy} -
CrC4-alkyI, [(CrCe-alkylamino^arbonylarninoJ-Ci^-alkyl, [Di(CrCe- alkylamino)carboπylamino]-Ci-C4-alkyl;C 1 -C 4 -alkyl, [(C 1 -C 6 -alkylamino) arbonylarnino-C 1 -C 4 -alkyl, [di (C 1 -C 6 -alkylamino) carbodiylamino] -Ci-C 4 -alkyl;
Phenyl-d-d-alkyl, Phenyl-C2-C4-a!kenyl, Phenyl-C2-C4-alkinyl, Phenyl-d- C4-halogenalkyl, Phenyl-C2-C4-halogena!kenyl, Phenyl-C2-d- halogenalkinyl, Pheny!-CrC4-hydroxyalkyl, Phenyl-C2-C4-hydroxyalkenyl,Phenyl-dd-alkyl, phenyl-C2-C 4 -a! -Alkenyl, phenyl-C 2 -C 4 alkynyl, phenyl-d- C 4 -haloalkyl, phenyl-C 2 -C 4 Halogena! -Alkenyl, phenyl-C2 d-halogenoalkynyl, phenyl-C 1 -C 4 -hydroxyalkyl, phenyl-C 2 -C 4 -hydroxyalkenyl,
Phenyl-C;KVhydroxyalkiπy(, Phenylcarbonyl-d-CA-alkyl, Phenylcarbo- nylamiπo-Ci-C/t-alkyl, Phenylcarbony!oxy-CrC4-aikyi, Phenyloxycarbonyl- CrC4-alkyl, Phenyloxy-Ci-CValkyl, Phenylthio-CrC4-alkyl, Phenylsulfinyl- CrC4-a[kyl, Pheπylsu!fony[-d-C4-alkyl, Heteroaryi-d-C4-alkyl, Heteroaryl-C2-C4-alkenyl, Heteroaryl-C2-C4-alkinyl,Phenyl-C; KVhydroxyalkiπy (, phenylcarbonyl-d-CA-alkyl, Phenylcarbo- nylamiπo-C / t-alkyl, Phenylcarbony oxy-CrC 4 -alkyl, phenyloxycarbonyl -C 4 alkyl, phenyloxy-Ci-CValkyl, phenylthio! -CrC 4 -alkyl, phenylsulfinyl-CrC 4 -a [kyl, phenylsulfony [-dC 4 -alkyl, heteroaryl-dC 4 -alkyl, heteroaryl-C 2 -C 4 -alkenyl, heteroaryl-C 2 -C 4 -alkynyl,
Heteroaryl-CrC4-halogenalky), Heteroaryl-C2-C4-halogenalkenyl, Heteroa- ryl-C2-C4-haiogenalkinyl, Heteroaryf-CrC4-hydroxyalkyl, Heteroary!-C2-C4- hydroxyalkenyl, Heteroary!-C2-C4-hydroxyalkäπyl, Heteroarylcarbonyl-CrC4- alkyl, Heteroarylcarbonyloxy-Ci-C4-alkyl, Heteroaryloxycarboπyl-Crd-alkyl, Heteroaryloxy-Ci-C4-alkyl, Heteroarylthio-CrC4-alkyl, Heteroarylsulfinyl-CrHeteroaryl CRC4 halogenalky), heteroaryl-C 2 -C 4 haloalkenyl, heteroaryl-C2-C4 -haiogenalkinyl, Heteroaryf CRC4 hydroxyalkyl, heteroaryl! -C2-C4-hydroxyalkenyl, heteroaryl! -C2-C4 Hydroxyalkäπyl, heteroarylcarbonyl-C 1 -C 4 -alkyl, heteroarylcarbonyloxy-C 1 -C 4 -alkyl, heteroaryloxycarbonyl-C 1 -C 4 -alkyl, heteroaryloxy-C 1 -C 4 -alkyl, heteroarylthio-C 1 -C 4 -alkyl, heteroarylsulfinyl-Cr
CValkyl, Heteroarylsulfonyl-Ci-C4-alky[, wobei die vorstehend genannten Phenyl- und Heteroarylreste partiell oder vollständig halogeniert sein können und/oder ein bis drei Reste aus der Gruppe Cyano, Nitro, CrCe-Alkyl, d-Cβ-Halogenalkyl, Hy- droxy, d-Ce-Alkoxy, Ci-Cβ-Halogenalkoxy, Hydroxycarbonyl, C1-CO-C 1 -C 3 -alkyl, heteroarylsulfonyl-C 1 -C 4 -alkyl [where the abovementioned phenyl and heteroaryl radicals can be partially or completely halogenated and / or one to three radicals from the group cyano, nitro, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, Hydroxy, d-Ce-alkoxy, Ci-Cβ-haloalkoxy, hydroxycarbonyl, C 1 -CO-
Alkoxycarbonyl, Hydroxycarbonyl-d-Cβ-alkoxy, CrCe-Alkoxy- carbonyl-d-Ce-alkoxy, Amino, d-Cβ-Alkylamino, Di(CrC6-alkyl)- amino, d-Ce-Alkylsulfonylamino, d-Cβ-Halogenalkylsulfonylamino, (CrC6-Alkylamino)carbonylamino, Di-(d-C6-alkyl)-aminocarbonyl- amino, Aryl und Aryl(Ci-C6-alkyl) tragen können;Alkoxycarbonyl, hydroxycarbonyl-d-Cβ-alkoxy, CrCe-alkoxycarbonyl-d-Ce-alkoxy, amino, C 1 -C 6 -alkylamino, di (C 1 -C 6 -alkyl) -amino, C 1 -C 6 -alkylsulfonylamino, C 1 -C 6 -alkoxy Halogenoalkylsulfonylamino, (C 1 -C 6 -alkylamino) carbonylamino, di (C 1 -C 6 -alkyl) aminocarbonylamino, aryl and aryl (C 1 -C 6 -alkyl);
R7 CrCe-Alkyl, d-C6-Halogenalkyl oder Phenyl, wobei der Phenyfrest partiell oder vollständig haiogeniert sein kann und/oder eine bis drei der folgenden Gruppen tragen kann: CrCε- Alkyl, CrCe-Halogenalky! oder d-Ce-Alkoxy;R 7 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl 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 -alkyl, C 1 -C 6 -haloalky! or d-Ce-alkoxy;
sowie deren landwirtschaftlich brauchbaren Salze.and their agriculturally useful salts.
2. Heteroaroylsubstituierte Serin-Amide der Forme! I gemäß Anspruch 1 wobei A für 5- oder 6-gliedriges Heteroaryl ausgewählt aus der Gruppe PyrroJyl, Thienyl,2. Heteroaroyl-substituted serine amides of the forms! I according to claim 1 wherein A is 5- or 6-membered heteroaryl selected from the group PyrroJyl, thienyl,
Furyl, Pyrazolyl, Imidazolyl, Thiazolyl, Oxazoiyl, Tetrazolyl, Pyridyl und Pyrimidi- nyl; wobei die genannten Heteroarylreste partiell oder vollständig halogeniert sein können und/oder 1 bis 3 Reste aus der Gruppe Cyano, d-Ce-Alkyl, C3-C6-Cycloalkyl, d-Cθ-Halogenalkyl, CrC6-Alkoxy, CrC6-Halogenalkoxy und Ci-C6-Alkoxy-Ci-C4-alkyl tragen können, steht.Furyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, tetrazolyl, pyridyl and pyrimidinyl; wherein said heteroaryl partially or fully halogenated can be and / or 1 to 3 radicals from the group cyano, d-Ce-alkyl, C3-C6-cycloalkyl, d-Cθ-haloalkyl, -C 6 alkoxy, C r C 6 haloalkoxy and Ci-C6-alkoxy -Ci-C4-alkyl, stands.
3. Heteroaroylsubstituierte Serin-Amide der Forme! I gemäß Ansprüchen 1 oder 2, wobei R1, R2 und R5 für Wasserstoff stehen.3. Heteroaroyl-substituted serine amides of the forms! I according to claims 1 or 2, wherein R 1 , R 2 and R 5 are hydrogen.
4. Heteroaroylsubstituierte Serin-Amide der Forme! I gemäß. Ansprüchen 1 bis 3, wobei R6 für d-Ce-Alkyl, C2-C6-Alkenyl, C2-C6-AIkJOyI, d-Ce-Halogenalkyl, C2-4. Heteroaroyl-substituted serine amides of the forms! I according to. Claims 1 to 3, wherein R 6 is C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -
C6-Halogena!keny[, CrCe-Halogenalkinyl, CrCe-Cyanoalkyl, d-Cθ-Hydroxyalkyl, C2-C6-Hydroxyalkenyi, C2-C6-Hydroxyalkinyl, Cj-Ce-Cycloalkyl, C3-Cg- Cycloalkenyl, 3- bis 6-gliedriges Heterocyclyl, wobei die voranstehen genannten Cycloalkyl, Cycloalkenyl oder 3- bis 6- gliedrigen Heterocyclylreste partiell oder vollständig halogeniert sein können und/oder einen bis drei Rest aus der Gruppe Oxo, d-CB-Alkyl, d-C6- Halogenalkyl, Hydroxycarbonyl und d-Ce-Alkoxycarbonyl tragen können,C6-Halogena keny [!, CRCE haloalkynyl, CRCE-cyanoalkyl, d-Cθ-hydroxyalkyl, C 2 -C 6 Hydroxyalkenyi, C 2 -C 6 -Hydroxyalkinyl, Cj-Ce-cycloalkyl, C 3 -Cg- cycloalkenyl, 3 - to 6-membered heterocyclyl, wherein the above-mentioned cycloalkyl, cycloalkenyl or 3- to 6-membered heterocyclyl may be partially or fully halogenated and / or one to three radical from the group oxo, d-CB-alkyl, dC 6 - haloalkyl , Hydroxycarbonyl and d-Ce-alkoxycarbonyl,
Ci-C6-Alkoxy-Ci-C4-alkyl, d-C6-Halσgenalkoxy-d-C4-alkyl, CrC6-AIkOXy-CrC4- alkoxy-Ci-C4-alkyl, CrC6-Alkylthio-Ci-C4-alkyl, Ci-Ce-Alkylsulfonylamino-Crd- alkyl, Hydroxycarbonyl, CrC6-Alkoxycarbonyl, Hydroxycarbonyl-d-d-alkyl, Cr C6-Alkoxycarbonyl~CrC4-alkyl, Ci-Ce-Halogenalkoxycarbσnyl-Ci-d-alkyl, d-Ce- Aikylcarbonyloxy-CrCralkyl, d-Ce-Alkylcarbonylamino-Ci-Cralkyl, Di(CrCo- AlkyOcarbonylamino-Crd-alkyl, [Di(Ci-C6-alky])aminocarbonyloxy]CrC4-alkylI {Di[di(CrC6-alkyl)amino]carbonyloxy}Ci-C4-alkyl,Ci-C 6 alkoxy-Ci-C4-alkyl, dC 6 -Halσgenalkoxy-dC 4 alkyl, -C 6 -alkoxy-CrC 4 - alkoxy-Ci-C4-alkyl, CRC6 alkylthio-Ci-C4-alkyl, C 1 -C 6 -alkylsulfonylamino-C 1 -C -alkyl, hydroxycarbonyl, C 1 -C 6 -alkoxycarbonyl, hydroxycarbonyl-d-d-alkyl, C 1 -C 6 -alkoxycarbonyl-C 1 -C 4 -alkyl, C 1 -C 4 -haloalkoxycarbonyloxy-C 1 -d-alkyl, C 1 -C 6 -cyclocarbonyloxyCrCralkyl , d-Ce-alkylcarbonylamino-C 1 -C -alkyl, di (C 1 -C 4 -alkylcarbonylamino-C 1 -C 5 -alkyl, [di (C 1 -C 6 -alky)] aminocarbonyloxy] C 1 -C 4 -alkyl I [di (C 1 -C 6 -alkyl) amino] carbonyloxy} C 1 -C 4 -alkyl,
Phenyl-CrC4-aikyl, Pheπyl-C2~C4-alkeπyl, Pheπyl-C2-C4-alkinyl, Phenyl-d-C4- halogenaikyl, Phenyl-C2-C4-halogenalkenyl, Phenyl-CrC4-hydroxyalkyl, Pheny- loxy-CrC4-alkyl, Phenylthio-d-C4-alkyl, Phenylsulfinyl-CrC4-alkyl, Phenylsulfo- nyl-CrC4-alkyl,Phenyl-CrC 4 -alkyl, C 2 ~ Pheπyl-C4-alkeπyl, Pheπyl-C 2 -C 4 alkynyl, phenyl-dC 4 - halogenaikyl, phenyl-C 2 -C 4 haloalkenyl, phenyl-CRC4 hydroxyalkyl, phenylethyl loxy -C r C 4 alkyl, phenylthio-d-C4-alkyl, phenylsulfinyl--C 4 -alkyl, phenylsulfonyl--C 4 alkyl,
Heteroaryl-CrC4-alkyl, Heteroary!-Ci-C4-hydroxyalkyl, Heteroary!oxy-CrC4-alkyl, Heteroarylthio-CrC4-afkyl, Heteroarylsulfiny!-Ci-C4-alkyl, Heteroarylsu!fonyl-Cr C4-alkyl, wobei die vorstehend genannten Phenyl- und Heteroarylreste oder voll- ständig halogeniert sein können und/oder ein bis drei Reste aus der Gruppe! Heteroaryl -C 4 alkyl, heteroaryl -C-C 4 hydroxyalkyl, heteroaryl oxy--C 4 alkyl, heteroarylthio -C 4 -afkyl, Heteroarylsulfiny -C-C4 alkyl, Heteroarylsu fonyl-Cr C 4! - alkyl, where the abovementioned phenyl and heteroaryl radicals or may be completely halogenated and / or one to three radicals from the group
Cyano, Nitro, CrC6-Alkyl, d-Ce-Halogenalkyl, Hydroxy, CrC6-Alkoxy, Cr Ce-Haiogenaikoxy, Hydroxycarbony!, CrCβ-Alkoxycarbonyl, Hydroxycarbo- nyl-d-Cε-alkoxy, CrCe-Alkylsulfonylamino und CrCe- Halogenalkylsulfonylamino tragen können; steht. Cyano, nitro, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, hydroxyl, 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 -alkylsulfonylamino and C 1 -C 4 -alkoxy Can carry halogenoalkylsulfonylamino; stands.
5. Verfahren zur Herstellung von heteroaroylsubstituierten Serin-Amide der Formel I gemäß Anspruch 1, dadurch gekennzeichnet dass Serinderivate der Formel V5. A process for preparing heteroaroyl-substituted serine amides of the formula I according to claim 1, characterized in that serine derivatives of the formula V
wobei R1, R4, R5 und R6 die unter Anspruch 1 genannten Bedeutungen haben und L1 für Hydroxy oder Ci-Cβ-Alkoxy steht, where R 1 , R 4 , R 5 and R 6 have the meanings mentioned under claim 1 and L 1 is hydroxyl or C 1 -C 6 -alkoxy,
mit Heteroarylsäure(derivate)n der Formel !Vwith heteroaryl acid (derivatives) n of the formula! V
OO
A ^L2 wobei A die unter Anspruch 1 genannten Bedeutung hat und L2 für Hydroxy, Ha- logen, CrCe-Alkylcarbonyl, C-i-Ce-Alkoxycarbonyl, CrC4-AlkylsuJfonyl, Phospho- ryl oder Isoureyl steht,A 2 L 2 wherein A has the meaning given in claim 1 and L 2 is hydroxyl, halogen, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, C 1 -C 4 -alkylsulfonyl, phosphoryl or isoureyl,
zu entsprechenden Heteroaroylderivaten der Formelto corresponding heteroaroyl derivatives of the formula
wobei A, R1 S R4, R5 und R6 die unter Anspruch 1 genannten Bedeutungen haben und L1 für Hydroxy oder d-Cβ-Alkoxy steht, und anschließend die erhaltenen Heteroaroylderivate der Formel IiI mit einem where A, R 1 S R 4 , R 5 and R 6 have the meanings mentioned under claim 1 and L 1 is hydroxy or C 1 -C 6 alkoxy, and then the resulting heteroaroyl derivatives of the formula IiI having a
Amin der Formel IlAmine of the formula II
HNR2R3 II, wobei R2 und R3 die unter Anspruch 1 genannten Bedeutungen haben, umgesetzt werden.HNR 2 R 3 II, wherein R 2 and R 3 have the meanings mentioned under claim 1, are reacted.
6. Verfahren zur Herstellung von heteroaroylsubstituierten Serin-Amiden der Formel i gemäß Anspruch 5, wobei R4 und R5 für Wasserstoff stehen, dadurch ge- kennzeichnet dass Heteroaroylderivate der Formel III, wobei R4 und R5 für Wasserstoff stehen, durch Acylierung von Ketoverbindungen der Formel XIII6. A process for preparing heteroaroyl-substituted serine amides of the formula I according to claim 5, wherein R 4 and R 5 are hydrogen, characterized in that Heteroaroylderivate of formula III, wherein R 4 and R 5 are hydrogen, by acylation of Keto compounds of the formula XIII
wobei R1 die unter Anspruch 1 genannten Bedeutungen hat und L1 für Hydroxy oder CrCδ-Alkoxy steht, where R 1 has the meanings mentioned under claim 1 and L 1 is hydroxy or C 1 -C 6 -alkoxy,
mit Heteroarylsäure(derivate)n der Formel IV zu N-Acyl-Ketoverbindungen der Formel XIIwith heteroaryl acid (derivatives) n of the formula IV to N-acyl keto compounds of the formula XII
wobei A sowie R1 und R6 die unter Anspruch 1 genannten Bedeutungen haben und L1 für Hydroxy oder CrC6-Alkoxy steht, where A and R 1 and R 6 have the meanings mentioned under claim 1 and L 1 is hydroxy or C r C 6 alkoxy,
und anschließender Reduktion der Ketogruppe hergestellt werden.and subsequent reduction of the keto group.
7. Heteroaroylderivate7. Heteroaroyl derivatives
wobei A, R1, R4, R5 und R6 die unter Anspruch 1 genannten Bedeutungen haben und L1 für eine nucleophil verdrängbare Abgangsgruppe steht. where A, R 1 , R 4 , R 5 and R 6 have the meanings mentioned under claim 1 and L 1 represents a nucleophilically displaceable leaving group.
8. Mittel, enthaltend eine herbizid wirksame Menge mindestens eines heteroaroyl- substituierten Seriπ-Amids der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I gemäß den Ansprüchen 1 bis 4 und für die Formulierung von Pflanzenschutzmitteln übliche Hilfsmittel.8. A composition comprising a herbicidally effective amount of at least one heteroaroyl-substituted Seriπ-amide of the formula I or an agriculturally useful salt of I according to claims 1 to 4 and for the formulation of pesticides customary auxiliaries.
9. Verfahren zur Herstellung von Mitteln gemäß Anspruch 8, dadurch gekennzeichnet, daß man eine herbizid wirksame Menge mindestens eines heteroaroyl- substituierteπ Serin-Amids der Formel I oder eines landwirtschaftlich brauchba- ren Salzes von i gemäß den Ansprüchen 1 bis 4 und für die Formulierung von9. A process for the preparation of agents according to claim 8, characterized in that a herbicidally effective amount of at least one heteroaroyl-substituted Serin amide of the formula I or an agriculturally useful salt of i according to claims 1 to 4 and for the formulation from
Pflanzenschutzmitteln übliche Hilfsmittel mischt.Pesticides usual auxiliaries mixes.
10. Verfahren zur Bekämpfung von unerwünschtem Pflanzeπwuchs, dadurch gekennzeichnet, daß man eine herbizid wirksame Menge mindestens eines hetero- aroylsubstituierten Serin-Amids der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I gemäß den Ansprüchen 1 bis 4 auf Pflanzen, deren Lebensraum und/oder auf Samen einwirken läßt. 10. A method for controlling unwanted Pflanzenπwuchs, characterized in that comprising a herbicidally effective amount of at least one hetero aroylsubstituierten serine amide of the formula I or an agriculturally useful salt of I according to claims 1 to 4 on plants, their habitat and / or to act on seeds.
11. Verwendung der heteroaroylsubstituierten Serin-Amide der Forme! I und deren landwirtschaftlich brauchbaren Satze gemäß den Ansprüchen 1 bis 4 als Herbizide. 11. Use of the heteroaroyl-substituted serine amides of the forms! I and their agriculturally useful sets according to claims 1 to 4 as herbicides.
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