EP1047693A1 - Herbicides 3-(benzazol-4-yl)pyrimidine-dione-derivatives - Google Patents

Herbicides 3-(benzazol-4-yl)pyrimidine-dione-derivatives

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Publication number
EP1047693A1
EP1047693A1 EP98963564A EP98963564A EP1047693A1 EP 1047693 A1 EP1047693 A1 EP 1047693A1 EP 98963564 A EP98963564 A EP 98963564A EP 98963564 A EP98963564 A EP 98963564A EP 1047693 A1 EP1047693 A1 EP 1047693A1
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EP
European Patent Office
Prior art keywords
alkyl
carbonyl
butyl
ethyl
halogen
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
EP98963564A
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German (de)
French (fr)
Inventor
Robert Reinhard
Gerhard Hamprecht
Markus Menges
Olaf Menke
Peter Schäfer
Cyrill Zagar
Elisabeth Heistracher
Martina Otten
Helmut Walter
Karl-Otto Westphalen
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom

Definitions

  • Herbicides 3 - (Benzazole - 4 -yD pyrimidinedione derivatives
  • the present invention relates to new 3- (benzazol-4-yl) pyrimidinedione derivatives of the formula I.
  • R 1 is hydrogen, amino, C ⁇ -Cg-alkyl or Ci-C ⁇ -haloalkyl
  • R 2 is hydrogen, halogen, Ci-Cg-alkyl, Ci-Cg-haloalkyl,
  • R 3 is hydrogen, halogen or C ⁇ -Cg-alkyl
  • R 4 is hydrogen or halogen
  • R 5 cyano, halogen, Ci-Cg-alkyl, -C-C 6 haloalkyl, C ⁇ -C 6 alkoxy or Ci-Cg-haloalkoxy;
  • Ci-Cg-alkyl which by cyano, Ci-Cg-alkoxy, C ⁇ -C 6 -alkylthio, (C ⁇ -C 6 -alkoxy) carbonyl, (Ci-Cg-alkylamino) carbonyl, di (Ci-Cg-alkyl) aminocarbonyl or (Ci-Cg-alkyl) carbonyloxy may be substituted; l a chemical bond, oxygen, sulfur, -S (O) -, -S (0) 2 -, -NH- or -N (R 8 ) -;
  • R 7 and R 8 are independent of one another
  • each heterocyclyl ring can contain a carbonyl or thiocarbonyl ring member, and wherein each cycloalkyl, phenyl and heterocyclyl ring can be unsubstituted or can carry one to four substituents, each selected from the group consisting of cyano, nitro, amino, hydroxy, Carboxy, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy,
  • R 7 and R 8 together form a 1, 3-propylene, tetramethylene, pentamethylene or ethyleneoxyethylene chain, which are each unsubstituted or one to four C ⁇ -C 4 alkyl groups or one or two (C ⁇ -C 4 alkoxy ) can carry carbonyl groups;
  • the invention also relates to
  • WO 97/08170 describes certain 3 - (benz (ox / thi) azol-7-yl) -6- (trifluoromethyl) uracils as herbicides. Further 3- (benzthiazol -7-yl) uracils and their use as herbicides and for the desiccation / defoliation of plants are taught in WO 97/08171.
  • WO 97/12886 relates inter alia to certain 3-benzisoxazol-7 -yl-2, 4 - (1H, 3H) pyrimidinediones, which are said to have a herbicidal and desiccant effect.
  • the object of the present invention was to provide new herbicidally active uracil compounds which can be used to specifically control undesired plants better than the known ones.
  • herbicidal compositions which contain the compounds I and have a very good herbicidal action.
  • processes for the preparation of these compositions and processes for controlling unwanted vegetation using the compounds I have been found.
  • the compounds of the formula I can contain one or more centers of chirality and are then present as mixtures of enantiomers or diastereomers.
  • E / Z isomers may also be possible.
  • the invention relates both to the pure enantiomers or diastereomers and to their mixtures.
  • Agriculturally useful salts include, in particular, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the herbicidal activity of the compounds I. So come as cations in particular the ions of the alkali metals, preferably sodium and potassium, the alkaline earth metals, preferably calcium, magnesium and barium, and the transition metals, preferably manganese, copper, zinc and iron, as well as the ammonium ion, the one to four C ⁇ if desired -C 4 alkyl and / or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably
  • Tri (C ⁇ -C 4 alkyl) sulfonium and sulfoxonium ions preferably tri (C ⁇ -C alkyl) sulfoxonium, into consideration.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C von-C 4 -alkanoic acids, preferably Formate, acetate, propionate and butyrate. They can be formed by reacting I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • All carbon chains ie all alkyl, haloalkyl, cyanoalkyl, hydroxyalkyl, aminoalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, phenyl - alkyl, heterocyclylalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, Alkyl - sulfonyl, haloalkylsulfonyl, alkenyl, haloalkenyl, cyanoalkenyl, alkenyloxy, alkenylthio, alkenylsulfinyl, alkenylsulfonyl, alkynyl, haloalkynyl, cyanoalkynyl, alkynyloxy, alkynylthio, alkynylsulfinyl and
  • - C ⁇ -C 4 -haloalkyl for: a C ⁇ -C 4 -alkyl radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example CH F, CHF, CF 3 , CHC1 , CH (C1), C (C1) 3 , chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2, 2, 2- Trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 2, 2, 2-trichloroethyl, C 2 Fs, 2-fluoropropyl, 3- Fluoropropyl, 2,
  • Cx-C ß- alkyl for: a C ⁇ -C -alkyl radical as mentioned above, or for example n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n- Hexyl,
  • - C ⁇ -Cg-haloalkyl for: a C ⁇ -Cg-alkyl radical as mentioned above, which is partially or completely by fluorine, chlorine,
  • Bromine and / or iodine is substituted, for example one of the radicals mentioned under C ⁇ -C 4 -haloalkyl or for 5-fluoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1-pentyl, 5-iodine -l-pentyl, 5, 5, 5 -Tri - chloro-1-penyl, undecafluoropentyl, 6-fluoro-1-hexyl, 6 -chloro-1-hexyl, 6-bromo-1-hexyl, 6-iodo-1 -hexyl, 6, 6, 6-trichloro-l-hexyl or dodecafluorohexyl;
  • Cyano -C ⁇ -C 4 alkyl for: CHCN, 1-cyanoethyl, 2-cyanoethyl, 1-cyanoprop-l-yl, 2-cyanoprop-l-yl, 3-cyanoprop-1-yl, 1-cyano-but -l-yl, 2-cyanobut-l-yl, 3-cyanobut-1-yl, 4-cyanobut-1-yl, l-cyanobut-2-yl, 2-cyanobut-2-yl, 3-cyanobut-2 -yl, 4-cyano-but-2-yl, 1- (CH 2 CN) eth-1-yl, 1- (CH 2 CN) -1 - (CH 3 ) -eth-l-yl or 1- ( CHCN) prop-1-yl;
  • Hydroxy-C ⁇ -C 4 -alkyl for: CH 2 OH, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxyprop-l-yl, 2-hydroxyprop-l-yl, 3-hydroxyprop-1-yl, 1 -hydroxybut - 1 -yl, 2 -hydroxybut - 1 -yl, 3 -hydroxybut - 1 -yl, 4-hydroxybut-l-yl, 1-hydroxybut-2 -yl, 2 -hydroxybut- 2 -yl, 3 -hydroxybut- 2 - yl, 4-hydroxybut-2-yl, 1- (CH 2 OH) eth-1-yl, 1- (CH 2 OH) -1- (CH 3 ) -eth-1-yl or 1- (CH 2 OH ) per -1-yl;
  • Amino-C ⁇ -C 4 -alkyl for: CH 2 NH, 1-aminoethyl, 2-aminoethyl, 1-aminoprop-l-yl, 2-aminoprop-l-yl, 3-aminoprop-1-yl, 1-amino- but-l-yl, 2-aminobut-l-yl, 3-aminobut-1-yl, 4-aminobut-1-yl, l-aminobut-2-yl, 2-aminobut-2-yl, 3-aminobut- 2-yl, 4-amino-but-2-yl, 1- (CH 2 NH 2 ) eth-1-yl, 1- (CH 2 NH 2 ) -1 - (CH 3 ) -eth-1-yl or 1- (CH 2 NH 2 ) prop -1-yl;
  • Heterocyclyl-C ⁇ -C-alkyl for: heterocyclylmethyl, 1-heterocyclic-ethyl, 2-heterocyclyl-ethyl, 1-heterocyclyl-prop-l-yl,
  • C ⁇ -C 4 -haloalkoxy for: a C ⁇ -C-alkoxy radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, e.g. OCHF, OCHF, OCF 3 , 0CH 2 C1, OCH ( Cl) 2 , 0C (C1) 3 , chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 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, OC F 5 , 2-fluoropropoxy, 3-fluoropropoxy, 2,
  • - C ⁇ -Cg-alkoxy for: a C ⁇ -C 4 alkoxy radical as mentioned above, or for example n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2, 2-dimethylpropoxy, 1-ethylpropoxy, n -Hexoxy, 1,1-dimethylpropoxy, 1, 2-dimethylpropoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy, 1, 3 -Dimethylbutoxy, 2, 2-dimethylbutoxy,
  • - C ⁇ -Cg-haloalkoxy for: a C ⁇ -Cg-alkoxy radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example one of the radicals mentioned under C ⁇ -C 4 -haloalkoxy or for 5 - fluorine-1-pentoxy, 5-chloro-1-pentoxy, 5-bromo-1-pentoxy, 5-iodo-1-pentoxy, 5, 5, 5-trichloro-1-pentoxy, undecafluoropentoxy, 6-fluorine l-hexoxy, 6-chloro-l-hexoxy, 6-bromo-l-hexoxy, 6-iodo-l-hexoxy, 6,6,6-trichloro-1-hexoxy or dodecafluorohexoxy;
  • C ⁇ -C -haloalkylthio for: a C ⁇ -C 4 -alkylthio radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example SCH F, SCHF 2 , SCF 3 SCH 2 C1, SCH (C1) 2 , SC (C1) 3 , chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2, 2-difluoroethylthio, 2, 2, 2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2, 2-dichloro-2-fluoroethylthio, 2, 2, 2-t
  • - C ⁇ -C 6 -alkylthio for: a C ⁇ -C 4 -alkylthio radical as mentioned above, or for example n-pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2, 2-dirnethylpropylthio, 1-ethyl- propylthio, n-hexylthio, 1, 1-dimethylpropylthio, 1, 2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1, 1-dimethylbutylthio, 1,2-di- methylbutylthio, 1, 3-dimethylbutylthio, 2, 2-dimethylbutylthio, 2, 3-dimethylbutylthio, 3, 3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio
  • C ⁇ -C -alkoxy-C ⁇ -C 4 -alkyl for: C ⁇ -C 4 -alkoxy - as mentioned above - substituted C ⁇ -C 4 -alkyl, for example for CH 2 -OCH 3 , CH 2 -OC 2 H 5 , n-propoxymethyl, CH 2 -OCH (CH 3 ) 2 , n-butoxymethyl, (l-methylpropoxy) methyl, (2-methylpropoxy) methyl, CH 2 -OC (CH 3 ) 3 , 2- (Methoxy) ethyl, 2- (ethoxy) ethyl, 2- (n-propoxy) ethyl, 2- (1-methylethoxy) ethyl, 2- (n-butoxy) ethyl, 2- (1-methylpropoxy) ethyl, 2- (2-methylpropoxy) ethyl, 2- (l, l-dimethylethoxy) ethyl, 2- (methoxy) propyl
  • C ⁇ -C-haloalkoxy-C ⁇ -C 4 ⁇ alkyl for: C ⁇ -C 4 -haloalkoxy substituted as mentioned above C ⁇ -C 4 alkyl, for example for 2- (OCHF 2 ) ethyl, 2- (OCF 3 ) ethyl or 2- (OC 2 F 5 ) ethyl;
  • C ⁇ -C 4 -Alkylthio-C C-C -alkyl for: C ⁇ -C 4 -alkylthio - as mentioned above - substituted C C-C-alkyl, for example for CH 2 -SCH 3 , CH 2 -SC 2 H 5 , n-propylthiomethyl, CH 2 -SCH (CH 3 ) 2 , n-butylthiomethyl, (l-methylpropylthio) methyl, (2-methylpropylthio) methyl, CH 2 -SC (CH 3 ) 3 , 2- (methylthio) ethyl, 2- (ethylthio) - ethyl, 2- (n-propylthio) ethyl, 2- (1-methylethylthio) ethyl, 2- (n-butylthio) ethyl, 2- (1-methylpropylthio) ethyl, 2- (2 -Methyl-propyl,
  • C ⁇ -C4-haloalkylthio-C ⁇ -C 4 alkyl by C ⁇ -C 4 halo-alkylthio as mentioned above substituted C ⁇ -C4 alkyl, that is ethyl for example, 2- (SCHF 2), 2- ( SCF 3 ) ethyl or 2- (SC 2 F 5 ) ethyl;
  • C ⁇ -C 4 alkyl carbonyl for: C0-CH 3 , CO-C 2 H 5 , CO-CH 2 -C 2 H 5 , CO-CH (CH 3 ) 2 , n-butylcarbonyl, CO-CH (CH 3 ) -C 2 H 5 , CO-CH 2 -CH (CH 3 ) 2 or CO-C (CH 3 ) 3 , preferably for CO-CH 3 or CO-C 2 Hs;
  • (C ⁇ -C 4 -haloalkyl) carbonyl for: a (C ⁇ -C 4 -alkyl) carbonyl radical - as mentioned above - which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example CO- CH 2 F, CO-CHF 2 , CO-CF 3 , C0-CH 2 C1, C0-CH (C1) 2 , C0-C (C1) 3 , chlorofluoromethylcarbonyl, dichlorofluoromethylcarbonyl, chlorodifluoromethylcarbonyl, 2-fluoroethylcarbonyl, 2- Chloroethylcarbonyl, 2-bromoethylcarbonyl, 2-iodoethylcarbonyl, 2, 2-difluoroethylcarbonyl, 2, 2, 2-trifluoroethylcarbonyl, 2-chloro-2-fluoroethylcarbonyl, 2-chloro-2, 2-di
  • (C ⁇ -Cg-alkyl) carbonyl for: one of the abovementioned (Cx -C 4 alkyl) carbonyl radicals, or for example n-pentyl-CO, 1-methyl-butyl-CO, 2-methylbutyl -C0, 3-methylbutyl- CO, 2, 2-dimethylpropyl-CO, 1-ethylpropyl-CO, n-hexyl-CO, 1, 1-dimethylpropyl-CO, 1,2-dirnethylpropyl -C0, 1-methylpentyl-CO, 2-methylpentyl- CO, 3-methylpentyl-CO, 4-methylpentyl-CO, 1, 1-dimethylbutyl-CO, 1,2-dimethylbutyl-CO, 1, 3-dimethylbutyl -CO, 2, 2-dimethylbutyl - CO, 2,3-dimethylbutyl-CO, 3, 3-dimethylbutyl -CO, 1-ethylbutyl-
  • (C ⁇ -Cg-haloalkyl) carbonyl for: a (C ⁇ -Cg-alkyl) carbonyl radical - as mentioned above - which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example CO-CH 2 F, CO-CHF 2 , CO-CF 3 , C0-CH 2 C1, C0-CH (C1) 2 , C0-C (C1) 3 , chlorofluoromethylcarbonyl, dichlorofluoromethylcarbonyl, chlorodifluoromethylcarbonyl, 2-fluoroethylcarbonyl, 2-chloroethylcarbo- nyl, 2-bromoethylcarbonyl, 2-iodoethylcarbonyl, 2, 2-difluoroethyl - __ carbonyl, 2, 2, 2-trifluoroethylcarbonyl, 2-chloro-2-fluoroethylcarbonyl, 2-ch
  • (C ⁇ -C-Alkyl) carbonyloxy for: 0-CO-CH 3 , 0-CO-C 2 H 5 , 0-CO-CH 2 -C 2 H 5 , 0-CO-CH (CH 3 ) 2 , 0 -CO-CH 2 -CH 2 -C 2 H 5 , O-CO-CH (CH 3 ) -C 2 H 5 , 0 0-CO-CH 2 -CH (CH 3 ) 2 or O-CO-C ( CH 3 ) 3 , preferably for 0-CO-CH 3 or 0-CO-C 2 H 5 ;
  • (C ⁇ -C haloalkyl) carbonyloxy for: a (C ⁇ -C 4 alkyl) carbonyl radical - as mentioned above - which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 0 -CO-CH 2 F, 0-CO-CHF 2 , 0-CO-CF 3 , 0-CO-CH 2 Cl, O-CO-CH (CD 2 , O-CO-C (CD 3 , chlorofluoromethylcarbonyloxy, dichlorofluoromethylcarbonyloxy , Chlorodifluoromethylcarbonyloxy, 2-fluoroethylcarbonyloxy, 2-chloroethylcarbonyloxy, 2-bromoethyl-0 carbonyloxy, 2-iodoethylcarbonyloxy, 2, 2-difluoroethylcarbonyloxy, 2,2, 2-trifluoroethylcarbonyloxy, 2-chloro-2
  • (C ⁇ -C-alkyl) carbonyloxy for: one of the above (C ⁇ -C 4 -alkyl) carbonyloxy radicals, or for example n-pentyl-COO,
  • (C ⁇ -C 6 alkyl) thiocarbonyl for: CS-CH 3 , CS-C 2 H 5 , CS-CH 2 -C 2 H 5 , CS-CH (CH 3 ) 2 , CS- (nC 4 H 9 ) , CS-CH (CH 3 ) -C 2 H 5 , CS-CH 2 -CH (CH 3 ) 2 , CS-C (CH 3 ) 3 , CS- (nC 5 H ⁇ ), CS-CH (CH 3 ) -CH 2 -C 2 H 5 , CS-CH 2 -CH (CH 3 ) -C 2 H 5 , CS-CH 2 CH 2 -CH (CH 3 ) 2 , CS-C (CH 3 ) 2 -C 2 H 5 , CS-CH (CH 3 ) -CH (CH 3 ) 2 , CS-CH 2 -C (CH 3 ) 3 , CS-CH (C 2 H 5 -C 2
  • (C ⁇ -C -alkoxy) carbonyl for: CO-OCH 3 , CO-OC 2 H 5 , CO-OCH 2 -C 2 H 5 , CO-OCH (CH 3 ) 2 , n-butoxycarbonyl, CO-OCH (CH 3 ) -C 2 H 5 , CO-OCH 2 -CH (CH 3 ) 2 or CO-OC (CH 3 ) 3 , preferably for CO-OCH 3 or CO-OC 2 H 5 ;
  • (C ⁇ -C 6 -alkoxy) carbonyl for: one of the above (C ⁇ -C-alkoxy) carbonyl radicals, or for example n-pentoxy-CO, 1-methylbutoxy-CO, 2-methylbutoxy-CO, 3-methylbutoxy- CO, 2, 2-dimethyl-propoxy-CO, 1-ethylpropoxy-CO, n-hexoxy-CO, 1, 1-dimethyl-propoxy-CO, 1, 2-dimethylpropoxy-CO, 1-methylpentoxy-CO, 2- Methylpentoxy-CO, 3-methylpentoxy-CO, 4-methylpentoxy-CO, 1,1-dimethylbutoxy-CO, 1, 2-dimethylbutoxy-CO, 1, 3-dimethylbutoxy-CO, 2, 2-dimethylbutoxy-CO, 2, 3-dimethylbutoxy-CO, 3, 3-dimethylbutoxy-CO, 1-ethylbutoxy-CO, 2-ethylbutoxy-CO, 1, 1, 2-trimethylpropoxy-CO, 1,2,2-trimethylpropoxy
  • (C ⁇ -Cg-Alkoxy) thiocarbonyl for: e.g. CS-OCH 3 , CS-OC 2 H 5 , CS-OCH 2 -C 2 H 5 , CS-OCH (CH 3 ) 2 , CS-0 (nC 4 H 9 ), CS-OCH (CH 3 ) -C 2 H 5 , CS-OCH 2 -CH (CH 3 ) 2 , CS-OC (CH 3 ) 3 , CS-0 (nC 5 H ⁇ ), CS-OCH (CH 3 ) -CH 2 -C 2 H 5 , CS-OCH 2 -CH (CH 3 ) -C 2 H 5 , CS-OCH 2 CH 2 -CH (CH 3 ) 2 , CO-OCH 2 -C (CH 3 ) 3 , CS- OCH (C 2 H 5 ) -C 2 H 5 , CS-0 (n-CgH 13 ), CS-
  • CO-SCH 3 CO-SC 2 H 5 , CO-SCH 2 -C 2 H 5 , CO-SCH (CH 3 ) 2 .
  • CO-SCH 2 CH 2 -C 2 H 5 CO-SCH (CH 3 ) -C 2 H 5 , CO-SCH 2 -CH (CH 3 ) 2 or CO-SC (CH 3 ) 3 , preferably for CO- SCH 3 or CO-SC H 5 ;
  • a C ⁇ -C -alkylsulf inyl for: a C ⁇ -C -alkylsulf inylrest such as SO-CH 3 , SO-C 2 H 5 , SO-CH 2 -C 2 H 5 , SO-CH (CH 3 ) 2 , SO - (nC 4 H 9 ), SO-CH (CH 3 ) -C 2 H 5 , SO-CH 2 -CH (CH 3 ) 2 or SO-C (CH 3 ) 3 , or for example SO- (nC 5 H ⁇ ), 1-methylbutyl-SO, 2-methylbutyl-SO, 3-methylbutyl-SO, 2,2-dryness thylpropyl-SO, 1-ethylpropyl-SO, n-hexyl-SO, 1,1-dimethylpropyl -SO, 1, 2-dimethylpropyl-SO, 1-methylpentyl-
  • C ⁇ -C 4 -alkylsulfinyl-C ⁇ -C 4 -alkyl for: C ⁇ -C 4 -alkylsulfinyl substituted as above-mentioned C ⁇ -C-alkyl, for example for CH 2 SOCH 3 , CH 2 SOC 2 H 5 , n- Propylsulfinylmethyl, CH 2 SOCH (CH 3 ) 2 , n-butylsulfinylmethyl, (1-methylpropylsulfinyDmethyl, (2-methylpropylsulfinyDmethyl, (1, 1-dimethylethylsulfinyl) methyl, 2-methylsulfinylethyl, 2-ethylsulfinylethyl, 2- (n-propylsulfinyl ethyl, 2- (1-methylethylsulfinyl) ethyl, 2- (n-butylsulfinyl) e
  • C ⁇ -C -haloalkylsulfinyl-C ⁇ -C 4 -alkyl for: C ⁇ -C -haloalkylsulfinyl substituted as mentioned above C -C -alkyl, for example for 2- (2, 2, 2-trifluoroethylsulfinyl) ethyl;
  • - C ⁇ -C 4 -haloalkylsulfonyl for: a C ⁇ -C 4 -alkylsulfonyl radical - as mentioned above - which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example S0 2 -CH 2 F, S0 2 - CHF 2 , S0 2 -CF 3 , S0 2 -CH 2 C1, S0 2 -CH (C1) 2 , S0 2 -C (C1) 3 , chlorofluoroethylsulfonyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl , 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2, 2-difluoroethy
  • S0 2 -CF 2 -C 2 F 5 1- (fluoromethyl) -2-fluoroethylsulfonyl, 1- (chloromethyl) -2-chloroethylsulfonyl, 1- (bromomethyl) -2-bromethyl- sulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4-bromobutylsulfonyl or nonafluorobutylsulfonyl, preferably for S0 2 -CHC1, S0 -CF 3 or 2, 2, 2-trifluoroethylsulfonyl;
  • C ⁇ -Cg-alkylsulfonyl for: a C ⁇ -C 4 -alkylsulfonyl radical as mentioned above, or for example S0 - (n-CsH ⁇ ), 1-methylbutyl-S0 2 , 2-methylbutyl - S0 2 , 3-methylbutyl - S0 2 , 2 , 2-Dirnethylpropyl - S0 2 , 1-ethylpropyl-S0 2 , n-hexyl-S0 2 , 1, 1-dimethylpropyl-S0 2 , 1,2-dimethylpropyl - SO2, 1-methylpentyl-S0 2 , 2- Methylpentyl-S0 2 , 3-methylpentyl-S0 2 , 4-methylpentyl-S0 2 , 1, 1-dimethylbutyl-S0 2 , 1,2-dirnethylbutyl -S0 2 , 1, 3-dimethylbutyl
  • C ⁇ -C 4 alkylsulfonyl-C ⁇ -C 4 alkyl by C ⁇ -C 4 alkylsulfonyl as mentioned above substituted C ⁇ -C4 alkyl, eg CH 2 S0 2 CH 3, CH 2 SO 2 -C 2 H 5 , CH 2 S0 2 -CH 2 -C 2 H 5 , CH 2 S0 2 -CH (CH 3 ) 2 , CH 2 SO 2 -CH 2 CH 2 -C 2 H 5 , (l-methylpropylsulfonyl) methyl , (2-MethylpropylsulfonyDmethyl, CH 2 S0 2 -C (CH 3 ) 3 , CH (CH 3 ) S0 2 -CH 3 , CH (CH 3 ) S0 2 -C 2 H 5 , CH 2 CH 2 S0 2 -CH 3 , CH 2 CH 2 SO 2 -C 2 H 5 , CH 2 CH 2 S0 2 -CH 2 -C 2 H 5 ,
  • C ⁇ -C 4 -alkylamino-C ⁇ -C -alkyl for: by C Maschinen-C 4 -alkylamino such as H 3 C-NH-, H 5 C 2 - H-, n-propyl-NH-, 1-methylethyl-NH -, n-Butyl- H-, 1-methylpropyl-NH-, 2-methylpropyl-NH- and 1, 1-dimethylethyl-NH-, preferably H 3 C-NH- or H 5 C 2 - H-, substi- tuiert C ⁇ -C 4 alkyl, for example for CH 2 CH 2 -NH-CH 3 , CH 2 CH 2 -N (CH 3 ) 2 , CH 2 CH 2 -NH-C 2 H 5 or CH 2 CH 2 - N (C 2 H 5 ) 2 ;
  • CO-NH-CH 3 CO-NH-C 2 H 5 , n-propyl - a ino, CO-NH-CH (CH 3 ) 2 , CO-NH- CH 2 CH 2 -C 2 H 5 , CO-NH-CH (CH 3 ) -C 2 H 5 , CO-NH-CH 2 -CH (CH 3 ) 2 or CO-NH-C (CH 3 ) 3 , preferably for CO-NH-CH 3 or CO-NH-C 2 H 5 ;
  • (C ⁇ -Cg-alkylamino) carbonyl for: one of the abovementioned (C ⁇ -C 4 -alkylamino) carbonyl radicals, or for example CO-NH- (n-CsH ⁇ ), 1-methylbutyl-NHCO-, 2-methylbutyl -NHCO-, 3-Methylbutyl-NHCO-, 2, 2-Dirnethylpropyl -NHCO-, 1-Ethylpropyl-NHCO-, CO-NH- (nC 6 H 13 ), 1,1-Dimethylpropyl-NHCO-, 1, 2-Dirnethylpropyl -NHCO -, 1-Methyl-pentyl-NHCO-, 2-methylpentyl-NHCO-, 3-methylpentyl-NHCO-, 4-methylpentyl-NHCO-, 1, 1-dimethylbutyl -NHCO-, 1, 2-dirnethylbutyl - NHCO -, 1, 3-D
  • (C ⁇ -C 4 -alkylamino) carbonyl-C ⁇ -C 4 -alkyl for: (C ⁇ -C 4 -alkylamino) carbonyl as mentioned above, preferably CO-NH-CH 3 or CO-NH-C 2 H 5 , substituted C ⁇ -C-alkyl, for example for CH 2 -CO-NH-CH 3 , CH 2 -CO-NH-C 2 H 5 , CH 2 -CO-NH-CH 2 -C 2 H 5 , CH 2 - CO-NH-CH (CH 3 ) 2 , CH 2 -CO-NH-CH 2 CH 2 -C 2 H 5 , CH 2 -CO-NH-CH (CH 3 ) -C 2 H 5 , CH 2 -CO -NH-CH 2 -CH (CH 3 ) 2, CH 2 -CO-NH-C (CH 3 ) 3 , CH (CH 3 ) -CO-NH-CH 3 , CH (CH 3 ) -CO-NH- C 2
  • Di (C ⁇ -C 4 alkyl) aminocarbonyl for: CO-N (CH 3 ) 2 , CO-N (C 2 H 5 ), CO-N (CH 2 -C 2 H 5 ) 2 , CO-N [CH (CH 3 ) 2 ] 2 , N, N-dibutylaminocarbonyl, CO-N [CH (CH 3 ) -C 2 H 5 ] 2, CO-N [CH 2 -CH (CH 3 ) 2 ] 2, CO-N [C (CH 3 ) 3] 2 , N-ethyl-N-methylaminocarbonyl, N-methyl-N-propylaminocarbonyl, N-methyl-N- [CH (CH 3 ) 2 ] aminocarbonyl, N-butyl-N-methylamino - carbonyl, N-methyl-N- (1-methylpropyl) aminocarbonyl, N-methyl-N- (2-methylpropyl) aminocarbonyl, N- [C (CH 3 )
  • Di (C ⁇ -Cg-alkyl) aminocarbonyl for: one of the aforementioned di (C 1 -C 4 alkyl) aminocarbonyl radicals or, for example, N (CH 3 ) - (nC 5 H ⁇ ), N (C 2 H 5 ) - (nC 5 H ⁇ ), N (CH 2 -C 2 H 5 ) - (nC 5 H ⁇ ),
  • Di (C ⁇ -C 4 -alkyl) aminocarbonyl-C ⁇ -C-alkyl for: by di (C ⁇ -C 4 -alkyl) aminocarbonyl as mentioned above, preferably CO-N (CH 3 ) 2 or CO-N (C2H 5 ) 2 , substituted C ⁇ -C 4 alkyl, for example for CH 2 -CO-N (CH 3 ) 2 , CH 2 -CO-N (C 2 H 5 ) 2 , CH (CH 3 ) -CO-N (CH 3 ) 2 or CH (CH 3 ) -CO-N (C 2 H 5 ) 2 , preferably for CH 2 -CO-N (CH 3 ) 2 or CH (CH 3 ) -CO-N (CH 3 ) 2 ;
  • N-butyl-N- (2-methylpropyl) phosphonyl N-butyl-N- (1, 1-dimethylethyl) phosphonyl, N- (1-methylpropyl) -N- (2-methylpropyl) - phosphonyl, N- (1, 1-dimethylethyl) -N- (1-methylpropyl) phosphonyl or N- (1, 1-dimethylethyl) -N- (2-methylpropyl) phosphonyl, preferably -PO (OCH 3 ) 2 or - PO (OC 2 Hs) 2 , substituted C 1 -C 4 alkyl, e.g.
  • CH 2 -PO (OCH 3 ) 2 CH 2 -PO (OC 2 H 5 ) 2 , CH (CH 3 ) -PO ( OCH 3 ) 2 or CH (CH 3 ) -PO (OC 2 H 5 ) 2 ;
  • haloalkenyl for: C 3 -Cg alkenyl as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 2-chloroallyl, 3-chloroallyl, 2,3- Dichlorallyl, 3, 3-dichlorallyl, 2, 3, 3-trichlorallyl,
  • Cyano -C 3 -C 6 alkenyl for: for example 2-cyanoallyl, 3-cyanoallyl,
  • haloalkynyl for: C 3 -Cg alkynyl as mentioned above, partially or completely by fluorine, chlorine, bromine and / or
  • Iodine is substituted, e.g. 1, 1-difluoroprop-2-in-l-yl, 4-fluorobut-2-in-l-yl, 4-chlorobut-2-in-l-yl, 1, 1-difluorobut-2-in-l- yl, 5-fluoropent-3-in-1-yl or 6-fluorohex-4-in-1-yl;
  • Cyano-C 3 -Cg-alkynyl for: for example 3-cyanopropargyl, 4-cyanobut-2-in-l-yl, 5-cyanopent-3 -in-l-yl and 6-cyanohex-4 -in-l-yl ;
  • C 3 -C 4 alkenyloxy-C ⁇ -C 4 alkyl for: by C 3 -C 4 alkenyloxy such as allyloxy, but-l-en-3-yloxy, but-l-en-4-yloxy, but-2 -en-l-yloxy, l-methylprop-2-enyloxy or 2-methylprop-2-enyloxy substituted C ⁇ -C 4 alkyl, for example for allyloxymethyl, 2-allyloxyethyl or but-l-en-4-yloxymethyl, in particular for 2-allyloxyethyl;
  • C 3 -C 4 alkynyloxy-C ⁇ -C 4 alkyl for: by C 3 -C 4 alkynyloxy such as propargyloxy, but-l-in-3-yloxy, but-l-in-4-yloxy, but-2 -in-1-yloxy, 1-methylprop-2-ynyloxy or 2-methylprop-2-ynyloxy, preferably propargyloxy, substituted C ⁇ -C alkyl, for example for propargyloxymethyl or 2-propargyloxyethyl, especially for 2-propargyloxyethyl;
  • C 3 -C 4 alkenylthio-C ⁇ -C alkyl for: by C 3 -C alkenylthio such as allylthio, but-l-en-3-ylthio, but-l-en-4-ylthio, but-2- en-l-yl-thio, l-methylprop-2-enylthio or 2-methylprop-2-enylthio substituted C ⁇ -C-alkyl, so for example for allylthio-methyl, 2-allylthioethyl or but-l-en-4-ylthiomethyl , especially for 2- (allylthio) ethyl;
  • C 3 -C 4 alkynylthio-C ⁇ -C 4 alkyl for: by C 3 -C 4 alkynylthio such as propargylthio, but-l-in-3-ylthio, but-l-in-4-ylthio, but- 2-in-l-ylthio, l-methylprop-2-inylthio or 2-methyl-prop-2-inylthio, preferably propargylthio, substituted C ⁇ -C 4 alkyl, for example for propargylthiomethyl or 2-propargylthioethyl, especially for 2- (propargylthio) ethyl;
  • C 3 -C 4 alkynylthio such as propargylthio, but-l-in-3-ylthio, but-l-in-4-ylthio, but- 2-in-l-ylthio, l-methylprop-2-inylthio or 2-methyl-prop-2-inylthio,
  • C 3 -C 4 alkenylsulfinyl-C ⁇ -C 4 alkyl for: by C 3 -C 4 alkenylsulfyl such as allylsulfinyl, but-l-en-3-ylsulfinyl, but-l-en-4-yl- sulfinyl, but-2-en-l-ylsulfinyl, l-methylprop-2-enylsulfinyl or 2-methylprop-2-enylsulfinyl substituted C ⁇ -C 4 ⁇ alkyl, for example for allylsulfinylmethyl, 2-allylsulfinylethyl or but-l-en- 4-ylsulfinylmethyl, especially for 2- (allylsulfinyl) ethyl;
  • C 3 -C 4 alkenylsulfyl such as allylsulfinyl, but-l-en-3-ylsulfin
  • C 3 -C 4 -Alkynylsulfinyl-C ⁇ -C 4 -alkyl for: by C 3 -C -alkynyl-sulfinyl such as propargylsulfinyl, but-l-in-3-ylsulfinyl, but-1- in-4-ylsulfinyl, but -2-in-l-ylsulfinyl, l-methylprop-2-inylsulfinyl or 2-methylprop-2-inylsulfinyl, preferably propargylsulfinyl, substituted C ⁇ -C 4 alkyl, for example for propargylsulfinylmethyl or 2-propargylsulfinylethyl, in particular for 2 - (propargylsulfinyl) ethyl;
  • C 3 -C -alkynyl-sulfinyl such as propargylsulf
  • C 3 -C 4 alkenylsulfonyl-C ⁇ -C 4 alkyl for: by C 3 -C alkenylsulfonyl such as allylsulfonyl, but-1-en-3-ylsulfonyl, but-1-en-4-yl-sulfonyl, But-2-en-l-ylsulfonyl, l-methylprop-2-enylsulfonyl or 2-methylprop-2-enylsulfonyl substituted C ⁇ -C 4 alkyl, e.g. for allylsulfonylmethyl, 2-allylsulfonylethyl or but-l-en- 4-ylsulfonylmethyl, especially for 2- (allylsulfonyl) ethyl;
  • C 3 -C 4 alkynylsulfonyl-C ⁇ -C 4 -alkyl for: by C 3 -C 4 -alkynylsulfonyl such as propargylsulfonyl, but-l-in-3-ylsulfonyl, but-l-in-4-ylsulfonyl, but -2-in-l-ylsulfonyl, l-methylprop-2-inylsulfonyl or 2-methylprop-2-inylsulfonyl, preferably propargylsulfonyl, substituted C ⁇ -C 4 alkyl, that is, for example, for propargylsulfonylmethyl or 2-propargylsulfonylethyl, in particular for 2 - (propargylsulfonyl) ethyl;
  • C 3 -C 4 -alkynylsulfonyl such as propargyls
  • cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
  • cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl;
  • C 3 -C 8 cycloalkyloxy-C ⁇ -C 4 alkyl for: cyclopropyloxymethyl, 1-cyclopropyloxy-ethyl, 2-cyclopropyloxy-ethyl, 1-cyclopropyl-oxy-prop-1-yl, 2-cyclopropyloxy-prop-l- yl, 3-cyclopropyloxy-prop-1-yl, 1-cyclopropyloxy-but-l-yl, 2-cyclopropyloxy-but-1-yl, 3-cyclopropyloxy-but-l-yl, 4-cyclopropyloxy-but-l- yl, l-cyclopropyloxy-but-2-yl, 2-cyclopropyloxy-but-2-yl, 3-cyclopropyloxy-but-2-yl, 3-cyclopropyloxy-but-2-yl, 4-cyclopropyl-oxy-but-2-yl, 1- (cyclopropyloxymethyl) -eth-l-
  • heterocycles with one to three heteroatoms selected from a group consisting of one to three nitrogen atoms, one or two oxygen and - one or two sulfur atoms.
  • saturated heterocycles which can contain a carbonyl or thiocarbonyl ring member are: oxiranyl, thiiranyl, aziridin-1-yl, aziridin-2-yl, diaziridin-1-yl, diaziridin-3-yl, oxetan-2- yl, oxetan-3-yl, thietan-2-yl, thietan-3-yl, azetidin-1-yl, azetidin-2-yl, azetidin-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3- yl, tetrahydrothiophene-2-yl, tetrahydrothiophene-3-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, 1, 3-dioxolan-2-yl, 1, 3-dio
  • unsaturated heterocycles which may contain a carbonyl or thiocarbonyl ring member are: dihydrofuran-2-yl, 1, 2-oxazolin-3 -yl, 1, 2-oxazolin-5 -yl, 1, 3 -oxazolin- 2-yl;
  • heteroaromatics the 5- and 6-membered ones are preferred, e.g.
  • Furyl such as 2-furyl and 3-furyl, thienyl such as 2-thienyl and 3-thienyl, pyrrolyl such as 2-pyrrolyl and 3-pyrrolyl, isoxazolyl such as 3-isoxazolyl, 4-isoxazolyl and 5-isoxazolyl, isothiazolyl such as 3-isothiazolyl, 4-isothiazolyl and 5-isothiazolyl, pyrazolyl such as 3-pyrazolyl, 4-pyrazolyl and 5-pyrazolyl, oxazolyl such as 2-oxazolyl, 4-0xazolyl and 5-oxazolyl, thiazolyl such as 2-thiazolyl, 4-thiazolyl and 5-thiazolyl, Imidazolyl such as 2-imidazolyl and 4-imidazolyl, oxadiazolyl such as 1, 2, 4-oxadiazol-3-yl,
  • All phenyl, carbocyclic and heteroeyclic rings are preferably unsubstituted.
  • R 1 is hydrogen, amino or C ⁇ -Cg-alkyl, in particular hydrogen or C ⁇ -C 4 -alkyl, particularly preferably hydrogen or methyl;
  • R 2 is hydrogen, halogen, C ⁇ -Cg-alkyl, C ⁇ -Cg-haloalkyl or C ⁇ -Cg-alkylsulfonyl, especially trifluoromethyl;
  • R 3 is hydrogen
  • R 4 is hydrogen, fluorine or chlorine
  • R 5 cyano or halogen, especially chlorine
  • R 6 C ⁇ -C 6 alkyl, C 3 -Cg alkenyl, C 3 -Cg alkynyl, Cx -Cg alkylsulfonyl, (C ⁇ -Cg alkyl) carbonyl, (C ⁇ -Cg alkyl) thiocarbonyl, (C ⁇ - Cg-alkoxy) carbonyl or C ⁇ -Cg-alkyl, which can be substituted by cyano, (C ⁇ -Cg-alkoxy) carbonyl, di (C ⁇ -Cg-alkyl) aminocarbonyl or (C ⁇ -Cg-alkyl) - carbonyloxy can, in particular C ⁇ -Cg-alkyl, C 3 -Cg-alkynyl, C ⁇ -Cg -alkylsulfonyl or (C ⁇ -C 6 -alkoxy) carbonyl.
  • L 1 represents a common leaving group such as halogen, preferably chlorine, bromine or iodine, (halogen) alkylsulfonyloxy, preferably methylsulfonyloxy or trifluoromethylsulfonyloxy, arylsulfonyloxy, preferably toluenesulfonyloxy, and alkoxysulfonyloxy, preferably methoxysulfonyloxy or ethoxysulfonyloxy.
  • halogen preferably chlorine, bromine or iodine
  • alkylsulfonyloxy preferably methylsulfonyloxy or trifluoromethylsulfonyloxy
  • arylsulfonyloxy preferably toluenesulfonyloxy
  • alkoxysulfonyloxy preferably methoxysulfonyloxy or ethoxysulfonyloxy.
  • an inert organic solvent for example in a protic solvent such as the lower alcohols, preferably in methanol or ethanol, if desired in a mixture with water, or in an aprotic solvent, e.g. in an aliphatic or cyclic ether such as methyl tert.
  • -butyl ether 1, 2-dimethoxyethane, tetrahydrofuran and dioxane, in an aliphatic ketone such as acetone, diethyl ketone and ethyl methyl ketone, in an amide such as dimethylformamide and N-methylpyrrolidone, in a sulfoxide such as dimethyl sulfoxide, in a urea such as tetramethyl urea and 1, 3 -Dimethyltetrahydro-2 (IH) pyrimidinone, in a carboxylic acid ester such as ethyl acetate, or in a halogenated aliphatic or aromatic hydrocarbon such as dichloromethane, dichloroethane, chlorobenzene and the dichlorobenzenes.
  • an aliphatic ketone such as acetone, diethyl ketone and ethyl methyl ketone
  • amide such as dimethylformamide
  • a base both inorganic bases, e.g. Carbonates such as sodium carbonate and potassium carbonate, hydrogen carbonates such as
  • Bases for example amines such as triethylamine, pyridine and N, N-diethylaniline, or alkali metal alcoholates such as sodium methoxide, sodium ethoxide and potassium tert. -butanolate are suitable.
  • reaction temperature is from 0 ° C to the boiling point of the reaction mixture, in particular from 0 to 60 ° C.
  • the salts of those compounds I in which R 1 is hydrogen can also be obtained in a manner known per se from the process products of methods C) to F).
  • the aqueous solution of an inorganic or organic base is mixed with the 3 - (benzazole-4-yDpyrimidinedione derivative I, in which R 1 is hydrogen.
  • the salt formation is then usually already at 20 to 25 ° C. with sufficient Speed.
  • the corresponding salt of 3 - (benzazol-4-yDpyrimidinedione derivative I can then be used, for example, by precipitation with a suitable inert solvent or by evaporation of the solvent can be isolated.
  • Salts of the 3 - (benzazole-4-yDpyrimidinedione derivatives I, the metal ion of which is not an alkali metal ion, can usually be prepared by salting the corresponding alkali metal salt in aqueous solution, as well as ammonium, Phosphonium, sulfonium and sulfoxonium salts using ammonia, phosphonium, sulfonium or sulfoxonium hydroxides.
  • 2,4-dinitrophenoxyamine has proven particularly useful as an amination reagent, however, e.g. hydroxylamine-O-sulfonic acid (HOSA) can also be used, which is already known from the literature as an amination reagent (cf. e.g.
  • HOSA hydroxylamine-O-sulfonic acid
  • the amination can be carried out in a manner known per se (see, for example, T. Sheradsky, Tetrahedron Lett. 1968, 1909; MP Wentland et al., J. Med. Chem. 22 (1984) 1103 and in particular EP-A 240 194, EP -A 476 697 and EP-A 517 181, where the amination of uracil is taught).
  • reaction is carried out in a polar solvent, e.g. in dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or in ethyl acetate, which has so far proven to be particularly suitable.
  • a polar solvent e.g. in dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or in ethyl acetate, which has so far proven to be particularly suitable.
  • Suitable bases are, for example, alkali metal carbonates such as potassium carbonate, alkali metal alcoholates such as sodium methylate and potassium tert. -butanolate or alkali metal hydrides such as sodium hydride.
  • the amount of base and aminating agent is preferably 0.5 to 2 times the molar amount, based on the amount of starting compound.
  • the sulfurization is usually carried out in an inert solvent or diluent, for example in an aromatic hydrocarbon such as toluene and the xylenes, in an ether such as diethyl ether, 1, 2-dimethoxyethane and tetrahydrofuran, or in an organic amine such as pyridine.
  • an inert solvent or diluent for example in an aromatic hydrocarbon such as toluene and the xylenes, in an ether such as diethyl ether, 1, 2-dimethoxyethane and tetrahydrofuran, or in an organic amine such as pyridine.
  • Phosphorus (V) sulfide and 2,4-bis (4-methoxyphenyl) -1,3,4,4-dithiadiphosphetane-2,4-dithione are particularly suitable as the sulfurization reagent.
  • the reaction temperature is normally 20 to 200 ° C, preferably 40 ° C to the boiling point of the reaction mixture.
  • L 2 means low molecular weight alkyl, preferably C ⁇ -C 4 alkyl, or phenyl.
  • cyclization is carried out in an inert organic solvent or diluent which is aprotic, for example in an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aromatic compound such as benzene and toluene or in a polar solvent such as dimethylformamide and dimethyl sulfoxide.
  • a polar solvent such as dimethylformamide and dimethyl sulfoxide.
  • polar solvent such as dimethylformamide and dimethyl sulfoxide
  • water can also be suitable as a diluent.
  • Suitable bases are preferably alkali metal alcoholates, in particular the sodium alcoholates, alkali metal hydroxides, in particular sodium hydroxide and potassium hydroxide, alkali metal carbonates, in particular sodium carbonate and potassium carbonate, and metal hydrides, in particular sodium hydride.
  • sodium hydride it has proven advantageous to work in an aliphatic or cyclic ether, in dimethylformamide or in dimethyl sulfoxide. Normally, 0.5 to 2 times the molar amount of base, based on the amount of IV or V, is sufficient for the reaction to succeed.
  • reaction temperature is from (-78) ° C to the boiling point of the respective reaction mixture, in particular from (-60) to 60 ° C.
  • R 1 in formula III or IV is hydrogen
  • the product of the process is obtained as a metal salt, the metal corresponding to the cation of the base used.
  • the ring closure reaction can be carried out by a method known per se (cf. e.g. Houben-Weyl, Methods of Organic Chemistry,
  • the reaction is preferably carried out in acidic, aqueous media, but lower carboxylic acids such as acetic acid are also suitable diluents.
  • Dilute mineral acids for example 10% hydrochloric acid, are particularly suitable as acidic aqueous solvents.
  • the nitrous acid is advantageously prepared in situ by adding an alkali metal nitrite - in bulk or in aqueous solution - to the reaction mixture consisting of the diaminobenzene in acidic aqueous solution or in a carboxylic acid.
  • a suitable reaction temperature is in particular 0 to 20 ° C., very particularly about 5 ° C.
  • the starting materials are expediently used in approximately stoichiometric amounts or one works with an excess of the theoretically expected amount of nitrous acid of not more than 10 mol%.
  • the condensation reaction of the bifunctional benzenes V with the carbonic acid or carboxylic acid derivatives are carried out in a manner known per se (see, for example, Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag Stuttgart, Vol. E8c, 1st Edition 1994, pp. 247- 284; Vol. E8b, 1st edition 1994, pp. 881-901; Vol. E8a, 1st edition 1993, pp. 1032-1078).
  • Preferred carbonic acid or carboxylic acid derivatives are the corresponding anhydrides, acid chlorides, orthoesters, diimides, nitriles, trichloromethyl-substituted compounds, isocyanates and their thio analogues.
  • Suitable solvents / diluents are, in particular, organic solvents, for example aromatic hydrocarbons such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, lower alcohols such as methanol and ethanol, ali- phatic or cyclic ethers such as dimethoxyethane, tetrahydrofuran and dioxane, carboxylic acid esters such as ethyl acetate or aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide.
  • aromatic hydrocarbons such as benzene, toluene and o-, m-, p-xylene
  • halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane
  • lower alcohols such as methanol and ethanol
  • the reaction can be accelerated by adding catalytic amounts of an acid.
  • acids are mineral acids such as hydrochloric acids or sulfonic acids such as p-toluenesulfonic acid.
  • the amounts of acid are preferably 0.1 to 5 mol percent, based on the amount of V.
  • the reaction temperatures are preferably from 20 ° C. to the reflux temperature of the respective reaction mixture, in particular from 60 ° C. to the reflux temperature.
  • the carbonic acid or carboxylic acid derivative is used either in approx., Stoichiometric amount or in excess. In suitable cases, a very large excess can also be used or a solvent can be used. About stoichiometric amounts or an excess of up to 10 molar equivalents, based on the amount of V, are preferred.
  • the substituted 2 -aminophenols, -thiophenols and -anilines (V) are advantageously obtained by reducing the corresponding 2 -nitrophenols, -thiophenols or -anilines VIII (cf., for example, Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag Stuttgart, Vol. XI / 1, 4th edition 1957, p. 431ff.):
  • elemental metals such as iron, tin and zinc are used as reducing agents, Hydrogen in the presence of suitable catalysts such as palladium or platinum on carbon or Raney nickel, or complex hydrides such as LiAlH and NaBH 4 , if appropriate in the presence of catalysts.
  • Suitable solvents are usually - depending on the reducing agent - carboxylic acids such as acetic acid and propionic acid, alcohols such as methanol and ethanol, ethers such as diethyl ether, methyl tert. -butyl ether, tetrahydrofuran and dioxane, aromatics such as benzene and toluene, and mixtures of such solvents.
  • carboxylic acids such as acetic acid and propionic acid
  • alcohols such as methanol and ethanol
  • ethers such as diethyl ether, methyl tert. -butyl ether, tetrahydrofuran and dioxane
  • aromatics such as benzene and toluene, and mixtures of such solvents.
  • the reactions can be carried out at temperatures from (-100) ° C. to the boiling point of the respective reaction mixture.
  • the starting compounds are usually used in approximately stoichiometric amounts; in individual cases, however, an excess of one or the other component, up to about 10 mol%, can also be advantageous.
  • Protection usual protective group that protects phenols or thiophenols as ether or the amino group as amide.
  • the protective groups can be split off by methods known per se (cf., for example, Greene / Wuts: Protective Groups in Organic Synthesis, John Wiley & Sons, Inc., 2nd edition 1991, pp. 145ff. And pp. 279ff. ).
  • cleavage reagents for alkylphenols: trimethylsilyl iodide, boron tribromide,
  • Boron trichloride aluminum trichloride, lithium chloride or hydrogen bromide; in the case of optionally substituted benzylphenols or thiophenols: boron trifluoride, hydrofluoric acid or hydrogen / catalyst, preferably noble metal catalysts such as palladium or platinum.
  • the solvent / diluent should preferably be chosen so that it is inert to the particular cleaving reagent.
  • halides trimethylsilyl iodide, bortribromide, boron trichloride or aluminum trichloride, halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride and dichloroethane are particularly preferred.
  • Hydrogen bromide is preferably used in aqueous solution, very particularly preferably as a 48% solution; Lithium chloride is preferably used in polar solvents such as lower alcohols, dimethyl sulfoxide and dimethylformamide; Hydrogenolytic methods are preferably carried out in lower alcohols or carboxylic acids, all with the addition of a hydrogen transfer agent such as cyclohexene and cyclohexadiene.
  • the temperature for the cleavage reaction is preferably from 0 ° C. to the boiling point of the respective reaction mixture.
  • the cleavage reagent is preferably used in approximately stoichiometric amounts or in excess.
  • the excess is particularly preferably between one and ten molar equivalents, based on the amount of IX.
  • the protected nitro compounds IX are finally obtainable in a manner known per se by nitrating (protected) phenols, thiophenols or anilines X (see, for example, Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag Stuttgart, Vol. 10/1, 1971, P. 479ff.):
  • nitrating acid mixed with sulfuric acid or acetic anhydride, or nitronium salts, especially nitronium tetrafluoroborate, are used as nitrating reagents. dress.
  • the mixture consisting of nitric acid and sulfuric acid, can consist of any proportions of the two mixing partners; preference is given to mixtures in which the sulfuric acid content is predominant or is used as a solvent. The same applies to the mixture of nitric acid and acetic anhydride.
  • Nitronium tetrafluoroborate is preferably used in aprotic, polar solvents, e.g. in acetonitrile or nitromethane.
  • the reaction temperature is generally from (-80) to 80 ° C, in particular (-20) ° C to 30 ° C.
  • the nitrations with the nitric acid reagent are preferably carried out with an approximately equimolar amount or particularly preferably with an excess of nitrating reagent.
  • the excess can be a multiple of the amount of X.
  • Nitronium tetrafluoroborate is preferably used in equimolar amounts to the substrate or in a small excess between 1.1 and 1.5 molar equivalents.
  • L 2 stands for low molecular weight alkyl, preferably C ⁇ -C 4 alkyl, or phenyl.
  • Suitable solvents or diluents are, in particular, water solvents which are azeotropically miscible with water, for example aromatics such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, aliphatic and cyclic ethers such as 1, 2 -Dimethoxyethane, tetrahydrofuran and dioxane, or cyclohexane, but also alcohols such as methanol and ethanol, into consideration.
  • aromatics such as benzene, toluene and o-, m-, p-xylene
  • halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene
  • aliphatic and cyclic ethers such as 1, 2 -Dimethoxye
  • Suitable acidic catalysts are preferably strong mineral acids such as sulfuric acid and hydrochloric acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid, organic acids such as p-toluenesulfonic acid and acidic cation exchangers such as "Amberlyst 15" (Fluka).
  • Suitable basic catalysts are, for example, alkali metal hydrides such as sodium hydride and particularly preferably alkali metal alcoholates such as sodium methoxide and ethanolate.
  • XIV and the ß-ketocarboxylic acid ester XIII are used in approximately stoichiometric amounts or one works with a slight excess of one or the other component, up to about 10 mol%.
  • reaction is carried out at a temperature of 60 to 120 ° C., for the rapid removal of water formed, preferably at the boiling point of the reaction mixture.
  • L 2 and L 3 each represent low molecular weight alkyl, preferably C ⁇ -C 4 alkyl, or phenyl.
  • the reaction is preferably carried out in an inert, water-miscible, organic solvent, for example an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or a lower alcohol, in particular ethanol, the reaction temperature ture is normally 50 to 100 ° C, preferably at the boiling point of the reaction mixture.
  • an inert, water-miscible, organic solvent for example an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or a lower alcohol, in particular ethanol
  • the reaction temperature ture is normally 50 to 100 ° C, preferably at the boiling point of the reaction mixture.
  • reaction can also be carried out in an aromatic diluent such as benzene, toluene and o-, m-, p-xylene, in which case the addition of either an acidic catalyst such as hydrochloric acid and p-toluenesulfonic acid or a base, e.g. an alkali metal alcoholate such as sodium methoxide and sodium ethanolate is recommended.
  • an acidic catalyst such as hydrochloric acid and p-toluenesulfonic acid or a base
  • an alkali metal alcoholate such as sodium methoxide and sodium ethanolate
  • the reaction temperature is normally 50 to 100 ° C., but preferably 60 to 80 ° C.
  • L 2 stands for low molecular weight alkyl, preferably C ⁇ -C 4 alkyl, or phenyl.
  • an essentially anhydrous aprotic organic solvent or diluent for example an aliphatic or cyclic ether such as diethyl ether, 1, 2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene and o-, m-, p-xylene, a halogenated, aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide, or a mixture of the solvents mentioned.
  • an essentially anhydrous aprotic organic solvent or diluent for example an aliphatic or cyclic ether such as diethyl ether, 1, 2-dimethoxyethan
  • work can also be carried out in the presence of a metal hydride base such as sodium and potassium hydride or an organic tertiary base such as triethylamine and pyridine. the, wherein the organic base can simultaneously serve as a solvent.
  • a metal hydride base such as sodium and potassium hydride
  • an organic tertiary base such as triethylamine and pyridine.
  • the starting materials are expediently used in stoichiometric amounts or one works with a slight excess of one or the other component, up to about 10 mol%. If one works without solvent in the presence of an organic base, this is present in a large excess.
  • the reaction temperature is preferably (-80) to 50 ° C, in particular (-60) to 30 ° C.
  • the enamine ester III obtained is converted directly (i.e. "in situ") according to process D) into the corresponding product of value I using excess base.
  • L 2 and L 4 independently of one another represent low molecular weight alkyl, preferably C ⁇ -C 4 alkyl, or phenyl.
  • This reaction is advantageously carried out in an aprotic, polar solvent or diluent such as dimethylformamide, 2-butanone, dimethyl sulfoxide and acetonitrile, advantageously in the presence of a base, for example an alkali metal or alkaline earth metal alcoholate, in particular a sodium alcoholate such as sodium methoxide, an alkali metal or alkaline earth metal carbonates, in particular sodium carbonate, or an alkali metal hydride such as lithium and sodium hydride.
  • a base for example an alkali metal or alkaline earth metal alcoholate, in particular a sodium alcoholate such as sodium methoxide, an alkali metal or alkaline earth metal carbonates, in particular sodium carbonate, or an alkali metal hydride such as lithium and sodium hydride.
  • reaction temperature is generally 80 to 180 ° C, preferably at the boiling point of the reaction mixture.
  • a sodium alcoholate is used as the base and the alcohol formed in the course of the reaction is distilled off continuously.
  • the urethanes XIX are e.g. can be produced from carbonic acid chlorides XX and anilines XXI:
  • an auxiliary base such as triethylamine, pyridine or the alkali metal carbonates must generally be added to trap the hydrogen chloride formed in the reaction.
  • Pyridine is particularly suitable because it can also be used as a solvent.
  • the solvents / diluents used are in particular aromatic hydrocarbons such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, lower alcohols such as methanol and ethanol, aliphatic or cyclic ethers such as dimethoxyethane , Tetrahydrofuran and dioxane, carboxylic acid esters such as ethyl acetate, or aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide.
  • aromatic hydrocarbons such as benzene, toluene and o-, m-, p-xylene
  • halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane
  • lower alcohols such as methanol and ethanol
  • aliphatic or cyclic ethers such as dimethoxye
  • the reaction temperature is generally from 0 ° C. to the reflux temperature of the respective reaction mixture.
  • the starting materials are expediently used either in approximately stoichiometric amounts or an excess of carbonic acid chloride of at most 10 mol percent is chosen.
  • the auxiliary base is usually used in an approximately equimolar amount, based on the amount of XX or XXI, or in excess up to about 2 times the molar amount. If pyridine is used as the auxiliary base, an even larger excess is recommended, in which case it is possible to work without additional solvent.
  • L 2 stands for low molecular weight alkyl, preferably C ⁇ -C 4 alkyl, or phenyl.
  • This reaction is expediently carried out in an essentially anhydrous, aprotic, organic solvent or diluent, for example in the presence of an aliphatic or cyclic ether such as diethyl ether, 1, 2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene , Toluene and o-, m-, p-xylene, a halogenated, aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1, 2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide, or a mixture of the mentioned solvents.
  • an aliphatic or cyclic ether such as diethyl ether, 1, 2-dimethoxyethane,
  • a metal hydride base such as sodium and potassium hydride, an alkali metal or alkaline earth metal alcoholate such as sodium methoxide, ethanolate and potassium tert. -butanolate, or an organic nitrogen base such as triethylamine and pyridine, where the organic base can simultaneously serve as a solvent.
  • a metal hydride base such as sodium and potassium hydride
  • an alkali metal or alkaline earth metal alcoholate such as sodium methoxide, ethanolate and potassium tert. -butanolate
  • an organic nitrogen base such as triethylamine and pyridine
  • the reaction temperature is generally from (-80) to 150 ° C, preferably from (-30) ° C to the boiling point of the reaction mixture.
  • arylanilides of formula IV are also new; they too can be prepared in a manner known per se, for example by reacting an amide XXIII with a urethane XXIV according to process M):
  • L 2 stands for low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
  • the reaction is advantageously carried out in a largely anhydrous solvent / diluent at atmospheric pressure, particularly preferably in the presence of an acid catalyst.
  • Suitable solvents / diluents are, in particular, water which is azeotropically miscible with water, for example aromatics such as benzene, toluene and o-, m-, p-xylene or halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene.
  • Suitable catalysts are, in particular, strong mineral acids such as sulfuric acid, organic acids such as p-toluene sulfonic acid, acids containing phosphorus such as orthophosphoric acid and polyphosphoric acid or acidic cation exchangers such as "Amberlyst 15" (from Fluka).
  • reaction temperature of about 70 to 150 ° C is sufficient; To rapidly remove the water of reaction formed, however, it is expedient to work at the boiling point of the respective reaction mixture.
  • XXIII and XXIV are usually used in approximately stoichiometric amounts; XXIV is preferably used in a slight excess of up to about 20 mol%.
  • the amide XXIII can be prepared as follows (process N)):
  • the reaction is preferably carried out in an anhydrous, inert aprotic solvent, for example in a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, an aromatic hydrocarbon such as benzene, toluene and o-, m-, p-xylene, or an aliphatic or cyclic ether such as Diethyl ether, dibutyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane.
  • a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene
  • an aromatic hydrocarbon such as benzene, toluene and o-, m-, p-xylene
  • an aliphatic or cyclic ether such as Diethyl ether, dibutyl ether, 1,2-dimethoxyethane,
  • the reaction temperature is generally about 70 to 140 ° C, especially 100 to 120 ° C.
  • XXV and XXI are usually used in approximately stoichiometric amounts, or one of the components is used in excess, up to about 10 mol%.
  • the isocyanates XVIII can be obtained, for example, from the aniline derivatives XXI according to process 0):
  • the process can be carried out in an inert, essentially anhydrous solvent or diluent or without solvent, the aniline derivatives XXI preferably being reacted with phosgene, a "phosgene equivalent” such as diphosgene, triphosgene and carbonyldiimidazole or with chloroformic acid trichloromethyl ester.
  • phosgene a "phosgene equivalent” such as diphosgene, triphosgene and carbonyldiimidazole or with chloroformic acid trichloromethyl ester.
  • Suitable solvents or diluents are, in particular, aprotic, organic solvents, for example dimethylformamide or aromatics such as toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene, aliphatic or cyclic ethers such as 1 , 2-dimethoxyethane, tetrahydrofuran and dioxane, or esters such as ethyl acetate, and mixtures of these solvents.
  • aprotic, organic solvents for example dimethylformamide or aromatics such as toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene, aliphatic or cyclic ethers such as 1 , 2-dimethoxyethan
  • the starting materials are expediently used in approximately stoichiometric amounts, or one of the components in excess, up to approximately 200 mol%.
  • the addition of a base such as triethylamine may be advantageous, for example in 0.5 to 2 times the molar amount, based on the amount of XXI.
  • the reaction temperature is generally from (-20) ° C to the reflux temperature of the particular solvent or reaction mixture.
  • aniline derivatives XXI are, in turn, in a manner known per se (see, for example, Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag Stuttgart, Vol. XI / 1, 4th edition 1957, p. 431ff.) By reducing the corresponding nitroderivate XXVI available:
  • Compounds XXVIII and XXI can also contain one or more centers of chirality and are then usually obtained as mixtures of enantiomers or diastereomers. If desired, the mixtures can be prepared by the usual methods, e.g. by means of crystallization or chromatography on an optically active adsorbate into which the largely pure isomers are separated. Pure optically active isomers can also be produced, for example, from corresponding optically active starting materials.
  • reaction mixtures are generally worked up by methods known per se, for example by diluting the
  • the compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides.
  • the herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly when high amounts are applied. In crops such as wheat, rice, maize, soybeans and cotton, they work against weeds and grass weeds without causing any significant damage to crops. This effect occurs especially at low application rates.
  • the compounds I or herbicidal compositions comprising them can also be used in a further number of crop plants for eliminating undesired plants.
  • the following crops are considered, for example:
  • the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • the compounds I or the herbicidal compositions comprising them can be sprayed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents or granules , Atomizing, dusting, scattering or pouring can be used.
  • the application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • inert auxiliaries mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated Benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, for example amines such as N-methylpyrrolidone and water.
  • mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons eg paraffins, tetrahydronaphthalene, alkylated naphthalenes and
  • Aqueous use forms can be prepared from emulsion concentrates, Sus pensions, pastes, wettable powders or water-dispersible granules by adding water.
  • 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, adhesives, dispersants or emulsifiers.
  • concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols as well as of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives Formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylpheny
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.
  • Solid carriers are mineral soils such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urea and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range.
  • the formulations contain from about 0.001 to 98% by weight, preferably 0.01 to 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 the NMR spectrum).
  • the active ingredients I or the herbicidal compositions can be applied pre- or post-emergence. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit as far as possible, while the active ingredients are applied to the leaves of undesirable plants growing below them or the uncovered floor area (post-directed, lay-by).
  • active ingredient I is 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (as), depending on the control target, season, target plants and growth stage.
  • active ingredient I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups and applied together.
  • reaction mixture was poured onto an ice-cold, saturated aqueous sodium chloride solution.
  • the solid product of value was then separated off, washed with water and dried in a drying cabinet at 20 ° C. under reduced pressure for several hours. Yield: 62.3 g;
  • Precursor 7.4 was reacted analogously to Example 5 with 3-amino-4,4,4,4-trifluoro-10-but-2-enoic acid ethyl ester.
  • the crude product was purified by means of medium pressure liquid chromatography (eluent:
  • Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels.
  • the seeds of the test plants were sown separately according to species.
  • the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles.
  • the vessels were sprinkled lightly to promote germination and growth, and then pervaded plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.
  • test plants were each according to the growth habit, only grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water.
  • 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 post-emergence treatment was 15.6 or 7.8 g / ha aS (active substance).
  • the plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species.

Abstract

The invention relates to 3-(benzazol-4-yl)pyrimidine-dione-derivatives of formula (I) and the salts thereof, whereby X = O, S; R1 = H, NH¿2?, C1-C6-alkyl, C1-C6-alkyl halide; R?2¿ = H, halogen, C¿1?-C6-alkyl, C1-C6-alkyl halide, C1-C6-alkylthio, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl; R?3¿ = H, halogen, C¿1?-C6-alkyl; R?4¿ = H, halogen; R5 = CN, halogen, C¿1?-C6-alkyl, C1-C6-alkyl halide, C1-C6-alkoxyl, C1-C6-alkoxyl halide; =Y- = a group =N-N(R?6¿)-, =C(ZR7)-N(R6)-, =C(ZR7)-O-, =C(ZR?7)-S-; R6 = C¿1-C6-alkyl, C1-C4-alkyl halide, C3-C6-cycloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkyl-SO2, C1-C6-alkyl-CO, C1-C6-alkyl halide-CO, C1-C6-alkyl-CS, C1-C6-alkoxyl-CO, C1-C6-alkoxyl-CS or optionally substituted C1-C6-alkyl; Z = chemical bond, O, S, -S(O)-, -SO2-, -NH-, -N(R?8)-; R7, R8 = C¿1-C6-alkyl, C1-C6-alkyl halide, hydroxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkoxyl-C1-C4-alkyl, C1-C4-alkoxyl halide-C1-C4-alkyl, C3-C4-alkenyloxyl-C1-C4-alkyl, C3-C4-alkynyloxyl-C1-C4-alkyl, C3-C8-cycloalkoxyl-C1-C4-alkyl, amino-C1-C4-alkyl, C1-C4-alkylamino-C1-C4-alkyl, di(C1-C4-alkyl)amino-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkylthio halide-C1-C4-alkyl, C3-C4-alkenylthio-C1-C4-alkyl, C3-C4-alkynylthio-C1-C4-alkyl, C1-C4-alkylsulfinyl-C1-C4-alkyl, C1-C4-alkylsulfinyl halide-C1-C4-alkyl, C3-C4-alkenylsulfinyl-C1-C4-alkyl, C3-C4-alkynylsulfinyl-C1-C4-alkyl, C3-C6-alkenyl, cyano-C3-C6-alkenyl, C3-C6-alkenyl halide, C3-C6-alkynyl, cyano-C3-C6-alkynyl, C3-C6-alkynyl halide, HO-CO-C1-C4-alkyl, (C1-C4-alkoxyl)CO-C1-C4-alkyl, (C1-C4-alkyl)CS-C1-C4-alkyl, H2N-CO-C1-C4-alkyl, C1-C4-alkyl-NHCO-C1-C4-alkyl, di(C1-C4-alkyl)NCO-C1-C4-alkyl, di(C1-C4-alkyl)phosphonyl-C1-C4-alkyl, optionally substituted C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenyl-C1-C4-alkyl, 3- to 7-linked heterocyclyl or heterocyclyl-C1-C4-alkyl, whereby each heterocyclyl ring can contain a CO-ring link or CS-ring link, or provided that Z = chemical bond, R7 also H, OH, CN, SH, NH¿2?, halogen, -CH(OH)-CH2-R?9¿, -CH(halogen)-CH¿2?-R?9, -CH¿2-CH(halogen)-R9, -CH=CH-R9 or -CH=C(halogen)-R9, whereby R9 = COOH, (C¿1?-C4-alkoxyl)carbonyl, (C1-C4-alkylthio)carbonyl, CONH2, C1-C4-alkyl-NHCO or di(C1-C4-alkyl)NCO, or R?7 + R8¿ = an optionally substituted 1,3-propylene-, tetramethylene-, pentamethylene- or ethylene oxyethylene-chain.

Description

Herbizide 3 - (Benzazol - 4 -yD pyrimidindion-DerivateHerbicides 3 - (Benzazole - 4 -yD pyrimidinedione derivatives
Beschreibungdescription
Die vorliegende Erfindung betrifft neue 3- (Benzazol-4-yl)pyrimi- dindion-Derivate der Formel IThe present invention relates to new 3- (benzazol-4-yl) pyrimidinedione derivatives of the formula I.
in der die Variablen folgende Bedeutungen haben:in which the variables have the following meanings:
X Sauerstoff oder Schwefel;X oxygen or sulfur;
R1 Wasserstoff, Amino, Cχ-Cg-Alkyl oder Ci-Cδ-Halogenalkyl;R 1 is hydrogen, amino, Cχ-Cg-alkyl or Ci-C δ -haloalkyl;
R2 Wasserstoff, Halogen, Ci-Cg-Alkyl, Ci-Cg-Halogenalkyl,R 2 is hydrogen, halogen, Ci-Cg-alkyl, Ci-Cg-haloalkyl,
Ci-Cg-Alkylthio, Cι-C6-Alkylsulfinyl oder Cι-C6-Alkylsulfonyl;Ci-Cg-alkylthio, -CC 6 alkylsulfinyl or -C 6 -alkyl sulfonyl;
R3 Wasserstoff, Halogen oder Cχ-Cg-Alkyl;R 3 is hydrogen, halogen or Cχ-Cg-alkyl;
R4 Wasserstoff oder Halogen;R 4 is hydrogen or halogen;
R5 Cyano, Halogen, Ci-Cg-Alkyl, Cι-C6-Halogenalkyl, Cι-C6-Alkoxy oder Ci-Cg-Halogenalkoxy;R 5 cyano, halogen, Ci-Cg-alkyl, -C-C 6 haloalkyl, Cι-C 6 alkoxy or Ci-Cg-haloalkoxy;
=Y- eine Gruppe =N-N(R6)-, =C (ZR7) -N(R6) -, =C(ZR7)-0- oder =C(ZR7)-S-;= Y- a group = NN (R 6 ) -, = C (ZR 7 ) -N (R 6 ) -, = C (ZR 7 ) -0- or = C (ZR 7 ) -S-;
R6 Cι-C6-Alkyl, Cx-C^Halogenalkyl, C3-C6-Cycloalkyl, C3-C6-Alkenyl, C3-C6-Alkinyl, Cι-C6-Alkylsulfonyl, (Ci-Cg-Alkyl) carbonyl, (Ci-Cδ-Halogenalkyl) carbonyl, (Ci-Cß-Alkyl) thiocarbonyl , (Ci-Cg-Alkoxy) carbonyl, (Ci-Cg-Alkoxy) thiocarbonyl oderR 6 -C-C 6 alkyl, Cx-C ^ haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, Cι-C 6 alkylsulfonyl, (Ci-Cg -Alkyl) carbonyl, (Ci-C δ -haloalkyl) carbonyl, (Ci-C ß- alkyl) thiocarbonyl, (Ci-Cg-alkoxy) carbonyl, (Ci-Cg-alkoxy) thiocarbonyl or
Ci-Cg-Alkyl, das durch Cyano, Ci-Cg-Alkoxy, Cι-C6-Alkylthio, (Cι-C6-Alkoxy) carbonyl , (Ci-Cg-Alkylamino) carbonyl , Di (Ci-Cg-alkyl) aminocarbonyl oder (Ci-Cg-Alkyl) carbonyloxy substituiert sein kann; l eine chemische Bindung, Sauerstoff, Schwefel, -S(O)-, -S(0)2-, -NH- oder -N(R8)-;Ci-Cg-alkyl, which by cyano, Ci-Cg-alkoxy, Cι-C 6 -alkylthio, (Cι-C 6 -alkoxy) carbonyl, (Ci-Cg-alkylamino) carbonyl, di (Ci-Cg-alkyl) aminocarbonyl or (Ci-Cg-alkyl) carbonyloxy may be substituted; l a chemical bond, oxygen, sulfur, -S (O) -, -S (0) 2 -, -NH- or -N (R 8 ) -;
R7 und R8 unabhängig voneinanderR 7 and R 8 are independent of one another
Ci-Cg-Alkyl, Cι-C6-Halogenalkyl, Hydroxy-Cι-C4-alkyl, Cyano-Cι-C4-alkyl, Cι-C4-Alkoxy-Cι-C -alkyl, Cι-C -Halogenalk- oxy-Cι-C4-alkyl, C3-C4-Alkenyloxy-Cι-C -alkyl, C3-C4-Alkinyl- oxy-Cχ-C -alkyl , C3-C8-Cycloalkoxy-Cι-C -alkyl ,Ci-Cg-alkyl, -C-C 6 -haloalkyl, hydroxy-Cι-C 4 -alkyl, cyano-Cι-C 4 -alkyl, Cι-C 4 -alkoxy-Cι-C -alkyl, Cι-C -haloalk- oxy-C 1 -C 4 -alkyl, C 3 -C 4 -alkenyloxy-C-C -alkyl, C 3 -C 4 -alkynyloxy-Cχ-C -alkyl, C 3 -C 8 -cycloalkoxy-Cι-C -alkyl,
Amino-Cι-C -alkyl , Cι-C -Alkylamino-Cι-C4-alkyl , Di (Cι-C -alkyl) amino-Cι-C -alkyl, Cι-C -Alkylthio-Cι-C -alkyl, Cι-C -Halogenalkylthio-Cι-C -alkyl, C3-C -Alkenyl- thio-Cι-C4-alkyl, C3-C -Alkinylthio-C1-C4-alkyl, Cι-C -Alkyl- sulfinyl-Cι-C -alkyl , Cι-C -Halogenalkylsulfinyl-Cι-C -alkyl , C3-C -Alkenylsulfinyl-Cι-C -alkyl , C3-C -Alkinylsulfinyl- Cι-C -alkyl, Cι-C -Alkylsulfonyl-Cι-C4-alkyl , Cι-C4-Halogen- alkylsulfonyl-Cι-C -alkyl , C3-C -Alkenylsulfonyl-Cι-C -alkyl , C3-C -Alkinylsulfonyl-Cι-C -alkyl , C3-C6-Alkenyl , Cyano-C3-C6-alkenyl, C3-C3-Halogenalkenyl, C3-C6-Alkinyl, Cyano-C3-C6-alkinyl, C3-Cg-Halogenalkinyl, Hydroxycar- bonyl-Cι-C -alkyl , (Cι-C -Alkoxy) carbonyl-Cι-C -alkyl , (Cι-C4-Alkylthio) carbonyl-Cι-C -alkyl, Aminocarbo- nyl-Cι-C4-alkyl, (Cι-C4-Alkylamino) carbonyl-Cι-C4-alkyl, Di (Cι-C4-alkyl) aminocarbonyl-Cι-C4-alkyl, Di(Cι-C4-al- kyl) phosphonyl -Ci -C4 - alkyl ,Amino-C 1 -C 4 -alkyl, C 1 -C 4 -alkyl-C 1 -C 4 -alkyl, di (C 1 -C -alkyl) amino-Cι-C -alkyl, Cι-C -alkylthio-Cι-C -alkyl, Cι -C -Halogenalkylthio-Cι-C -alkyl, C 3 -C -Alkenyl- thio-Cι-C 4 -alkyl, C 3 -C -alkynylthio-C 1 -C 4 -alkyl, Cι-C -alkyl- sulfinyl- -C-C -alkyl, -C-C -haloalkylsulfinyl-Cι-C -alkyl, C 3 -C -Alkenylsulfinyl-Cι-C -alkyl, C 3 -C -alkynylsulfinyl- Cι-C -alkyl, Cι-C -alkylsulfonyl- Cι-C 4 -alkyl, halo-C 4 alkylsulfonyl-Cι-C alkyl, C 3 -C alkenylsulfonyl-Cι-C alkyl, C 3 -C alkynylsulfonyl-Cι-C alkyl, C 3 -C 6 alkenyl, cyano-C 3 -C 6 alkenyl, C 3 -C 3 haloalkenyl, C 3 -C 6 alkynyl, cyano-C 3 -C 6 alkynyl, C 3 -Cg haloalkynyl, hydroxycar - carbonyl-Cι-C alkyl, (Cι-C -alkoxy) carbonyl-Cι-C alkyl, (Cι-C 4 -alkylthio) carbonyl-Cι-C alkyl, Cι-Aminocarbo- nyl-C 4 alkyl , (-C 4 -alkylamino) carbonyl -CC-C 4 alkyl, di (-C-C 4 -alkyl) aminocarbonyl-Cι-C 4 -alkyl, di (Cι-C 4 -alkyl) phosphonyl -Ci -C 4 - alkyl,
C3-C8-Cycloalkyl, C3-C8-Cycloalkyl-Cι-C -alkyl, Phenyl, Phenyl-Cχ-C4-alkyl, 3- bis 7-gliedriges Heterocyclyl oder Heterocyclyl-Cι-C4-alkyl, wobei jeder Heterocyclyl-Ring ein Carbonyl- oder Thiocarbonyl-Ringglied enthalten kann, und wobei jeder Cycloalkyl-, Phenyl- und Heterocyclylring unsubstituiert sein oder ein bis vier Substituenten tragen kann, jeweils ausgewählt aus der Gruppe bestehend aus Cyano, Nitro, Amino, Hydroxy, Carboxy, Halogen, Cι-C -Alkyl, Cι-C -Halogenalkyl, Cι-C4-Alkoxy, Cι-C -Halogenalkoxy,C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-C 1 -C 4 -alkyl, phenyl, phenyl-Cχ-C 4 -alkyl, 3- to 7-membered heterocyclyl or heterocyclyl -CC 4 -alkyl, wherein each heterocyclyl ring can contain a carbonyl or thiocarbonyl ring member, and wherein each cycloalkyl, phenyl and heterocyclyl ring can be unsubstituted or can carry one to four substituents, each selected from the group consisting of cyano, nitro, amino, hydroxy, Carboxy, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy,
Cχ-C4-Alkylthio, Cι-C -Halogenalkylthio, Cι-C4-Alkylsulfonyl, Cι-C -Halogenalkylsulfonyl , (Cι-C4-Alkoxy) carbonyl , (Cι-C4-Alkyl) carbonyl, (Cχ-C4-Halogenalkyl) carbonyl, (Cι-C -Alkyl) carbonyloxy, (Cι-C4-Halogenalkyl) carbonyloxy und Di (Cι-C4-alkyl) amino,Cχ-C 4 -alkylthio, Cι-C -haloalkylthio, Cι-C 4 -alkylsulfonyl, Cι-C -haloalkylsulfonyl, (Cι-C 4 -alkoxy) carbonyl, (Cι-C 4 -alkyl) carbonyl, (Cχ-C 4 -haloalkyl) carbonyl, (-C-C4-alkyl) carbonyloxy, (-C-C 4 -haloalkyl) carbonyloxy and di (Cι-C 4 -alkyl) amino,
oder, sofern Z eine chemische Bindung bedeutet, R7 ge- wünschtenfalls auch Wasserstoff, Hydroxy, Cyano, Mercapto, Amino, Halogen, -CH (OH) -CH2-R9 , -CH (Halogen) -CH2-R9, -CH2-CH (Halogen) -R9, -CH=CH-R9 oder -CH=C (Halogen) -R9 , wobei R9 für Hydroxycarbonyl , (Cχ-C4~Alkoxy) carbonyl, (Cχ-C -Alkyl- thio) carbonyl, Aminocarbonyl , (Cχ-C -Alkylamino) carbonyl oder Di (Cχ-C4-alkyl) aminocarbonyl steht,or, if Z is a chemical bond, R 7 if desired also hydrogen, hydroxy, cyano, mercapto, amino, halogen, -CH (OH) -CH 2 -R 9 , -CH (halogen) -CH 2 -R 9 , -CH 2 -CH (halogen) -R 9 , -CH = CH-R 9 or -CH = C (halogen) -R 9 , where R 9 represents hydroxycarbonyl, (Cχ-C 4 ~ alkoxy) carbonyl, (Cχ-C-alkyl- thio) carbonyl, aminocarbonyl, (Cχ-C-alkylamino) carbonyl or di (Cχ-C 4 -alkyl) aminocarbonyl,
oder R7 und R8 zusammen eine 1, 3-Propylen-, Tetramethylen-, Pentamethylen- oder Ethylenoxyethylen-Kette, die jeweils unsubstituiert sein oder ein bis vier Cχ-C4-Alkylgruppen oder ein oder zwei (Cχ-C4-Alkoxy) carbonylgruppen tragen kann;or R 7 and R 8 together form a 1, 3-propylene, tetramethylene, pentamethylene or ethyleneoxyethylene chain, which are each unsubstituted or one to four Cχ-C 4 alkyl groups or one or two (Cχ-C 4 alkoxy ) can carry carbonyl groups;
sowie die landwirtschaftlich brauchbaren Salze der Verbindungen I.and the agriculturally useful salts of the compounds I.
Außerdem betrifft die ErfindungThe invention also relates to
- die Verwendung der Verbindungen I als Herbizide, - herbizide Mittel, welche die Verbindungen I als wirksame Substanzen enthalten,the use of the compounds I as herbicides, herbicidal compositions which contain the compounds I as active substances,
- Verfahren zur Herstellung der Verbindungen I und von herbiziden Mitteln unter Verwendung der Verbindungen I,- Process for the preparation of the compounds I and herbicidal compositions using the compounds I,
- Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs mit den Verbindungen I, sowie- Method for controlling unwanted vegetation with the compounds I, and
- Zwischenprodukte der Formeln III, IV und V zur Herstellung der Verbindungen I .- Intermediates of the formulas III, IV and V for the preparation of the compounds I.
In der WO 97/08170 werden bestimmte 3 - (Benz (ox/thi) azol- 7-yl) -6- (trifluormethyl) -uracile als Herbizide beschrieben. Weitere 3- (Benzthiazol -7-yl) uracile sowie deren Verwendung als Herbizide und zur Desikkation/Defoliation von Pflanzen werden in der WO 97/08171 gelehrt. Gegenstand der WO 97/12886 sind u.a. bestimmte 3 -Benzisoxazol-7 -yl-2, 4 - (1H, 3H)pyrimidindione, denen eine herbizide und desikkante Wirkung zugeschrieben wird.WO 97/08170 describes certain 3 - (benz (ox / thi) azol-7-yl) -6- (trifluoromethyl) uracils as herbicides. Further 3- (benzthiazol -7-yl) uracils and their use as herbicides and for the desiccation / defoliation of plants are taught in WO 97/08171. WO 97/12886 relates inter alia to certain 3-benzisoxazol-7 -yl-2, 4 - (1H, 3H) pyrimidinediones, which are said to have a herbicidal and desiccant effect.
Aufgabe der vorliegenden Erfindung war es, neue herbizid wirksame Uracil -Verbindungen bereitzustellen, mit denen sich unerwünschte Pflanzen besser als mit den bekannten gezielt bekämpfen lassen.The object of the present invention was to provide new herbicidally active uracil compounds which can be used to specifically control undesired plants better than the known ones.
Demgemäß wurden die vorliegenden 3 - (Benzazol-4-yl)pyrimidindion- Derivate der Formel I gefunden.Accordingly, the present 3 - (benzazol-4-yl) pyrimidinedione derivatives of the formula I have been found.
Ferner wurden herbizide Mittel gefunden, die 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. Die Verbindungen der Formel I können je nach Substitutionsmuster ein oder mehrere Chiralitätszentren enthalten und liegen dann als Enantiomeren- oder Diastereomerengemische vor. Bei Verbindungen I mit mindestens einem olefinischen Rest sind gege- benenfalls auch E-/Z- Isomere möglich. Gegenstand der Erfindung sind sowohl die reinen Enantiomeren oder Diastereomeren als auch deren Gemische.Furthermore, herbicidal compositions have been found which contain the compounds I and have a very good herbicidal action. In addition, processes for the preparation of these compositions and processes for controlling unwanted vegetation using the compounds I have been found. Depending on the substitution pattern, the compounds of the formula I can contain one or more centers of chirality and are then present as mixtures of enantiomers or diastereomers. In the case of compounds I with at least one olefinic radical, E / Z isomers may also be possible. The invention relates both to the pure enantiomers or diastereomers and to their mixtures.
Für manche erfindungsgemäßen Verbindungen stellt deren allgemei- nen Formel I nur eine der möglichen Schreibweisen dar. So können beispielsweise diejenigen Verbindungen I mit R7 = Hydroxy auch als Tautomere I' [-N=C(0H)-<—»-NH-CO-] geschrieben werden:For some compounds according to the invention, their general formula I represents only one of the possible spellings. For example, those compounds I with R 7 = hydroxy can also be used as tautomers I '[-N = C (0H) - <- »- NH-CO -] to be written:
Unter landwirtschaftlich brauchbaren Salzen kommen vor allem die Salze derjenigen Kationen oder die Säureadditionssalze derjenigen Säuren in Betracht, deren Kationen beziehungsweise Anionen die herbizide Wirkung der Verbindungen I nicht negativ beeinträchtigen. So kommen als Kationen insbesondere die Ionen der Alkalimetalle, vorzugsweise Natrium und Kalium, der Erdalkalimetalle, vorzugsweise Calcium, Magnesium und Barium, und der Übergangs - metalle, vorzugsweise Mangan, Kupfer, Zink und Eisen, sowie das Ammoniumion, das gewünschtenfalls ein bis vier Cχ-C4-Alkyl- substituenten und/oder einen Phenyl- oder Benzylsubstituenten tragen kann, vorzugsweise Diisopropylammonium, Tetramethyl - ammonium, Tetrabutylammonium, Trimethylbenzylammonium, des weiteren Phosphoniumionen, Sulfoniumionen, vorzugsweiseAgriculturally useful salts include, in particular, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the herbicidal activity of the compounds I. So come as cations in particular the ions of the alkali metals, preferably sodium and potassium, the alkaline earth metals, preferably calcium, magnesium and barium, and the transition metals, preferably manganese, copper, zinc and iron, as well as the ammonium ion, the one to four Cχ if desired -C 4 alkyl and / or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably
Tri (Cχ-C4-alkyl) sulfonium und Sulfoxoniumionen, vorzugsweise Tri (Cχ-C -alkyl) sulfoxonium, in Betracht.Tri (Cχ-C 4 alkyl) sulfonium and sulfoxonium ions, preferably tri (Cχ-C alkyl) sulfoxonium, into consideration.
Anionen von brauchbaren Säureadditionssalzen sind in erster Linie Chlorid, Bromid, Fluorid, Hydrogensulfat, Sulfat, Dihydrogen- phosphat, Hydrogenphosphat, Phosphat, Nitrat, Hydrogencarbonat, Carbonat, Hexafluorosilikat, Hexafluorophosphat, Benzoat, sowie die Anionen von Cχ-C4-Alkansäuren, vorzugsweise Formiat, Acetat, Propionat und Butyrat. Sie können durch Reaktion von I mit einer Säure des entsprechenden Anions, vorzugsweise der Chlorwasserstoffsäure, Bromwasserstoffsäure, Schwefelsäure, Phosphorsäure oder Salpetersäure, gebildet werden. Die bei der Definition der Substituenten R1 bis R3 und R5 bis R9 oder als Reste an Cycloalkyl-, Phenyl- oder heterocyclisehen Ringen genannten organischen Molekülteile stellen - wie die Bedeutung Halogen - Sammelbegriffe für individuelle Aufzählungen der einzelnen Gruppenmitglieder dar. Sämtliche Kohlenstoffketten, also alle Alkyl-, Halogenalkyl-, Cyanoalkyl-, Hydroxyalkyl-, Aminoalkyl-, Hydroxycarbonylalkyl-, Aminocarbonylalkyl-, Phenyl - alkyl-, Heterocyclylalkyl-, Alkoxy- , Halogenalkoxy- , Alkylthio-, Halogenalkylthio - , Alkylsulfinyl- , Halogenalkylsulfinyl- , Alkyl - sulfonyl-, Halogenalkylsulfonyl- , Alkenyl-, Halogenalkenyl-, Cya- noalkenyl-, Alkenyloxy- , Alkenylthio- , Alkenylsulfinyl- , Alkenyl- sulfonyl-, Alkinyl-, Halogenalkinyl-, Cyanoalkinyl-, Alkinyloxy-, Alkinylthio- , Alkinylsulfinyl- und Alkinylsulfonyl -Teile können geradkettig oder verzweigt sein. Halogenierte Substituenten tra- gen vorzugsweise ein bis fünf gleiche oder verschiedene Halogen- atome. Die Bedeutung Halogen steht jeweils für Fluor, Chlor, Brom oder Iod.Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C von-C 4 -alkanoic acids, preferably Formate, acetate, propionate and butyrate. They can be formed by reacting I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid. The organic molecule parts mentioned in the definition of the substituents R 1 to R 3 and R 5 to R 9 or as radicals on cycloalkyl, phenyl or heterocyclic rings represent - like the meaning halogen - collective terms for individual lists of the individual group members. All carbon chains , ie all alkyl, haloalkyl, cyanoalkyl, hydroxyalkyl, aminoalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, phenyl - alkyl, heterocyclylalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, Alkyl - sulfonyl, haloalkylsulfonyl, alkenyl, haloalkenyl, cyanoalkenyl, alkenyloxy, alkenylthio, alkenylsulfinyl, alkenylsulfonyl, alkynyl, haloalkynyl, cyanoalkynyl, alkynyloxy, alkynylthio, alkynylsulfinyl and alkynylsulfonyl parts can be straight-chain or branched. Halogenated substituents preferably carry one to five identical or different halogen atoms. Halogen is fluorine, chlorine, bromine or iodine.
Ferner stehen beispielsweise:Furthermore, for example:
- Cχ-C4-Alkyl für: CH3, C2H5, CH2-C2H5, CH(CH3)2, n-Butyl, CH(CH3) -C2H5, CH2-CH(CH3)2 oder C(CH3)3;- Cχ-C 4 alkyl for: CH 3 , C 2 H 5 , CH 2 -C 2 H 5 , CH (CH 3 ) 2 , n-butyl, CH (CH 3 ) -C 2 H 5 , CH 2 - CH (CH 3 ) 2 or C (CH 3 ) 3 ;
- Cχ-C4-Halogenalkyl für: einen Cχ-C4-Alkylrest wie vorstehend ge- nannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder Iod substituiert ist, also z.B. CH F, CHF , CF3 , CHC1, CH(C1) , C(C1)3, Chlorfluormethyl, Dichlorfluormethyl, Chlor- difluormethyl, 2-Fluorethyl, 2-Chlorethyl, 2-Bromethyl, 2-Iod- ethyl, 2,2-Difluorethyl, 2, 2, 2-Trifluorethyl, 2-Chlor-2-fluor- ethyl, 2-Chlor-2 , 2-difluorethyl, 2 , 2-Dichlor-2-fluorethyl, 2 , 2, 2-Trichlorethyl, C2Fs, 2-Fluorpropyl, 3-Fluorpropyl, 2, 2-Difluorpropyl, 2, 3-Difluorpropyl, 2-Chlorpropyl, 3-Chlor- propyl, 2, 3-Dichlorpropyl, 2-Brompropyl, 3-Brompropyl, 3, 3, 3-Trifluorpropyl, 3 , 3 , 3-Trichlorpropyl, CH2-C2F5, CF2-C2F5, 1- (Fluormethyl) -2-fluorethyl, 1- (Chlormethyl) -2-chlorethyl,- Cχ-C 4 -haloalkyl for: a Cχ-C 4 -alkyl radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example CH F, CHF, CF 3 , CHC1 , CH (C1), C (C1) 3 , chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2, 2, 2- Trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 2, 2, 2-trichloroethyl, C 2 Fs, 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, CH 2 -C 2 F 5 , CF 2 -C 2 F 5 , 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl,
1- (Brommethyl) -2-bromethyl, 4-Fluorbutyl, 4-Chlorbutyl, 4-Brom- butyl oder Nonafluorbutyl;1- (bromomethyl) -2-bromethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl;
Cx-Cß-Alkyl für: einen Cχ-C -Alkylrest wie vorstehend genannt, oder z.B. n-Pentyl, 1-Methylbutyl , 2-Methylbutyl, 3-Methyl- butyl, 2,2-Dimethylpropyl, 1-Ethylpropyl, n-Hexyl,Cx-C ß- alkyl for: a Cχ-C -alkyl radical as mentioned above, or for example n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n- Hexyl,
1, 1-Dimethylpropyl, 1, 2-Dimethylpropyl, 1-Methylpentyl,1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl,
2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1 , 1-Dimethyl - butyl, 1,2-Dirnethylbutyl, 1, 3-Dimethylbutyl, 2, 2-Dimethylbutyl,2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl,
2,3-Dimethylbutyl, 3 , 3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethyl- butyl, 1,1,2-Trimethylpropyl, 1, 2 , 2-Trimethylpropyl,2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1, 2, 2-trimethylpropyl,
1-Ethyl-l-methylpropyl oder l-Ethyl-2-methylpropyl, Vorzugs- weise für CH3, C2H5, CH2-C2H5, CH(CH3)2, n-Butyl, C(CH3)3, n-Pentyl oder n-Hexyl;1-ethyl-l-methylpropyl or l-ethyl-2-methylpropyl, preferred for CH 3 , C 2 H 5 , CH 2 -C 2 H 5 , CH (CH 3 ) 2 , n-butyl, C (CH 3 ) 3 , n-pentyl or n-hexyl;
- Cχ-Cg-Halogenalkyl für: einen Cχ-Cg-Alkylrest wie vorstehend genannt, der partiell oder vollständig durch Fluor, Chlor,- Cχ-Cg-haloalkyl for: a Cχ-Cg-alkyl radical as mentioned above, which is partially or completely by fluorine, chlorine,
Brom und/oder Iod substituiert ist, also z.B. einen der unter Cχ-C4-Halogenalkyl genannten Reste oder für 5-Fluor-l-pentyl, 5-Chlor-l-pentyl, 5-Brom-l-pentyl, 5-Iod-l-pentyl, 5, 5, 5 -Tri - chlor-1-penyl, Undecafluorpentyl, 6-Fluor-l-hexyl, 6 -Chlor- 1- hexyl, 6-Brom-l-hexyl, 6-Iod-l-hexyl, 6, 6, 6-Trichlor-l-hexyl oder Dodecafluorhexyl;Bromine and / or iodine is substituted, for example one of the radicals mentioned under Cχ-C 4 -haloalkyl or for 5-fluoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1-pentyl, 5-iodine -l-pentyl, 5, 5, 5 -Tri - chloro-1-penyl, undecafluoropentyl, 6-fluoro-1-hexyl, 6 -chloro-1-hexyl, 6-bromo-1-hexyl, 6-iodo-1 -hexyl, 6, 6, 6-trichloro-l-hexyl or dodecafluorohexyl;
- Cyano -Cχ-C4-alkyl für: CHCN, 1-Cyanoethyl, 2 -Cyanoethyl, 1-Cyanoprop-l-yl, 2-Cyanoprop-l-yl, 3 -Cyanoprop-1-yl, 1 -Cyano - but-l-yl, 2-Cyanobut-l-yl, 3 -Cyanobut-1-yl, 4 -Cyanobut-1-yl, l-Cyanobut-2-yl, 2-Cyanobut-2-yl, 3 -Cyanobut-2-yl, 4-Cyano- but-2-yl, 1- (CH2CN) eth-1-yl, 1- (CH2CN) -1 - (CH3) -eth-l-yl oder 1- (CHCN) prop-1-yl;- Cyano -Cχ-C 4 alkyl for: CHCN, 1-cyanoethyl, 2-cyanoethyl, 1-cyanoprop-l-yl, 2-cyanoprop-l-yl, 3-cyanoprop-1-yl, 1-cyano-but -l-yl, 2-cyanobut-l-yl, 3-cyanobut-1-yl, 4-cyanobut-1-yl, l-cyanobut-2-yl, 2-cyanobut-2-yl, 3-cyanobut-2 -yl, 4-cyano-but-2-yl, 1- (CH 2 CN) eth-1-yl, 1- (CH 2 CN) -1 - (CH 3 ) -eth-l-yl or 1- ( CHCN) prop-1-yl;
Hydroxy-Cχ-C4-alkyl für: CH2OH, 1-Hydroxyethyl, 2 -Hydroxyethyl, 1-Hydroxyprop-l-yl, 2-Hydroxyprop-l-yl, 3 -Hydroxyprop-1-yl, 1 -Hydroxybut - 1 -yl , 2 -Hydroxybut - 1 -yl , 3 -Hydroxybut - 1 -yl , 4-Hydroxybut-l-yl, 1-Hydroxybut-2 -yl, 2 -Hydroxybut- 2 -yl, 3 -Hydroxybut- 2 -yl, 4 -Hydroxybut-2 -yl, 1- (CH2OH) eth-l-yl, 1- (CH2OH) -1- (CH3) -eth-l-yl oder 1- (CH2OH) pro -1-yl;Hydroxy-Cχ-C 4 -alkyl for: CH 2 OH, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxyprop-l-yl, 2-hydroxyprop-l-yl, 3-hydroxyprop-1-yl, 1 -hydroxybut - 1 -yl, 2 -hydroxybut - 1 -yl, 3 -hydroxybut - 1 -yl, 4-hydroxybut-l-yl, 1-hydroxybut-2 -yl, 2 -hydroxybut- 2 -yl, 3 -hydroxybut- 2 - yl, 4-hydroxybut-2-yl, 1- (CH 2 OH) eth-1-yl, 1- (CH 2 OH) -1- (CH 3 ) -eth-1-yl or 1- (CH 2 OH ) per -1-yl;
Amino-Cχ-C4-alkyl für: CH2NH , 1-Aminoethyl, 2 -Aminoethyl, 1-Aminoprop-l-yl, 2-Aminoprop-l-yl, 3 -Aminoprop-1-yl, 1-Amino- but-l-yl, 2-Aminobut-l-yl, 3 -Aminobut-1-yl, 4 -Aminobut-1-yl, l-Aminobut-2-yl, 2 -Aminobut-2-yl, 3 -Aminobut-2-yl, 4-Amino- but-2-yl, 1- (CH2NH2) eth-l-yl, 1- (CH2NH2) - 1 - (CH3) -eth- 1-yl oder 1- (CH2NH2) prop -1-yl;Amino-Cχ-C 4 -alkyl for: CH 2 NH, 1-aminoethyl, 2-aminoethyl, 1-aminoprop-l-yl, 2-aminoprop-l-yl, 3-aminoprop-1-yl, 1-amino- but-l-yl, 2-aminobut-l-yl, 3-aminobut-1-yl, 4-aminobut-1-yl, l-aminobut-2-yl, 2-aminobut-2-yl, 3-aminobut- 2-yl, 4-amino-but-2-yl, 1- (CH 2 NH 2 ) eth-1-yl, 1- (CH 2 NH 2 ) -1 - (CH 3 ) -eth-1-yl or 1- (CH 2 NH 2 ) prop -1-yl;
- Hydroxycarbonyl-Cχ-C4-alkyl für: CHCOOH, 1- (COOH) ethyl,- Hydroxycarbonyl-Cχ-C 4 alkyl for: CHCOOH, 1- (COOH) ethyl,
2- (COOH) ethyl, 1- (COOH) prop- 1-yl, 2- (COOH) rop- 1-yl, 3 -(COOH) prop-1-yl, 1- (COOH) but-l-yl, 2 - (COOH) but- 1-yl, 3-(COOH)but- 1-yl, 4- (COOH) but -1-yl, 1- (COOH)but-2 -yl, 2 - (COOH)but-2 -yl, 3- (COOH)but-2-yl, 4- (COOH) but- 2 -yl, 1- (CH2COOH) eth-1 -yl, 1- (CH2COOH) -1- (CH3) -eth-l-yl oder 1- (CH2COOH) prop -1-yl;2- (COOH) ethyl, 1- (COOH) prop-1-yl, 2- (COOH) rop-1-yl, 3 - (COOH) prop-1-yl, 1- (COOH) but-l-yl , 2 - (COOH) but-1-yl, 3- (COOH) but-1-yl, 4- (COOH) but -1-yl, 1- (COOH) but-2 -yl, 2 - (COOH) but-2 -yl, 3- (COOH) but-2-yl, 4- (COOH) but-2 -yl, 1- (CH 2 COOH) eth-1 -yl, 1- (CH 2 COOH) -1 - (CH 3 ) -eth-l-yl or 1- (CH 2 COOH) prop -1-yl;
- Aminocarbonyl -Cχ-C4-alkyl für: CH2CONH2, 1- (CONH2) ethyl, 2- (CONH2) ethyl, 1- (CONH2) prop -1-yl, 2- (CO H2) prop -1-yl, 3- (CONH2) prop- 1-yl, 1- (CONH2) but -1-yl, 2 - (CONH2) but- 1-yl, 3- (CO H2) but -1-yl, 4 - (C0NH2) but- 1-yl , 1 - (CO H2) but-2 -yl, 2- (CONH2)but-2-yl, 3 - (CONH2) but-2 -yl, 4 - (CONH2) but-2 -yl, 1- (CH2CONH2) eth-l-yl, 1- (CH2CONH2) -1- (CH3) -eth-l-yl oder 1- (CH2CONH2) prop -1-yl; - Phenyl-Cχ-C -alkyl für: Benzyl, 1-Phenylethyl, 2-Phenylethyl, 1-Phenylprop-l-yl, 2-Phenylprop-l-yl, 3-Phenylprop-l-yl, 1-Phenylbut-l-yl, 2-Phenylbut-l-yl, 3-Phenylbut-l-yl, 4-Phenyl- but-l-yl, l-Phenylbut-2-yl, 2-Phenylbut-2-yl, 3-Phenylbut- 2-yl, 4-Phenylbut-2-yl, 1- (Benzyl) -eth-l-yl, 1- (Benzyl) -1-- Aminocarbonyl -Cχ-C 4 alkyl for: CH 2 CONH 2 , 1- (CONH 2 ) ethyl, 2- (CONH 2 ) ethyl, 1- (CONH 2 ) prop -1-yl, 2- (CO H 2 ) prop -1-yl, 3- (CONH 2 ) prop- 1-yl, 1- (CONH 2 ) but -1-yl, 2 - (CONH 2 ) but- 1-yl, 3- (CO H 2 ) but 1-yl, 4 - (C0NH 2) but-1-yl, 1 - (CO 2 H) but-2-yl, 2- (CONH2) but-2-yl, 3 - (CONH 2) but -2 -yl, 4 - (CONH 2 ) but-2 -yl, 1- (CH 2 CONH 2 ) eth-l-yl, 1- (CH 2 CONH 2 ) -1- (CH 3 ) -eth-l -yl or 1- (CH 2 CONH 2 ) prop -1-yl; - Phenyl-Cχ-C -alkyl for: benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-l-yl, 2-phenylprop-l-yl, 3-phenylprop-l-yl, 1-phenylbut-l- yl, 2-phenylbut-l-yl, 3-phenylbut-l-yl, 4-phenylbut-l-yl, l-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2- yl, 4-phenylbut-2-yl, 1- (benzyl) -eth-l-yl, 1- (benzyl) -1-
(methyl) -eth-l-yl oder 1- (Benzyl) -prop-1-yl, vorzugsweise für Benzyl oder 2-Phenylethyl;(methyl) -eth-l-yl or 1- (benzyl) prop-1-yl, preferably for benzyl or 2-phenylethyl;
- Heterocyclyl-Cχ-C -alkyl für: Heterocyclylmethyl , 1-Hetero- cyclyl-ethyl, 2-Heterocyclyl-ethyl, 1-Heterocyclyl-prop-l-yl,- Heterocyclyl-Cχ-C-alkyl for: heterocyclylmethyl, 1-heterocyclic-ethyl, 2-heterocyclyl-ethyl, 1-heterocyclyl-prop-l-yl,
2-Heterocyclyl-prop-l-yl, 3-Heterocyclyl-prop-l-yl, 1-Hetero- cyclyl-but-1-yl, 2-Heterocyclyl-but-l-yl, 3-Heterocyclyl- but-l-yl, 4-Heterocyclyl-but-l-yl, l-Heterocyclyl-but-2-yl, 2-Heterocyclyl-but-2-yl, 3-Heterocyclyl-but-2-yl, 3-Hetero- cyclyl-but-2-yl, 4-Heterocyclyl-but-2-yl, 1- (Heterocyclylmethyl) -eth-l-yl, 1- (Heterocyclylmethyl) -1- (methyl) -eth-l-yl oder 1- (Heterocyclylmethyl) -prop-1-yl, vorzugsweise Heterocyclylmethyl oder 2-Heterocyclyl-ethyl;2-heterocyclyl-prop-l-yl, 3-heterocyclyl-prop-l-yl, 1-heterocyclic-but-1-yl, 2-heterocyclyl-but-l-yl, 3-heterocyclyl-but-l- yl, 4-heterocyclyl-but-l-yl, l-heterocyclyl-but-2-yl, 2-heterocyclyl-but-2-yl, 3-heterocyclyl-but-2-yl, 3-heterocyclic-but- 2-yl, 4-heterocyclyl-but-2-yl, 1- (heterocyclylmethyl) -eth-l-yl, 1- (heterocyclylmethyl) -1- (methyl) -eth-l-yl or 1- (heterocyclylmethyl) - prop-1-yl, preferably heterocyclylmethyl or 2-heterocyclyl-ethyl;
- Cχ-C4-Alkoxy für : OCH3 , OC2H5 , OCH2-C2H5 , OCH (CH3 ) 2 , n-Butoxy, OCH (CH3 ) -C2H5 , OCH -CH (CH3 ) 2 oder C (CH3 ) 3 , vorzugsweise für OCH3 , OC2H5 oder OCH (CH3 ) 2 ;- Cχ-C 4 alkoxy for: OCH 3 , OC 2 H 5 , OCH 2 -C 2 H 5 , OCH (CH 3 ) 2 , n-butoxy, OCH (CH 3 ) -C 2 H 5 , OCH -CH (CH 3 ) 2 or C (CH 3 ) 3 , preferably for OCH 3 , OC 2 H 5 or OCH (CH 3 ) 2 ;
Cχ-C4-Halogenalkoxy für: einen Cχ-C-Alkoxyrest wie vorstehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder Iod substituiert ist, also z.B. OCHF, OCHF , OCF3, 0CH2C1, OCH (Cl) 2, 0C(C1)3, Chlorfluormethoxy, Dichlorfluormeth- oxy, Chlordifluormethoxy, 2-Fluorethoxy, 2-Chlorethoxy, 2-Brom- ethoxy, 2-Iodethoxy, 2, 2-Difluorethoxy, 2, 2, 2-Trifluorethoxy, 2-Chlor-2-fluorethoxy, 2-Chlor-2, 2-difluorethoxy, 2,2-Dichlor- 2-fluorethoxy, 2, 2, 2-Trichlorethoxy, OC F5, 2-Fluorpropoxy, 3-Fluorpropoxy, 2 , 2-Difluorpropoxy, 2 , 3-Difluorpropoxy, 2-Chlorpropoxy, 3-Chlorpropoxy, 2, 3-Dichlorpropoxy, 2-Brom- propoxy, 3-Brompropoxy, 3, 3 , 3-Trifluorpropoxy, 3 , 3 , 3-Trichlor- propoxy, OCH2-C2F5, OCF2-C2F5, 1- (CH2F) -2-fluorethoxy, 1-(CH2C1)- 2-chlorethoxy, 1- (CH2Br) -2-bromethoxy, 4-Fluorbutoxy, 4-Chlor- butoxy, 4-Brombutoxy oder Nonafluorbutoxy, vorzugsweise für OCHF , OCF3, Dichlorfluormethoxy, Chlordifluormethoxy oder 2,2, 2 -Trifluorethoxy;Cχ-C 4 -haloalkoxy for: a Cχ-C-alkoxy radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, e.g. OCHF, OCHF, OCF 3 , 0CH 2 C1, OCH ( Cl) 2 , 0C (C1) 3 , chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 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, OC F 5 , 2-fluoropropoxy, 3-fluoropropoxy, 2, 2-difluoropropoxy, 2, 3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2, 3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3, 3, 3-trifluoropropoxy, 3, 3, 3-trichloro- propoxy, OCH 2 -C 2 F 5 , OCF 2 -C 2 F 5 , 1- (CH 2 F) -2-fluoroethoxy, 1- (CH 2 C1) - 2-chloroethoxy, 1- (CH 2 Br) - 2-bromethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy, preferably for OCHF, OCF 3 , dichlorofluoromethoxy, chlorodifluoromethoxy or 2,2,2-trifluoro ethoxy;
- Cχ-Cg-Alkoxy für: einen Cχ-C4-Alkoxyrest wie vorstehend genannt, oder z.B. n-Pentoxy, 1-Methylbutoxy, 2-Methylbutoxy, 3-Methyl- butoxy, 2, 2-Dimethylpropoxy, 1-Ethylpropoxy, n-Hexoxy, 1,1-Di- methylpropoxy, 1, 2-Dimethylpropoxy, 1-Methylpentoxy, 2-Methyl- pentoxy, 3-Methylpentoxy, 4-Methylpentoxy, 1, 1-Dimethylbutoxy, 1, 2-Dimethylbutoxy, 1, 3-Dimethylbutoxy, 2 , 2-Dimethylbutoxy,- Cχ-Cg-alkoxy for: a Cχ-C 4 alkoxy radical as mentioned above, or for example n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2, 2-dimethylpropoxy, 1-ethylpropoxy, n -Hexoxy, 1,1-dimethylpropoxy, 1, 2-dimethylpropoxy, 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-Ethyl- butoxy, 1, 1, 2-Trimethylpropoxy, 1, 2 , 2-Trimethylpropoxy, 1-Ethyl-l-methylpropoxy oder l-Ethyl-2-methylpropoxy, vorzugsweise für OCH3, OC H5, OCH2-C2H5, OCH(CH3) , n-Butoxy, OC(CH3)3, n-Pentoxy oder n-Hexoxy;2, 3-dimethylbutoxy, 3, 3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 1, 2-trimethylpropoxy, 1, 2, 2-trimethylpropoxy, 1-ethyl-l-methylpropoxy or l-ethyl-2-methylpropoxy, preferably for OCH 3 , OC H 5 , OCH 2 -C 2 H 5 , OCH (CH 3 ), n-butoxy, OC (CH 3 ) 3 , n-pentoxy or n-hexoxy;
- Cχ-Cg-Halogenalkoxy für: einen Cχ-Cg-Alkoxyrest wie vorstehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder Iod substituiert ist, also z.B. einen der unter Cχ-C4-Halogenalkoxy genannten Reste oder für 5 - Fluor -1-pentoxy, 5-Chlor-l-pentoxy, 5-Brom-l-pentoxy, 5-Iod-l-pentoxy, 5, 5, 5-Trichlor-l-pentoxy, Undecafluorpentoxy, 6-Fluor-l-hexoxy, 6-Chlor-l-hexoxy, 6-Brom-l-hexoxy, 6-Iod-l-hexoxy, 6,6,6-Tri- chlor-1-hexoxy oder Dodecafluorhexoxy;- Cχ-Cg-haloalkoxy for: a Cχ-Cg-alkoxy radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example one of the radicals mentioned under Cχ-C 4 -haloalkoxy or for 5 - fluorine-1-pentoxy, 5-chloro-1-pentoxy, 5-bromo-1-pentoxy, 5-iodo-1-pentoxy, 5, 5, 5-trichloro-1-pentoxy, undecafluoropentoxy, 6-fluorine l-hexoxy, 6-chloro-l-hexoxy, 6-bromo-l-hexoxy, 6-iodo-l-hexoxy, 6,6,6-trichloro-1-hexoxy or dodecafluorohexoxy;
- Cχ-C4-Alkylthio für: SCH3, SC2H5, SCH2-C H5, SCH(CH3)2, n-Butyl - thio, SCH(CH3) -C2H5, SCH2-CH (CH3) 2 oder SC(CH3)3, vorzugsweise für SCH3 oder SC2H5;- Cχ-C 4 -alkylthio for: SCH 3 , SC 2 H 5 , SCH 2 -CH 5 , SCH (CH 3 ) 2 , n-butyl - thio, SCH (CH 3 ) -C 2 H 5 , SCH 2 - CH (CH 3 ) 2 or SC (CH 3 ) 3 , preferably for SCH 3 or SC 2 H 5 ;
- Cχ-C -Halogenalkylthio für: einen Cχ-C4-Alkylthiorest wie vorstehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder Iod substituiert ist, also z.B. SCH F, SCHF2, SCF3 SCH2C1, SCH(C1)2, SC(C1)3, Chlorfluormethylthio, Dichlorfluormethylthio, Chlordifluormethylthio, 2-Fluorethyl- thio, 2-Chlorethylthio, 2-Bromethylthio, 2-Iodethylthio, 2, 2-Difluorethylthio, 2 , 2 , 2-Trifluorethylthio, 2-Chlor-2-fluorethylthio, 2-Chlor-2,2-difluorethylthio, 2 , 2-Dichlor-2-fluor- ethylthio, 2, 2, 2-Trichlorethylthio, SC2F5, 2-Fluorpropylthio, 3-Fluorpropylthio, 2, 2-Difluorpropylthio, 2, 3-Difluorpropyl - thio, 2-Chlorpropylthio, 3-Chlorpropylthio, 2, 3-Dichlorpropyl- thio, 2-Brompropylthio, 3-Brompropylthio, 3, 3 , 3-Trifluor- propylthio, 3 , 3 , 3-Trichlorpropylthio, SCH2-C2F5, SCF2-C2F5, 1- (CH2F) -2-fluorethylthio, 1- (CH2C1) -2-chlorethylthio,Cχ-C -haloalkylthio for: a Cχ-C 4 -alkylthio radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example SCH F, SCHF 2 , SCF 3 SCH 2 C1, SCH (C1) 2 , SC (C1) 3 , chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2, 2-difluoroethylthio, 2, 2, 2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2, 2-dichloro-2-fluoroethylthio, 2, 2, 2-trichloroethylthio, SC 2 F 5 , 2-fluoropropylthio, 3-fluoropropylthio , 2, 2-difluoropropylthio, 2, 3-difluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2, 3-dichloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 3, 3, 3-trifluoropropylthio, 3 , 3, 3-trichloropropylthio, SCH 2 -C 2 F 5 , SCF 2 -C 2 F 5 , 1- (CH 2 F) -2-fluoroethylthio, 1- (CH 2 C1) -2-chloroethylthio,
1- (CHBr) -2-bromethylthio, 4-Fluorbutylthio, 4-Chlorbutylthio,1- (CHBr) -2-bromethylthio, 4-fluorobutylthio, 4-chlorobutylthio,
4-Brombutylthio oder SCF -CF2-C F5, vorzugsweise für SCHF2,4-bromobutylthio or SCF -CF 2 -CF 5 , preferably for SCHF 2 ,
SCF3, Dichlorfluormethylthio, Chlordifluormethylthio oderSCF 3 , dichlorofluoromethylthio, chlorodifluoromethylthio or
2,2,2- rifluorethylthio;2,2,2-rifluoroethylthio;
- Cχ-C6-Alkylthio für: einen Cχ-C4-Alkylthiorest wie vorstehend genannt, oder z.B. n-Pentylthio, 1-Methylbutylthio, 2-Methyl- butylthio, 3-Methylbutylthio, 2, 2-Dirnethylpropylthio, 1-Ethyl- propylthio, n-Hexylthio, 1, 1-Dimethylpropylthio, 1, 2-Dimethyl- propylthio, 1-Methylpentylthio, 2-Methylpentylthio, 3-Methyl- pentylthio, 4-Methylpentylthio, 1, 1-Dimethylbutylthio, 1,2-Di- methylbutylthio, 1, 3-Dimethylbutylthio, 2, 2-Dirnethylbutylthio, 2, 3-Dimethylbutylthio, 3 , 3-Dirnethylbutylthio, 1-Ethylbutylthio, 2-Ethylbutylthio, 1, 1,2-Trimethylpropylthio, 1, 2, 2-Trimethyl- propylthio, 1-Ethyl-l-methylpropylthio oder l-Ethyl-2-methyl- propylthio, vorzugsweise für SCH3, SC2H5, SCH2-C2H5, SCH(CH3)2, n-Butylthio, SC(CH3)3, n-Pentylthio oder n-Hexylthio;- Cχ-C 6 -alkylthio for: a Cχ-C 4 -alkylthio radical as mentioned above, or for example n-pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2, 2-dirnethylpropylthio, 1-ethyl- propylthio, n-hexylthio, 1, 1-dimethylpropylthio, 1, 2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1, 1-dimethylbutylthio, 1,2-di- methylbutylthio, 1, 3-dimethylbutylthio, 2, 2-dimethylbutylthio, 2, 3-dimethylbutylthio, 3, 3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1, 1,2-trimethylpropylthio, 1, 2, 2-trimethyl propylthio, 1-ethyl-l-methylpropylthio or l-ethyl-2-methyl- propylthio, preferably for SCH 3 , SC 2 H 5 , SCH 2 -C 2 H 5 , SCH (CH 3 ) 2 , n-butylthio, SC (CH 3 ) 3 , n-pentylthio or n-hexylthio;
- Cχ-C -Alkoxy-Cχ-C4-alkyl für: durch Cχ-C4-Alkoxy - wie vor- stehend genannt - substituiertes Cχ-C4-Alkyl, also z.B. für CH2-OCH3, CH2-OC2H5, n-Propoxymethyl, CH2-OCH (CH3) 2, n-Butoxy- methyl, (l-Methylpropoxy)methyl, (2-Methylpropoxy)methyl, CH2-OC(CH3)3, 2-(Methoxy)ethyl, 2- (Ethoxy) ethyl, 2-(n-Prop- oxy) ethyl, 2- (1-Methylethoxy) ethyl, 2- (n-Butoxy) ethyl, 2- (1-Methylpropoxy) ethyl, 2- (2-Methylpropoxy) ethyl, 2-(l,l-Di- methylethoxy) ethyl , 2- (Methoxy) propyl , 2- (Ethoxy) propyl , 2- (n-Propoxy) propyl, 2- (1-Methylethoxy) propyl , 2- (n-Butoxy) - propyl, 2- (1-Methylpropoxy) propyl, 2- (2-Methylpropoxy) propyl, 2- (1, 1-Dimethylethoxy) propyl, 3- (Methoxy) propyl, 3- (Ethoxy) - propyl, 3- (n-Propoxy) propyl, 3- (1-Methylethoxy) propyl,- Cχ-C -alkoxy-Cχ-C 4 -alkyl for: Cχ-C 4 -alkoxy - as mentioned above - substituted Cχ-C 4 -alkyl, for example for CH 2 -OCH 3 , CH 2 -OC 2 H 5 , n-propoxymethyl, CH 2 -OCH (CH 3 ) 2 , n-butoxymethyl, (l-methylpropoxy) methyl, (2-methylpropoxy) methyl, CH 2 -OC (CH 3 ) 3 , 2- (Methoxy) ethyl, 2- (ethoxy) ethyl, 2- (n-propoxy) ethyl, 2- (1-methylethoxy) ethyl, 2- (n-butoxy) ethyl, 2- (1-methylpropoxy) ethyl, 2- (2-methylpropoxy) ethyl, 2- (l, l-dimethylethoxy) ethyl, 2- (methoxy) propyl, 2- (ethoxy) propyl, 2- (n-propoxy) propyl, 2- (1- Methylethoxy) propyl, 2- (n-butoxy) propyl, 2- (1-methylpropoxy) propyl, 2- (2-methylpropoxy) propyl, 2- (1, 1-dimethylethoxy) propyl, 3- (methoxy) propyl, 3- (ethoxy) propyl, 3- (n-propoxy) propyl, 3- (1-methylethoxy) propyl,
3- (n-Butoxy) propyl, 3- (1-Methylpropoxy) propyl, 3-(2-Methyl- propoxy) propyl , 3- (1, 1-Dimethylethoxy) propyl, 2- (Methoxy) butyl, 2- (Ethoxy) butyl, 2- (n-Propoxy) butyl, 2- (1-Methylethoxy) butyl, 2- (n-Butoxy) butyl, 2- (1-Methylpropoxy) butyl, 2-(2-Methyl- propoxy) butyl , 2- (1, 1-Dimethylethoxy) butyl, 3- (Methoxy) butyl, 3- (Ethoxy) butyl, 3- (n-Propoxy) butyl, 3- (1-Methylethoxy) butyl, 3- (n-Butoxy) butyl, 3- (1-Methylpropoxy) butyl, 3- (2-Methylprop- oxy) butyl, 3- (1, 1-Dimethylethoxy) butyl, 4- (Methoxy) butyl, 4- (Ethoxy) butyl, 4- (n-Propoxy) butyl, 4- (1-Methylethoxy) butyl, 4- (n-Butoxy) butyl, 4- (1-Methylpropoxy) butyl, 4- (2-Methylprop- oxy)butyl oder 4- (1, 1-Dimethylethoxy) butyl, vorzugsweise für CH2-OCH3, CH2-OC2H5, 2- (OCH3) ethyl oder 2- (OC2H5) ethyl;3- (n-butoxy) propyl, 3- (1-methylpropoxy) propyl, 3- (2-methylpropoxy) propyl, 3- (1, 1-dimethylethoxy) propyl, 2- (methoxy) butyl, 2- ( Ethoxy) butyl, 2- (n-propoxy) butyl, 2- (1-methylethoxy) butyl, 2- (n-butoxy) butyl, 2- (1-methylpropoxy) butyl, 2- (2-methylprooxy) butyl , 2- (1, 1-dimethylethoxy) butyl, 3- (methoxy) butyl, 3- (ethoxy) butyl, 3- (n-propoxy) butyl, 3- (1-methylethoxy) butyl, 3- (n-butoxy ) butyl, 3- (1-methylpropoxy) butyl, 3- (2-methylpropoxy) butyl, 3- (1, 1-dimethylethoxy) butyl, 4- (methoxy) butyl, 4- (ethoxy) butyl, 4- (n-propoxy) butyl, 4- (1-methylethoxy) butyl, 4- (n-butoxy) butyl, 4- (1-methylpropoxy) butyl, 4- (2-methylpropoxy) butyl or 4- (1, 1-dimethylethoxy) butyl, preferably for CH 2 -OCH 3 , CH 2 -OC 2 H 5 , 2- (OCH 3 ) ethyl or 2- (OC 2 H 5 ) ethyl;
Cχ-C -Halogenalkoxy-Cχ-C4~alkyl für: durch Cχ-C4-Halogenalkoxy wie vorstehend genannt substituiertes Cχ-C4-Alkyl, also z.B. für 2-(OCHF2)ethyl, 2- (OCF3) ethyl oder 2- (OC2F5) ethyl;Cχ-C-haloalkoxy-Cχ-C 4 ~ alkyl for: Cχ-C 4 -haloalkoxy substituted as mentioned above Cχ-C 4 alkyl, for example for 2- (OCHF 2 ) ethyl, 2- (OCF 3 ) ethyl or 2- (OC 2 F 5 ) ethyl;
- Cχ-C4-Alkylthio-Cχ-C -alkyl für: durch Cχ-C4-Alkylthio - wie vorstehend genannt - substituiertes Cχ-C -Alkyl, also z.B. für CH2-SCH3, CH2-SC2H5, n-Propylthiomethyl, CH2-SCH (CH3) 2, n-Butylthiomethyl, (l-Methylpropylthio)methyl, (2-Methylpropyl- thio)methyl, CH2-SC (CH3) 3, 2- (Methylthio) ethyl, 2- (Ethylthio) - ethyl, 2- (n-Propylthio) ethyl, 2- (1-Methylethylthio) ethyl, 2- (n-Butylthio) ethyl, 2- (1-Methylpropylthio) ethyl, 2-(2-Methyl- propylthio) ethyl, 2- (1, 1-Dimethylethylthio) ethyl, 2- (Methyl - thio) propyl, 2- (Ethylthio) propyl, 2- (n-Propylthio) propyl, 2- (1-Methylethylthio) propyl, 2- (n-Butylthio) propyl, 2- (1-Methylpropylthio) propyl, 2- (2-Methylpropylthio) propyl , 2- (1, 1-Dimethylethylthio) propyl, 3- (Methylthio) propyl, 3- (Ethylthio) propyl, 3- (n-Propylthio) propyl, 3- (1-Methylethyl- thio) propyl, 3- (n-Butylthio) propyl, 3- (1-Methylpropylthio) - propyl, 3- (2-Methylpropylthio) propyl, 3- (1, 1-Dimethylethyl - thio) propyl, 2- (Methylthio) butyl, 2- (Ethylthio) butyl, 2- (n-Propylthio) butyl, 2- (1-Methylethylthio) butyl, 2- (n-Butylthio) butyl, 2- (1-Methylpropylthio) butyl , 2-(2-Methyl- propylthio) butyl, 2- (1, 1-Dimethylethylthio) butyl, 3- (Methylthio) butyl, 3- (Ethylthio) butyl, 3- (n-Propylthio) butyl, 3- (1-Methylethylthio) butyl, 3- (n-Butylthio) butyl, 3-(l-Methyl- propylthio) butyl, 3- (2-Methylpropylthio) butyl, 3- (1, 1-Dimethylethylthio) butyl, 4- (Methylthio) butyl, 4- (Ethylthio) butyl, 4- (n- Propylthio) butyl, 4- (1-Methylethylthio) butyl, 4- (n-Butylthio) - butyl, 4- (1-Methylpropylthio) butyl, 4- (2-Methylpropylthio) butyl oder 4- (1, 1-Dimethylethylthio) butyl, vorzugsweise CH2-SCH3, CH2-SC2H5, 2-(SCH3)ethyl oder 2- (SC2H5) ethyl ;- Cχ-C 4 -Alkylthio-C C-C -alkyl for: Cχ-C 4 -alkylthio - as mentioned above - substituted C C-C-alkyl, for example for CH 2 -SCH 3 , CH 2 -SC 2 H 5 , n-propylthiomethyl, CH 2 -SCH (CH 3 ) 2 , n-butylthiomethyl, (l-methylpropylthio) methyl, (2-methylpropylthio) methyl, CH 2 -SC (CH 3 ) 3 , 2- (methylthio) ethyl, 2- (ethylthio) - ethyl, 2- (n-propylthio) ethyl, 2- (1-methylethylthio) ethyl, 2- (n-butylthio) ethyl, 2- (1-methylpropylthio) ethyl, 2- (2 -Methyl-propylthio) ethyl, 2- (1, 1-dimethylethylthio) ethyl, 2- (methyl-thio) propyl, 2- (ethylthio) propyl, 2- (n-propylthio) propyl, 2- (1-methylethylthio) propyl, 2- (n-butylthio) propyl, 2- (1-methylpropylthio) propyl, 2- (2-methylpropylthio) propyl, 2- (1, 1-dimethylethylthio) propyl, 3- (methylthio) propyl, 3- ( Ethylthio) propyl, 3- (n-propylthio) propyl, 3- (1-methylethylthio) propyl, 3- (n-butylthio) propyl, 3- (1-methylpropylthio) propyl, 3- (2-methylpropylthio) propyl, 3- (1, 1-dimethylethylthio) propyl, 2- (Methylthio) butyl, 2- (ethylthio) butyl, 2- (n-propylthio) butyl, 2- (1-methylethylthio) butyl, 2- (n-butylthio) butyl, 2- (1-methylpropylthio) butyl, 2- (2-methylpropylthio) butyl, 2- ( 1, 1-dimethylethylthio) butyl, 3- (methylthio) butyl, 3- (ethylthio) butyl, 3- (n-propylthio) butyl, 3- (1-methylethylthio) butyl, 3- (n-butylthio) butyl, 3 - (l-Methylpropylthio) butyl, 3- (2-methylpropylthio) butyl, 3- (1, 1-dimethylethylthio) butyl, 4- (methylthio) butyl, 4- (ethylthio) butyl, 4- (n-propylthio ) butyl, 4- (1-methylethylthio) butyl, 4- (n-butylthio) butyl, 4- (1-methylpropylthio) butyl, 4- (2-methylpropylthio) butyl or 4- (1, 1-dimethylethylthio) butyl , preferably CH 2 -SCH 3 , CH 2 -SC 2 H 5 , 2- (SCH 3 ) ethyl or 2- (SC 2 H 5 ) ethyl;
- Cχ-C4-Halogenalkylthio-Cχ-C4-alkyl für: durch Cχ-C4-Halogen- alkylthio wie vorstehend genannt substituiertes Cχ-C4-Alkyl, also z.B. für 2- (SCHF2) ethyl, 2- (SCF3) ethyl oder 2- (SC2F5) ethyl;- Cχ-C4-haloalkylthio-Cχ-C 4 alkyl: by Cχ-C 4 halo-alkylthio as mentioned above substituted Cχ-C4 alkyl, that is ethyl for example, 2- (SCHF 2), 2- ( SCF 3 ) ethyl or 2- (SC 2 F 5 ) ethyl;
- (Cχ-C4-Alkyl) carbonyl für: C0-CH3, CO-C2H5, CO-CH2-C2H5, CO-CH(CH3)2, n-Butylcarbonyl, CO-CH (CH3) -C2H5, CO-CH2-CH (CH3) 2 oder CO-C(CH3)3, vorzugsweise für CO-CH3 oder CO-C2Hs;- (Cχ-C 4 alkyl) carbonyl for: C0-CH 3 , CO-C 2 H 5 , CO-CH 2 -C 2 H 5 , CO-CH (CH 3 ) 2 , n-butylcarbonyl, CO-CH (CH 3 ) -C 2 H 5 , CO-CH 2 -CH (CH 3 ) 2 or CO-C (CH 3 ) 3 , preferably for CO-CH 3 or CO-C 2 Hs;
- (Cχ-C4-Halogenalkyl) carbonyl für: einen (Cχ-C4-Alkyl) carbonyl - rest - wie vorstehend genannt - der partiell oder vollständig durch Fluor, Chlor, Brom und/oder Iod substituiert ist, also Z.B. CO-CH2F, CO-CHF2, CO-CF3, C0-CH2C1, C0-CH(C1)2, C0-C(C1)3, Chlorfluormethylcarbonyl, Dichlorfluormethylcarbonyl, Chlordi- fluormethylcarbonyl, 2-Fluorethylcarbonyl, 2-Chlorethylcarbo- nyl, 2-Bromethylcarbonyl, 2-Iodethylcarbonyl, 2, 2-Difluorethyl - carbonyl, 2, 2, 2-Trifluorethylcarbonyl, 2-Chlor-2-fluorethylcar- bonyl, 2-Chlor-2, 2-difluorethylcarbonyl, 2, 2-Dichlor-2-fluorethylcarbonyl, 2,2,2-Trichlorethylcarbonyl, CO-C2F5, 2-Fluor- propylcarbonyl, 3-Fluorpropylcarbonyl, 2, 2-Difluorpropyl - carbonyl, 2, 3-Difluorpropylcarbonyl, 2-Chlorpropylcarbonyl, 3-Chlorpropylcarbonyl, 2, 3-Dichlorpropylcarbonyl, 2-Brompropyl- carbonyl, 3-Brompropylcarbonyl, 3 , 3 , 3-Trifluorpropylcarbonyl, 3,3,3-Trichlorpropylcarbonyl, CO-CH2-C2F5, CO-CF2-C F5, 1- (CH2F) -2-fluorethylcarbonyl, 1- (CH2C1) -2-chlorethylcarbonyl, 1- (CH2Br) -2-bromethylcarbonyl, 4-Fluorbutylcarbonyl, 4-Chlor- butylcarbonyl, 4-Brombutylcarbonyl oder Nonafluorbutylcarbonyl, vorzugsweise für CO-CF3, C0-CH2C1 oder 2 , 2 , 2 -Trifluorethylcarbonyl ;- (Cχ-C 4 -haloalkyl) carbonyl for: a (Cχ-C 4 -alkyl) carbonyl radical - as mentioned above - which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example CO- CH 2 F, CO-CHF 2 , CO-CF 3 , C0-CH 2 C1, C0-CH (C1) 2 , C0-C (C1) 3 , chlorofluoromethylcarbonyl, dichlorofluoromethylcarbonyl, chlorodifluoromethylcarbonyl, 2-fluoroethylcarbonyl, 2- Chloroethylcarbonyl, 2-bromoethylcarbonyl, 2-iodoethylcarbonyl, 2, 2-difluoroethylcarbonyl, 2, 2, 2-trifluoroethylcarbonyl, 2-chloro-2-fluoroethylcarbonyl, 2-chloro-2, 2-difluoroethylcarbonyl, 2, 2-dichloro-2-fluoroethylcarbonyl, 2,2,2-trichloroethylcarbonyl, CO-C 2 F 5 , 2-fluoropropylcarbonyl, 3-fluoropropylcarbonyl, 2, 2-difluoropropylcarbonyl, 2, 3-difluoropropylcarbonyl, 2-chloropropylcarbonyl , 3-chloropropylcarbonyl, 2, 3-dichloropropylcarbonyl, 2-bromopropylcarbonyl, 3-bromopropylcarbonyl, 3, 3, 3-trifluoropropylcarbonyl, 3,3,3-trichloropropylcarbonyl, CO-CH 2 -C 2 F 5 , CO-CF 2 -CF 5 , 1- (CH 2 F) -2-fluoroethyl carbonyl, 1- (CH 2 C1) -2-chloroethylcarbonyl, 1- (CH 2 Br) -2-bromethylcarbonyl, 4-fluorobutylcarbonyl, 4-chlorobutylcarbonyl, 4-bromobutylcarbonyl or nonafluorobutylcarbonyl, preferably for CO-CF 3 , CO -CH 2 C1 or 2, 2, 2 -trifluoroethylcarbonyl;
(Cχ-Cg-Alkyl) carbonyl für: einen der vorstehend genannten (Cx -C4 -Alkyl ) carbonylreste, oder z.B. n-Pentyl-CO, 1-Methyl - butyl-CO, 2-Methylbutyl -C0, 3-Methylbutyl-CO, 2, 2-Dimethyl- propyl-CO, 1-Ethylpropyl-CO, n-Hexyl-CO, 1, 1-Dimethylpropyl-CO, 1,2-Dirnethylpropyl -C0, 1-Methylpentyl-CO, 2-Methylpentyl-CO, 3-Methylpentyl-CO, 4-Methylpentyl-CO, 1, 1-Dimethylbutyl-CO, 1,2-Dimethylbutyl-CO, 1, 3-Dimethylbutyl -CO, 2 , 2-Dimethylbutyl - CO, 2,3-Dimethylbutyl-CO, 3 , 3-Dimethylbutyl -CO, 1-Ethylbutyl - CO, 2-Ethylbutyl-CO, 1, 1, 2-Trimethylpropyl -CO, 1, 2, 2-Trimethylpropyl -CO, 1-Ethyl-l-methylpropyl-CO oder l-Ethyl-2-methyl- propyl-CO, vorzugsweise für CO-CH3, CO-C H5, CO-CH2-CH5, 5 CO-CH(CH3)2, n-Butyl-CO, CO-C(CH3)3, CO- (n-C5Hχχ) oder CO- (n-C6Hχ3) ;(Cχ-Cg-alkyl) carbonyl for: one of the abovementioned (Cx -C 4 alkyl) carbonyl radicals, or for example n-pentyl-CO, 1-methyl-butyl-CO, 2-methylbutyl -C0, 3-methylbutyl- CO, 2, 2-dimethylpropyl-CO, 1-ethylpropyl-CO, n-hexyl-CO, 1, 1-dimethylpropyl-CO, 1,2-dirnethylpropyl -C0, 1-methylpentyl-CO, 2-methylpentyl- CO, 3-methylpentyl-CO, 4-methylpentyl-CO, 1, 1-dimethylbutyl-CO, 1,2-dimethylbutyl-CO, 1, 3-dimethylbutyl -CO, 2, 2-dimethylbutyl - CO, 2,3-dimethylbutyl-CO, 3, 3-dimethylbutyl -CO, 1-ethylbutyl-CO, 2-ethylbutyl-CO, 1, 1, 2-trimethylpropyl -CO, 1, 2, 2-trimethylpropyl -CO, 1-ethyl-l-methylpropyl-CO or l-ethyl-2-methylpropyl-CO, preferably for CO-CH 3 , CO-C H 5 , CO-CH 2 -CH 5 , 5 CO-CH (CH 3 ) 2 , n-butyl-CO, CO-C (CH 3 ) 3 , CO- (nC 5 Hχχ) or CO- (nC 6 Hχ 3 );
(Cχ-Cg-Halogenalkyl) carbonyl für: einen (Cχ-Cg-Alkyl) carbonyl - rest - wie vorstehend genannt - der partiell oder vollständig 0 durch Fluor, Chlor, Brom und/oder Iod substituiert ist, also z.B. CO-CH2F, CO-CHF2, CO-CF3 , C0-CH2C1, C0-CH(C1)2, C0-C(C1)3, Chlorfluormethylcarbonyl, Dichlorfluormethylcarbonyl, Chlordi- fluormethylcarbonyl, 2-Fluorethylcarbonyl, 2-Chlorethylcarbo- nyl, 2-Bromethylcarbonyl, 2-Iodethylcarbonyl, 2 , 2-Difluorethyl - __ carbonyl, 2, 2, 2-Trifluorethylcarbonyl, 2-Chlor-2-fluorethylcarbonyl, 2-Chlor-2, 2-difluorethylcarbonyl, 2, 2-Dichlor-2-fluorethylcarbonyl, 2,2,2-Trichlorethylcarbonyl, CO-C2F5, 2-Fluor- propylcarbonyl, 3-Fluorpropylcarbonyl, 2 , 2-Difluorpropyl - carbonyl, 2, 3-Difluorpropylcarbonyl, 2-Chlorpropylcarbonyl, 3-Chlorpropylcarbonyl, 2, 3-Dichlorpropylcarbonyl, 2-Brompropyl- 0 carbonyl , 3-Brompropylcarbonyl , 3,3, 3-Trifluorpropylcarbonyl , 3,3,3-Trichlorpropylcarbonyl, CO-CH2-C2F5, CO-CF2-C2F5, 1- (CH2F) -2-fluorethylcarbonyl, 1- (CH2C1) -2-chlorethylcarbonyl, 1- (CH2Br) -2-bromethylcarbonyl, 4-Fluorbutylcarbonyl, 4-Chlor- butylcarbonyl, 4-Brombutylcarbonyl oder Nonafluorbutylcarbonyl, 5 vorzugsweise für CO-CF3 C0-CH2C1 oder 2, 2, 2 -Trifluorethylcarbonyl ;(Cχ-Cg-haloalkyl) carbonyl for: a (Cχ-Cg-alkyl) carbonyl radical - as mentioned above - which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example CO-CH 2 F, CO-CHF 2 , CO-CF 3 , C0-CH 2 C1, C0-CH (C1) 2 , C0-C (C1) 3 , chlorofluoromethylcarbonyl, dichlorofluoromethylcarbonyl, chlorodifluoromethylcarbonyl, 2-fluoroethylcarbonyl, 2-chloroethylcarbo- nyl, 2-bromoethylcarbonyl, 2-iodoethylcarbonyl, 2, 2-difluoroethyl - __ carbonyl, 2, 2, 2-trifluoroethylcarbonyl, 2-chloro-2-fluoroethylcarbonyl, 2-chloro-2, 2-difluoroethylcarbonyl, 2, 2-dichloro -2-fluoroethylcarbonyl, 2,2,2-trichloroethylcarbonyl, CO-C 2 F 5 , 2-fluoropropylcarbonyl, 3-fluoropropylcarbonyl, 2, 2-difluoropropylcarbonyl, 2, 3-difluoropropylcarbonyl, 2-chloropropylcarbonyl, 3- Chloropropylcarbonyl, 2, 3-dichloropropylcarbonyl, 2-bromopropyl-0 carbonyl, 3-bromopropylcarbonyl, 3,3, 3-trifluoropropylcarbonyl, 3,3,3-trichloropropylcarbonyl, CO-CH 2 -C 2 F 5 , CO-CF 2 - C 2 F 5 , 1- (CH 2 F) -2-fluorene thylcarbonyl, 1- (CH 2 C1) -2-chloroethylcarbonyl, 1- (CH 2 Br) -2-bromethylcarbonyl, 4-fluorobutylcarbonyl, 4-chlorobutylcarbonyl, 4-bromobutylcarbonyl or nonafluorobutylcarbonyl, 5 preferably for CO-CF 3 CO -CH 2 C1 or 2, 2, 2 -trifluoroethylcarbonyl;
(Cχ-C -Alkyl) carbonyloxy für: 0-CO-CH3, 0-CO-C2H5, 0-CO-CH2-C2H5, 0-CO-CH(CH3)2, 0-CO-CH2-CH2-C2H5, O-CO-CH (CH3) -C2H5 , 0 0-CO-CH2-CH(CH3)2 oder O-CO-C (CH3) 3 , vorzugsweise für 0-CO-CH3 oder 0-CO-C2H5;(Cχ-C-Alkyl) carbonyloxy for: 0-CO-CH 3 , 0-CO-C 2 H 5 , 0-CO-CH 2 -C 2 H 5 , 0-CO-CH (CH 3 ) 2 , 0 -CO-CH 2 -CH 2 -C 2 H 5 , O-CO-CH (CH 3 ) -C 2 H 5 , 0 0-CO-CH 2 -CH (CH 3 ) 2 or O-CO-C ( CH 3 ) 3 , preferably for 0-CO-CH 3 or 0-CO-C 2 H 5 ;
(Cχ-C -Halogenalkyl) carbonyloxy für: einen (Cχ-C4-Alkyl) car- bonylrest - wie vorstehend genannt - der partiell oder voll- ^ ständig durch Fluor, Chlor, Brom und/oder Iod substituiert ist, also z.B. 0-CO-CH2F, 0-CO-CHF2, 0-CO-CF3, 0-CO-CH2Cl, O-CO-CH (CD 2, O-CO-C (CD 3, Chlorfluormethylcarbonyloxy, Dichlorfluormethylcarbonyloxy, Chlordifluormethylcarbonyloxy, 2-Fluorethylcarbonyloxy, 2-Chlorethylcarbonyloxy, 2-Bromethyl- 0 carbonyloxy, 2-Iodethylcarbonyloxy, 2, 2-Difluorethylcarbonyl - oxy, 2,2, 2-Trifluorethylcarbonyloxy, 2-Chlor-2-fluorethyl - carbonyloxy, 2-Chlor-2, 2-difluorethylcarbonyloxy, 2,2-Dichlor- 2-fluorethylcarbonyloxy, 2,2, 2-Trichlorethylcarbonyloxy, 0-CO-C2F5, 2-Fluorpropylcarbonyloxy, 3-Fluorpropylcarbonyloxy, 5 2, 2-Difluorpropylcarbonyloxy, 2, 3-Difluorpropylcarbonyloxy, 2-Chlorpropylcarbonyloxy, 3-Chlorpropylcarbonyloxy, 2,3-Di- chlorpropylcarbonyloxy, 2-Brompropylcarbonyloxy, 3-Brompropyl- carbonyloxy, 3 , 3 , 3-Trifluorpropylcarbonyloxy, 3, 3 , 3-Trichlor- propylcarbonyloxy, 0-CO-CH2-C2F5, 0-C0-CF2 -C2F5, l-(CH2F)-2- fluorethylcarbonyloxy, 1- (CH2C1) -2-chlorethylcarbonyloxy, 1- (CH2Br) -2-bromethylcarbonyloxy, 4-Fluorbutylcarbonyloxy, 4-Chlorbutylcarbonyloxy, 4-Brombutylcarbonyloxy oder Nonafluor- butylcarbonyloxy, vorzugsweise für 0-C0-CF3 , 0-CO-CH2Cl oder 2,2,2 -Trifluorethylcarbonyloxy;(Cχ-C haloalkyl) carbonyloxy for: a (Cχ-C 4 alkyl) carbonyl radical - as mentioned above - which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 0 -CO-CH 2 F, 0-CO-CHF 2 , 0-CO-CF 3 , 0-CO-CH 2 Cl, O-CO-CH (CD 2 , O-CO-C (CD 3 , chlorofluoromethylcarbonyloxy, dichlorofluoromethylcarbonyloxy , Chlorodifluoromethylcarbonyloxy, 2-fluoroethylcarbonyloxy, 2-chloroethylcarbonyloxy, 2-bromoethyl-0 carbonyloxy, 2-iodoethylcarbonyloxy, 2, 2-difluoroethylcarbonyloxy, 2,2, 2-trifluoroethylcarbonyloxy, 2-chloro-2-fluoroethyl - carbonyloxy, 2- Chloro-2, 2-difluoroethylcarbonyloxy, 2,2-dichloro-2-fluoroethylcarbonyloxy, 2,2, 2-trichloroethylcarbonyloxy, 0-CO-C 2 F 5 , 2-fluoropropylcarbonyloxy, 3-fluoropropylcarbonyloxy, 5 2, 2-difluoropropylcarbonyloxy, 2,3-difluoropropylcarbonyloxy, 2-chloropropylcarbonyloxy, 3-chloropropylcarbonyloxy, 2,3-di-chloropropylcarbonyloxy, 2-bromopropylcarbonyloxy, 3-bromopropyl- carbonyloxy, 3, 3, 3-trifluoropropylcarbonyloxy, 3, 3, 3-trichloropropylcarbonyloxy, 0-CO-CH 2 -C 2 F 5 , 0-C0-CF 2 -C 2 F 5 , l- (CH 2 F ) -2-fluoroethylcarbonyloxy, 1- (CH 2 C1) -2-chloroethylcarbonyloxy, 1- (CH 2 Br) -2-bromethylcarbonyloxy, 4-fluorobutylcarbonyloxy, 4-chlorobutylcarbonyloxy, 4-bromobutylcarbonyloxy or nonafluorobutylcarbonyloxy, preferably for 0- CO-CF 3 , 0-CO-CH 2 Cl or 2,2,2-trifluoroethylcarbonyloxy;
(Cχ-C -Alkyl) carbonyloxy für: einen der vorstehend genannten (Cχ-C4-Alkyl) carbonyloxyreste, oder z.B. n-Pentyl-COO,(Cχ-C-alkyl) carbonyloxy for: one of the above (Cχ-C 4 -alkyl) carbonyloxy radicals, or for example n-pentyl-COO,
1-Methylbutyl-COO, 2-Methylbutyl-COO, 3-Methylbutyl-COO, 2, 2-Dirnethylpropyl -COO, 1-Ethylpropyl -COO, n-Hexyl-COO, 1,1-Di- methylpropyl-COO, 1, 2-Dirnethylpropyl -COO, 1-Methylpentyl-COO, 2-Methylpentyl-COO, 3-Methylpentyl-COO, 4-Methylpentyl-COO, 1,1-Dimethylbutyl -COO, 1, 2-Dimethylbutyl-COO, 1, 3-Dimethylbutyl -COO, 2,2-Dimethylbutyl-COO, 2 , 3-Dimethylbutyl -COO, 3, 3-Dimethylbutyl -COO, 1-Ethylbutyl-COO, 2-Ethylbutyl -COO, 1,1,2-Tri- methylpropyl-COO, 1, 2, 2-Trimethylpropyl -COO, 1-Ethyl-l-methyl- propyl-COO oder l-Ethyl-2-methylpropyl-COO, vorzugsweise für 0-CO-CH3, 0-CO-C2H5, 0-CO-CH2-C2H5, O-CO-CH (CH3) 2, n-Butyl-COO, 0-CO-C(CH3)3, O-CO- (n-C5Hχχ) oder O-CO- (n-C6H13) ;1-methylbutyl-COO, 2-methylbutyl-COO, 3-methylbutyl-COO, 2, 2-dirnethylpropyl -COO, 1-ethylpropyl -COO, n-hexyl-COO, 1,1-dimethylpropyl-COO, 1, 2-Dirnethylpropyl -COO, 1-methylpentyl-COO, 2-methylpentyl-COO, 3-methylpentyl-COO, 4-methylpentyl-COO, 1,1-dimethylbutyl -COO, 1, 2-dimethylbutyl-COO, 1, 3- Dimethylbutyl -COO, 2,2-dimethylbutyl-COO, 2, 3-dimethylbutyl -COO, 3, 3-dimethylbutyl -COO, 1-ethylbutyl-COO, 2-ethylbutyl -COO, 1,1,2-trimethylpropyl- COO, 1, 2, 2-trimethylpropyl -COO, 1-ethyl-l-methylpropyl-COO or l-ethyl-2-methylpropyl-COO, preferably for 0-CO-CH 3 , 0-CO-C 2 H 5 , 0-CO-CH 2 -C 2 H 5 , O-CO-CH (CH 3 ) 2 , n-butyl-COO, 0-CO-C (CH 3 ) 3 , O-CO- (nC 5 Hχχ ) or O-CO- (nC 6 H 13 );
(Cχ-C6-Alkyl) thiocarbonyl für: CS-CH3, CS-C2H5, CS-CH2-C2H5, CS-CH(CH3)2, CS-(n-C4H9), CS-CH (CH3) -C2H5 , CS-CH2-CH (CH3) 2, CS-C(CH3)3, CS-(n-C5Hχχ) , CS-CH (CH3) -CH2-C2H5, CS-CH2-CH(CH3)-C2H5, CS-CH2CH2-CH (CH3) 2 , CS-C (CH3) 2-C2H5, CS-CH(CH3)-CH(CH3)2, CS-CH2-C (CH3) 3, CS-CH (C2H5) -C2H5, CS-(n-C6H13) , CS-CH (CH3) - (n-CH9) , CS-CH2-CH (CH3) -CH2-C2H5, CS-CH2CH2-CH(CH3)-C2H5, CS-CH2CH2CH2-CH (CH3) 2 , CS-C (CH3 ) 2-CH2-C2H5 , CS-CH (CH3 ) -CH (CH3 ) -C2H5 , CS-CH (CH3)-CH2-CH(CH3)2, CS-CH2-C (CH3) 2-C2H5 ,(Cχ-C 6 alkyl) thiocarbonyl for: CS-CH 3 , CS-C 2 H 5 , CS-CH 2 -C 2 H 5 , CS-CH (CH 3 ) 2 , CS- (nC 4 H 9 ) , CS-CH (CH 3 ) -C 2 H 5 , CS-CH 2 -CH (CH 3 ) 2 , CS-C (CH 3 ) 3 , CS- (nC 5 Hχχ), CS-CH (CH 3 ) -CH 2 -C 2 H 5 , CS-CH 2 -CH (CH 3 ) -C 2 H 5 , CS-CH 2 CH 2 -CH (CH 3 ) 2 , CS-C (CH 3 ) 2 -C 2 H 5 , CS-CH (CH 3 ) -CH (CH 3 ) 2 , CS-CH 2 -C (CH 3 ) 3 , CS-CH (C 2 H 5 ) -C 2 H 5 , CS- (nC 6 H 13 ), CS-CH (CH 3 ) - (n-CH 9 ), CS-CH 2 -CH (CH 3 ) -CH 2 -C 2 H 5 , CS-CH 2 CH 2 -CH (CH 3 ) -C 2 H 5 , CS-CH 2 CH 2 CH 2 -CH (CH 3 ) 2 , CS-C (CH 3 ) 2 -CH 2 -C 2 H 5 , CS-CH (CH 3 ) -CH (CH 3 ) -C 2 H 5 , CS-CH (CH 3 ) -CH 2 -CH (CH 3 ) 2 , CS-CH 2 -C (CH 3 ) 2 -C 2 H 5 ,
CS-CH2-CH (CH3 ) -CH (CH3) 2 , CS-CH2CH2-C (CH3 ) 3 , CS-CH (C2H5) -CH2-C2H5 , CS-CH2-CH(C2H5)-C2H5, CS-C (CH3) 2-CH (CH3) 2, CS-CH (CH3) -C (CH3) 3 , CS-C(CH3) (C2H5)-C2H5 oder CS-CH (C2H5) -CH (CH3) 2, vorzugsweise CS-CH3, CS-C2H5, CS-CH2-C2H5, CS-CH(CH3)2 oder CS-(n-CH9);CS-CH 2 -CH (CH 3 ) -CH (CH 3 ) 2 , CS-CH 2 CH 2 -C (CH 3 ) 3 , CS-CH (C 2 H 5 ) -CH 2 -C 2 H 5 , CS-CH 2 -CH (C 2 H 5 ) -C 2 H 5 , CS-C (CH 3 ) 2 -CH (CH 3 ) 2 , CS-CH (CH 3 ) -C (CH 3 ) 3 , CS -C (CH 3 ) (C 2 H 5 ) -C 2 H 5 or CS-CH (C 2 H 5 ) -CH (CH 3 ) 2 , preferably CS-CH 3 , CS-C 2 H 5 , CS- CH 2 -C 2 H 5 , CS-CH (CH 3 ) 2 or CS- (n-CH 9 );
(Cχ-C -Alkoxy) carbonyl für: CO-OCH3, CO-OC2H5, CO-OCH2-C2H5, CO-OCH(CH3)2, n-Butoxycarbonyl , CO-OCH (CH3) -C2H5, CO-OCH2-CH(CH3)2 oder CO-OC(CH3)3, vorzugsweise für CO-OCH3 oder CO-OC2H5 ;(Cχ-C -alkoxy) carbonyl for: CO-OCH 3 , CO-OC 2 H 5 , CO-OCH 2 -C 2 H 5 , CO-OCH (CH 3 ) 2 , n-butoxycarbonyl, CO-OCH (CH 3 ) -C 2 H 5 , CO-OCH 2 -CH (CH 3 ) 2 or CO-OC (CH 3 ) 3 , preferably for CO-OCH 3 or CO-OC 2 H 5 ;
(Cχ-C6-Alkoxy) carbonyl für: einen der vorstehend genannten (Cχ-C -Alkoxy) carbonylreste, oder z.B. n-Pentoxy-CO, 1-Methyl- butoxy-CO, 2-Methylbutoxy-CO, 3-Methylbutoxy-CO, 2, 2-Dimethyl- propoxy-CO, 1-Ethylpropoxy-CO, n-Hexoxy-CO, 1, 1-Dimethyl - propoxy-CO, 1, 2-Dimethylpropoxy-CO, 1-Methylpentoxy-CO, 2-Me- thylpentoxy-CO, 3-Methylpentoxy-CO, 4-Methylpentoxy-CO, 1,1-Di- methylbutoxy-CO, 1, 2-Dimethylbutoxy-CO, 1, 3-Dimethylbutoxy-CO, 2, 2-Dimethylbutoxy-CO, 2 , 3-Dimethylbutoxy-CO, 3 , 3-Dimethylbut- oxy-CO, 1-Ethylbutoxy-CO, 2-Ethylbutoxy-CO, 1, 1, 2-Trimethylpro- poxy-CO, 1,2,2-Trimethylpropoxy-CO, 1-Ethyl-l-methylpropoxy-CO oder l-Ethyl-2-methylpropoxy-CO, vorzugsweise für CO-OCH3, CO- OC2H5, CO-OCH2-C2H5, CO-OCH (CH3) 2, n-Butoxy-CO, CO-OC(CH3)3, n- Pentoxy-CO oder n-Hexoxy-CO;(Cχ-C 6 -alkoxy) carbonyl for: one of the above (Cχ-C-alkoxy) carbonyl radicals, or for example n-pentoxy-CO, 1-methylbutoxy-CO, 2-methylbutoxy-CO, 3-methylbutoxy- CO, 2, 2-dimethyl-propoxy-CO, 1-ethylpropoxy-CO, n-hexoxy-CO, 1, 1-dimethyl-propoxy-CO, 1, 2-dimethylpropoxy-CO, 1-methylpentoxy-CO, 2- Methylpentoxy-CO, 3-methylpentoxy-CO, 4-methylpentoxy-CO, 1,1-dimethylbutoxy-CO, 1, 2-dimethylbutoxy-CO, 1, 3-dimethylbutoxy-CO, 2, 2-dimethylbutoxy-CO, 2, 3-dimethylbutoxy-CO, 3, 3-dimethylbutoxy-CO, 1-ethylbutoxy-CO, 2-ethylbutoxy-CO, 1, 1, 2-trimethylpropoxy-CO, 1,2,2-trimethylpropoxy-CO, 1-ethyl-l-methylpropoxy-CO or l-ethyl-2-methylpropoxy-CO, preferably for CO-OCH 3 , CO-OC 2 H 5 , CO-OCH 2 -C 2 H 5 , CO-OCH (CH 3 ) 2 , n-butoxy-CO, CO-OC (CH 3 ) 3 , n-pentoxy-CO or n-hexoxy-CO;
(Cχ-C -Alkoxy) carbonyl-Cχ-C -alkyl für: durch (Cχ-C4-Alkoxy) - carbonyl - wie vorstehend genannt - substituiertes Cχ-C4-Alkyl, also z.B. für CH2-CO-OCH3, CH2-CO-OC2H5, CH2 -CO-OCH2-C2H5, CH2-CO-OCH (CH3 ) 2 , n-Butoxycarbonylmethyl ,(Cχ-C -alkoxy) carbonyl-Cχ-C -alkyl viewed by (Cχ-C 4 alkoxy) - carbonyl - as mentioned above - substituted Cχ-C4 alkyl, eg CH 2 -CO-OCH 3 , CH 2 -CO-OC 2 H 5 , CH 2 -CO-OCH 2 -C 2 H 5 , CH 2 -CO-OCH (CH 3 ) 2 , n-butoxycarbonylmethyl,
CH2-CO-OCH(CH3)-C2H5, CH2-CO-OCH2-CH (CH3) 2 , CH2-CO~OC (CH3) 3 , 1- (CO-OCH3) ethyl, 1- (CO-OC2H5) ethyl , 1- (CO-OCH2 -C2H5) ethyl , 1-[CH(CH3)2] ethyl, 1- (n-Butoxycarbonyl) ethyl, 1- [1-Methylprop- oxycarbonyl] ethyl, 1- [2-Methylpropoxycarbonyl] ethyl, 2-(CO- OCH3) ethyl, 2- (CO-OC2H5) ethyl, 2- (CO-OCH2 -C2H5) ethyl, 2- [CO- OCH (CH3) 2] ethyl , 2- (n-Butoxycarbonyl) ethyl, 2- [1-Methylpropoxy- carbonyl] ethyl, 2- [2-Methylpropoxycarbonyl] ethyl, 2-[CO- OC(CH3)3] ethyl, 2- (CO-OCH3) propyl, 2- (CO-OC2H5) propyl, 2-(CO- OCH2-C2H5) propyl, 2- [CO-OCH (CH3) 2] propyl, 2- (n-Butoxycarbonyl) propyl , 2- [1-Methylpropoxycarbonyl] propyl, 2- [2-Me- thylpropoxycarbonyl] propyl, 2- [CO-OC (CH3) 3] propyl, 3-(CO-OCH3)- propyl, 3- (CO-OC2H5) propyl, 3- (CO-OCH2-C2H5) propyl , 3- [CO- OCH (CH3) 2] propyl, 3- (n-Butoxycarbonyl) propyl, 3- [1-Methylprop- oxycarbonyl] propyl, 3- [2-Methylpropoxycarbonyl] propyl, 3- [CO- OC (CH3) 3] propyl, 2-(CO-OCH3)butyl, 2- (CO-OC2H5) butyl, 2- (CO- OC^ -C2H5) butyl, 2- [CO-OCH (CH3)21 butyl, 2- (n-Butoxycarbo- nyDbutyl, 2- [1-Methylpropoxycarbonyl] butyl, 2- [2-Methylprop- oxycarbonyl] butyl, 2- [CO-OC (CH3) 3]butyl, 3- (CO-OCH3) butyl, 3-(CO-OC2H5)butyl, 3- (CO-OCH2 -C2H5)butyl, 3- [CO-OCH (CH3) 2] butyl , 3- (n-Butoxycarbonyl) butyl, 3- [1-Methylpropoxycarbonyl] butyl, 3- [2-Methylpropoxycarbonyl] butyl, 3- [CO-OC (CH3) 3] butyl, 4-(CO- OCH3) butyl, 4-(CO-OC2H5)butyl, 4- (CO-OCH2-C2H5) butyl, 4- [CO- OCH (CH3) 2] butyl, 4- (n-Butoxycarbonyl) butyl, 4- [1-Methylpropoxy- carbonyl] butyl, 4- [2-Methylpropoxycarbonyl] butyl oder 4-[CO- OC(CH3)3] butyl, vorzugsweise für CH2-CO-OCH3, CH2-CO-OC2H5, l-(CO-OCH3) ethyl oder 1- (CO-OC2H5) ethyl;CH 2 -CO-OCH (CH 3 ) -C 2 H 5 , CH 2 -CO-OCH 2 -CH (CH 3 ) 2 , CH 2 -CO ~ OC (CH 3 ) 3 , 1- (CO-OCH 3 ) ethyl, 1- (CO-OC 2 H 5 ) ethyl, 1- (CO-OCH 2 -C 2 H 5 ) ethyl, 1- [CH (CH 3 ) 2 ] ethyl, 1- (n-butoxycarbonyl) ethyl , 1- [1-methylpropoxycarbonyl] ethyl, 1- [2-methylpropoxycarbonyl] ethyl, 2- (CO-OCH 3 ) ethyl, 2- (CO-OC 2 H 5 ) ethyl, 2- (CO-OCH 2 -C 2 H 5 ) ethyl, 2- [CO-OCH (CH 3 ) 2 ] ethyl, 2- (n-butoxycarbonyl) ethyl, 2- [1-methylpropoxycarbonyl] ethyl, 2- [2-methylpropoxycarbonyl] ethyl , 2- [CO- OC (CH 3 ) 3 ] ethyl, 2- (CO-OCH 3 ) propyl, 2- (CO-OC 2 H 5 ) propyl, 2- (CO- OCH 2 -C 2 H 5 ) propyl, 2- [CO-OCH (CH 3 ) 2 ] propyl, 2- (n-butoxycarbonyl) propyl, 2- [1-methylpropoxycarbonyl] propyl, 2- [2-methylpropoxycarbonyl] propyl, 2- [CO- OC (CH 3 ) 3 ] propyl, 3- (CO-OCH 3 ) propyl, 3- (CO-OC 2 H 5 ) propyl, 3- (CO-OCH 2 -C 2 H 5 ) propyl, 3- [ CO-OCH (CH 3 ) 2 ] propyl, 3- (n-butoxycarbonyl) propyl, 3- [1-methylpropoxycarbonyl] propyl, 3- [2-methylpropoxycarbonyl] propyl , 3- [CO- OC (CH 3 ) 3 ] propyl, 2- (CO-OCH 3 ) butyl, 2- (CO-OC 2 H 5 ) butyl, 2- (CO- OC ^ -C 2 H 5 ) butyl, 2- [CO-OCH (CH 3 ) 2 1 butyl, 2- (n-butoxycarbonyl-butyl, 2- [1-methylpropoxycarbonyl] butyl, 2- [2-methylpropoxycarbonyl] butyl, 2- [CO- OC (CH 3 ) 3 ] butyl, 3- (CO-OCH 3 ) butyl, 3- (CO-OC 2 H 5 ) butyl, 3- (CO-OCH 2 -C 2 H 5 ) butyl, 3- [CO -OCH (CH 3 ) 2 ] butyl, 3- (n-butoxycarbonyl) butyl, 3- [1-methylpropoxycarbonyl] butyl, 3- [2-methylpropoxycarbonyl] butyl, 3- [CO-OC (CH 3 ) 3 ] butyl , 4- (CO-OCH 3 ) butyl, 4- (CO-OC 2 H 5 ) butyl, 4- (CO-OCH 2 -C 2 H 5 ) butyl, 4- [CO-OCH (CH 3 ) 2 ] butyl, 4- (n-butoxycarbonyl) butyl, 4- [1-methylpropoxycarbonyl] butyl, 4- [2-methylpropoxycarbonyl] butyl or 4- [CO- OC (CH 3 ) 3 ] butyl, preferably for CH 2 - CO-OCH 3 , CH 2 -CO-OC 2 H 5 , 1- (CO-OCH 3 ) ethyl or 1- (CO-OC 2 H 5 ) ethyl;
(Cχ-Cg-Alkoxy) thiocarbonyl für: z.B. CS-OCH3, CS-OC2H5, CS- OCH2-C2H5, CS-OCH(CH3)2, CS-0 (n-C4H9) , CS-OCH (CH3) -C2H5, CS- OCH2-CH(CH3)2, CS-OC(CH3)3, CS-0 (n-C5Hχχ) , CS-OCH (CH3) -CH2-C2H5, CS-OCH2-CH(CH3)-C2H5, CS-OCH2CH2-CH (CH3) 2, CO-OCH2-C (CH3) 3 , CS- OCH (C2H5) -C2H5 , CS-0(n-CgH13) , CS-OC (CH3) 2-C2H5, CS-OCH (CH3)-CH(CH3) 2, CS-OCH (CH3) - (n-C4H9) , CS-OCH2-CH (CH3) -CH2-C2H5 , CS-OCH2CH2-CH (CH3) -C2H5 , CS-OCH2CH2CH2-CH(CH3)2, CS-OC (CH3) 2-CH2-C2H5,(Cχ-Cg-Alkoxy) thiocarbonyl for: e.g. CS-OCH 3 , CS-OC 2 H 5 , CS-OCH 2 -C 2 H 5 , CS-OCH (CH 3 ) 2 , CS-0 (nC 4 H 9 ), CS-OCH (CH 3 ) -C 2 H 5 , CS-OCH 2 -CH (CH 3 ) 2 , CS-OC (CH 3 ) 3 , CS-0 (nC 5 Hχχ), CS-OCH (CH 3 ) -CH 2 -C 2 H 5 , CS-OCH 2 -CH (CH 3 ) -C 2 H 5 , CS-OCH 2 CH 2 -CH (CH 3 ) 2 , CO-OCH 2 -C (CH 3 ) 3 , CS- OCH (C 2 H 5 ) -C 2 H 5 , CS-0 (n-CgH 13 ), CS-OC (CH 3 ) 2 -C 2 H 5 , CS-OCH (CH 3 ) - CH (CH 3 ) 2 , CS-OCH (CH 3 ) - (nC 4 H 9 ), CS-OCH 2 -CH (CH 3 ) -CH 2 -C 2 H 5 , CS-OCH 2 CH 2 -CH ( CH 3 ) -C 2 H 5 , CS-OCH 2 CH 2 CH 2 -CH (CH 3 ) 2 , CS-OC (CH 3 ) 2 -CH 2 -C 2 H 5 ,
CS-OCH(CH3)-CH(CH3)-C2H5, CS-OCH (CH3) -CH2-CH (CH3) 2 - CS-CS-OCH (CH 3 ) -CH (CH 3 ) -C 2 H 5 , CS-OCH (CH 3 ) -CH 2 -CH (CH 3 ) 2 - CS-
OCH2-C (CH3 ) 2-C2H5 , CS-OCH2-CH (CH3 ) -CH ( CH3 ) 2 , CS-OCH2CH2-C (CH3 ) 3 , CS-OC (C2H5 ) -CH2-C2H5 , CS-OCH2-CH (C2H5 ) -C2H5 , CS-OC (CH3 ) 2"CH (CH3 ) 2 , CS-OCH (CH3)-C(CH3)3, CS-OC (CH3) (C2H5)-C2H5 oder CS- OCH (C2H5) -CH (CH3) 2. vorzugsweise für CS-OCH3 oder CS-OC H5;OCH 2 -C (CH 3 ) 2 -C 2 H 5 , CS-OCH 2 -CH (CH 3 ) -CH (CH 3 ) 2 , CS-OCH 2 CH 2 -C (CH 3 ) 3 , CS-OC (C 2 H 5 ) -CH 2 -C 2 H 5 , CS-OCH 2 -CH (C 2 H 5 ) -C 2 H 5 , CS-OC (CH 3 ) 2 "CH (CH 3 ) 2 , CS-OCH (CH 3 ) -C (CH 3 ) 3 , CS-OC (CH 3 ) (C 2 H 5 ) -C 2 H 5 or CS-OCH (C 2 H 5 ) -CH (CH 3 ) 2. preferably for CS-OCH 3 or CS-OC H 5 ;
- (Cχ-C4-Alkyl thio) carbonyl für: CO-SCH3, CO-SC2H5, CO-SCH2-C2H5, CO-SCH (CH3) 2. CO-SCH2CH2-C2H5, CO-SCH (CH3) -C2H5, CO-SCH2-CH (CH3) 2 oder CO-SC(CH3)3, vorzugsweise für CO-SCH3 oder CO-SC H5;- (Cχ-C 4 alkyl thio) carbonyl for: CO-SCH 3 , CO-SC 2 H 5 , CO-SCH 2 -C 2 H 5 , CO-SCH (CH 3 ) 2 . CO-SCH 2 CH 2 -C 2 H 5 , CO-SCH (CH 3 ) -C 2 H 5 , CO-SCH 2 -CH (CH 3 ) 2 or CO-SC (CH 3 ) 3 , preferably for CO- SCH 3 or CO-SC H 5 ;
- (Cχ-C4-Alkylthio) carbonyl-Cχ-C4-alkyl für: durch (Cχ-C4-Alkyl- thio) carbonyl - wie vorstehend genannt - substituiertes- (Cχ-C 4 -Alkylthio) carbonyl-Cχ-C 4 -alkyl for: substituted by (Cχ-C 4 -alkyl thio) carbonyl - as mentioned above - substituted
Cχ-C -Alkyl, also z.B. für CH -CO-SCH3, CH2-CO-SC2H5 , CH2-CO-SCH2-C2H5, CH2-CO-SCH(CH3)2, CH2-CO-SCH2CH2-C2H5 , CH2-CO-SCH(CH3)-C2H5, CH2-CO-SCH2-CH (CH3) 2, CH2-CO-SC (CH3) 3, 1-(C0-SCH3) ethyl, 1- (CO-SC H5) ethyl, 1- (CO-SCH2-C2H5) ethyl, l-[CO-SCH(CH3)2]ethyl, 1- (CO-SCH2CH2-C2H5) ethyl,Cχ-C-alkyl, e.g. for CH -CO-SCH 3 , CH 2 -CO-SC 2 H 5 , CH 2 -CO-SCH 2 -C 2 H 5 , CH 2 -CO-SCH (CH 3 ) 2 , CH 2 -CO-SCH 2 CH 2 -C 2 H 5 , CH 2 -CO-SCH (CH 3 ) -C 2 H 5 , CH 2 -CO-SCH 2 -CH (CH 3 ) 2 , CH 2 - CO-SC (CH 3 ) 3 , 1- (CO-SCH 3 ) ethyl, 1- (CO-SC H 5 ) ethyl, 1- (CO-SCH 2 -C 2 H 5 ) ethyl, l- [CO- SCH (CH 3 ) 2 ] ethyl, 1- (CO-SCH 2 CH 2 -C 2 H 5 ) ethyl,
1- [CO-SCH (CH3) -C2H5] ethyl, 1- [CO-SCH2-CH (CH3) 2] ethyl, l-[CO-SC(CH3)3] ethyl, 2- (CO-SCH3) ethyl, 2- (CO-SC2H5) ethyl,1- [CO-SCH (CH 3 ) -C 2 H 5 ] ethyl, 1- [CO-SCH 2 -CH (CH 3 ) 2 ] ethyl, 1- [CO-SC (CH 3 ) 3 ] ethyl, 2 - (CO-SCH 3 ) ethyl, 2- (CO-SC 2 H 5 ) ethyl,
2- (CO-SCH2-C2H5) ethyl, 2- [CO-SCH (CH3 ) 2] ethyl,2- (CO-SCH 2 -C 2 H 5 ) ethyl, 2- [CO-SCH (CH 3 ) 2 ] ethyl,
2- (CO-SCH2CH2-C2H5) ethyl, 2- [CO-SCH (CH3) -C2H5] ethyl,2- (CO-SCH 2 CH 2 -C 2 H 5 ) ethyl, 2- [CO-SCH (CH 3 ) -C 2 H 5 ] ethyl,
2-[CO-SCH2-CH(CH3)2]ethyl, 2- [CO-SC (CH3) 3] ethyl, 2-(CO-SCH3)- propyl, 2- (CO-SC2H5) propyl, 2- (CO-SCH2-C2H5) propyl,2- [CO-SCH 2 -CH (CH 3 ) 2 ] ethyl, 2- [CO-SC (CH 3 ) 3 ] ethyl, 2- (CO-SCH 3 ) propyl, 2- (CO-SC 2 H 5 ) propyl, 2- (CO-SCH 2 -C 2 H 5 ) propyl,
2- [CO-SCH (CH3)2] propyl, 2- (CO-SCH2CH2-C2H5) propyl,2- [CO-SCH (CH 3 ) 2 ] propyl, 2- (CO-SCH 2 CH 2 -C 2 H 5 ) propyl,
2- [CO-SCH (CH3) -C2H5] propyl , 2- [CO-SCH2-CH (CH3 ) 2] propyl , 2- [CO-SC (CH3)3] propyl, 3- (CO-SCH3) propyl, 3- (CO-SC2H5) propyl, 3- (CO-SCH2-C2H5) propyl, 3- [CO-SCH (CH3) 2] propyl,2- [CO-SCH (CH 3 ) -C 2 H 5 ] propyl, 2- [CO-SCH 2 -CH (CH 3 ) 2 ] propyl, 2- [CO-SC (CH 3 ) 3 ] propyl, 3 - (CO-SCH 3 ) propyl, 3- (CO-SC 2 H 5 ) propyl, 3- (CO-SCH 2 -C 2 H 5 ) propyl, 3- [CO-SCH (CH 3 ) 2 ] propyl,
3- (CO-SCH2CH2-C2H5) propyl , 3- [CO-SCH (CH3 ) -C2H5] propyl , 3-[CO-SCH2-CH(CH3)2]propyl, 3- [CO-SC (CH3) 3] propyl, 2-(CO-SCH3)butyl, 2- (CO-SC2H5) butyl, 2- (CO-SCH2-C2H5) butyl, 2- [CO-SCH (CH3) 2] butyl , 2- (CO-SCH2CH2-C2H5) butyl , 2- [CO-SCH(CH3) -C2H5]butyl, 2- [CO-SCH2-CH (CH3) 2] butyl, 2- [CO-SC (CH3)3]butyl, 3- (CO-SCH3) butyl, 3- (CO-SC2H5) butyl, 3-(CO-SCH2-C2H5)butyl, 3- [CO-SCH (CH3) 2] butyl, 3-(CO-SCH2CH2-C2H5)butyl, 3- [CO-SCH (CH3) -C2H5] butyl , 3-[CO-SCH2-CH(CH3)2]butyl, 3- [CO-SC (CH3) 3] butyl, 4-(CO-SCH3)- butyl, 4-(CO-SC2H5)butyl, 4- (CO-SCH2-C2H5) butyl, 4- [CO-SCH (CH3) 2] butyl, 4- (CO-SCH2CH2-C2H5) butyl,3- (CO-SCH 2 CH 2 -C 2 H 5 ) propyl, 3- [CO-SCH (CH 3 ) -C 2 H 5 ] propyl, 3- [CO-SCH 2 -CH (CH 3 ) 2 ] propyl, 3- [CO-SC (CH 3 ) 3 ] propyl, 2- (CO-SCH 3 ) butyl, 2- (CO-SC 2 H 5 ) butyl, 2- (CO-SCH 2 -C 2 H 5 ) butyl, 2- [CO-SCH (CH 3 ) 2 ] butyl, 2- (CO-SCH 2 CH 2 -C 2 H 5 ) butyl, 2- [CO-SCH (CH 3 ) -C 2 H 5 ] butyl, 2- [CO-SCH 2 -CH (CH 3 ) 2 ] butyl, 2- [CO-SC (CH 3 ) 3 ] butyl, 3- (CO-SCH 3 ) butyl, 3- (CO-SC 2 H 5 ) butyl, 3- (CO-SCH 2 -C 2 H 5 ) butyl, 3- [CO-SCH (CH 3 ) 2 ] butyl, 3- (CO-SCH 2 CH 2 -C 2 H 5 ) butyl , 3- [CO-SCH (CH 3 ) -C 2 H 5 ] butyl, 3- [CO-SCH 2 -CH (CH 3 ) 2 ] butyl, 3- [CO-SC (CH 3 ) 3 ] butyl, 4- (CO-SCH 3 ) - butyl, 4- (CO-SC 2 H 5 ) butyl, 4- (CO-SCH 2 -C 2 H 5 ) butyl, 4- [CO-SCH (CH 3 ) 2 ] butyl, 4- (CO-SCH 2 CH 2 -C 2 H 5 ) butyl,
4- [CO-SCH (CH3)-C2H5] butyl, 4- [CO-SCH2-CH (CH3) 21 butyl oder 4- [CO-SC (CH3) 3] butyl, vorzugsweise für CH2-CO-SCH3, CH2-CO-SC2H5, l-(CO-SCH3) ethyl oder 1- (CO-SC2H5) ethyl;4- [CO-SCH (CH 3 ) -C 2 H 5 ] butyl, 4- [CO-SCH 2 -CH (CH 3 ) 2 1 butyl or 4- [CO-SC (CH 3 ) 3 ] butyl, preferably for CH 2 -CO-SCH 3 , CH 2 -CO-SC 2 H 5 , 1- (CO-SCH 3 ) ethyl or 1- (CO-SC 2 H 5 ) ethyl;
- Cχ-C6-Alkylsulf inyl für: einen Cχ-C -Alkylsulf inylrest wie SO-CH3, SO-C2H5, SO-CH2-C2H5, SO-CH(CH3)2, SO- (n-C4H9) , SO-CH(CH3)-C2H5, SO-CH2-CH(CH3)2 oder SO-C(CH3)3, oder z.B. SO- (n-C5Hχχ) , 1-Methylbutyl-SO, 2 -Me thylbutyl -SO, 3-Methylbu- tyl-SO, 2, 2 -Dirne thylpropyl -SO, 1-Ethylpropyl-SO, n-Hexyl-SO, 1, 1-Dime thylpropyl -SO, 1, 2-Dimethylpropyl-SO, 1-Methylpentyl-- Cχ-C 6 -Alkylsulf inyl for: a Cχ-C -alkylsulf inylrest such as SO-CH 3 , SO-C 2 H 5 , SO-CH 2 -C 2 H 5 , SO-CH (CH 3 ) 2 , SO - (nC 4 H 9 ), SO-CH (CH 3 ) -C 2 H 5 , SO-CH 2 -CH (CH 3 ) 2 or SO-C (CH 3 ) 3 , or for example SO- (nC 5 Hχχ ), 1-methylbutyl-SO, 2-methylbutyl-SO, 3-methylbutyl-SO, 2,2-dryness thylpropyl-SO, 1-ethylpropyl-SO, n-hexyl-SO, 1,1-dimethylpropyl -SO, 1, 2-dimethylpropyl-SO, 1-methylpentyl-
SO, 2-Methylpentyl-SO, 3-Methylpentyl-SO, 4-Methylpentyl-SO, 1, 1-Dimethylbutyl-SO, 1, 2-Dimethylbutyl-SO, 1 , 3-Dimethylbutyl - SO, 2,2-Dimethylbutyl-SO, 2 , 3-Dimethylbutyl -SO, 3 , 3-Dimethyl - butyl -SO, 1-Ethylbutyl-SO, 2-Ethylbutyl-SO, 1, 1, 2-Trimethylpropyl -SO, 1,2, 2-Trimethylpropyl -SO, 1-Ethyl-l-methylpropyl-SO oder l-Ethyl-2-methylpropyl-SO, vorzugsweise für SO-CH3, SO-C2H5, SO-CH2-C2H5, SO-CH(CH3)2, SO- (n-C4H9) , SO-C(CH3)3, SO- (n-C5Hχχ) oder SO- (n-C6H13) ;SO, 2-methylpentyl-SO, 3-methylpentyl-SO, 4-methylpentyl-SO, 1, 1-dimethylbutyl-SO, 1, 2-dimethylbutyl-SO, 1, 3-dimethylbutyl - SO, 2,2-dimethylbutyl-SO, 2, 3-dimethylbutyl -SO, 3, 3-dimethylbutyl -SO, 1-ethylbutyl-SO, 2-ethylbutyl-SO, 1, 1, 2-trimethylpropyl -SO, 1,2, 2-Trimethylpropyl -SO, 1-ethyl-l-methylpropyl-SO or l-ethyl-2-methylpropyl-SO, preferably for SO-CH 3 , SO-C 2 H 5 , SO-CH 2 -C 2 H 5 , SO-CH (CH 3 ) 2 , SO- (nC 4 H 9 ), SO-C (CH 3 ) 3 , SO- (nC 5 Hχχ) or SO- (nC 6 H 13 );
- Cχ-C4-Alkylsulfinyl-Cχ-C4-alkyl für: durch Cχ-C4-Alkylsulfinyl wie vorstehend genannt substituiertes Cχ-C -Alkyl, also z.B. für CH2SOCH3, CH2SOC2H5, n-Propylsulfinylmethyl, CH2SOCH (CH3) 2, n-Butylsulfinylmethyl, (1-MethylpropylsulfinyDmethyl, (2-MethylpropylsulfinyDmethyl, (1, 1-Dimethylethylsulfinyl) - methyl, 2-Methylsulfinylethyl, 2-Ethylsulfinylethyl, 2- (n-Propylsulfinyl) ethyl, 2- (1-Methylethylsulfinyl) ethyl, 2- (n-Butylsulfinyl) ethyl, 2- (1-Methylpropylsulfinyl) ethyl, 2- (2-Methylpropylsulfinyl) ethyl, 2- (1, 1-Dimethylethyl - sulfinyl) ethyl, 2- (SOCH3) propyl, 3- (SOCH3) propyl, 2-(SOC2H5)- propyl, 3- (SOCH5) propyl, 3- (Propylsulfinyl) propyl, 3- (Butyl - sulfinyl) propyl, 4- (SOCH3)butyl, 4- (SOC2H5) butyl , 4-(n-Propyl- sulfinyDbutyl oder 4- (n-Butylsulfinyl) butyl, insbesondere für 2-(SOCH3)ethyl;- Cχ-C 4 -alkylsulfinyl-Cχ-C 4 -alkyl for: Cχ-C 4 -alkylsulfinyl substituted as above-mentioned Cχ-C-alkyl, for example for CH 2 SOCH 3 , CH 2 SOC 2 H 5 , n- Propylsulfinylmethyl, CH 2 SOCH (CH 3 ) 2 , n-butylsulfinylmethyl, (1-methylpropylsulfinyDmethyl, (2-methylpropylsulfinyDmethyl, (1, 1-dimethylethylsulfinyl) methyl, 2-methylsulfinylethyl, 2-ethylsulfinylethyl, 2- (n-propylsulfinyl ethyl, 2- (1-methylethylsulfinyl) ethyl, 2- (n-butylsulfinyl) ethyl, 2- (1-methylpropylsulfinyl) ethyl, 2- (2-methylpropylsulfinyl) ethyl, 2- (1, 1-dimethylethylsulfinyl) ethyl , 2- (SOCH 3 ) propyl, 3- (SOCH 3 ) propyl, 2- (SOC 2 H 5 ) propyl, 3- (SOCH 5 ) propyl, 3- (propylsulfinyl) propyl, 3- (butylsulfinyl) propyl, 4- (SOCH 3 ) butyl, 4- (SOC 2 H 5 ) butyl, 4- (n-propylsulfinyDbutyl or 4- (n-butylsulfinyl) butyl, especially for 2- (SOCH 3 ) ethyl;
Cχ-C -Halogenalkylsulfinyl-Cχ-C4-alkyl für: durch Cχ-C -Halogen- alkylsulfinyl wie vorstehend genannt substituiertes C -C -Alkyl, also z.B. für 2- (2 , 2 , 2-Trifluorethylsulfinyl) - ethyl ;Cχ-C -haloalkylsulfinyl-Cχ-C 4 -alkyl for: Cχ-C -haloalkylsulfinyl substituted as mentioned above C -C -alkyl, for example for 2- (2, 2, 2-trifluoroethylsulfinyl) ethyl;
- Cχ-C4-Alkylsulfonyl für: S02-CH3, S02-C2H5, SO2-CH2-C2H5,- Cχ-C 4 alkylsulfonyl for: S0 2 -CH 3 , S0 2 -C 2 H 5 , SO 2 -CH 2 -C 2 H 5 ,
S0 -CH(CH3)2, n-Butylsulfonyl, S02-CH (CH3) -C2H5, S02-CH2-CH (CH3) 2 oder S02-C(CH3)3, vorzugsweise für Sθ2"CH3 oder SO2-C2H5;S0 -CH (CH 3 ) 2 , n-butylsulfonyl, S0 2 -CH (CH 3 ) -C 2 H 5 , S0 2 -CH 2 -CH (CH 3 ) 2 or S0 2 -C (CH 3 ) 3 , preferably for Sθ 2 "CH 3 or SO 2 -C 2 H 5 ;
- Cχ-C4-Halogenalkylsulfonyl für: einen Cχ-C4-Alkylsulfonylrest - wie vorstehend genannt - der partiell oder vollständig durch Fluor, Chlor, Brom und/oder Iod substituiert ist, also z.B. S02-CH2F, S02-CHF2, S02-CF3, S02-CH2C1, S02-CH(C1)2, S02-C(C1)3, Chlorfluor ethylsulfonyl, Dichlorfluormethylsulfonyl, Chlordifluormethylsulfonyl, 2-Fluorethylsulfonyl, 2-Chlorethyl- sulfonyl, 2-Bromethylsulfonyl, 2-Iodethylsulfonyl, 2, 2-Difluorethylsulfonyl, 2, 2, 2-Trifluorethylsulfonyl, 2-Chlor-2-fluorethylsulfonyl, 2-Chlor-2,2-difluorethylsulfonyl, 2,2-Dichlor- 2-fluorethylsulfonyl, 2, 2, 2-Trichlorethylsulfonyl, S0 -C2F5, 2-Fluorpropylsulfonyl, 3-Fluorpropylsulfonyl, 2,2-Difluor- propylsulfonyl, 2, 3-Difluorpropylsulfonyl, 2-Chlorpropyl - sulfonyl, 3-Chlorpropylsulfonyl, 2, 3-Dichlorpropylsulfonyl, 2-Brompropylsulfonyl, 3-Brompropylsulfonyl, 3 , 3 , 3-Trifluor- propylsulfonyl, 3 , 3 , 3-Trichlorpropylsulfonyl, S02-CH2-C2F5,- Cχ-C 4 -haloalkylsulfonyl for: a Cχ-C 4 -alkylsulfonyl radical - as mentioned above - which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example S0 2 -CH 2 F, S0 2 - CHF 2 , S0 2 -CF 3 , S0 2 -CH 2 C1, S0 2 -CH (C1) 2 , S0 2 -C (C1) 3 , chlorofluoroethylsulfonyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl , 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2, 2-difluoroethylsulfonyl, 2, 2, 2-trifluoroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl , 2, 2, 2-trichloroethylsulfonyl, S0 -C 2 F 5 , 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2,2-difluoropropylsulfonyl, 2, 3-difluoropropylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 3-chloropropylsulfonyl 3-dichloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 3, 3, 3-trifluoropropylsulfonyl, 3, 3, 3-trichloropropylsulfonyl, S0 2 -CH 2 -C 2 F 5 ,
S02-CF2-C2F5, 1- (Fluormethyl) -2-fluorethylsulfonyl, 1- (Chlormethyl) -2-chlorethylsulfonyl, 1- (Brommethyl) -2-bromethyl- sulfonyl, 4-Fluorbutylsulfonyl , 4-Chlorbutylsulfonyl , 4-Brom- butylsulfonyl oder Nonafluorbutylsulfonyl, vorzugsweise für S02-CHC1, S0 -CF3 oder 2 , 2, 2 -Trifluorethylsulfonyl;S0 2 -CF 2 -C 2 F 5 , 1- (fluoromethyl) -2-fluoroethylsulfonyl, 1- (chloromethyl) -2-chloroethylsulfonyl, 1- (bromomethyl) -2-bromethyl- sulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4-bromobutylsulfonyl or nonafluorobutylsulfonyl, preferably for S0 2 -CHC1, S0 -CF 3 or 2, 2, 2-trifluoroethylsulfonyl;
Cχ-Cg-Alkylsulfonyl für: einen Cχ-C4 -Alkylsulfonylrest wie vorstehend genannt, oder z.B. S0 - (n-CsHχχ) , 1-Methylbutyl-S02, 2-Methylbutyl - S02 , 3-Methylbutyl - S02 , 2,2-Dirnethylpropyl - S02 , 1-Ethylpropyl-S02, n-Hexyl-S02, 1, 1-Dimethylpropyl-S02, 1,2-Di- methylpropyl - SO2 , 1-Methylpentyl-S02, 2-Methylpentyl-S02, 3-Methylpentyl-S02, 4-Methylpentyl-S02, 1, 1-Dimethylbutyl-S02, 1,2-Dirnethylbutyl -S02, 1, 3-Dimethylbutyl -SO2, 2, 2-Dirnethylbutyl -S02, 2,3-Dimethylbutyl-S02, 3 , 3-Dimethylbutyl -S02, 1-Ethyl- butyl-S02, 2-Ethylbutyl-S02, 1, 1, 2-Trimethylpropyl -S02, 1,2, 2-Trimethylpropyl -S02, l-Ethyl-l-methylpropyl-S02 oder l-Ethyl-2-methylpropyl-S02, vorzugsweise für Sθ2"CH3, SO2-C2H5, SO2-CH2-C2H5, S02-CH(CH3)2, S02- (n-C4H9) , S02-C(CH3)3, S02- (n-C5Hχχ) oder S02- (n-C6H13) ;Cχ-Cg-alkylsulfonyl for: a Cχ-C 4 -alkylsulfonyl radical as mentioned above, or for example S0 - (n-CsHχχ), 1-methylbutyl-S0 2 , 2-methylbutyl - S0 2 , 3-methylbutyl - S0 2 , 2 , 2-Dirnethylpropyl - S0 2 , 1-ethylpropyl-S0 2 , n-hexyl-S0 2 , 1, 1-dimethylpropyl-S0 2 , 1,2-dimethylpropyl - SO2, 1-methylpentyl-S0 2 , 2- Methylpentyl-S0 2 , 3-methylpentyl-S0 2 , 4-methylpentyl-S0 2 , 1, 1-dimethylbutyl-S0 2 , 1,2-dirnethylbutyl -S0 2 , 1, 3-dimethylbutyl -SO 2 , 2, 2- Dirnethylbutyl -S0 2, 2,3-dimethylbutyl-S0 2, 3, 3-dimethylbutyl -S0 2, 1-ethylbutyl S0 2, S0 2-2-ethylbutyl, 1, 1, 2-trimethylpropyl -S0 2 1,2, 2-Trimethylpropyl -S0 2 , l-ethyl-l-methylpropyl-S0 2 or l-ethyl-2-methylpropyl-S0 2 , preferably for Sθ 2 "CH 3 , SO 2 -C 2 H 5 , SO 2 -CH 2 -C 2 H 5 , S0 2 -CH (CH 3 ) 2 , S0 2 - (nC 4 H 9 ), S0 2 -C (CH 3 ) 3 , S0 2 - (nC 5 Hχχ) or S0 2 - (nC 6 H 13 );
Cχ-C4-Alkylsulfonyl-Cχ-C4-alkyl für: durch Cχ-C4-Alkylsulfonyl wie vorstehend genannt substituiertes Cχ-C4-Alkyl, also z.B. für CH2S02-CH3, CH2SO2-C2H5, CH2S02-CH2-C2H5, CH2S02-CH (CH3) 2 , CH2SO2-CH2CH2-C2H5, (l-Methylpropylsulfonyl)methyl, (2-Methyl- propylsulfonyDmethyl, CH2S02-C (CH3) 3, CH (CH3) S02-CH3, CH(CH3)S02-C2H5, CH2CH2S02-CH3, CH2CH2SO2-C2H5 , CH2CH2S02-CH2-C2H5 , CH2CH2S02-CH(CH3)2, CH2CH2S02-CH2CH2-C2H5 , 2- (1-Methylpropylsul - fonyl) ethyl, 2- (2-Methylpropylsulfonyl) ethyl, CH2CH2S02-C (CH3) 3, 2- (S02-CH3) propyl, 2- (S02-C2H5) propyl, 2- (S02-CH2-C2H5) propyl, 2-[S02-CH(CH3) ]propyl, 2- (S02-CH2CH2-C H5) propyl, 2-(l-Methyl- propylsulfonyl) propyl, 2- (2-Methylpropylsulfonyl) propyl, 2- [S02-C(CH3)3] propyl, 3- (S02-CH3) propyl, 3- (S02-C2H5) propyl, 3- (S02-CH2-C2H5) propyl, 3- [S02-CH (CH3) 2] propyl, 3- (S02-CH2CH2-C2H5) propyl, 3- (1-Methylpropylsulfonyl) propyl, 3- (2-Methylpropylsulfonyl) propyl, 3- [S02-C (CH3) 3] propyl, 2-(S02-CH3)butyl, 2- (S02-C2H5) butyl, 2- (SO2-CH2-C2H5) butyl, 2-[S02-CH(CH3)2]butyl, 2- (S02-CH2CH2-C2H5) butyl, 2-(l-Methyl- propylsulfonyl) butyl, 2- (2-Methylpropylsulfonyl) butyl,Cχ-C 4 alkylsulfonyl-Cχ-C 4 alkyl: by Cχ-C 4 alkylsulfonyl as mentioned above substituted Cχ-C4 alkyl, eg CH 2 S0 2 CH 3, CH 2 SO 2 -C 2 H 5 , CH 2 S0 2 -CH 2 -C 2 H 5 , CH 2 S0 2 -CH (CH 3 ) 2 , CH 2 SO 2 -CH 2 CH 2 -C 2 H 5 , (l-methylpropylsulfonyl) methyl , (2-MethylpropylsulfonyDmethyl, CH 2 S0 2 -C (CH 3 ) 3 , CH (CH 3 ) S0 2 -CH 3 , CH (CH 3 ) S0 2 -C 2 H 5 , CH 2 CH 2 S0 2 -CH 3 , CH 2 CH 2 SO 2 -C 2 H 5 , CH 2 CH 2 S0 2 -CH 2 -C 2 H 5 , CH 2 CH 2 S0 2 -CH (CH 3 ) 2 , CH 2 CH 2 S0 2 -CH 2 CH 2 -C 2 H 5 , 2- (1-methylpropylsulfonyl) ethyl, 2- (2-methylpropylsulfonyl) ethyl, CH 2 CH 2 S0 2 -C (CH 3 ) 3 , 2- (S0 2 -CH 3 ) propyl, 2- (S0 2 -C 2 H 5 ) propyl, 2- (S0 2 -CH 2 -C 2 H 5 ) propyl, 2- [S0 2 -CH (CH 3 )] propyl, 2- (S0 2 -CH 2 CH 2 -CH 5 ) propyl, 2- (l-methylpropylsulfonyl) propyl, 2- (2-methylpropylsulfonyl) propyl, 2- [S0 2 -C (CH 3 ) 3 ] propyl , 3- (S0 2 -CH 3 ) propyl, 3- (S0 2 -C 2 H 5 ) propyl, 3- (S0 2 -CH 2 -C 2 H 5 ) propyl, 3- [ S0 2 -CH (CH 3 ) 2 ] propyl, 3- (S0 2 -CH 2 CH 2 -C 2 H 5 ) propyl, 3- (1-methylpropylsulfonyl) propyl, 3- (2-methylpropylsulfonyl) propyl, 3- [S0 2 -C (CH 3 ) 3 ] propyl, 2- (S0 2 -CH 3 ) butyl, 2- (S0 2 -C 2 H 5 ) butyl, 2- (SO 2 -CH 2 -C 2 H 5 ) butyl, 2- [S0 2 -CH (CH 3 ) 2 ] butyl, 2- (S0 2 -CH 2 CH 2 -C 2 H 5 ) butyl, 2- (l-methylpropylsulfonyl) butyl, 2- ( 2-methylpropylsulfonyl) butyl,
2- [S02-C(CH3)3] butyl, 3- (S02-CH3) butyl, 3- (S02-C2H5) butyl, 3-(S02-CH2-C2H5)butyl, 3- [S02-CH(CH3) 2]butyl, 3-(Sθ2-CH2CH2-C2H5)butyl, 3- (1-Methylpropylsulfonyl) butyl,2- [S0 2 -C (CH 3 ) 3 ] butyl, 3- (S0 2 -CH 3 ) butyl, 3- (S0 2 -C 2 H 5 ) butyl, 3- (S0 2 -CH 2 -C 2 H 5 ) butyl, 3- [S0 2 -CH (CH 3 ) 2 ] butyl, 3- (Sθ 2 -CH 2 CH 2 -C 2 H 5 ) butyl, 3- (1-methylpropylsulfonyl) butyl,
3- (2-Methylpropylsulfonyl) butyl, 3- [S02-C (CH3) 3] butyl, 4-(S02-CH3)butyl, 4- (S02-C2H5) butyl , 4- (SO2-CH2-C2H5) butyl,3- (2-methylpropylsulfonyl) butyl, 3- [S0 2 -C (CH 3 ) 3 ] butyl, 4- (S0 2 -CH 3 ) butyl, 4- (S0 2 -C 2 H 5 ) butyl, 4- (SO 2 -CH 2 -C 2 H 5 ) butyl,
4-[S02-CH(CH3)2]butyl, 4- (S02-CH2CH2-C2H5) butyl , 4-(l-Methyl- propylsulfonyl) butyl, 4- (2-Methylpropylsulfonyl) butyl oder4- [S0 2 -CH (CH 3 ) 2 ] butyl, 4- (S0 2 -CH 2 CH 2 -C 2 H 5 ) butyl, 4- (l-methylpropylsulfonyl) butyl, 4- (2-methylpropylsulfonyl ) butyl or
4- [S02-C(CH3)3] butyl, insbesondere für CH2CH2S02-CH3 oder CH2CH2S02-C2H5; - Cχ-C4-Halogenalkylsulfonyl-Cχ-C4-alkyl für: durch Cχ-C - Halogenalkylsulfonyl wie vorstehend genannt substituiertes Cχ-C4-Alkyl, also z.B. für 2- (2, 2, 2-Trifluorethylsulfonyl) - ethyl ;4- [S0 2 -C (CH 3 ) 3 ] butyl, especially for CH 2 CH 2 S0 2 -CH 3 or CH 2 CH 2 S0 2 -C 2 H 5 ; - Cχ-C 4 -haloalkylsulfonyl-Cχ-C 4 -alkyl for: Cχ-C - haloalkylsulfonyl substituted as mentioned above C substitu-C 4 alkyl, for example for 2- (2, 2, 2-trifluoroethylsulfonyl) ethyl;
- Cχ-C4-Alkylamino-Cχ-C -alkyl für: durch Cχ-C4-Alkylamino wie H3C-NH-, H5C2- H-, n-Propyl-NH-, 1-Methylethyl-NH-, n-Butyl- H-, 1-Methylpropyl-NH-, 2-Methylpropyl-NH- und 1, 1-Dimethylethyl-NH-, vorzugsweise H3C-NH- oder H5C2- H-, substi- tuiertes Cχ-C4-Alkyl, also beispielsweise für CH2CH2-NH-CH3, CH2CH2-N(CH3)2, CH2CH2-NH-C2H5 oder CH2CH2-N(C2H5) 2;- Cχ-C 4 -alkylamino-Cχ-C -alkyl for: by C durch-C 4 -alkylamino such as H 3 C-NH-, H 5 C 2 - H-, n-propyl-NH-, 1-methylethyl-NH -, n-Butyl- H-, 1-methylpropyl-NH-, 2-methylpropyl-NH- and 1, 1-dimethylethyl-NH-, preferably H 3 C-NH- or H 5 C 2 - H-, substi- tuiert Cχ-C 4 alkyl, for example for CH 2 CH 2 -NH-CH 3 , CH 2 CH 2 -N (CH 3 ) 2 , CH 2 CH 2 -NH-C 2 H 5 or CH 2 CH 2 - N (C 2 H 5 ) 2 ;
- (Cχ-C4-Alkylamino) carbonyl für: CO-NH-CH3, CO-NH-C2H5, n-Propyl - a ino, CO-NH-CH (CH3) 2, CO-NH-CH2CH2-C2H5, CO-NH-CH (CH3) -C2H5, CO-NH-CH2-CH(CH3)2 oder CO-NH-C (CH3) 3, vorzugsweise für CO-NH-CH3 oder CO-NH-C2H5;- (Cχ-C 4 alkylamino) carbonyl for: CO-NH-CH 3 , CO-NH-C 2 H 5 , n-propyl - a ino, CO-NH-CH (CH 3 ) 2 , CO-NH- CH 2 CH 2 -C 2 H 5 , CO-NH-CH (CH 3 ) -C 2 H 5 , CO-NH-CH 2 -CH (CH 3 ) 2 or CO-NH-C (CH 3 ) 3 , preferably for CO-NH-CH 3 or CO-NH-C 2 H 5 ;
(Cχ-Cg-Alkylamino) carbonyl für: einen der vorstehend genannten (Cχ-C4-Alkylamino) carbonylreste, oder z.B. CO-NH- (n-CsHχχ) , 1-Methylbutyl-NHCO-, 2-Methylbutyl -NHCO- , 3-Methylbutyl-NHCO- , 2, 2-Dirnethylpropyl -NHCO-, 1-Ethylpropyl-NHCO- , CO-NH- (n-C6H13) , 1,1-Dimethylpropyl-NHCO-, 1, 2-Dirnethylpropyl -NHCO- , 1-Methyl- pentyl-NHCO-, 2-Methylpentyl-NHCO- , 3-Methylpentyl-NHCO- , 4-Me- thylpentyl-NHCO-, 1, 1-Dimethylbutyl -NHCO- , 1, 2-Dirnethylbutyl - NHCO-, 1, 3-Dimethylbutyl -NHCO- , 2 , 2-Dirnethylbutyl -NHCO- , 2, 3-Dirnethylbutyl -NHCO-, 3 , 3-Dimethylbutyl -NHCO- , 1-Ethylbutyl- NHCO-, 2-Ethylbutyl-NHCO- , 1, 1, 2-Trimethylpropyl -NHCO- , 1,2, 2-Trimethylpropyl -NHCO-, 1-Ethyl-l-methylpropyl-NHCO- oder l-Ethyl-2-methylpropyl-NHCO- , vorzugsweise für CO-NH-CH3, CO- NH-C2H5, CO-NH-CH2-C2H5, CO-NH-CH(CH3)2, CO-NH- (n-C4H9 ) , CO-NH- C(CH3)3, CO-NH- (n-C5Hχχ) oder CO-NH- (n-C6H13) ;(Cχ-Cg-alkylamino) carbonyl for: one of the abovementioned (Cχ-C 4 -alkylamino) carbonyl radicals, or for example CO-NH- (n-CsHχχ), 1-methylbutyl-NHCO-, 2-methylbutyl -NHCO-, 3-Methylbutyl-NHCO-, 2, 2-Dirnethylpropyl -NHCO-, 1-Ethylpropyl-NHCO-, CO-NH- (nC 6 H 13 ), 1,1-Dimethylpropyl-NHCO-, 1, 2-Dirnethylpropyl -NHCO -, 1-Methyl-pentyl-NHCO-, 2-methylpentyl-NHCO-, 3-methylpentyl-NHCO-, 4-methylpentyl-NHCO-, 1, 1-dimethylbutyl -NHCO-, 1, 2-dirnethylbutyl - NHCO -, 1, 3-Dimethylbutyl -NHCO-, 2, 2-dimethylbutyl -NHCO-, 2, 3-dimethylbutyl -NHCO-, 3, 3-dimethylbutyl -NHCO-, 1-ethylbutyl- NHCO-, 2-ethylbutyl-NHCO -, 1, 1, 2-trimethylpropyl -NHCO-, 1,2, 2-trimethylpropyl -NHCO-, 1-ethyl-l-methylpropyl-NHCO- or l-ethyl-2-methylpropyl-NHCO-, preferably for CO- NH-CH 3 , CO- NH-C 2 H 5 , CO-NH-CH 2 -C 2 H 5 , CO-NH-CH (CH 3 ) 2 , CO-NH- (nC 4 H 9 ), CO- NH-C (CH 3 ) 3 , CO-NH- (nC 5 Hχχ) or CO-NH- (nC 6 H 13 );
(Cχ-C4-Alkylamino) carbonyl-Cχ-C4-alkyl für: (Cχ-C4-Alkyl- amino) carbonyl wie vorstehend genannt, vorzugsweise CO-NH-CH3 oder CO-NH-C2H5, substituiertes Cχ-C -Alkyl, als z.B. für CH2-CO-NH-CH3, CH2-CO-NH-C2H5, CH2-CO-NH-CH2-C2H5, CH2-CO-NH-CH(CH3)2, CH2-CO-NH-CH2CH2-C2H5, CH2-CO-NH-CH(CH3)-C2H5, CH2-CO-NH-CH2-CH (CH3) 2, CH2-CO-NH-C(CH3)3, CH(CH3) -CO-NH-CH3, CH (CH3) -CO-NH-C2H5 , 2-(CO-NH-CH3)ethyl, 2- (CO-NH-C2H5) ethyl , 2- (CO-NH-CH2-C2H5) - ethyl , 2- [CH2-CO-NH-CH (CH3 ) 2] ethyl , 2 - ( CO-NH-CH2CH2-C2H5 ) ethyl ,(Cχ-C 4 -alkylamino) carbonyl-Cχ-C 4 -alkyl for: (Cχ-C 4 -alkylamino) carbonyl as mentioned above, preferably CO-NH-CH 3 or CO-NH-C 2 H 5 , substituted Cχ-C-alkyl, for example for CH 2 -CO-NH-CH 3 , CH 2 -CO-NH-C 2 H 5 , CH 2 -CO-NH-CH 2 -C 2 H 5 , CH 2 - CO-NH-CH (CH 3 ) 2 , CH 2 -CO-NH-CH 2 CH 2 -C 2 H 5 , CH 2 -CO-NH-CH (CH 3 ) -C 2 H 5 , CH 2 -CO -NH-CH 2 -CH (CH 3 ) 2, CH 2 -CO-NH-C (CH 3 ) 3 , CH (CH 3 ) -CO-NH-CH 3 , CH (CH 3 ) -CO-NH- C 2 H 5 , 2- (CO-NH-CH 3 ) ethyl, 2- (CO-NH-C 2 H 5 ) ethyl, 2- (CO-NH-CH 2 -C 2 H 5 ) ethyl, 2 - [CH 2 -CO-NH-CH (CH 3 ) 2 ] ethyl, 2 - (CO-NH-CH 2 CH 2 -C 2 H 5 ) ethyl,
2 - [CO-NH-CH (CH3 ) -C2H5] ethyl , 2 - [CO-NH-CH2-CH ( CH3 ) 2] ethyl , 2 - [CO-NH-C (CH3 ) 3 ] ethyl , 2- (CO-NH-CH3 ) propyl , 2 - (CO-NH-C2H5 ) propyl , 2- (CO-NH-CH2-C2H5 ) propyl , 2 - [CH2 -CO-NH-CH ( CH3 ) 2 ] propyl , 2 - ( CO-NH-CH2CH2 -C2H5 ) propyl , 2- [CO-NH-CH (CH3 ) -C2H5] propyl , 2- [CO-NH-CH2-CH (CH3 ) 2] propyl ,2 - [CO-NH-CH (CH 3 ) -C 2 H 5 ] ethyl, 2 - [CO-NH-CH 2 -CH (CH 3 ) 2 ] ethyl, 2 - [CO-NH-C (CH 3 ) 3 ] ethyl, 2- (CO-NH-CH 3 ) propyl, 2 - (CO-NH-C2H5) propyl, 2- (CO-NH-CH 2 -C 2 H 5 ) propyl, 2 - [CH 2 -CO-NH-CH (CH 3 ) 2 ] propyl, 2 - (CO-NH-CH 2 CH 2 -C 2 H 5 ) propyl, 2- [CO-NH-CH (CH 3 ) -C 2 H 5 ] propyl, 2- [CO-NH-CH 2 -CH (CH 3 ) 2 ] propyl,
2- [CO-NH-C (CH3 ) 3 ] propyl , 3 - (CO-NH-CH3 ) propyl , 3 - (CO-NH-C2H5 ) propyl , 3 - (CO-NH-CH2-C2H5 ) propyl , 3- [CH2-CO-NH-CH (CH3) 2] propyl , 3- (CO-NH-CH2CH2-C2H5) propyl , 3- [CO-NH-CH (CH3) -C2H5] propyl , 3- [CO-NH-CH2-CH (CH3) 2] propyl, 3- [CO-NH-C (CH3)3] propyl, 2- (CO-NH-CH3) butyl, 2- (CO-NH-C2H5) - butyl, 2-(CO-NH-CH2-C2H5)butyl, 2- [CH2-CO-NH-CH (CH3) 2] butyl, 2-(CO-NH-CH2CH2-C2H5)butyl, 2- [CO-NH-CH (CH3) -C2H5] butyl,2- [CO-NH-C (CH 3 ) 3 ] propyl, 3 - (CO-NH-CH 3 ) propyl, 3 - (CO-NH-C2H5) propyl, 3 - (CO-NH-CH 2 -C 2 H 5 ) propyl, 3- [CH 2 -CO-NH-CH (CH 3 ) 2 ] propyl, 3- (CO-NH-CH 2 CH 2 -C 2 H 5 ) propyl, 3- [CO-NH-CH (CH 3 ) -C 2 H 5 ] propyl, 3- [CO-NH-CH 2 -CH (CH 3 ) 2 ] propyl, 3- [CO-NH-C (CH 3 ) 3 ] propyl, 2- (CO-NH- CH 3 ) butyl, 2- (CO-NH-C 2 H 5 ) - butyl, 2- (CO-NH-CH 2 -C 2 H 5 ) butyl, 2- [CH 2 -CO-NH-CH (CH 3 ) 2 ] butyl, 2- (CO-NH-CH 2 CH 2 -C 2 H 5 ) butyl, 2- [CO-NH-CH (CH 3 ) -C 2 H 5 ] butyl,
2- [CO-NH-CH2-CH(CH3)2] butyl, 2- [CO-NH-C (CH3) 3] butyl, 3-(CO-NH-CH3)butyl, 3- (CO-NH-C2H5) butyl , 3- (CO-NH-CH2-C2H5) - butyl, 3-[CH2-CO-NH-CH(CH3)2]butyl, 3- (CO-NH-CH2CH2-C2H5) butyl ,2- [CO-NH-CH 2 -CH (CH 3 ) 2 ] butyl, 2- [CO-NH-C (CH 3 ) 3 ] butyl, 3- (CO-NH-CH 3 ) butyl, 3- ( CO-NH-C 2 H 5 ) butyl, 3- (CO-NH-CH 2 -C 2 H 5 ) - butyl, 3- [CH 2 -CO-NH-CH (CH 3 ) 2 ] butyl, 3- (CO-NH-CH 2 CH 2 -C 2 H 5 ) butyl,
3- [CO-NH-CH (CH3 ) -C2H5] butyl , 3- [CO-NH-CH2-CH (CH3 ) ] butyl, 3- [CO-NH-C (CH3)3] butyl, 4- (CO-NH-CH3) butyl, 4- (CO-NH-C2H5) butyl, 4-(CO-NH-CH2-C2H5)butyl, 4- [CH2-CO-NH-CH (CH3) 2] butyl,3- [CO-NH-CH (CH 3 ) -C 2 H 5 ] butyl, 3- [CO-NH-CH 2 -CH (CH 3 )] butyl, 3- [CO-NH-C (CH 3 ) 3 ] butyl, 4- (CO-NH-CH 3 ) butyl, 4- (CO-NH-C 2 H 5 ) butyl, 4- (CO-NH-CH 2 -C 2 H 5 ) butyl, 4- [ CH 2 -CO-NH-CH (CH 3 ) 2 ] butyl,
4- (CO-NH-CH2CH2-C2H5) butyl , 4- [CO-NH-CH (CH3 ) -C2H5] butyl , 4-[CO-NH-CH2-CH(CH3)2]butyl oder 4- [CO-NH-C (CH3) 3] butyl, vorzugsweise für CH2-CO-NH-CH3, CH2-CO-NH-C2H5, CH (CH3) -CO-NH-CH3 oder CH(CH3) -CO-NH-C2H5.4- (CO-NH-CH 2 CH 2 -C 2 H 5 ) butyl, 4- [CO-NH-CH (CH 3 ) -C 2 H 5 ] butyl, 4- [CO-NH-CH 2 -CH (CH 3 ) 2 ] butyl or 4- [CO-NH-C (CH 3 ) 3 ] butyl, preferably for CH 2 -CO-NH-CH 3 , CH 2 -CO-NH-C 2 H 5 , CH ( CH 3 ) -CO-NH-CH 3 or CH (CH 3 ) -CO-NH-C 2 H 5 .
- Di (Cχ-C4-alkyl) amino für: N(CH3)2, N(C2H5)2, N,N-Dipropylamino, N,N-Di- (1-methylethyl) amino, N,N-Dibutylamino, N,N-Di-(1- methylpropyl) amino , N,N-Di- (2-methylpropyl) amino, N,N-Di- (1, 1-dimethy1ethyl) amino, N-Ethyl-N-methylamino, N-Methyl-N- propylamino, N-Methyl-N- (1-methylethyl) amino, N-Butyl-N-methyl - amino, N-Methyl-N- (1-methylpropyl) amino, N-Methyl-N- (2-methyl- propyl) amino, N- (1, 1-Dimethylethyl) -N-methylamino, N-Ethyl-N- propylamino, N-Ethyl-N- (1-methylethyl) amino, N-Butyl-N-ethyl- amino, N-Ethyl-N- (1-methylpropyl) amino, N-Ethyl-N- (2-methyl- propyl) amino, N-Ethyl-N- (1 , 1-dimethylethyl) amino , N- ( 1-Methyl - ethyl) -N-propylamino, N-Butyl-N-propylamino , N- ( 1-Methyl - propyl) -N-propylamino, N- (2-Methylpropyl) -N-propylamino, N- (1, 1-Dimethylethyl) -N-propylamino, N-Butyl-N- (1-methylethyl) amino, N- (1-Methylethyl) -N- ( 1-methylpropyl) amino, N- (1-Methylethyl) -N- (2-methylpropyl) mino, N- (1, 1-Dimethylethyl) -N- ( 1-methylethyl) amino, N-Butyl-N- ( 1-methylpropyl) amino , N-Butyl-N- (2-methylpropyl) amino, N-Butyl-N- (1, 1-dimethylethyl) - amino, N- (1-Methylpropyl) -N- (2-methylpropyl) amino, N- (1, 1-Dimethylethyl) -N- (1-methylpropyl) amino oder N- (1, 1-Dimethyl- ethyl) -N- (2-methylpropyl) amino, vorzugsweise für N(CH3)2 oder N(C2H5)2;- Di (Cχ-C 4 -alkyl) amino for: N (CH 3 ) 2 , N (C 2 H 5 ) 2 , N, N-dipropylamino, N, N-di- (1-methylethyl) amino, N, N-dibutylamino, N, N-di- (1-methylpropyl) amino, N, N-di- (2-methylpropyl) amino, N, N-di- (1, 1-dimethylethyl) amino, N-ethyl-N -methylamino, N-methyl-N-propylamino, N-methyl-N- (1-methylethyl) amino, N-butyl-N-methyl-amino, N-methyl-N- (1-methylpropyl) amino, N-methyl -N- (2-methyl-propyl) amino, N- (1, 1-dimethylethyl) -N-methylamino, N-ethyl-N-propylamino, N-ethyl-N- (1-methylethyl) amino, N-butyl -N-ethyl-amino, N-ethyl-N- (1-methylpropyl) amino, N-ethyl-N- (2-methylpropyl) amino, N-ethyl-N- (1, 1-dimethylethyl) amino, N- (1-methyl-ethyl) -N-propylamino, N-butyl-N-propylamino, N- (1-methyl-propyl) -N-propylamino, N- (2-methylpropyl) -N-propylamino, N- (1, 1-dimethylethyl) -N-propylamino, N-butyl-N- (1-methylethyl) amino, N- (1-methylethyl) -N- (1-methylpropyl) amino, N- (1-methylethyl) - N- (2-methylpropyl) mino, N- (1, 1-dimethylethyl) -N- (1-methylethyl ) amino, N-butyl-N- (1-methylpropyl) amino, N-butyl-N- (2-methylpropyl) amino, N-butyl-N- (1, 1-dimethylethyl) - amino, N- (1- Methylpropyl) -N- (2-methylpropyl) amino, N- (1, 1-dimethylethyl) -N- (1-methylpropyl) amino or N- (1, 1-dimethylethyl) -N- (2-methylpropyl) amino, preferably for N (CH 3 ) 2 or N (C 2 H 5 ) 2 ;
- Di (Cχ-C4-alkyl) amino-Cχ-C4-alkyl für: durch Di (Cχ-C4-alkyl) - amino wie vorstehend genannt substituiertes Cχ-C4-Alkyl, also Z.B. für CH2N(CH3)2, CH2N(C2H5)2, N,N-Dipropylaminomethyl ,- di (Cχ-C 4 alkyl) amino-Cχ-C 4 alkyl: by di (Cχ-C 4 alkyl) - amino as mentioned above substituted Cχ-C4 alkyl, ie Z .B. for CH 2 N (CH 3 ) 2 , CH 2 N (C 2 H 5 ) 2 , N, N-dipropylaminomethyl,
N,N-Di [CH(CH3) 21 aminomethyl, N,N-Dibutylaminomethyl, N,N-Di- ( 1-methylpropyl) aminomethyl, N,N-Di (2-methylpropyl) aminomethyl, N,N-Di [C (CH3) 3] aminomethyl, N-Ethyl-N-methylaminomethyl, N-Methyl-N-propylaminomethyl, N-Methyl-N- [CH(CH3) 2] aminomethyl, N-Butyl-N-methylaminomethyl, N-Methyl-N- (1-methylpropyl) aminomethyl, N-Methyl-N- (2-methylpropyl) aminomethyl, N- [C (CH3) 3] -N- methylaminomethyl , N-Ethyl-N-propylaminomethyl, N-Ethyl-N- [CH (CH3 ) 2] aminomethyl , N-Butyl-N-ethylaminomethyl , N-Ethyl-N-N, N-Di [CH (CH 3 ) 2 1 aminomethyl, N, N-dibutylaminomethyl, N, N-Di- (1-methylpropyl) aminomethyl, N, N-Di (2-methylpropyl) aminomethyl, N, N- Di [C (CH 3 ) 3 ] aminomethyl, N-ethyl-N-methylaminomethyl, N-methyl-N-propylaminomethyl, N-methyl-N- [CH (CH 3 ) 2 ] aminomethyl, N-butyl-N-methylaminomethyl , N-methyl-N- (1-methylpropyl) aminomethyl, N-methyl-N- (2-methylpropyl) aminomethyl, N- [C (CH 3 ) 3 ] -N-methylaminomethyl, N-ethyl-N-propylaminomethyl, N-ethyl-N- [CH (CH 3 ) 2 ] aminomethyl, N-butyl-N-ethylaminomethyl, N-ethyl-N-
(1-methylpropyl) aminomethyl, N-Ethyl-N- (2-methylpropyl) aminomethyl, N-Ethyl-N- [C(CH3)3] aminomethyl, N- [CH (CH3) ] -N-propyl - aminomethyl, N-Butyl-N-propylaminomethyl, N- (1-Methylpropyl) - N-propylaminomethyl , N- (2-Methylpropyl) -N-propylaminomethyl , N- [C (CH3) 3] -N-propylaminomethyl, N-Butyl-N- (1-methylethyl) - aminomethyl , N- [CH (CH3 ) 2] -N- ( 1-methylpropyl ) aminomethyl , N- [CH(CH3) 2] -N- (2-methylpropyl) aminomethyl, N- [C (CH3) 3] -N-(1-methylpropyl) aminomethyl, N-ethyl-N- (2-methylpropyl) aminomethyl, N-ethyl-N- [C (CH 3 ) 3 ] aminomethyl, N- [CH (CH 3 )] -N-propyl - aminomethyl, N-butyl-N-propylaminomethyl, N- (1-methylpropyl) - N-propylaminomethyl, N- (2-methylpropyl) -N-propylaminomethyl, N- [C (CH 3 ) 3 ] -N-propylaminomethyl, N -Butyl-N- (1-methylethyl) aminomethyl, N- [CH (CH 3 ) 2 ] -N- (1-methylpropyl) aminomethyl, N- [CH (CH 3 ) 2 ] -N- (2-methylpropyl ) aminomethyl, N- [C (CH 3 ) 3 ] -N-
[CH(CH3) 2] aminomethyl, N-Butyl-N- (1-methylpropyl) aminomethyl, N-Butyl-N- (2-methylpropyl) -aminomethyl, N-Butyl-N- [C (CH3) 3] - aminomethyl, N- (1-Methylpropyl) -N- (2-methylpropyl) aminomethyl, N- [C(CH3)3] -N- (1-methylpropyl) aminomethyl, N- [C(CH3)3] - N- (2-methylpropyl) aminomethyl, N,N-Dimethylaminoethyl, N,N-Di- ethylaminoethyl, N, N-Di (n-propyl) aminoethyl , N,N-Di- [CH (CH3) 2] - aminoethyl, N,N-Dibutylaminoethyl, N, N-Di (1-methylpropyl) aminoethyl, N, N-Di (2-methylpropyl) aminoethyl, N,N-Di- [C (CH3) 3] - aminoethyl, N-Ethyl-N-methylaminoethyl, N-Methyl-N-propyl- aminoethyl , N-Methyl-N- [CH (CH3 ) 2] aminoethyl , N-Butyl-N-methyl - aminoethyl, N-Methyl-N- (1-methylpropyl) aminoethyl, N-Methyl-N-[CH (CH 3 ) 2 ] aminomethyl, N-butyl-N- (1-methylpropyl) aminomethyl, N-butyl-N- (2-methylpropyl) aminomethyl, N-butyl-N- [C (CH 3 ) 3 ] - aminomethyl, N- (1-methylpropyl) -N- (2-methylpropyl) aminomethyl, N- [C (CH 3 ) 3 ] -N- (1-methylpropyl) aminomethyl, N- [C (CH 3 ) 3 ] - N- (2-methylpropyl) aminomethyl, N, N-dimethylaminoethyl, N, N-di-ethylaminoethyl, N, N-di (n-propyl) aminoethyl, N, N-di- [CH (CH 3 ) 2 ] - aminoethyl, N, N-dibutylaminoethyl, N, N-Di (1-methylpropyl) aminoethyl, N, N-Di (2-methylpropyl) aminoethyl, N, N-Di- [C (CH 3 ) 3 ] - aminoethyl , N-ethyl-N-methylaminoethyl, N-methyl-N-propylaminoethyl, N-methyl-N- [CH (CH 3 ) 2 ] aminoethyl, N-butyl-N-methylaminoethyl, N-methyl-N - (1-methylpropyl) aminoethyl, N-methyl-N-
(2-methylpropyl) aminoethyl, N- [C (CH3) 3] -N-methylaminoethyl , N-Ethyl-N-propylaminoethyl , N-Ethyl-N- [CH (CH3 ) 2] .aminoethyl , N-Butyl-N-ethylaminoethyl , N-Ethyl-N- (1-methylpropyl) amino- ethyl, N-Ethyl-N- (2-methylpropyl) aminoethyl, N-Ethyl-N-(2-methylpropyl) aminoethyl, N- [C (CH 3 ) 3 ] -N-methylaminoethyl, N-ethyl-N-propylaminoethyl, N-ethyl-N- [CH (CH 3 ) 2 ] .aminoethyl, N-butyl -N-ethylaminoethyl, N-ethyl-N- (1-methylpropyl) aminoethyl, N-ethyl-N- (2-methylpropyl) aminoethyl, N-ethyl-N-
[C (CH3) 3] aminoethyl, N- [CH(CH3) ] -N-propylaminoethyl, N-Butyl- N-propylaminoethyl , N- (1-Methylpropyl) -N-propylaminoethyl , N- (2-Methylpropyl) -N-propylaminoethyl, N- [C (CH3) 3] -N-propylaminoethyl, N-Butyl-N- [CH(CH3) 2] aminoethyl, N- [CH (CH3) 2] -N-[C (CH 3 ) 3 ] aminoethyl, N- [CH (CH 3 )] -N-propylaminoethyl, N-butyl-N-propylaminoethyl, N- (1-methylpropyl) -N-propylaminoethyl, N- (2-methylpropyl ) -N-propylaminoethyl, N- [C (CH 3 ) 3 ] -N-propylaminoethyl, N-butyl-N- [CH (CH 3 ) 2 ] aminoethyl, N- [CH (CH 3 ) 2 ] -N-
(1-methylpropyl) aminoethyl, N- [CH(CH3) 2] -N- (2-methylpropyl) - aminoethyl, N- [C (CH3) 3] -N- [CH(CH3) 2] aminoethyl, N-Butyl-N-(1-methylpropyl) aminoethyl, N- [CH (CH 3 ) 2 ] -N- (2-methylpropyl) aminoethyl, N- [C (CH 3 ) 3 ] -N- [CH (CH 3 ) 2 ] aminoethyl , N-butyl-N-
( 1-methylpropyl) aminoethyl, N-Butyl-N- (2-methylpropyl) aminoethyl, N-Butyl-N- [C(CH3) 3] aminoethyl, N- (1-Methylpropyl) -N-(1-methylpropyl) aminoethyl, N-butyl-N- (2-methylpropyl) aminoethyl, N-butyl-N- [C (CH 3 ) 3 ] aminoethyl, N- (1-methylpropyl) -N-
(2-methylpropyl) aminoethyl, N- [C (CH3) 3] -N- (1-methylpropyl) - aminoethyl oder N- [C (CH3) 3] -N- (2-methylpropyl) aminoethyl, insbesondere für N,N-Dimethylaminoethyl oder N,N-Diethylamino- ethyl ;(2-methylpropyl) aminoethyl, N- [C (CH 3 ) 3 ] -N- (1-methylpropyl) aminoethyl or N- [C (CH 3 ) 3 ] -N- (2-methylpropyl) aminoethyl, especially for N, N-dimethylaminoethyl or N, N-diethylaminoethyl;
Di (Cχ-C4-alkyl) aminocarbonyl für: CO-N(CH3)2, CO-N(C2H5), CO-N(CH2-C2H5)2, CO-N[CH(CH3)2]2, N, N-Dibutylaminocarbonyl , CO-N[CH(CH3)-C2H5]2, CO-N [CH2-CH (CH3 ) 2] 2, CO-N [C (CH3) 3] 2 , N-Ethyl-N-methylaminocarbonyl , N-Methyl-N-propylaminocarbonyl , N-Methyl-N- [CH (CH3 ) 2] aminocarbonyl , N-Butyl-N-methylamino - carbonyl, N-Methyl-N- (1-methylpropyl) aminocarbonyl, N-Methyl- N- (2-methylpropyl) aminocarbonyl, N- [C (CH3) 3] -N-methylamino- carbonyl, N-Ethyl-N-propylaminocarbonyl, N-Ethyl-N- [CH(CH3)2] - aminocarbonyl, N-Butyl-N-ethylaminocarbonyl, N-Ethyl-N- (1-methylpropyl) aminocarbonyl, N-Ethyl-N- (2-methylpropyl) aminocarbonyl, N-Ethyl-N- [C(CH3) 3] aminocarbonyl, N- [CH (CH3) 2] - N-propylaminocarbonyl , N-Butyl-N-propylaminocarbonyl , N- (1-Methylpropyl) -N-propylaminocarbonyl, N- (2-Methylpropyl) - N-propylaminocarbonyl, N- [C (CH3) 3] -N-propylaminocarbonyl, N-Butyl-N- [CH (CH3) 2] aminocarbonyl, N- [CH (CH3) 2] -N- (1-methylpropyl) aminocarbonyl, N- [CH(CH3) 2] -N- (2-methylpropyl) amino- carbonyl, N- [C (CH3) 3] -N- [CH(CH3) 2] aminocarbonyl, N-Butyl-Di (Cχ-C 4 alkyl) aminocarbonyl for: CO-N (CH 3 ) 2 , CO-N (C 2 H 5 ), CO-N (CH 2 -C 2 H 5 ) 2 , CO-N [CH (CH 3 ) 2 ] 2 , N, N-dibutylaminocarbonyl, CO-N [CH (CH 3 ) -C 2 H 5 ] 2, CO-N [CH 2 -CH (CH 3 ) 2 ] 2, CO-N [C (CH 3 ) 3] 2 , N-ethyl-N-methylaminocarbonyl, N-methyl-N-propylaminocarbonyl, N-methyl-N- [CH (CH 3 ) 2 ] aminocarbonyl, N-butyl-N-methylamino - carbonyl, N-methyl-N- (1-methylpropyl) aminocarbonyl, N-methyl-N- (2-methylpropyl) aminocarbonyl, N- [C (CH 3 ) 3 ] -N-methylamino-carbonyl, N-ethyl-N -propylaminocarbonyl, N-ethyl-N- [CH (CH 3 ) 2 ] - aminocarbonyl, N-butyl-N-ethylaminocarbonyl, N-ethyl-N- (1-methylpropyl) aminocarbonyl, N-ethyl-N- (2- methylpropyl) aminocarbonyl, N-ethyl-N- [C (CH 3 ) 3 ] aminocarbonyl, N- [CH (CH 3 ) 2 ] - N-propylaminocarbonyl, N-butyl-N-propylaminocarbonyl, N- (1-methylpropyl) -N-propylaminocarbonyl, N- (2-methylpropyl) - N-propylaminocarbonyl, N- [C (CH 3 ) 3 ] -N-propylaminocarbonyl, N-butyl-N- [CH (CH 3 ) 2 ] aminocarbonyl, N- [CH (CH 3 ) 2 ] -N- (1-methylpropyl) aminocarbonyl, N- [CH (CH 3 ) 2 ] -N- (2-methylpropyl) aminocarbonyl, N- [ C (CH 3 ) 3 ] -N- [CH (CH 3 ) 2 ] aminocarbonyl, N-butyl-
N- (1-methylpropyl) aminocarbonyl, N-Butyl-N- (2-methylpropyl) - aminocarbonyl, N-Butyl-N- [C (CH3) 3] aminocarbonyl, N-(1-Methylpropyl) -N- (2-methylpropyl) aminocarbonyl, N- [C (CH3) 3] -N- (1- methylpropyl) aminocarbonyl oder N- [C (CH3) 3] -N- (2-methyl- propyl) aminocarbonyl , vorzugsweise für CO-N(CH3)2 oder CO-N(C2H5)2;N- (1-methylpropyl) aminocarbonyl, N-butyl-N- (2-methylpropyl) - aminocarbonyl, N-butyl-N- [C (CH 3 ) 3 ] aminocarbonyl, N- (1-methylpropyl) -N- ( 2-methylpropyl) aminocarbonyl, N- [C (CH 3 ) 3 ] -N- (1-methylpropyl) aminocarbonyl or N- [C (CH 3 ) 3 ] -N- (2-methyl-propyl) aminocarbonyl, preferably for CO-N (CH 3 ) 2 or CO-N (C 2 H 5 ) 2 ;
Di (Cχ-Cg-alkyl) aminocarbonyl für: einen der vorstehend genannten Di (C1-C4-alkyl) aminocarbonylreste oder z.B. N(CH3)-(n-C5Hιι), N(C2H5)-(n-C5Hιι), N (CH2-C2H5) - (n-C5Hχχ) ,Di (Cχ-Cg-alkyl) aminocarbonyl for: one of the aforementioned di (C 1 -C 4 alkyl) aminocarbonyl radicals or, for example, N (CH 3 ) - (nC 5 Hιι), N (C 2 H 5 ) - (nC 5 Hιι), N (CH 2 -C 2 H 5 ) - (nC 5 Hχχ),
N(n-C4H9)-(n-C5Hιι) , N(n-C5Hχχ) - (n-C5Hχχ) , N(n-C6H13) - (n-C5Hχχ) , N(CH3)-(n-CgHχ3) , N(C2H5)-(n-C6Hi3) , N(CH2-C2H5) - (n-C6Hχ3) , N(n-C4H9)-(n-C6Hχ3) , N(n-C5Hχχ) - (n-C6Hχ3) oder N(n-CeHχ3)2;N (nC 4 H 9 ) - (nC 5 Hιι), N (nC 5 Hχχ) - (nC 5 Hχχ), N (nC 6 H 13 ) - (nC 5 Hχχ), N (CH 3 ) - (n- CgHχ 3 ), N (C 2 H 5 ) - (nC 6 Hi 3 ), N (CH 2 -C 2 H 5 ) - (nC 6 Hχ 3 ), N (nC 4 H 9 ) - (nC 6 Hχ 3 ), N (nC 5 Hχχ) - (nC 6 Hχ 3 ) or N (nC e Hχ 3 ) 2 ;
Di (Cχ-C4-alkyl)aminocarbonyl-Cχ-C-alkyl für: durch Di (Cχ-C4- alkyl) aminocarbonyl wie vorstehend genannt, vorzugsweise CO-N(CH3)2 oder CO-N(C2H5)2, substituiertes Cχ-C4-Alkyl, also z.B. für CH2-CO-N(CH3)2, CH2-CO-N(C2H5) 2 , CH (CH3) -CO-N(CH3) 2 oder CH(CH3)-CO-N(C2H5)2, vorzugsweise für CH2 -CO-N(CH3) 2 oder CH(CH3) -CO-N(CH3)2;Di (Cχ-C 4 -alkyl) aminocarbonyl-Cχ-C-alkyl for: by di (Cχ-C 4 -alkyl) aminocarbonyl as mentioned above, preferably CO-N (CH 3 ) 2 or CO-N (C2H 5 ) 2 , substituted Cχ-C 4 alkyl, for example for CH 2 -CO-N (CH 3 ) 2 , CH 2 -CO-N (C 2 H 5 ) 2 , CH (CH 3 ) -CO-N (CH 3 ) 2 or CH (CH 3 ) -CO-N (C 2 H 5 ) 2 , preferably for CH 2 -CO-N (CH 3 ) 2 or CH (CH 3 ) -CO-N (CH 3 ) 2 ;
Di (Cχ-C4-alkyl) phosphonyl -Cχ-C4-alkyl für: durch Di (C1-C4-alkyl) phosphonyl wie -PO(OCH3) , -PO(OC2H5)2, N,N-Dipropylphosphonyl, N,N-Di- (1-methylethyl) phosphonyl, N, N-Dibutylphosphonyl , N, N-Di- (1-methylpropyl) phosphonyl , N,N-Di- (2-methylpropyl) phosphonyl, N,N-Di- (1, 1-dimethyl- ethyl) phosphonyl , N-Ethyl-N-methylphosphonyl, N-Methyl-N- propylphosphonyl, N-Methyl-N- (1-methylethyl) phosphonyl , N-Butyl-N-methylphosphonyl, N-Methyl-N- (1-methylpropyl) - phosphonyl, N-Methyl-N- (2-methylpropyl) phosphonyl, N-(1,1-Di- methylethyl) -N-methylphosphonyl, N-Ethyl-N-propylphosphonyl,Di (Cχ-C 4 -alkyl) phosphonyl -Cχ-C 4 -alkyl for: by di (C 1 -C 4 -alkyl) phosphonyl such as -PO (OCH 3 ), -PO (OC 2 H 5 ) 2 , N , N-dipropylphosphonyl, N, N-di- (1-methylethyl) phosphonyl, N, N-dibutylphosphonyl, N, N-di- (1-methylpropyl) phosphonyl, N, N-di- (2-methylpropyl) phosphonyl, N, N-di- (1, 1-dimethyl-ethyl) phosphonyl, N-ethyl-N-methylphosphonyl, N-methyl-N-propylphosphonyl, N-methyl-N- (1-methylethyl) phosphonyl, N-butyl- N-methylphosphonyl, N-methyl-N- (1-methylpropyl) phosphonyl, N-methyl-N- (2-methylpropyl) phosphonyl, N- (1,1-dimethylethyl) -N-methylphosphonyl, N-ethyl -N-propylphosphonyl,
N-Ethyl-N- (1-methylethyl) phosphonyl, N-Butyl-N-ethylphosphonyl, N-Ethyl-N- (1-methylpropyl) phosphonyl, N-Ethyl-N- (2-methyl- propyl) phosphonyl, N-Ethyl-N- (1, 1-dimethylethyl) phosphonyl, N- (1-Methylethyl) -N-propylphosphonyl , N-Butyl-N-propyl - phosphonyl, N- (1-Methylpropyl) -N-propylphosphonyl, N-(2-Methylpropyl) -N-propylphosphonyl, N- (1, 1-Dimethylethyl) -N-propylphosphonyl , N-Butyl-N- (1-methylethyl) phosphonyl , N- (1-Methyl - ethyl) -N- (1-methylpropyl) phosphonyl , N- (1-Methylethyl) -N- (2-methylpropyl) phosphonyl, N- (1, 1-Dimethylethyl) -N- (1-methyl- ethyl) phosphonyl , N-Butyl-N- (1-methylpropyl) phosphonyl ,N-ethyl-N- (1-methylethyl) phosphonyl, N-butyl-N-ethylphosphonyl, N-ethyl-N- (1-methylpropyl) phosphonyl, N-ethyl-N- (2-methylpropyl) phosphonyl, N -Ethyl-N- (1, 1-dimethylethyl) phosphonyl, N- (1-methylethyl) -N-propylphosphonyl, N-butyl-N-propyl-phosphonyl, N- (1-methylpropyl) -N-propylphosphonyl, N- (2-methylpropyl) -N-propylphosphonyl, N- (1, 1-dimethylethyl) -N-propylphosphonyl, N-butyl-N- (1-methylethyl) phosphonyl, N- (1-methylethyl) -N- ( 1-methylpropyl) phosphonyl, N- (1-methylethyl) -N- (2-methylpropyl) phosphonyl, N- (1, 1-dimethylethyl) -N- (1-methylethyl) phosphonyl, N-butyl-N- (1-methylpropyl) phosphonyl,
N-Butyl-N- (2-methylpropyl) phosphonyl, N-Butyl-N- (1, 1-dimethylethyl) phosphonyl, N- (1-Methylpropyl) -N- (2-methylpropyl) - phosphonyl , N- ( 1 , 1-Dimethylethyl) -N- ( 1-methylpropyl) phosphonyl oder N- (1, 1-Dimethylethyl) -N- (2-methylpropyl) phosphonyl, vorzugsweise -PO(OCH3)2 oder -PO(OC2Hs)2, substituiertes C1-C4 -Alkyl, also z.B. für CH2-PO (OCH3) 2, CH2-PO (OC2H5) 2, CH(CH3) -PO(OCH3)2 oder CH (CH3) -PO (OC2H5) 2 ;N-butyl-N- (2-methylpropyl) phosphonyl, N-butyl-N- (1, 1-dimethylethyl) phosphonyl, N- (1-methylpropyl) -N- (2-methylpropyl) - phosphonyl, N- (1, 1-dimethylethyl) -N- (1-methylpropyl) phosphonyl or N- (1, 1-dimethylethyl) -N- (2-methylpropyl) phosphonyl, preferably -PO (OCH 3 ) 2 or - PO (OC 2 Hs) 2 , substituted C 1 -C 4 alkyl, e.g. for CH 2 -PO (OCH 3 ) 2 , CH 2 -PO (OC 2 H 5 ) 2 , CH (CH 3 ) -PO ( OCH 3 ) 2 or CH (CH 3 ) -PO (OC 2 H 5 ) 2 ;
- C3~Cg-Alkenyl für: Prop-1-en-l-yl, Allyl, 1-Methylethenyl, 1-Buten-l-yl, l-Buten-2-yl, l-Buten-3-yl, 2-Buten-l-yl, 1-Methyl-prop-l-en-l-yl, 2-Methyl-prop-l-en-l-yl, 1-Methyl- prop-2-en-l-yl, 2-Methyl-prop-2-en-l-yl, n-Penten-1-yl, n-Penten-2-yl, n-Penten-3-yl, n-Penten-4-yl, 1-Methyl-but- 1-en-l-yl, 2-Methyl-but-l-en-l-yl, 3-Methyl-but-l-en-l-yl, l-Methyl-but-2-en-l-yl, 2-Methyl-but-2-en-l-yl, 3-Methyl- but-2-en-l-yl, l-Methyl-but-3-en-l-yl, 2-Methyl-but-3-en-l-yl, 3-Methyl-but-3-en-l-yl, 1, 1-Dimethyl-prop-2-en-l-yl, 1,2-Di- methyl-prop-1-en-l-yl, 1, 2-Dimethyl-prop-2-en-l-yl, 1-Ethyl- prop-l-en-2-yl, l-Ethyl-prop-2-en-l-yl, n-Hex-1-en-l-yl, n-Hex-2-en-l-yl, n-Hex-3-en-l-yl, n-Hex-4-en-l-yl, n-Hex- 5-en-l-yl, 1-Methyl-pent-l-en-l-yl, 2-Methyl-pent-l-en-l-yl, 3-Methyl-pent-1-en-l-yl, 4-Methyl-pent-l-en-l-yl, 1-Methyl- pent-2-en-l-yl, 2-Methyl-pent-2-en-l-yl, 3-Methyl-pent-2-en- 1-yl, 4-Methyl-pent-2-en-l-yl, l-Methyl-pent-3-en-l-yl, 2-Methyl-pent-3-en-l-yl, 3-Methyl-pent-3-en-l-yl, 4-Methyl- pent-3-en-l-yl, l-Methyl-pent-4-en-l-yl, 2-Methyl-pent-4-en- 1-yl, 3-Methyl-pent-4-en-l-yl, 4-Methyl-pent-4-en-l-yl, 1, 1-Dimethyl-but-2-en-l-yl, 1, 1-Dimethyl-but-3-en-l-yl, 1, 2-Dimethyl- but-1-en-l-yl, 1, 2-Dimethyl-but-2-en-l-yl, 1, 2-Dimethyl-but- 3-en-l-yl, 1, 3-Dimethyl-but-l-en-l-yl, 1, 3-Dimethyl-but-2-en- 1-yl, l,3-Dimethyl-but-3-en-l-yl, 2, 2-Dirnethyl-but-3-en-1-yl, 2,3-Dimethyl-but-l-en-l-yl, 2, 3-Dimethyl-but-2-en-l-yl, 2,3-Di- methyl-but-3-en-l-yl, 3 , 3-Dimethyl-but-l-en-l-yl, 3 , 3-Dimethyl- but-2-en-l-yl, 1-Ethyl-but-l-en-l-yl, l-Ethyl-but-2-en-l-yl, l-Ethyl-but-3-en-l-yl, 2-Ethyl-but-l-en-l-yl, 2-Ethyl-but-2-en- 1-yl, 2-Ethyl-but-3-en-l-yl, 1, 1, 2-Trimethyl-prop-2-en-l-yl, l-Ethyl-l-methyl-prop-2-en-l-yl, l-Ethyl-2-methyl-prop-l-en- 1-yl oder l-Ethyl-2-methyl-prop-2-en-l-yl;- C 3 ~ Cg-alkenyl for: prop-1-en-l-yl, allyl, 1-methylethenyl, 1-buten-l-yl, l-buten-2-yl, l-buten-3-yl, 2 -Butene-1-yl, 1-methyl-prop-1-en-1-yl, 2-methyl-prop-1-en-1-yl, 1-methyl-prop-2-en-1-yl, 2 -Methyl-prop-2-en-l-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methyl-but - 1-en-l-yl, 2-methyl-but-l-en-l-yl, 3-methyl-but-l-en-l-yl, l-methyl-but-2-en-l-yl , 2-methyl-but-2-en-l-yl, 3-methyl-but-2-en-l-yl, l-methyl-but-3-en-l-yl, 2-methyl-but-3 -en-1-yl, 3-methyl-but-3-en-1-yl, 1, 1-dimethyl-prop-2-en-1-yl, 1,2-dimethyl-prop-1-ene -l-yl, 1,2-dimethyl-prop-2-en-l-yl, 1-ethyl-prop-l-en-2-yl, l-ethyl-prop-2-en-l-yl, n -Hex-1-en-l-yl, n-hex-2-en-l-yl, n-hex-3-en-l-yl, n-hex-4-en-l-yl, n-hex - 5-en-1-yl, 1-methyl-pent-1-en-1-yl, 2-methyl-pent-1-en-1-yl, 3-methyl-pent-1-en-1-yl , 4-methyl-pent-1-en-1-yl, 1-methyl-pent-2-en-1-yl, 2-methyl-pent-2-en-1-yl, 3-methyl-pent-2 -en- 1-yl, 4-methyl-pent-2-en-1-yl, 1-methyl-pent-3-en-1-yl, 2-methyl-pent-3-en-1-yl, 3 -Methyl-pent-3-en-l-yl , 4-methyl-pent-3-en-1-yl, 1-methyl-pent-4-en-1-yl, 2-methyl-pent-4-en-1-yl, 3-methyl-pent-4 -en-1-yl, 4-methyl-pent-4-en-1-yl, 1, 1-dimethyl-but-2-en-1-yl, 1, 1-dimethyl-but-3-en-1 -yl, 1, 2-dimethyl-but-1-en-l-yl, 1, 2-dimethyl-but-2-en-l-yl, 1, 2-dimethyl-but-3-en-l-yl , 1,3-dimethyl-but-l-en-l-yl, 1,3-dimethyl-but-2-en-1-yl, 1,3-dimethyl-but-3-en-l-yl, 2nd , 2-Dirnethyl-but-3-en-1-yl, 2,3-dimethyl-but-l-en-l-yl, 2, 3-dimethyl-but-2-en-l-yl, 2,3 -Dimethyl-but-3-en-l-yl, 3, 3-dimethyl-but-l-en-l-yl, 3, 3-dimethyl-but-2-en-l-yl, 1-ethyl -but-l-en-l-yl, l-ethyl-but-2-en-l-yl, l-ethyl-but-3-en-l-yl, 2-ethyl-but-l-en-l -yl, 2-ethyl-but-2-en-1-yl, 2-ethyl-but-3-en-l-yl, 1, 1, 2-trimethyl-prop-2-en-l-yl, l -Ethyl-l-methyl-prop-2-en-l-yl, l-ethyl-2-methyl-prop-l-en-1-yl or l-ethyl-2-methyl-prop-2-en-l -yl;
- C3-Cg-Halogenalkenyl für: C3-Cg-Alkenyl wie vorstehend genannt, das partiell oder vollständig durch Fluor, Chlor, Brom und/oder Iod substituiert ist, also z.B. 2-Chlorallyl, 3-Chlorallyl, 2,3-Dichlorallyl, 3, 3-Dichlorallyl, 2, 3 , 3-Trichlorallyl,- C 3 -Cg haloalkenyl for: C 3 -Cg alkenyl as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 2-chloroallyl, 3-chloroallyl, 2,3- Dichlorallyl, 3, 3-dichlorallyl, 2, 3, 3-trichlorallyl,
2, 3-Dichlorbut-2-enyl, 2-Bromallyl, 3-Bromallyl, 2,3-Dibrom- allyl, 3, 3-Dibromallyl, 2, 3 , 3-Tribromallyl oder 2,3-Dibrom- but-2-enyl;2, 3-dichlorobut-2-enyl, 2-bromoallyl, 3-bromoallyl, 2,3-dibromoallyl, 3, 3-dibromoallyl, 2, 3, 3-tribromoallyl or 2,3-dibromo-but-2- enyl;
- Cyano -C3-C6-alkenyl für: z.B. 2 -Cyanoallyl, 3 -Cyanoallyl,Cyano -C 3 -C 6 alkenyl for: for example 2-cyanoallyl, 3-cyanoallyl,
4-Cyanobut-2-enyl, 4 -Cyanobut-3 -enyl oder 5 -Cyanopent-4-enyl; - C3-Cg-Alkinyl für: Prop-1-in-l-yl, Prop-2-in-l-yl, n-But-1-in- 1-yl, n-But-l-in-3-yl, n-But-l-in-4-yl, n-But-2-in-l-yl, n-Pent-1-in-l-yl, n-Pent-l-in-3-yl, n-Pent-l-in-4-yl, n-Pent- l-in-5-yl, n-Pent-2-in-l-yl, n-Pent-2-in-4-yl, n-Pent-2-in- 5-yl, 3-Methyl-but-l-in-3-yl, 3-Methyl-but-l-in-4-yl, n-Hex- 1-in-l-yl, n-Hex-l-in-3-yl, n-Hex-l-in-4-yl, n-Hex-l-in-5-yl, n-Hex-l-in-6-yl, n-Hex-2-in-l-yl, n-Hex-2-in-4-yl, n-Hex-2-in- 5-yl, n-Hex-2-in-6-yl, n-Hex-3-in-l-yl, n-Hex-3-in-2-yl, 3-Methyl-pent-l-in-l-yl, 3-Methyl-pent-l-in-3-yl, 3-Methyl- pent-l-in-4-yl, 3-Methyl-pent-l-in-5-yl, 4-Methyl-pent-l-in- 1-yl, 4-Methyl-pent-2-in-4-yl und 4-Methyl-pent-2-in-5-yl, vorzugsweise für Prop-2-in-l-yl;4-cyanobut-2-enyl, 4-cyanobut-3-enyl or 5-cyanopent-4-enyl; - C 3 -Cg alkynyl for: prop-1-in-l-yl, prop-2-in-l-yl, n-but-1-in-1-yl, n-but-l-in-3 -yl, n-but-l-in-4-yl, n-but-2-in-l-yl, n-pent-1-in-l-yl, n-pent-l-in-3-yl , n-pent-1-in-4-yl, n-pent-1-in-5-yl, n-pent-2-in-1-yl, n-pent-2-in-4-yl, n Pent-2-in-5-yl, 3-methyl-but-l-in-3-yl, 3-methyl-but-l-in-4-yl, n-hex-1-in-l-yl , n-hex-1-in-3-yl, n-hex-1-in-4-yl, n-hex-1-in-5-yl, n-hex-1-in-6-yl, n -Hex-2-in-1-yl, n-hex-2-in-4-yl, n-hex-2-in-5-yl, n-hex-2-in-6-yl, n-hex -3-in-1-yl, n-hex-3-in-2-yl, 3-methyl-pent-1-in-1-yl, 3-methyl-pent-1-in-3-yl, 3 -Methyl-pent-1-in-4-yl, 3-methyl-pent-1-in-5-yl, 4-methyl-pent-1-in-1-yl, 4-methyl-pent-2-in -4-yl and 4-methyl-pent-2-yn-5-yl, preferably for prop-2-yn-yl;
- C3-C5-Halogenalkinyl für: C3-Cg-Alkinyl wie vorstehend genannt, das partiell oder vollständig durch Fluor, Chlor, Brom und/oder- C 3 -C 5 haloalkynyl for: C 3 -Cg alkynyl as mentioned above, partially or completely by fluorine, chlorine, bromine and / or
Iod substituiert ist, also z.B. 1, 1-Difluorprop-2-in-l-yl, 4-Fluorbut-2-in-l-yl, 4-Chlorbut-2-in-l-yl, 1, 1-Difluorbut- 2-in-l-yl, 5-Fluorpent-3-in-l-yl oder 6-Fluorhex-4-in-l-yl;Iodine is substituted, e.g. 1, 1-difluoroprop-2-in-l-yl, 4-fluorobut-2-in-l-yl, 4-chlorobut-2-in-l-yl, 1, 1-difluorobut-2-in-l- yl, 5-fluoropent-3-in-1-yl or 6-fluorohex-4-in-1-yl;
Cyano-C3-Cg-alkinyl für: z.B. 3 -Cyanopropargyl, 4-Cyanobut- 2-in-l-yl, 5-Cyanopent-3 -in-l-yl und 6-Cyanohex-4 -in-l-yl;Cyano-C 3 -Cg-alkynyl for: for example 3-cyanopropargyl, 4-cyanobut-2-in-l-yl, 5-cyanopent-3 -in-l-yl and 6-cyanohex-4 -in-l-yl ;
C3-C4-Alkenyloxy-Cχ-C4-alkyl für: durch C3-C4-Alkenyloxy wie Allyloxy, But-l-en-3-yloxy, But-l-en-4-yloxy, But-2-en-l-yloxy, l-Methylprop-2-enyloxy oder 2-Methylprop-2-enyloxy substituiertes Cχ-C4-Alkyl, also beispielsweise für Allyloxymethyl, 2-Allyloxyethyl oder But-l-en-4-yloxymethyl, insbesondere für 2 -Allyloxyethyl ;C 3 -C 4 alkenyloxy-Cχ-C 4 alkyl for: by C 3 -C 4 alkenyloxy such as allyloxy, but-l-en-3-yloxy, but-l-en-4-yloxy, but-2 -en-l-yloxy, l-methylprop-2-enyloxy or 2-methylprop-2-enyloxy substituted Cχ-C 4 alkyl, for example for allyloxymethyl, 2-allyloxyethyl or but-l-en-4-yloxymethyl, in particular for 2-allyloxyethyl;
C3-C4-Alkinyloxy-Cχ-C4-alkyl für: durch C3-C4-Alkinyloxy wie Propargyloxy, But-l-in-3-yloxy, But-l-in-4-yloxy, But-2-in-l- yloxy, l-Methylprop-2-inyloxy oder 2-Methylprop-2-inyloxy, vorzugsweise Propargyloxy, substituiertes Cχ-C -Alkyl, also beispielsweise für Propargyloxymethyl oder 2-Propargyloxyethyl, insbesondere für 2 - Propargyloxyethyl ;C 3 -C 4 alkynyloxy-Cχ-C 4 alkyl for: by C 3 -C 4 alkynyloxy such as propargyloxy, but-l-in-3-yloxy, but-l-in-4-yloxy, but-2 -in-1-yloxy, 1-methylprop-2-ynyloxy or 2-methylprop-2-ynyloxy, preferably propargyloxy, substituted Cχ-C alkyl, for example for propargyloxymethyl or 2-propargyloxyethyl, especially for 2-propargyloxyethyl;
- C3-C4-Alkenylthio-Cχ-C -alkyl für: durch C3-C -Alkenylthio wie Allylthio, But-l-en-3-ylthio, But-l-en-4-ylthio, But-2-en-l-yl- thio, l-Methylprop-2-enylthio oder 2-Methylprop-2-enylthio substituiertes Cχ-C -Alkyl, also beispielsweise für Allylthio- methyl, 2-Allylthioethyl oder But-l-en-4-ylthiomethyl, insbesondere für 2- (Allylthio) ethyl;- C 3 -C 4 alkenylthio-Cχ-C alkyl for: by C 3 -C alkenylthio such as allylthio, but-l-en-3-ylthio, but-l-en-4-ylthio, but-2- en-l-yl-thio, l-methylprop-2-enylthio or 2-methylprop-2-enylthio substituted Cχ-C-alkyl, so for example for allylthio-methyl, 2-allylthioethyl or but-l-en-4-ylthiomethyl , especially for 2- (allylthio) ethyl;
- C3-C4-Alkinylthio-Cχ-C4-alkyl für: durch C3-C4-Alkinylthio wie Propargylthio, But-l-in-3-ylthio, But-l-in-4-ylthio, But-2-in-l-ylthio, l-Methylprop-2-inylthio oder 2-Methyl- prop-2-inylthio, vorzugsweise Propargylthio, substituiertes Cχ-C4-Alkyl, also beispielsweise für Propargylthiomethyl oder 2-Propargylthioethyl, insbesondere für 2- (Propargylthio) - ethyl ;- C 3 -C 4 alkynylthio-Cχ-C 4 alkyl for: by C 3 -C 4 alkynylthio such as propargylthio, but-l-in-3-ylthio, but-l-in-4-ylthio, but- 2-in-l-ylthio, l-methylprop-2-inylthio or 2-methyl-prop-2-inylthio, preferably propargylthio, substituted Cχ-C 4 alkyl, for example for propargylthiomethyl or 2-propargylthioethyl, especially for 2- (propargylthio) ethyl;
- C3-C4~Alkenylsulfinyl-Cχ-C4-alkyl für: durch C3-C4-Alkenylsul- finyl wie Allylsulfinyl, But-l-en-3-ylsulfinyl, But-l-en-4-yl- sulfinyl, But-2-en-l-ylsulfinyl, l-Methylprop-2-enylsulfinyl oder 2-Methylprop-2-enylsulfinyl substituiertes Cχ-C4~Alkyl, also beispielsweise für Allylsulfinylmethyl, 2-Allylsulfinylethyl oder But-l-en-4-ylsulfinylmethyl, insbesondere für 2- (Allylsulfinyl) ethyl;- C 3 -C 4 ~ alkenylsulfinyl-Cχ-C 4 alkyl for: by C 3 -C 4 alkenylsulfyl such as allylsulfinyl, but-l-en-3-ylsulfinyl, but-l-en-4-yl- sulfinyl, but-2-en-l-ylsulfinyl, l-methylprop-2-enylsulfinyl or 2-methylprop-2-enylsulfinyl substituted Cχ-C 4 ~ alkyl, for example for allylsulfinylmethyl, 2-allylsulfinylethyl or but-l-en- 4-ylsulfinylmethyl, especially for 2- (allylsulfinyl) ethyl;
- C3-C4-Alkinylsulfinyl-Cχ-C4-alkyl für: durch C3-C -Alkinyl- sulfinyl wie Propargylsulfinyl, But-l-in-3-ylsulfinyl, But-1- in-4-ylsulfinyl, But-2-in-l-ylsulfinyl, l-Methylprop-2-inylsul- finyl oder 2-Methylprop-2-inylsulfinyl, vorzugsweise Propargylsulfinyl, substituiertes Cχ-C4-Alkyl, also beispielsweise für Propargylsulfinylmethyl oder 2-Propargylsulfinylethyl, insbesondere für 2- (Propargylsulfinyl) ethyl;- C 3 -C 4 -Alkynylsulfinyl-Cχ-C 4 -alkyl for: by C 3 -C -alkynyl-sulfinyl such as propargylsulfinyl, but-l-in-3-ylsulfinyl, but-1- in-4-ylsulfinyl, but -2-in-l-ylsulfinyl, l-methylprop-2-inylsulfinyl or 2-methylprop-2-inylsulfinyl, preferably propargylsulfinyl, substituted Cχ-C 4 alkyl, for example for propargylsulfinylmethyl or 2-propargylsulfinylethyl, in particular for 2 - (propargylsulfinyl) ethyl;
C3-C4-Alkenylsulfonyl-Cχ-C4-alkyl für: durch C3-C -Alkenylsul- fonyl wie Allylsulfonyl, But-l-en-3-ylsulfonyl, But-l-en-4-yl- sulfonyl, But-2-en-l-ylsulfonyl, l-Methylprop-2-enylsulfonyl oder 2-Methylprop-2-enylsulfonyl substituiertes Cχ-C4-Alkyl, also beispielsweise für Allylsulfonylmethyl, 2-Allylsulfonyl- ethyl oder But-l-en-4-ylsulfonylmethyl, insbesondere für 2- (Allylsulfonyl) ethyl;C 3 -C 4 alkenylsulfonyl-Cχ-C 4 alkyl for: by C 3 -C alkenylsulfonyl such as allylsulfonyl, but-1-en-3-ylsulfonyl, but-1-en-4-yl-sulfonyl, But-2-en-l-ylsulfonyl, l-methylprop-2-enylsulfonyl or 2-methylprop-2-enylsulfonyl substituted Cχ-C 4 alkyl, e.g. for allylsulfonylmethyl, 2-allylsulfonylethyl or but-l-en- 4-ylsulfonylmethyl, especially for 2- (allylsulfonyl) ethyl;
C3-C4-Alkinylsulfonyl-Cχ-C4-alkyl für: durch C3-C4-Alkinylsul- fonyl wie Propargylsulfonyl, But-l-in-3-ylsulfonyl, But-l-in- 4-ylsulfonyl, But-2-in-l-ylsulfonyl, l-Methylprop-2-inylsul- fonyl oder 2-Methylprop-2-inylsulfonyl, vorzugsweise Propargylsulfonyl, substituiertes Cχ-C4-Alkyl, also beispielsweise für Propargylsulfonylmethyl oder 2-Propargylsulfonylethyl, insbesondere für 2 - (Propargylsulfonyl) ethyl;C 3 -C 4 alkynylsulfonyl-Cχ-C 4 -alkyl for: by C 3 -C 4 -alkynylsulfonyl such as propargylsulfonyl, but-l-in-3-ylsulfonyl, but-l-in-4-ylsulfonyl, but -2-in-l-ylsulfonyl, l-methylprop-2-inylsulfonyl or 2-methylprop-2-inylsulfonyl, preferably propargylsulfonyl, substituted Cχ-C 4 alkyl, that is, for example, for propargylsulfonylmethyl or 2-propargylsulfonylethyl, in particular for 2 - (propargylsulfonyl) ethyl;
- C3-Cg-Cycloalkyl für: Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl ;- C 3 -Cg cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
- C3-Cs-Cycloalkyl für: Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl oder Cyclooctyl;- C 3 -Cs cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl;
- C3-C8-Cycloalkyl-Cχ-Cg- alkyl für: z.B. Cyclopropylmethyl, Cyclo - butylmethyl, Cyclopentylmethyl , Cyclohexylmethyl , Cycloheptyl - methyl, Cyclooctylmethyl, 2 - (Cyclopropyl) ethyl, 2 - (Cyclobutyl) - ethyl, 2- (Cyclopentyl) ethyl, 2 - (Cyclohexyl) ethyl, 2-(Cyclo- heptyDethyl, 2- (Cyclooctyl) ethyl, 3 - (Cyclopropyl) propyl,- C 3 -C 8 -cycloalkyl-Cχ-Cg- alkyl for: e.g. cyclopropylmethyl, cyclo-butylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, 2 - (cyclopropyl) ethyl, 2 - (cyclobutyl) - ethyl, 2- (Cyclopentyl) ethyl, 2 - (cyclohexyl) ethyl, 2- (cyclo-heptydethyl, 2- (cyclooctyl) ethyl, 3 - (cyclopropyl) propyl,
3- (Cyclobutyl) propyl, 3 - (Cyclopentyl) propyl, 3 - (Cyclohexyl) - propyl, 3 - (Cycloheptyl) propyl, 3 - (Cyclooctyl) propyl, 4- (Cyclo- propyDbutyl, 4- (Cyclobutyl) butyl, 4 - (Cyclopentyl) butyl, 4- (Cyclohexyl) butyl, 4- (Cycloheptyl) butyl, 4- (Cyclooctyl) butyl, 5- (Cyclopropyl) pentyl, 5- (Cyclobutyl)pentyl, 5- (Cyclopentyl) - pentyl, 5- (Cyclohexyl) pentyl, 5- (Cycloheptyl) pentyl, 5-(Cyclo- octyDpentyl, 6- (Cyclopropyl) hexyl, 6- (Cyclobutyl) hexyl,3- (cyclobutyl) propyl, 3 - (cyclopentyl) propyl, 3 - (cyclohexyl) propyl, 3 - (cycloheptyl) propyl, 3 - (cyclooctyl) propyl, 4- (cyclo- propyDbutyl, 4- (cyclobutyl) butyl, 4 - (cyclopentyl) butyl, 4- (cyclohexyl) butyl, 4- (cycloheptyl) butyl, 4- (cyclooctyl) butyl, 5- (cyclopropyl) pentyl, 5- (cyclobutyl) pentyl , 5- (Cyclopentyl) pentyl, 5- (Cyclohexyl) pentyl, 5- (Cycloheptyl) pentyl, 5- (Cyclo-octypentyl, 6- (Cyclopropyl) hexyl, 6- (Cyclobutyl) hexyl,
6- (Cyclopentyl) hexyl, 6- (Cyclohexyl) hexyl, 6- (Cycloheptyl) hexyl oder 6- (Cyclooctyl) hexyl;6- (cyclopentyl) hexyl, 6- (cyclohexyl) hexyl, 6- (cycloheptyl) hexyl or 6- (cyclooctyl) hexyl;
C3-C8-Cycloalkyloxy-Cχ-C4-alkyl für: Cyclopropyloxymethyl , 1-Cyclopropyloxy-ethyl, 2-Cyclopropyloxy-ethyl, 1-Cyclopropyl - oxy-prop-1-yl, 2-Cyclopropyloxy-prop-l-yl, 3-Cyclopropyloxy- prop-1-yl, 1-Cyclopropyloxy-but-l-yl, 2-Cyclopropyloxy-but- 1-yl, 3-Cyclopropyloxy-but-l-yl, 4-Cyclopropyloxy-but-l-yl, l-Cyclopropyloxy-but-2-yl, 2-Cyclopropyloxy-but-2-yl, 3-Cyclo- propyloxy-but-2-yl, 3-Cyclopropyloxy-but-2-yl, 4-Cyclopropyl - oxy-but-2-yl, 1- (Cyclopropyloxymethyl) -eth-l-yl, 1- (Cyclopropyloxymethyl) -1- (CH3) -eth-l-yl, 1- (Cyclopropylmethyloxy) - prop-1-yl, Cyclobutyloxymethyl, 1-Cyclobutyloxy-ethyl , 2-Cyclo- butyloxy-ethyl , 1-Cyclobutyloxy-prop-l-yl, 2-Cyclobutyloxy- prop-1-yl, 3-Cyclobutyloxy-prop-l-yl, 1-Cyclobutyloxy-but-l-yl, 2-Cyclobutyloxy-but-l-yl, 3-Cyclobutyloxy-but-l-yl, 4-Cyclo- butyloxy-but-1-yl, l-Cyclobutyloxy-but-2-yl, 2-Cyclobutyloxy- but-2-yl, 3-Cyclobutyloxy-but-2-yl, 3-Cyclobutyloxy-but-2-yl, 4-Cyclobutyloxy-but-2-yl, 1- (Cyclobutyloxymethyl) eth-l-yl, 1- (Cyclobutyloxymethyl) -1- (CH3) -eth-l-yl, 1- (Cyclobutyloxymethyl)prop-l-yl, Cyclopentyloxymethyl, 1-Cyclopentyloxy-ethyl, 2-Cyclopentyloxy-ethyl, 1-Cyclopentyloxy-prop-l-yl, 2-Cyclo- pentyloxy-prop-1-yl, 3-Cyclopentyloxy-prop-l-yl, 1-Cyclopentyl- oxy-but-1-yl, 2-Cyclopentyloxy-but-l-yl, 3-Cyclopentyloxy-but- 1-yl, 4-Cyclopentyloxy-but-l-yl, l-Cyclopentyloxy-but-2-yl, 2-Cyclopentyloxy-but-2-yl, 3-Cyclopentyloxy-but-2-yl, 3-Cyclo- pentyloxy-but-2-yl, 4-Cyclopentyloxy-but-2-yl, 1- (Cyclopentyloxymethyl) eth-l-yl, 1- (Cyclopentyloxymethyl) -1- (CH3) -eth-l-yl, 1- (Cyclopentyloxymethyl) prop-1-yl , Cyclohexyloxymethyl , 1-Cyclohexyloxy-ethyl, 2-Cyclohexyloxy-ethyl, 1-Cyclohexyloxy- prop-1-yl, 2-Cyclohexyloxy-prop-l-yl, 3-Cyclohexyloxy-prop- 1-yl, 1-Cyclohexyloxy-but-l-yl, 2-Cyclohexyloxy-but-l-yl, 3-Cyclohexyloxy-but-l-yl, 4-Cyclohexyloxy-but-l-yl, 1-Cyclo- hexyloxy-but-2-yl, 2-Cyclohexyloxy-but-2-yl, 3-Cyclohexyloxy- but-2-yl, 3-Cyclohexyloxy-but-2-yl, 4-Cyclohexyloxy-but-2-yl, 1- (Cyclohexyloxymethyl) eth-l-yl, 1- (Cyclohexyloxymethyl) -C 3 -C 8 cycloalkyloxy-Cχ-C 4 alkyl for: cyclopropyloxymethyl, 1-cyclopropyloxy-ethyl, 2-cyclopropyloxy-ethyl, 1-cyclopropyl-oxy-prop-1-yl, 2-cyclopropyloxy-prop-l- yl, 3-cyclopropyloxy-prop-1-yl, 1-cyclopropyloxy-but-l-yl, 2-cyclopropyloxy-but-1-yl, 3-cyclopropyloxy-but-l-yl, 4-cyclopropyloxy-but-l- yl, l-cyclopropyloxy-but-2-yl, 2-cyclopropyloxy-but-2-yl, 3-cyclopropyloxy-but-2-yl, 3-cyclopropyloxy-but-2-yl, 4-cyclopropyl-oxy- but-2-yl, 1- (cyclopropyloxymethyl) -eth-l-yl, 1- (cyclopropyloxymethyl) -1- (CH 3 ) -eth-l-yl, 1- (cyclopropylmethyloxy) prop-1-yl, cyclobutyloxymethyl , 1-Cyclobutyloxy-ethyl, 2-Cyclobutyloxy-ethyl, 1-Cyclobutyloxy-prop-l-yl, 2-Cyclobutyloxy-prop-1-yl, 3-Cyclobutyloxy-prop-l-yl, 1-Cyclobutyloxy-but -l-yl, 2-cyclobutyloxy-but-l-yl, 3-cyclobutyloxy-but-l-yl, 4-cyclobutyloxy-but-1-yl, l-cyclobutyloxy-but-2-yl, 2-cyclobutyloxy - but-2-yl, 3-cyclobutyloxy-but-2-yl, 3-cyclobutyloxy-but-2-yl, 4-cyclobutyloxy-but-2-yl, 1- (cyclobutyloxymethyl) eth-ly l, 1- (cyclobutyloxymethyl) -1- (CH 3 ) -eth-l-yl, 1- (cyclobutyloxymethyl) prop-l-yl, cyclopentyloxymethyl, 1-cyclopentyloxy-ethyl, 2-cyclopentyloxy-ethyl, 1-cyclopentyloxy- prop-l-yl, 2-cyclopentyloxy-prop-1-yl, 3-cyclopentyloxy-prop-l-yl, 1-cyclopentyl-oxy-but-1-yl, 2-cyclopentyloxy-but-l-yl, 3-cyclopentyloxy-but-1-yl, 4-cyclopentyloxy-but-l-yl, l-cyclopentyloxy-but-2-yl, 2-cyclopentyloxy-but-2-yl, 3-cyclopentyloxy-but-2-yl, 3-cyclopentyloxy-but-2-yl, 4-cyclopentyloxy-but-2-yl, 1- (cyclopentyloxymethyl) eth-l-yl, 1- (cyclopentyloxymethyl) -1- (CH 3 ) -eth-l- yl, 1- (cyclopentyloxymethyl) prop-1-yl, cyclohexyloxymethyl, 1-cyclohexyloxy-ethyl, 2-cyclohexyloxy-ethyl, 1-cyclohexyloxy-prop-1-yl, 2-cyclohexyloxy-prop-l-yl, 3-cyclohexyloxy -prop- 1-yl, 1-cyclohexyloxy-but-l-yl, 2-cyclohexyloxy-but-l-yl, 3-cyclohexyloxy-but-l-yl, 4-cyclohexyloxy-but-l-yl, 1-cyclo hexyloxy-but-2-yl, 2-cyclohexyloxy-but-2-yl, 3-cyclohexyloxy-but-2-yl, 3-cyclohexyloxy-but-2-yl, 4-cyclohexyloxy-but-2-yl, 1- (cyclohexyloxymethyl) eth-l-yl, 1- (cyclohexyloxymethyl) -
1- (CH3) -eth-l-yl, 1- (Cyclohexyloxymethyl) -prop-1-yl, Cycloheptyloxymethyl, 1-Cycloheptyloxy-ethyl, 2-Cycloheptyloxy- ethyl, 1-Cycloheptyloxy-prop-l-yl, 2-Cycloheptyloxy-prop-l-yl, 3-Cycloheptyloxy-prop-l-yl, 1-Cycloheptyloxy-but-l-yl, 2-Cyclo- heptyloxy-but-1-yl, 3-Cycloheptyloxy-but-l-yl, 4-Cycloheptyl- oxy-but-1-yl, l-Cycloheptyloxy-but-2-yl, 2-Cycloheptyloxy-but- 2-yl, 3-Cycloheptyloxy-but-2-yl, 3-Cycloheptyloxy-but-2-yl, 4-Cycloheptyloxy-but-2-yl, 1- (Cycloheptyloxymethyl) eth-l-yl, 1- (Cycloheptyloxymethyl) -1- (CH3) -eth-l-yl, 1- (Cycloheptyloxymethyl) prop-1-yl, Cyclooctyloxymethyl, 1-Cyclooctyloxy-ethyl, 2-Cyclooctyloxy-ethyl, 1-Cyclooctyloxy-prop-l-yl, 2-Cyclooctyl- oxy-prop-1-yl, 3-Cyclooctyloxy-prop-l-yl, 1-Cyclooctyloxy-but- 1-yl, 2-Cyclooctyloxy-but-l-yl, 3-Cyclooctyloxy-but-l-yl, 4-Cyclooctyloxy-but-l-yl, l-Cyclooctyloxy-but-2-yl, 2-Cyclo- octyloxy-but-2-yl, 3-Cyclooctyloxy-but-2-yl, 3-Cyclooctyloxy- but-2-yl, 4-Cyclooctyloxy-but-2-yl, 1- (Cyclooctyloxymethyl) - eth-l-yl, 1- (Cyclooctyloxymethyl) -1- (CH3) -eth-l-yl oder1- (CH 3 ) -eth-l-yl, 1- (cyclohexyloxymethyl) prop-1-yl, cycloheptyloxymethyl, 1-cycloheptyloxy-ethyl, 2-cycloheptyloxy-ethyl, 1-cycloheptyloxy-prop-l-yl, 2 -Cycloheptyloxy-prop-l-yl, 3-cycloheptyloxy-prop-l-yl, 1-cycloheptyloxy-but-l-yl, 2-cycloheptyloxy-but-1-yl, 3-cycloheptyloxy-but-l-yl , 4-cycloheptyloxy-but-1-yl, l-cycloheptyloxy-but-2-yl, 2-cycloheptyloxy-but-2-yl, 3-cycloheptyloxy-but-2-yl, 3-cycloheptyloxy-but-2 -yl, 4-cycloheptyloxy-but-2-yl, 1- (cycloheptyloxymethyl) eth-l-yl, 1- (cycloheptyloxymethyl) -1- (CH 3 ) -eth-l-yl, 1- (cycloheptyloxymethyl) prop-1-yl , Cyclooctyloxymethyl, 1-Cyclooctyloxy-ethyl, 2-Cyclooctyloxy-ethyl, 1-Cyclooctyloxy-prop-l-yl, 2-Cyclooctyl-oxy-prop-1-yl, 3-Cyclooctyloxy-prop-l-yl, 1-Cyclooctyloxy -but-1-yl, 2-cyclooctyloxy-but-l-yl, 3-cyclooctyloxy-but-l-yl, 4-cyclooctyloxy-but-l-yl, l-cyclooctyloxy-but-2-yl, 2-cyclo - octyloxy-but-2-yl, 3-cyclooctyloxy-but-2-yl, 3-cyclooctyloxy-but-2-yl, 4-cyclooctyloxy-but-2-yl, 1- (cyclooctyloxymethyl) - eth-l-yl , 1- (Cyclooctyloxymethyl) -1- (CH 3 ) -eth-l-yl or
1- (Cyclooctyloxymethyl) prop-1-yl, insbesondere für C3-Cg-Cyclo- alkoxymethyl oder 2- (C3-Cg-Cycloalkoxy) ethyl.1- (Cyclooctyloxymethyl) prop-1-yl, especially for C 3 -Cg-cycloalkoxymethyl or 2- (C 3 -Cg-cycloalkoxy) ethyl.
Unter 3- bis 7gliedrigem Heterocyclyl sind sowohl gesättigte, partiell oder vollständig ungesättigte als auch aromatischeUnder 3- to 7-membered heterocyclyl are both saturated, partially or completely unsaturated and aromatic
Heterocyclen mit ein bis drei Heteroatomen, ausgewählt aus einer Gruppe bestehend aus ein bis drei Stickstoffatomen, einem oder zwei Sauerstoff- und - einem oder zwei Schwefelatomen, zu verstehen.To understand heterocycles with one to three heteroatoms, selected from a group consisting of one to three nitrogen atoms, one or two oxygen and - one or two sulfur atoms.
Beispiele für gesättigte Heterocyclen, die ein Carbonyl- oder Thiocarbonyl-Ringglied enthalten können, sind: Oxiranyl, Thiiranyl, Aziridin-1-yl, Aziridin-2-yl, Diaziridin- 1-yl, Diaziridin-3-yl, Oxetan-2-yl, Oxetan-3-yl, Thietan-2-yl, Thietan-3-yl, Azetidin-1-yl, Azetidin-2-yl, Azetidin-3-yl, Tetra- hydrofuran-2-yl, Tetrahydrofuran-3-yl, Tetrahydrothiophen-2-yl, Tetrahydrothiophen-3-yl, Pyrrolidin-1-yl, Pyrrolidin-2-yl, Pyrrolidin-3-yl, 1, 3-Dioxolan-2-yl, 1, 3-Dioxolan-4-yl, 1,3-Oxa- thiolan-2-yl, 1, 3-Oxathiolan-4-yl, 1, 3-Oxathiolan-5-yl, 1,3-Oxa- zolidin-2-yl, 1, 3-Oxazolidin-3-yl, 1, 3-Oxazolidin-4-yl, 1,3-Oxa- zolidin-5-yl, 1, 2-Oxazolidin-2-yl, 1, 2-Oxazolidin-3-yl, 1,2-Oxa- zolidin-4-yl, 1, 2-Oxazolidin-5-yl, 1, 3-Dithiolan-2-yl, 1,3-Di- thiolan-4-yl, Pyrrolidin-1-yl, Pyrrolidin-2-yl, Pyrrolidin-5-yl, Tetrahydropyrazol-1-yl, Tetrahydropyrazol-3-yl, Tetrahydropyr- azol-4-yl, Tetrahydropyran-2-yl, Tetrahydropyran-3-yl, Tetra- hydropyran-4-yl, Tetrahydrothiopyran-2-yl, Tetrahydrothiopyran- 3-yl, Tetrahydropyran-4-yl, Piperidin-1-yl, Piperidin-2-yl, Piperidin-3-yl, Piperidin-4-yl, 1, 3-Dioxan-2-yl, 1, 3-Dioxan-4-yl, 1, 3-Dioxan-5-yl, 1, 4-Dioxan-2-yl, 1, 3-Oxathian-2-yl, 1,3-Oxa- thian-4-yl, 1, 3-Oxathian-5-yl, 1, 3-Oxathian-6-yl, 1, 4-Oxathian- 2-yl, 1, 4-Oxathian-3-yl, Morpholin-2-yl, Morpholin-3-yl, Morpholin-4-yl , Hexahydropyridazin-1-yl , Hexahydropyridazin-3-yl , Hexahydropyridazin-4-yl, Hexahydropyrimidin-1-yl, Hexahydropyri - midin-2-yl, Hexahydropyrimidin-4-yl, Hexahydropyrimidin-5-yl, Piperazin-1-yl, Piperazin-2-yl, Piperazin-3-yl, Hexahydro-1, 3 , 5- triazin-1-yl, Hexahydro-1, 3 , 5-triazin-2-yl, Oxepan-2-yl, Oxepan- 3-yl, Oxepan-4-yl, Thiepan-2-yl, Thiepan-3-yl, Thiepan-4-yl, l,3-Dioxepan-2-yl, 1, 3-Dioxepan-4-yl, 1, 3-Dioxepan-5-yl, 1,3-Di- oxepan-6-yl, 1, 3-Dithiepan-2-yl, 1, 3-Dithiepan-2-yl, 1,3-Dithi- epan-2-yl, 1, 3-Dithiepan-2-yl, 1, 4-Dioxepan-2-yl, 1, 4-Dioxepan- 7-yl, Hexahydroazepin-1-yl, Hexahydroazepin-2-yl, Hexahydro- azepin-3-yl, Hexahydroazepin-4-yl, Hexahydro-1, 3-diazepin-l-yl, Hexahydro-1, 3-diazepin-2-yl, Hexahydro-1, 3-diazepin-4-yl, Hexa- hydro-l,4-diazepin-l-yl und Hexahydro-1, 4-diazepin-2-yl .Examples of saturated heterocycles which can contain a carbonyl or thiocarbonyl ring member are: oxiranyl, thiiranyl, aziridin-1-yl, aziridin-2-yl, diaziridin-1-yl, diaziridin-3-yl, oxetan-2- yl, oxetan-3-yl, thietan-2-yl, thietan-3-yl, azetidin-1-yl, azetidin-2-yl, azetidin-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3- yl, tetrahydrothiophene-2-yl, tetrahydrothiophene-3-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, 1, 3-dioxolan-2-yl, 1, 3-dioxolan-4- yl, 1,3-oxathiolan-2-yl, 1,3-oxathiolan-4-yl, 1,3-oxathiolan-5-yl, 1,3-oxazolidin-2-yl, 1,3- Oxazolidin-3-yl, 1,3-oxazolidin-4-yl, 1,3-oxazolidin-5-yl, 1,2-oxazolidin-2-yl, 1,2-oxazolidin-3-yl, 1,1 2-oxazolidin-4-yl, 1, 2-oxazolidin-5-yl, 1, 3-dithiolan-2-yl, 1,3-di-thiolan-4-yl, pyrrolidin-1-yl, pyrrolidin 2-yl, pyrrolidin-5-yl, tetrahydropyrazol-1-yl, tetrahydropyrazol-3-yl, tetrahydropyrazol-4-yl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, Tetrahydrothiopyran-2-yl, tetrahyd rothiopyran- 3-yl, tetrahydropyran-4-yl, piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, 1, 3-dioxan-2-yl, 1, 3- Dioxan-4-yl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, 1,3-oxathian-2-yl, 1,3-oxathian-4-yl, 1,1 3-oxathian-5-yl, 1,3-oxathian-6-yl, 1,4-oxathian-2-yl, 1,4-oxathian-3-yl, morpholin-2-yl, morpholin-3-yl, Morpholin-4-yl, hexahydropyridazin-1-yl, hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexahydropyrimidin-1-yl, hexahydropyri-midin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrlidin, 5-yl Piperazin-1-yl, piperazin-2-yl, piperazin-3-yl, hexahydro-1, 3, 5- triazin-1-yl, hexahydro-1,3,5-triazin-2-yl, oxepan-2-yl, oxepan- 3-yl, oxepan-4-yl, thiepan-2-yl, thiepan-3-yl, Thiepan-4-yl, 1,3-dioxepan-2-yl, 1,3-dioxepan-4-yl, 1,3-dioxepan-5-yl, 1,3-dioxoxan-6-yl, 1,1 3-dithiepan-2-yl, 1,3-dithiepan-2-yl, 1,3-dithie-epan-2-yl, 1,3-dithiepan-2-yl, 1,4-dioxepan-2-yl, 1,4-dioxepan- 7-yl, hexahydroazepin-1-yl, hexahydroazepin-2-yl, hexahydro-azepin-3-yl, hexahydroazepin-4-yl, hexahydro-1, 3-diazepin-l-yl, hexahydro- 1,3-diazepin-2-yl, hexahydro-1,3-diazepin-4-yl, hexa- hydro-l, 4-diazepin-l-yl and hexahydro-1,4-diazepin-2-yl.
Beispiele für ungesättigte Heterocyclen, die ein Carbonyl- oder Thiocarbonyl-Ringglied enthalten können, sind: Dihydrofuran-2-yl, 1, 2-Oxazolin-3 -yl, 1, 2-Oxazolin-5 -yl, 1, 3 -Oxazolin-2-yl;Examples of unsaturated heterocycles which may contain a carbonyl or thiocarbonyl ring member are: dihydrofuran-2-yl, 1, 2-oxazolin-3 -yl, 1, 2-oxazolin-5 -yl, 1, 3 -oxazolin- 2-yl;
Unter den Heteroaromaten sind die 5- und 6-gliedrigen bevorzugt, also z.B.Among the heteroaromatics, the 5- and 6-membered ones are preferred, e.g.
Furyl wie 2-Furyl und 3-Furyl, Thienyl wie 2-Thienyl und 3-Thienyl, Pyrrolyl wie 2-Pyrrolyl und 3-Pyrrolyl, Isoxazolyl wie 3-Isoxazolyl, 4-Isoxazolyl und 5-Isoxazolyl, Isothiazolyl wie 3-Isothiazolyl, 4-Isothiazolyl und 5-Isothiazolyl, Pyrazolyl wie 3-Pyrazolyl, 4-Pyrazolyl und 5-Pyrazolyl, Oxazolyl wie 2-Oxazolyl, 4-0xazolyl und 5-Oxazolyl, Thiazolyl wie 2-Thiazolyl, 4-Thiazolyl und 5-Thiazolyl, Imidazolyl wie 2-Imidazolyl und 4-Imidazolyl, Oxadiazolyl wie 1, 2, 4-Oxadiazol-3-yl,Furyl such as 2-furyl and 3-furyl, thienyl such as 2-thienyl and 3-thienyl, pyrrolyl such as 2-pyrrolyl and 3-pyrrolyl, isoxazolyl such as 3-isoxazolyl, 4-isoxazolyl and 5-isoxazolyl, isothiazolyl such as 3-isothiazolyl, 4-isothiazolyl and 5-isothiazolyl, pyrazolyl such as 3-pyrazolyl, 4-pyrazolyl and 5-pyrazolyl, oxazolyl such as 2-oxazolyl, 4-0xazolyl and 5-oxazolyl, thiazolyl such as 2-thiazolyl, 4-thiazolyl and 5-thiazolyl, Imidazolyl such as 2-imidazolyl and 4-imidazolyl, oxadiazolyl such as 1, 2, 4-oxadiazol-3-yl,
1, 2, 4-Oxadiazol-5-yl und 1, 3, 4-Oxadiazol-2-yl, Thiadiazolyl wie l,2,4-Thiadiazol-3-yl, 1, 2, 4-Thiadiazol-5-yl und l,3,4-Thiadiazol-2-yl, Triazolyl wie 1, 2, 4-Triazol-l-yl, l,2,4-Triazol-3-yl und 1,2, 4-Triazol-4-yl, Pyridinyl wie 2-Pyridinyl, 3-Pyridinyl und 4-Pyridinyl, Pyridazinyl wie1, 2, 4-oxadiazol-5-yl and 1, 3, 4-oxadiazol-2-yl, thiadiazolyl such as l, 2,4-thiadiazol-3-yl, 1, 2, 4-thiadiazol-5-yl and l, 3,4-thiadiazol-2-yl, triazolyl such as 1,2,4-triazol-l-yl, l, 2,4-triazol-3-yl and 1,2,4-triazol-4-yl, Pyridinyl such as 2-pyridinyl, 3-pyridinyl and 4-pyridinyl, pyridazinyl like
3-Pyridazinyl und 4-Pyridazinyl, Pyrimidinyl wie 2-Pyrimidinyl, 4-Pyrimidinyl und 5-Pyrimidinyl, des weiteren 2-Pyrazinyl, 1, 3 , 5-Triazin-2-yl und 1,2, 4-Triazin-3-yl, insbesondere Pyridyl, Pyrimidyl, Furanyl und Thienyl.3-pyridazinyl and 4-pyridazinyl, pyrimidinyl such as 2-pyrimidinyl, 4-pyrimidinyl and 5-pyrimidinyl, furthermore 2-pyrazinyl, 1, 3, 5-triazin-2-yl and 1,2, 4-triazin-3- yl, especially pyridyl, pyrimidyl, furanyl and thienyl.
Alle Phenyl-, carbocyclisehen und heteroeyclischen Ringe sind vorzugsweise unsubstituiert.All phenyl, carbocyclic and heteroeyclic rings are preferably unsubstituted.
Im Hinblick auf die Verwendung der 3 - (Benzazol-4 -yDpyrimidin- dion-Derivate I als Herbizide sind diejenigen Verbindungen I bevorzugt, bei denen die Variablen folgende Bedeutungen haben, und zwar jeweils für sich allein oder in Kombination: X Sauerstoff;With regard to the use of the 3 - (benzazole-4-yDpyrimidinedione derivatives I as herbicides, those compounds I are preferred in which the variables have the following meanings, in each case individually or in combination: X oxygen;
R1 Wasserstoff, Amino oder Cχ-Cg-Alkyl, insbesondere Wasserstoff oder Cχ-C4 -Alkyl, besonders bevorzugt Wasserstoff oder Methyl;R 1 is hydrogen, amino or Cχ-Cg-alkyl, in particular hydrogen or Cχ-C 4 -alkyl, particularly preferably hydrogen or methyl;
R2 Wasserstoff, Halogen, Cχ-Cg -Alkyl, Cχ-Cg-Halogenalkyl oder Cχ-Cg-Alkylsulfonyl, insbesondere Trifluormethyl;R 2 is hydrogen, halogen, Cχ-Cg-alkyl, Cχ-Cg-haloalkyl or Cχ-Cg-alkylsulfonyl, especially trifluoromethyl;
R3 Wasserstoff;R 3 is hydrogen;
R4 Wasserstoff, Fluor oder Chlor;R 4 is hydrogen, fluorine or chlorine;
R5 Cyano oder Halogen, insbesondere Chlor;R 5 cyano or halogen, especially chlorine;
=Y- =N-N(R6) - oder =C(ZR7)-S-, insbesondere =N-N(R6)-;= Y- = NN (R 6 ) - or = C (ZR 7 ) -S-, in particular = NN (R 6 ) -;
R6 Cχ-C6 -Alkyl, C3-Cg-Alkenyl, C3 -Cg-Alkinyl, Cx -Cg -Alkylsulfonyl, (Cχ-Cg -Alkyl) carbonyl, (Cχ-Cg -Alkyl) thiocarbonyl, (Cχ-Cg-Alk- oxy) carbonyl oder Cχ-Cg-Alkyl, das durch Cyano, (Cχ-Cg-Alk- oxy) carbonyl, Di (Cχ-Cg -alkyl) aminocarbonyl oder (Cχ-Cg-Alkyl) - carbonyloxy substituiert sein kann, insbesondere Cχ-Cg -Alkyl, C3 -Cg-Alkinyl, Cχ-Cg -Alkylsulfonyl oder (Cχ-C6 -Alkoxy) carbonyl .R 6 Cχ-C 6 alkyl, C 3 -Cg alkenyl, C 3 -Cg alkynyl, Cx -Cg alkylsulfonyl, (Cχ-Cg alkyl) carbonyl, (Cχ-Cg alkyl) thiocarbonyl, (Cχ- Cg-alkoxy) carbonyl or Cχ-Cg-alkyl, which can be substituted by cyano, (Cχ-Cg-alkoxy) carbonyl, di (Cχ-Cg-alkyl) aminocarbonyl or (Cχ-Cg-alkyl) - carbonyloxy can, in particular Cχ-Cg-alkyl, C 3 -Cg-alkynyl, Cχ-Cg -alkylsulfonyl or (Cχ-C 6 -alkoxy) carbonyl.
Besonders bevorzugt sind auch die 3- (Benzazol-4-yl)pyrimidindion- Derivate Ia { = I mit X = Sauerstoff, R1 = Methyl, R2 = Trifluormethyl, R3 = Wasserstoff, R4 = Fluor, R5 = Chlor und =Y- = =C(ZR7)-N(CH3) -}The 3- (benzazol-4-yl) pyrimidinedione derivatives Ia {= I with X = oxygen, R 1 = methyl, R 2 = trifluoromethyl, R 3 = hydrogen, R 4 = fluorine, R 5 = chlorine are also particularly preferred and = Y- = = C (ZR 7 ) -N (CH 3 ) -}
insbesondere die folgenden Verbindungen Ia.l bis Ia.272in particular the following compounds Ia.l to Ia.272
Tabelle 1Table 1
Des weiteren sind die 3- (Benzazol-4-yl)pyrimidindion-Derivate der Formeln Ib bis Ih besonders bevorzugt, insbesondereFurthermore, the 3- (benzazol-4-yl) pyrimidinedione derivatives of the formulas Ib to Ih are particularly preferred, in particular
- die Verbindungen Ib.l - Ib.272, die sich von den entsprechenden Verbindungen Ia.l - Ia.272 lediglich dadurch unterscheiden, daß R4 für Wasserstoff steht: - The compounds Ib.l - Ib.272, which differ from the corresponding compounds Ia.l - Ia.272 only in that R 4 is hydrogen:
die Verbindungen Ic.l - Ic.272, die sich von den entsprechenden Verbindungen Ia.l - Ia.272 lediglich dadurch unterscheiden, daß R1 für Wasserstoff steht:the compounds Ic.l - Ic.272, which differ from the corresponding compounds Ia.l - Ia.272 only in that R 1 is hydrogen:
ZR7 ZR 7
die Verbindungen Id.l - Id.272, die sich von den entsprechenden Verbindungen Ia.l - Ia.272 lediglich dadurch unterscheiden, daß R1 und R4 für Wasserstoff stehen:the compounds Id.l - Id.272, which differ from the corresponding compounds Ia.l - Ia.272 only in that R 1 and R 4 are hydrogen:
ZR7 ZR 7
die Verbindungen Ie.l - Ie.272, die sich von den entsprechenden Verbindungen Ia.l - Ia.272 lediglich dadurch unterscheiden, daß Y für =C(ZR7)-N(S02CH3)- steht:the compounds Ie.l - Ie.272, which differ from the corresponding compounds Ia.l - Ia.272 only in that Y is = C (ZR 7 ) -N (S0 2 CH 3 ) -:
ZR7 die Verbindungen If .1 - If .272, die sich von den entsprechenden Verbindungen Ia.l - Ia.272 lediglich dadurch unterscheiden, daß R4 für Wasserstoff und Y für =C (ZR7) -N(S02CH3) - stehen:ZR 7 the compounds If .1 - If .272, which differ from the corresponding compounds Ia.l - Ia.272 only in that R 4 for hydrogen and Y for = C (ZR 7 ) -N (S0 2 CH 3 ) - stand:
ZR7 ZR 7
die Verbindungen Ig.l - Ig.272, die sich von den entsprechenden Verbindungen Ia.l - Ia.272 lediglich dadurch unterscheiden, daß R1 für Wasserstoff und Y für =C (ZR7) -N(S02CH3) - stehen:the compounds Ig.l - Ig.272, which differ from the corresponding compounds Ia.l - Ia.272 only in that R 1 for hydrogen and Y for = C (ZR 7 ) -N (S0 2 CH 3 ) - stand:
die Verbindungen Ih.l - Ih.272, die sich von den entsprechenden Verbindungen Ia.l - Ia.272 lediglich dadurch unterscheiden, daß R1 und R4 für Wasserstoff und Y für =C(ZR7)-N(S0CH3) - stehen:the compounds Ih.l - Ih.272, which differ from the corresponding compounds Ia.l - Ia.272 only in that R 1 and R 4 for hydrogen and Y for = C (ZR 7 ) -N (S0CH 3 ) - stand:
ZR7 ZR 7
die Verbindungen Ii.l - Ii.272, die sich von den entsprechenden Verbindungen Ia.l - Ia.272 lediglich dadurch unterscheiden, daß =Y- für =C(ZR7)-0- steht: the compounds Ii.l - Ii.272, which differ from the corresponding compounds Ia.l - Ia.272 only in that = Y- is = C (ZR 7 ) -0-:
die Verbindungen Ik.l - Ik.272, die sich von den entsprechenden Verbindungen Ia.l - Ia.272 lediglich dadurch unterscheiden, daß =Y- für =C(ZR7)-0- und R4 für Wasserstoff stehen:the compounds Ik.l - Ik.272, which differ from the corresponding compounds Ia.l - Ia.272 only in that = Y- is = C (ZR 7 ) -0- and R 4 are hydrogen:
ZR7 ZR 7
die Verbindungen Im.l - Im.272, die sich von den entsprechenden Verbindungen Ia.l - Ia.272 lediglich dadurch unterscheiden, daß Y für =C(ZR7)-0- und R1 für Wasserstoff stehen:the compounds Im.l - Im.272, which differ from the corresponding compounds Ia.l - Ia.272 only in that Y is = C (ZR 7 ) -0- and R 1 is hydrogen:
die Verbindungen In.l - In.272, die sich von den entsprechenden Verbindungen Ia.l - Ia.272 lediglich dadurch unterscheiden, daß Y für =C(ZR7)-0- und R1 und R4 für Wasserstoff stehen:the compounds In.l - In.272, which differ from the corresponding compounds Ia.l - Ia.272 only in that Y is = C (ZR 7 ) -0- and R 1 and R 4 are hydrogen:
Die 3- (Benzazol-4-yl)pyrimidindion-Derivate der Formel I sind auf verschiedene Weise erhältlich, beispielsweise nach einem der folgenden Verfahren: The 3- (benzazol-4-yl) pyrimidinedione derivatives of the formula I can be obtained in various ways, for example by one of the following processes:
Verfahren A) :Procedure A):
Umsetzung eines 3 - (Benzazol-4-yl)pyrimidindion-Derivats I, bei dem R1 Wasserstoff bedeutet, mit einer Verbindung II auf an sich bekannte Weise:Reaction of a 3 - (benzazol-4-yl) pyrimidinedione derivative I, in which R 1 is hydrogen, with a compound II in a manner known per se:
L1 steht für eine übliche Abgangsgruppe wie Halogen, vorzugsweise Chlor, Brom oder Iod, (Halogen) alkylsulfonyloxy, vorzugsweise Methylsulfonyloxy oder Trifluormethylsulfonyloxy, Arylsulfonyloxy, vorzugsweise Toluolsulfonyloxy, und Alkoxy- sulfonyloxy, vorzugsweise Methoxysulfonyloxy oder Ethoxy- sulfonyloxy.L 1 represents a common leaving group such as halogen, preferably chlorine, bromine or iodine, (halogen) alkylsulfonyloxy, preferably methylsulfonyloxy or trifluoromethylsulfonyloxy, arylsulfonyloxy, preferably toluenesulfonyloxy, and alkoxysulfonyloxy, preferably methoxysulfonyloxy or ethoxysulfonyloxy.
Üblicherweise arbeitet man in einem inerten organischen Lösungsmittel, beispielsweise in einem protischen Lösungsmittel wie den niederen Alkoholen, vorzugsweise in Methanol oder Ethanol, gewünschtenfalls im Gemisch mit Wasser, oder in einem aprotischen Lösungsmittel, z.B. in einem aliphati- schen oder cyclischen Ether wie Methyl- tert. -butylether, 1, 2-Dimethoxyethan, Tetrahydrofuran und Dioxan, in einem aliphatischen Keton wie Aceton, Diethylketon und Ethyl - methylketon, in einem Amid wie Dimethylformamid und N-Methyl- pyrrolidon, in einem Sulfoxid wie Dimethylsulfoxid, in einem Harnstoff wie Tetramethylharnstoff und 1, 3 -Dimethyltetra- hydro-2 (IH) -pyrimidinon, in einem Carbonsäureester wie Essig- säureethylester, oder in einem halogenierten aliphatischen oder aromatischen Kohlenwasserstoff wie Dichlormethan, Dichlorethan, Chlorbenzol und den Dichlorbenzolen.Usually one works in an inert organic solvent, for example in a protic solvent such as the lower alcohols, preferably in methanol or ethanol, if desired in a mixture with water, or in an aprotic solvent, e.g. in an aliphatic or cyclic ether such as methyl tert. -butyl ether, 1, 2-dimethoxyethane, tetrahydrofuran and dioxane, in an aliphatic ketone such as acetone, diethyl ketone and ethyl methyl ketone, in an amide such as dimethylformamide and N-methylpyrrolidone, in a sulfoxide such as dimethyl sulfoxide, in a urea such as tetramethyl urea and 1, 3 -Dimethyltetrahydro-2 (IH) pyrimidinone, in a carboxylic acid ester such as ethyl acetate, or in a halogenated aliphatic or aromatic hydrocarbon such as dichloromethane, dichloroethane, chlorobenzene and the dichlorobenzenes.
Gewünschtenfalls kann in Gegenwart einer Base gearbeitet werden, wobei sowohl anorganische Basen, z.B. Carbonate wie Natriumcarbonat und Kaliumcarbonat, Hydrogencarbonate wieIf desired, work can be carried out in the presence of a base, both inorganic bases, e.g. Carbonates such as sodium carbonate and potassium carbonate, hydrogen carbonates such as
Natrium- und Kaliumhydrogencarbonat, oder Alkalimetallhydride wie Natriumhydrid und Kaliumhydrid, als auch organische Basen, z.B. Amine wie Triethylamin, Pyridin und N,N-Diethyl- anilin, oder Alkalimetallalkoholate wie Natriummethanolat, Natriumethanolat und Kalium- tert. -butanolat, geeignet sind.Sodium and potassium hydrogen carbonate, or alkali metal hydrides such as sodium hydride and potassium hydride, as well as organic ones Bases, for example amines such as triethylamine, pyridine and N, N-diethylaniline, or alkali metal alcoholates such as sodium methoxide, sodium ethoxide and potassium tert. -butanolate are suitable.
Die Menge an Base und Alkylierungsmittel II liegt vorzugsweise jeweils bei der 0,5- bis 2 -fachen molaren Menge, bezogen auf die Menge an AusgangsVerbindung I (mit R1 = Wasserstoff) .The amount of base and alkylating agent II is preferably 0.5 to 2 times the molar amount, based on the amount of starting compound I (with R 1 = hydrogen).
Im allgemeinen liegt die Reaktionstemperatur bei 0°C bis zur Siedetemperatur des Reaktionsgemisches, insbesondere bei 0 bis 60°C.In general, the reaction temperature is from 0 ° C to the boiling point of the reaction mixture, in particular from 0 to 60 ° C.
Eine bevorzugte Verfahrensvariante besteht darin, das aus der Cyclisierung von IV mit R1 = H oder V mit R1 = H gemäß Verfahren D) erhaltene Salz von I ohne Isolierung aus der Reaktionsmischung - die noch überschüssige Base, z.B. Natriumhydrid, Natriumalkoholat oder Natriumcarbonat, enthalten kann - zu alkylieren.A preferred process variant consists of the salt of I obtained from the cyclization of IV with R 1 = H or V with R 1 = H according to process D) without isolation from the reaction mixture - the excess base, for example sodium hydride, sodium alcoholate or sodium carbonate, may contain - to alkylate.
Sofern nicht unmittelbar durch die als Methode D) beschriebene Cyclisierung unter basischen Bedingungen herstellbar, können die Salze derjenigen Verbindungen I, bei denen R1 Wasserstoff bedeutet, auch in an sich bekannter Weise aus den Verfahrensprodukten der Methoden C) bis F) erhalten werden. Zu diesem Zweck versetzt man beispielsweise die wäßrige Lösung einer anorganischen oder organischen Base mit dem 3 - (Benzazol-4 -yDpyrimidindion-Derivat I, bei dem R1 für Wasserstoff steht. Die Salzbildung erfolgt dann normalerweise bereits bei 20 bis 25°C mit ausreichender Geschwindigkeit.Unless it can be produced directly under basic conditions by the cyclization described as method D), the salts of those compounds I in which R 1 is hydrogen can also be obtained in a manner known per se from the process products of methods C) to F). For this purpose, for example, the aqueous solution of an inorganic or organic base is mixed with the 3 - (benzazole-4-yDpyrimidinedione derivative I, in which R 1 is hydrogen. The salt formation is then usually already at 20 to 25 ° C. with sufficient Speed.
Besonders vorteilhaft ist es, das Natriumsalz durch Auflösen des 3 - (Benzazol-4 -yDpyrimidindion-Derivats I mit R1 = Wasserstoff in einer wäßrigen Natriumhydroxid- ösung bei 20 bis 25°C herzustellen, wobei etwa äquivalente Mengen an 3- (Benz - azol-4-yl)pyrimidindion-Derivat I (mit R1 = H) und Natriumhydroxid eingesetzt werden. Das entsprechende Salz des 3 - (Benzazol-4 -yDpyrimidindion-Derivats I kann dann z.B. durch Fällen mit einem geeigneten inerten Lösungsmittel oder durch Abdampfen des Lösungsmittels isoliert werden.It is particularly advantageous to prepare the sodium salt by dissolving the 3 - (benzazole-4-yDpyrimidinedione derivative I with R 1 = hydrogen in an aqueous sodium hydroxide solution at 20 to 25 ° C., with approximately equivalent amounts of 3- (benz - azol-4-yl) pyrimidinedione derivative I (with R 1 = H) and sodium hydroxide The corresponding salt of 3 - (benzazol-4-yDpyrimidinedione derivative I can then be used, for example, by precipitation with a suitable inert solvent or by evaporation of the solvent can be isolated.
Salze der 3 - (Benzazol-4 -yDpyrimidindion-Derivate I, deren Metallion kein Alkalimetallion ist, können üblicherweise durch Umsalzen des entsprechenden Alkalimetallsalzes in wäß- riger Lösung hergestellt werden, ebenso Ammonium-, Phosphonium- , Sulfonium- und Sulfoxoniumsalze mittels Ammoniak, Phosphonium- , Sulfonium- oder Sulfoxoniumhydroxiden.Salts of the 3 - (benzazole-4-yDpyrimidinedione derivatives I, the metal ion of which is not an alkali metal ion, can usually be prepared by salting the corresponding alkali metal salt in aqueous solution, as well as ammonium, Phosphonium, sulfonium and sulfoxonium salts using ammonia, phosphonium, sulfonium or sulfoxonium hydroxides.
Verfahren B) Umsetzung eines 3 - (Benzazol- 4 -yDpyrimidindion-Derivats der Formel I, wobei R1 Wasserstoff bedeutet, mit einem elektrophilen Aminierungsreagenz in Gegenwart einer Base:Process B) Reaction of a 3 - (benzazole-4-yDpyrimidinedione derivative of the formula I, where R 1 is hydrogen, with an electrophilic amination reagent in the presence of a base:
Als Aminierungsreagenz hat sich bisher 2, 4 -Dinitrophenoxyamin besonders bewährt, jedoch kann z.B. auch Hydroxylamin-O- sulfonsäure (HOSA) verwendet werden, die aus der Literatur bereits als Aminierungsreagenz bekannt ist (vgl. z.B.So far, 2,4-dinitrophenoxyamine has proven particularly useful as an amination reagent, however, e.g. hydroxylamine-O-sulfonic acid (HOSA) can also be used, which is already known from the literature as an amination reagent (cf. e.g.
E. Hofer et al . , Synthesis 1983, 466; W. Friedrichsen et al . , Heterocycles 20. (1983) 1271; H. Hart et al . , Tetrahedron Lett. 25. (1984) 2073; B. Vercek et al . , Monatsh. Chem. 114 (1983) 789; G. Sosnousky et al . , Z. Naturforsch. 3_8 (1983) 884; R.S. Atkinson et al . , J. Chem. Soc. Perkin Trans. 1987, 2787) .E. Hofer et al. , Synthesis 1983, 466; W. Friedrichsen et al. , Heterocycles 20. (1983) 1271; H. Hart et al. , Tetrahedron Lett. 25. (1984) 2073; B. Vercek et al. , Monthly Chem. 114 (1983) 789; G. Sosnousky et al. , Z. Naturforsch. 3_8 (1983) 884; R.S. Atkinson et al. , J. Chem. Soc. Perkin Trans. 1987, 2787).
Die Aminierung kann auf an sich bekannte Weise durchgeführt werden (siehe z.B. T. Sheradsky, Tetrahedron Lett. 1968, 1909; M.P. Wentland et al . , J. Med. Chem. 22 (1984) 1103 und insbesondere EP-A 240 194, EP-A 476 697 und EP-A 517 181, wo die Aminierung von Uracilen gelehrt wird) .The amination can be carried out in a manner known per se (see, for example, T. Sheradsky, Tetrahedron Lett. 1968, 1909; MP Wentland et al., J. Med. Chem. 22 (1984) 1103 and in particular EP-A 240 194, EP -A 476 697 and EP-A 517 181, where the amination of uracil is taught).
Normalerweise führt man die Umsetzung in einem polaren Lösungsmittel durch, z.B. in Dimethylformamid, N-Methyl- pyrrolidon, Dimethylsulfoxid oder in Ethylacetat, das sich bisher als besonders geeignet erwiesen hat.Usually the reaction is carried out in a polar solvent, e.g. in dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or in ethyl acetate, which has so far proven to be particularly suitable.
Als Base eignen sich beispielsweise Alkalimetallcarbonate wie Kaliumcarbonat, Alkalimetallalkoholate wie Natrium- methylat und Kalium- tert. -butanolat oder Alkalimetallhydride wie Natriumhydrid.Suitable bases are, for example, alkali metal carbonates such as potassium carbonate, alkali metal alcoholates such as sodium methylate and potassium tert. -butanolate or alkali metal hydrides such as sodium hydride.
Die Menge an Base und Aminierungsmittel liegt vorzugsweise jeweils bei der 0,5- bis 2 -fachen molaren Menge, bezogen auf die Menge an Ausgangsverbindung. Verfahren C)The amount of base and aminating agent is preferably 0.5 to 2 times the molar amount, based on the amount of starting compound. Process C)
Schwefelung eines 3 - (Benzazol-4 -yl)pyrimidindion-Derivats derSulfurization of a 3 - (benzazol-4 -yl) pyrimidinedione derivative of
Formel I, bei dem X Sauerstoff bedeutet:Formula I, where X means oxygen:
I (X = 0) I (X = S )I (X = 0) I (X = S)
Die Schwefelung erfolgt in der Regel in einem inerten Lösungs - oder Verdünnungsmittel, beispielsweise in einem aromatischen Kohlenwasserstoff wie Toluol und den Xylolen, in einem Ether wie Diethylether, 1, 2 -Dirnethoxyethan und Tetrahydrofuran, oder in einem organischen Amin wie Pyridin.The sulfurization is usually carried out in an inert solvent or diluent, for example in an aromatic hydrocarbon such as toluene and the xylenes, in an ether such as diethyl ether, 1, 2-dimethoxyethane and tetrahydrofuran, or in an organic amine such as pyridine.
Als Schwefelungsreagenz eignen sich besonders gut Phosphor (V) -sulfid und 2, 4 -Bis (4 -methoxyphenyl) -1, 3 , 2, 4 - dithiadiphosphetan-2, 4-dithion ("Lawesson-Reagenz") .Phosphorus (V) sulfide and 2,4-bis (4-methoxyphenyl) -1,3,4,4-dithiadiphosphetane-2,4-dithione ("Lawesson's reagent") are particularly suitable as the sulfurization reagent.
Üblicherweise ist die 1- bis 5 -fache molare Menge, bezogen auf die zu schwefelnde Ausgangsverbindung, für eine weitgehend vollständige Umsetzung ausreichend.Usually 1 to 5 times the molar amount, based on the starting compound to be sulfurized, is sufficient for a largely complete reaction.
Die Reaktionstemperatur liegt normalerweise bei 20 bis 200°C, vorzugsweise bei 40°C bis zur Siedetemperatur des Reaktions- gemisches . The reaction temperature is normally 20 to 200 ° C, preferably 40 ° C to the boiling point of the reaction mixture.
Verfahren D)Procedure D)
Cyclisierung eines Arylharnstoffs der Formel III oder einesCyclization of an arylurea of formula III or one
Arylanilids der Formel IV in Gegenwart einer Base:Arylanilides of the formula IV in the presence of a base:
I (X = 0)I (X = 0)
L2 bedeutet niedermolekulares Alkyl, vorzugsweise Cχ-C4 -Alkyl, oder Phenyl .L 2 means low molecular weight alkyl, preferably Cχ-C 4 alkyl, or phenyl.
In der Regel cyclisiert man in einem inerten organischen Lösungs- oder Verdünnungsmittel, das aprotisch ist, beispielsweise in einem aliphatischen oder cyclischen Ether wie 1, 2 -Dimethoxyethan, Tetrahydrofuran und Dioxan, in einem Aromaten wie Benzol und Toluol oder in einem polaren Solvens wie Dimethylformamid und Dimethylsulfoxid. Auch Mischungen aus polarem Solvens und einem Kohlenwasserstoff wie n-Hexan sind geeignet. Je nach Ausgangsverbindung kann auch Wasser als Verdünnungsmittel geeignet sein.As a rule, cyclization is carried out in an inert organic solvent or diluent which is aprotic, for example in an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aromatic compound such as benzene and toluene or in a polar solvent such as dimethylformamide and dimethyl sulfoxide. Mixtures of polar solvent and a hydrocarbon such as n-hexane are also suitable. Depending on the starting compound, water can also be suitable as a diluent.
Als Basen kommen vorzugsweise Alkalimetallalkoholate, insbesondere die Natriumalkoholate, Alkalimetallhydroxide, insbesondere Natriumhydroxid und Kaliumhydroxid, Alkali - metallcarbonate, insbesondere Natriumcarbonat und Kalium- carbonat, und Metallhydride, insbesondere Natriumhydrid, in Betracht. Bei der Verwendung von Natriumhydrid als Base hat es sich als vorteilhaft erwiesen, in einem aliphatischen oder cyclischen Ether, in Dimethylformamid oder in Dimethylsulfoxid zu arbeiten. Normalerweise ist die 0,5- bis 2 -fache molare Menge an Base, bezogen auf die Menge an IV oder V für das Gelingen der Reaktion ausreichend.Suitable bases are preferably alkali metal alcoholates, in particular the sodium alcoholates, alkali metal hydroxides, in particular sodium hydroxide and potassium hydroxide, alkali metal carbonates, in particular sodium carbonate and potassium carbonate, and metal hydrides, in particular sodium hydride. When using sodium hydride as the base, it has proven advantageous to work in an aliphatic or cyclic ether, in dimethylformamide or in dimethyl sulfoxide. Normally, 0.5 to 2 times the molar amount of base, based on the amount of IV or V, is sufficient for the reaction to succeed.
Im allgemeinen liegt die Reaktionstemperatur bei (-78)°C bis zur Siedetemperatur des jeweiligen Reaktionsgemisches, insbesondere bei (-60) bis 60°C.In general, the reaction temperature is from (-78) ° C to the boiling point of the respective reaction mixture, in particular from (-60) to 60 ° C.
Bedeutet R1 in Formel III oder IV Wasserstoff, so wird das Verfahrensprodukt als Metallsalz erhalten, wobei das Metall dem Kation der verwendeten Base entspricht. Das Salz kann auf an sich bekannte Weise isoliert und gereinigt oder gewünschtenfalls mittels Säure in die freie Verbindung I mit R1 = Wasserstoff übergeführt werden.If R 1 in formula III or IV is hydrogen, the product of the process is obtained as a metal salt, the metal corresponding to the cation of the base used. The salt can be isolated and purified in a manner known per se or, if desired, converted into the free compound I with R 1 = hydrogen by means of acid.
Verfahren E)Procedure E)
Behandlung eines substituierten 2 -Aminoanilins Va mit salpetrigerTreatment of a substituted 2-aminoaniline Va with nitrous oxide
Säureacid
VaVa
I {=Y- = =N-N(R6) -}I {= Y- = = NN (R 6 ) -}
Die Ringschlußreaktion kann nach an sich bekanntem Verfahren (vgl. z.B. Houben-Weyl, Methoden der organischen Chemie,The ring closure reaction can be carried out by a method known per se (cf. e.g. Houben-Weyl, Methods of Organic Chemistry,
Georg Thieme Verlag Stuttgart, Bd. E8d, 1. Auflage 1994, S. 409-415) durchgeführt werden.Georg Thieme Verlag Stuttgart, vol. E8d, 1st edition 1994, pp. 409-415).
Die Reaktion wird bevorzugt in sauren, wässrigen Medien aus- geführt, aber auch niedere Carbonsäuren wie Essigsäure sind geeignete Verdünnungsmittel. Als saure wässrige Solventien eignen sich insbesondere verdünnte Mineralsäuren, zum Beispiel 10 %ige Salzsäure.The reaction is preferably carried out in acidic, aqueous media, but lower carboxylic acids such as acetic acid are also suitable diluents. Dilute mineral acids, for example 10% hydrochloric acid, are particularly suitable as acidic aqueous solvents.
Die salpetrige Säure wird vorteilhaft in situ hergestellt, in dem man ein Alkalimetallnitrit - in Substanz oder in wässri- ger Lösung - zu der Reaktionsmischung, bestehend aus dem Diaminobenzol in saurer wässriger Lösung oder in einer Carbonsäure, zugibt. Als Reaktionstemperatur eignet sich insbesondere 0 bis 20°C, ganz besonders etwa 5°C.The nitrous acid is advantageously prepared in situ by adding an alkali metal nitrite - in bulk or in aqueous solution - to the reaction mixture consisting of the diaminobenzene in acidic aqueous solution or in a carboxylic acid. A suitable reaction temperature is in particular 0 to 20 ° C., very particularly about 5 ° C.
Zweckmäßig setzt man die Edukte in etwa stöchiometrisehen Mengen ein oder man arbeitet mit einem Überschuß der theoretisch zu erwartenden Menge an salpetriger Säure von nicht mehr als 10 mol-%.The starting materials are expediently used in approximately stoichiometric amounts or one works with an excess of the theoretically expected amount of nitrous acid of not more than 10 mol%.
Auf analoge Weise läßt sich folgende Zwischenstufe cyclisieren:The following intermediate stage can be cyclized in an analogous manner:
H2 H 2
VI VIIVI VII
Verfahren F> Kondensation eines substituierten 2 -Aminophenols, 2-Aminothio- phenols oder 2-Aminoanilins (V) mit Kohlensäure- oder Carbonsäurederivaten:Process F> Condensation of a substituted 2-aminophenol, 2-aminothiophenol or 2-aminoaniline (V) with carbonic acid or carboxylic acid derivatives:
l, Alkenyl oder Aryl) l, alkenyl or aryl)
Die Kondensationsreaktion der bifunktionellen Benzole V mit den Kohlensäure- oder Carbonsäurederivaten werden auf an sich bekannte Weise durchgeführt (vgl. z.B. Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag Stuttgart, Bd. E8c, 1. Auflage 1994, S. 247-284; Bd. E8b, 1. Auflage 1994, S. 881-901; Bd. E8a, 1. Auflage 1993, S. 1032-1078). Bevorzugte Kohlensäure- oder Carbonsäurederivate sind die entsprechenden Anhydride, Säurechloride, Orthoester, Diimide, Ni- trile, Trichlormethyl- substituierte Verbindungen, Isocyanate und deren Thioanaloga. Als Lösungs -/Verdünnungsmittel kommen insbesondere organische Lösungsmittel in Betracht, beispielsweise aromatische Kohlenwasserstoffe wie Benzol, Toluol und o-, m- , p-Xylol, haloge- nierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Dichlorethan, niedere Alkohole wie Methanol und Ethanol, ali- phatische oder cyclische Ether wie Dimethoxyethan, Tetrahydrofuran und Dioxan, Carbonsäureester wie Essigsäureethyl- ester oder aprotisch polare Solvention wie Dimethylformamid und Dimethylsulfoxid.The condensation reaction of the bifunctional benzenes V with the carbonic acid or carboxylic acid derivatives are carried out in a manner known per se (see, for example, Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag Stuttgart, Vol. E8c, 1st Edition 1994, pp. 247- 284; Vol. E8b, 1st edition 1994, pp. 881-901; Vol. E8a, 1st edition 1993, pp. 1032-1078). Preferred carbonic acid or carboxylic acid derivatives are the corresponding anhydrides, acid chlorides, orthoesters, diimides, nitriles, trichloromethyl-substituted compounds, isocyanates and their thio analogues. Suitable solvents / diluents are, in particular, organic solvents, for example aromatic hydrocarbons such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, lower alcohols such as methanol and ethanol, ali- phatic or cyclic ethers such as dimethoxyethane, tetrahydrofuran and dioxane, carboxylic acid esters such as ethyl acetate or aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide.
Die Reaktion kann gewünschtenfalls durch Zusatz katalytischer Mengen einer Säure beschleunigt werden. Als Säure eignen sich insbesondere Mineralsäuren wie Salzsäuren oder Sulfonsäuren wie p-Toluolsulfonsäure. Die Mengen an Säure liegen bevorzugt bei 0,1 bis 5 Molprozenten, bezogen auf die Menge an V.If desired, the reaction can be accelerated by adding catalytic amounts of an acid. Particularly suitable acids are mineral acids such as hydrochloric acids or sulfonic acids such as p-toluenesulfonic acid. The amounts of acid are preferably 0.1 to 5 mol percent, based on the amount of V.
Die Reaktionstemperaturen liegen bevorzugt bei 20°C bis Rück- flußtemperatur des jeweiligen Reaktionsgemisches, insbesondere bei 60°C bis Rückflußtemperatur.The reaction temperatures are preferably from 20 ° C. to the reflux temperature of the respective reaction mixture, in particular from 60 ° C. to the reflux temperature.
Das Kohlensäure- oder Carbonsäurederivat wird entweder in ca, stöchiometrischer Menge oder im Überschuß angewandt. In geeigneten Fällen kann auch ein sehr großer Überschuß eingesetzt oder ohne Lösungsmittel gearbeitet werden. Bevorzugt sind etwa stöchiometische Mengen oder ein Überschuß von bis zu 10 Moläquivalenten, bezogen auf die Menge an V.The carbonic acid or carboxylic acid derivative is used either in approx., Stoichiometric amount or in excess. In suitable cases, a very large excess can also be used or a solvent can be used. About stoichiometric amounts or an excess of up to 10 molar equivalents, based on the amount of V, are preferred.
Die substituierten 2 -Aminophenole, -thiophenole und -aniline (V) erhält man zweckmäßigerweise durch Reduktion entsprechen- der 2 -Nitrophenole, -thiophenole oder -aniline VIII (vgl. z.B. Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag Stuttgart, Bd. XI/1, 4. Auflage 1957, S. 431ff .) :The substituted 2 -aminophenols, -thiophenols and -anilines (V) are advantageously obtained by reducing the corresponding 2 -nitrophenols, -thiophenols or -anilines VIII (cf., for example, Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag Stuttgart, Vol. XI / 1, 4th edition 1957, p. 431ff.):
Als Reduktionsmittel kommen insbesondere elementare Metalle wie Eisen, Zinn und Zink, Wasserstoff in Gegenwart von geeigneten Katalysatoren wie Palladium oder Platin auf Kohle oder Raney-Nickel, oder komplexe Hydride wie LiAlH und NaBH4, ggf. in Gegenwart von Katalysatoren, in Betracht.In particular, elemental metals such as iron, tin and zinc are used as reducing agents, Hydrogen in the presence of suitable catalysts such as palladium or platinum on carbon or Raney nickel, or complex hydrides such as LiAlH and NaBH 4 , if appropriate in the presence of catalysts.
Als Lösungsmittel eignen sich üblicherweise - je nach Reduktionsmittel - Carbonsäuren wie Essigsäure und Propionsäure, Alkohole wie Methanol und Ethanol, Ether wie Diethylether, Methyl- tert. -butylether, Tetrahydrofuran und Dioxan, Aromaten wie Benzol und Toluol, sowie Gemische derartiger Solventien.Suitable solvents are usually - depending on the reducing agent - carboxylic acids such as acetic acid and propionic acid, alcohols such as methanol and ethanol, ethers such as diethyl ether, methyl tert. -butyl ether, tetrahydrofuran and dioxane, aromatics such as benzene and toluene, and mixtures of such solvents.
Die Umsetzungen können bei Temperaturen von (-100)°C bis zur Siedetemperatur des jeweiligen Reaktionsgemisches vorgenommen werden.The reactions can be carried out at temperatures from (-100) ° C. to the boiling point of the respective reaction mixture.
Üblicherweise werden die Ausgangsverbindungen in etwa stöchiometrisehen Mengen eingesetzt; in Einzelfällen kann jedoch auch ein Überschuß der einen oder anderen Komponente, bis etwa 10 mol-%, vorteilhaft sein.The starting compounds are usually used in approximately stoichiometric amounts; in individual cases, however, an excess of one or the other component, up to about 10 mol%, can also be advantageous.
Die 2-Nitrophenole, -thiophenole und -aniline VIII können ihrerseits aus dem entsprechenden geschützten Nitro-Verbindungen IX freigesetzt werden:The 2-nitrophenols, thiophenols and anilines VIII can in turn be released from the corresponding protected nitro compounds IX:
Schutz = übliche Schutzgruppe, die Phenole bzw. Thiophenole als Ether oder die Aminogruppe als Amid schützt.Protection = usual protective group that protects phenols or thiophenols as ether or the amino group as amide.
Das Abspalten der Schutzgruppen kann nach an sich bekannten Verfahren durchgeführt werden (vgl. z.B. Greene/Wuts: Protec- tive Groups in Organic Synthesis, John Wiley & Sons, Inc., 2. Auflage 1991, S. 145ff. und S. 279ff.).The protective groups can be split off by methods known per se (cf., for example, Greene / Wuts: Protective Groups in Organic Synthesis, John Wiley & Sons, Inc., 2nd edition 1991, pp. 145ff. And pp. 279ff. ).
Als Abspaltungsreagenzien kommen insbesondere in Betracht: - bei Alkylphenolen: Trimethylsilyliodid, Bortribromid,The following are particularly suitable as cleavage reagents: for alkylphenols: trimethylsilyl iodide, boron tribromide,
Bortrichlorid, Aluminiumtrichlorid, Lithiumchlorid oder Bromwasserstoff ; bei gegebenenfalls substituierten Benzylphenolen oder - thiophenolen: Bortrifluorid, Fluorwasserstoffsäure oder Wasserstoff/Katalysator, dabei bevorzugt Edelmetall -Katalysatoren wie Palladium oder Platin.Boron trichloride, aluminum trichloride, lithium chloride or hydrogen bromide; in the case of optionally substituted benzylphenols or thiophenols: boron trifluoride, hydrofluoric acid or hydrogen / catalyst, preferably noble metal catalysts such as palladium or platinum.
Das Lösungs -/Verdünnungsmittel ist bevorzugt so zu wählen, daß es gegenüber dem jeweiligen Abspaltungsreagenz inert ist. Bei Verwendung der Halogenide Trimethylsilyliodid, Bortribro- mid, Bortrichlorid oder Aluminiumtrichlorid sind halogenierte Lösungsmittel wie Dichlormethan, Chloroform, Tetrachlorkohlenstoff und Dichlorethan besonders bevorzugt. Bromwasserstoff wird bevorzugt in wäßriger Lösung angewandt, ganz besonders bevorzugt als ein 48 %ige Lösung; Lithiumchlorid wird bevorzugt in polaren Lösungsmitteln wie niederen Alkoholen, Dimethylsulfoxid und Dimethylformamid angewendet; hydrogeno- lytische Methoden werden bevorzugt in niederen Alkoholen oder Carbonsäuren durchgeführt, gegebenen alls unter Zusatz eines Wasserstoffüberträgers wie Cyclohexen und Cyclohexadien.The solvent / diluent should preferably be chosen so that it is inert to the particular cleaving reagent. When using the halides trimethylsilyl iodide, bortribromide, boron trichloride or aluminum trichloride, halogenated solvents such as dichloromethane, chloroform, carbon tetrachloride and dichloroethane are particularly preferred. Hydrogen bromide is preferably used in aqueous solution, very particularly preferably as a 48% solution; Lithium chloride is preferably used in polar solvents such as lower alcohols, dimethyl sulfoxide and dimethylformamide; Hydrogenolytic methods are preferably carried out in lower alcohols or carboxylic acids, all with the addition of a hydrogen transfer agent such as cyclohexene and cyclohexadiene.
Die Temperatur für die Abspaltungsreaktion liegt bevorzugt bei 0°C bis Siedetemperatur des jeweiligen Reaktionsgemisches .The temperature for the cleavage reaction is preferably from 0 ° C. to the boiling point of the respective reaction mixture.
Das Abspaltungsreagenz wird bevorzugt in etwa stöchiometri- sehen Mengen oder im Überschuß angewendet. Der Überschuß liegt besonders bevorzugt zwischen einem und zehn Moläquivalenten, bezogen auf die Menge an IX.The cleavage reagent is preferably used in approximately stoichiometric amounts or in excess. The excess is particularly preferably between one and ten molar equivalents, based on the amount of IX.
Die geschützten Nitroverbindungen IX sind schließlich auf an sich bekannte Weise durch Nitrierung von (geschützten) Phenolen, Thiophenolen oder Anilinen X erhältlich (vgl. z.B. Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag Stuttgart, Bd. 10/1, 1971, S. 479ff .) :The protected nitro compounds IX are finally obtainable in a manner known per se by nitrating (protected) phenols, thiophenols or anilines X (see, for example, Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag Stuttgart, Vol. 10/1, 1971, P. 479ff.):
-Schutz-Protection
Als Nitrierungsreagenzien kommen insbesondere Salpetersäure, im Gemisch mit Schwefelsäure oder Essigsäureanhydrid, oder Nitroniumsalze, speziell Nitroniumtetrafluoroborat, in Be- tracht. Das Gemisch, bestehend aus Salpetersäure und Schwefelsäure, kann aus beliebigen Mengenverhältnissen der beiden Mischungspartner bestehen; bevorzugt sind solche Mischungen, bei denen der Schwefelsäure-Anteil stark überwiegt oder als Lösungsmittel dient. Für die Mischung aus Salpetersäure und Essigsäureanhydrid gilt Analoges.In particular, nitrating acid, mixed with sulfuric acid or acetic anhydride, or nitronium salts, especially nitronium tetrafluoroborate, are used as nitrating reagents. dress. The mixture, consisting of nitric acid and sulfuric acid, can consist of any proportions of the two mixing partners; preference is given to mixtures in which the sulfuric acid content is predominant or is used as a solvent. The same applies to the mixture of nitric acid and acetic anhydride.
Nitroniumtetrafluoroborat wird bevorzugt in aprotisch, polaren Lösungsmitteln angewendet, z.B. in Acetonitril oder Nitromethan.Nitronium tetrafluoroborate is preferably used in aprotic, polar solvents, e.g. in acetonitrile or nitromethane.
Die Reaktionstemperatur liegt allgemein bei (-80) bis 80°C, insbesondere (-20)°C bis 30°C.The reaction temperature is generally from (-80) to 80 ° C, in particular (-20) ° C to 30 ° C.
Bei den Nitrierungen mit dem Reagenz Salpetersäure wird be- vorzugt mit einer etwa äquimolaren Menge oder besonders bevorzugt mit einem Überschuß an Nitrierungsreagenz gearbeitet. Der Überschuß kann ein Vielfaches der Menge an X betragen. Nitroniumtetrafluoroborat wird bevorzugt äquimolar zum Substrat oder im kleinen Überschuß zwischen 1.1 und 1.5 Moläqui- valenten eingesetzt.The nitrations with the nitric acid reagent are preferably carried out with an approximately equimolar amount or particularly preferably with an excess of nitrating reagent. The excess can be a multiple of the amount of X. Nitronium tetrafluoroborate is preferably used in equimolar amounts to the substrate or in a small excess between 1.1 and 1.5 molar equivalents.
Auf analoge Weise lassen sich auch die folgenden Zwischenstufen nitrieren:The following intermediate stages can also be nitrided in an analogous manner:
3 - (Benzazol-4 -yDpyrimidindion-Derivate der Formel I mit einem oder mehreren Chiralitätszentren fallen üblicherweise als3 - (Benzazol-4-yDpyrimidinedione derivatives of the formula I with one or more centers of chirality usually fall as
Enantiomeren- oder Diastereomerengemische an, die gewünschten- falls nach den hierfür üblichen Methoden, z.B. mittels Kristallisation oder Chromatographie an einem optisch aktiven Adsorbat, in die weitgehend reinen Isomeren getrennt werden können. Reine op- tisch aktive Isomere lassen sich vorteilhaft aus entsprechenden optisch aktiven Ausgangsmaterialien herstellen.Mixtures of enantiomers or diastereomers, which, if desired, according to the methods customary for this, e.g. by means of crystallization or chromatography on an optically active adsorbate, into which largely pure isomers can be separated. Pure optically active isomers can advantageously be prepared from corresponding optically active starting materials.
Diejenigen 3 - (Benzazol -4 -yDpyrimidindion-Derivate der Formel I, bei denen R1 Wasserstoff bedeutet, lassen sich auf an sich be- kannte Weise in ihre Salze überführen (siehe hierzu die Ausführungen unter Verfahren A) ) . Die Arylharnstoffe der Formel III sind neu. Ihre Herstellung kann nach an sich bekannten Methoden erfolgen, z.B. nach einem der folgenden Verfahren:Those 3 - (benzazole -4-yDpyrimidinedione derivatives of the formula I in which R 1 is hydrogen can be converted into their salts in a manner known per se (see the statements under process A)). The arylureas of the formula III are new. They can be produced by methods known per se, for example by one of the following processes:
Verfahren G)Procedure G)
Umsetzung eines ß-Ketocarbonsäureesters XIII mit einem Harnstoff XIV:Reaction of a β-ketocarboxylic acid ester XIII with a urea XIV:
XIII XIVXIII XIV
IIIIII
L2 steht für niedermolekulares Alkyl, vorzugsweise Cχ-C4- Alkyl , oder Phenyl .L 2 stands for low molecular weight alkyl, preferably Cχ-C 4 alkyl, or phenyl.
Vorzugsweise arbeitet man im wesentlichen wasserfrei in einem inerten Lösungs- oder Verdünnungsmittel, besonders bevorzugt in Gegenwart eines sauren oder basischen Katalysators.It is preferred to work essentially anhydrous in an inert solvent or diluent, particularly preferably in the presence of an acidic or basic catalyst.
Als Lösung- oder Verdünnungsmittel kommen insbesondere mit Wasser azeotrop mischbare organische Lösungsmittel, beispielsweise Aromate wie Benzol, Toluol und o-, m-, p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform, Tetrachlorkohlenstoff und Chlorbenzol, aliphatische und cyclische Ether wie 1, 2 -Dimethoxyethan, Tetrahydrofuran und Dioxan, oder Cyclohexan, aber auch Alkohole wie Methanol und Ethanol, in Betracht.Suitable solvents or diluents are, in particular, water solvents which are azeotropically miscible with water, for example aromatics such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, aliphatic and cyclic ethers such as 1, 2 -Dimethoxyethane, tetrahydrofuran and dioxane, or cyclohexane, but also alcohols such as methanol and ethanol, into consideration.
Als saure Katalysatoren eignen sich bevorzugt starke Mineral - säuren wie Schwefelsäure und Salzsäure, Phosphor enthaltende Säuren wie Orthophosphorsäure und Polyphosphorsäure, organische Säuren wie p-Toluolsulfonsäure sowie saure Kationenaustauscher wie "Amberlyst 15" (Firma Fluka) . Als basische Katalysatoren eignen sich z.B. Alkalimetall - hydride wie Natriumhydrid sowie besonders bevorzugt Alkali - metallalkoholate wie Natriummethanolat und -ethanolat.Suitable acidic catalysts are preferably strong mineral acids such as sulfuric acid and hydrochloric acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid, organic acids such as p-toluenesulfonic acid and acidic cation exchangers such as "Amberlyst 15" (Fluka). Suitable basic catalysts are, for example, alkali metal hydrides such as sodium hydride and particularly preferably alkali metal alcoholates such as sodium methoxide and ethanolate.
Zweckmäßig setzt man XIV und den ß-Ketocarbonsäureester XIII in etwa stöchiometrisehen Mengen ein oder man arbeitet mit einem geringen Überschuß der einen oder anderen Komponente, bis etwa 10 mol-%.Appropriately, XIV and the ß-ketocarboxylic acid ester XIII are used in approximately stoichiometric amounts or one works with a slight excess of one or the other component, up to about 10 mol%.
Normalerweise ist eine Katalysatormenge von 0,5 bis 2 mol-%, bezogen auf die Menge einer der Ausgangsverbindungen, ausreichend.Usually an amount of catalyst of 0.5 to 2 mol%, based on the amount of one of the starting compounds, is sufficient.
Im allgemeinen erfolgt die Reaktionsführung bei einer Temperatur von 60 bis 120°C, zur raschen Entfernung von entstehendem Wasser vorzugsweise bei der Siedetemperatur des Reaktionsgemisches.In general, the reaction is carried out at a temperature of 60 to 120 ° C., for the rapid removal of water formed, preferably at the boiling point of the reaction mixture.
Verfahren H) Reaktion eines Enolethers XV mit einem Harnstoff XVI:Process H) Reaction of an Enolether XV with a Urea XVI:
XV XVIXV XVI
III L2 und L3 stehen jeweils für niedermolekulares Alkyl, vorzugsweise Cχ-C4 -Alkyl, oder Phenyl.III L 2 and L 3 each represent low molecular weight alkyl, preferably Cχ-C 4 alkyl, or phenyl.
Die Reaktion wird vorzugsweise in einem inerten, mit Wasser mischbaren, organischen Lösungsmittel, z.B. einem aliphati- sehen oder cyclischen Ether wie 1, 2 -Dimethoxyethan, Tetrahydrofuran und Dioxan, oder einem niederen Alkohol, insbesondere Ethanol, durchgeführt, wobei die Reaktionstempera- tur normalerweise bei 50 bis 100°C, bevorzugt bei der Siedetemperatur des Reaktionsgemisches, liegt.The reaction is preferably carried out in an inert, water-miscible, organic solvent, for example an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or a lower alcohol, in particular ethanol, the reaction temperature ture is normally 50 to 100 ° C, preferably at the boiling point of the reaction mixture.
Die Reaktion kann jedoch auch in einem aromatischen Verdünnungsmittel wie Benzol, Toluol und o-, m-, p-Xylol durchgeführt werden, wobei in diesem Fall der Zusatz entweder eines sauren Katalysators wie Salzsäure und p-Toluolsulfon- säure oder einer Base, z.B. eines Alkalimetallalkoholates wie Natriummethanolat und Natriumethanolat, empfehlenswert ist. Auch bei dieser Verfahrensvariante liegt die Reaktions- temperatur normalerweise bei 50 bis 100°C, bevorzugt jedoch bei 60 bis 80°C.However, the reaction can also be carried out in an aromatic diluent such as benzene, toluene and o-, m-, p-xylene, in which case the addition of either an acidic catalyst such as hydrochloric acid and p-toluenesulfonic acid or a base, e.g. an alkali metal alcoholate such as sodium methoxide and sodium ethanolate is recommended. In this process variant too, the reaction temperature is normally 50 to 100 ° C., but preferably 60 to 80 ° C.
Bezüglich der Mengenverhältnisse gelten die Angaben für Methode G) .With regard to the quantitative ratios, the information for method G) applies.
Verfahren J>Procedure J>
Umsetzung eines Enaminoesters XVII mit einem Isocyanat XVIII;Reaction of an enamino ester XVII with an isocyanate XVIII;
XVII XVIII IIIXVII XVIII III
L2 steht für niedermolekulares Alkyl, vorzugsweise Cχ-C4 -Alkyl, oder Phenyl.L 2 stands for low molecular weight alkyl, preferably Cχ-C 4 alkyl, or phenyl.
Die Umsetzung erfolgt zweckmäßig in Gegenwart eines im wesentlichen wasserfreien aprotischen organischen Lösungs - oder Verdünnungsmittels, beispielsweise eines aliphatischen oder cyclischen Ethers wie Diethylether, 1, 2 -Dimethoxyethan, Tetrahydrofuran und Dioxan, eines aliphatischen oder aromatischen Kohlenwasserstoffs wie n-Hexan, Benzol, Toluol und o-, m- , p-Xylol, eines halogenierten, aliphatischen Kohlenwasserstoffs wie Methylenchlorid, Chloroform, Tetrachlorkohlen- stoff, 1, 2 -Dichlorethan und Chlorbenzol, eines aprotischen, polaren Lösungsmittels wie Dimethylformamid, Hexamethyl- phosphorsäuretriamid und Dimethylsulfoxid, oder eines Gemisches aus den genannten Solventien.The reaction is advantageously carried out in the presence of an essentially anhydrous aprotic organic solvent or diluent, for example an aliphatic or cyclic ether such as diethyl ether, 1, 2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene and o-, m-, p-xylene, a halogenated, aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide, or a mixture of the solvents mentioned.
Gewünschtenfalls kann auch in Gegenwart einer Metallhydridbase wie Natrium- und Kaliumhydrid oder einer organischen tertiären Base wie Triethylamin und Pyridin gearbeitet wer- den, wobei die organische Base gleichzeitig als Lösungsmittel dienen kann.If desired, work can also be carried out in the presence of a metal hydride base such as sodium and potassium hydride or an organic tertiary base such as triethylamine and pyridine. the, wherein the organic base can simultaneously serve as a solvent.
Zweckmäßig setzt man die Edukte in stöchiometrischen Mengen ein oder man arbeitet mit einem geringen Überschuß der einen oder anderen Komponente, bis etwa 10 mol-%. Arbeitet man ohne Lösungsmittel in Gegenwart einer organischen Base, so liegt diese in einem größeren Überschuß vor.The starting materials are expediently used in stoichiometric amounts or one works with a slight excess of one or the other component, up to about 10 mol%. If one works without solvent in the presence of an organic base, this is present in a large excess.
Die Reaktionstemperatur liegt vorzugsweise bei (-80) bis 50°C, insbesondere bei (-60) bis 30°C.The reaction temperature is preferably (-80) to 50 ° C, in particular (-60) to 30 ° C.
In einer besonders bevorzugten Ausführungsform wird der erhaltene Enaminester III mit überschüssiger Base direkt (d.h. "in situ") gemäß Verfahren D) in das entsprechende Wertprodukt I übergeführt.In a particularly preferred embodiment, the enamine ester III obtained is converted directly (i.e. "in situ") according to process D) into the corresponding product of value I using excess base.
Verfahren K>Method K>
Umsetzung eines Enaminoesters XVII mit einem Urethan XIX:Reaction of an enaminoester XVII with a urethane XIX:
XVII XIX IIIXVII XIX III
L2 und L4 stehen unabhängig voneinander für niedermolekulares Alkyl, vorzugsweise Cχ-C4-Alkyl, oder Phenyl.L 2 and L 4 independently of one another represent low molecular weight alkyl, preferably Cχ-C 4 alkyl, or phenyl.
Diese Reaktion erfolgt zweckmäßig in einem aprotischen, polaren Lösungs- oder Verdünnungsmittel wie Dimethylformamid, 2-Butanon, Dimethylsulfoxid und Acetonitril, und zwar vorteilhaft in Gegenwart einer Base, beispielsweise eines Alkalimetall- oder Erdalkalimetallalkoholates, insbesondere eines Natriumalkoholates wie Natriummethanolat, eines Alkali - metall- oder Erdalkalimetallcarbonates, insbesondere Natrium- carbonat, oder eines Alkalimetallhydrids wie Lithium- und Natriumhydrid.This reaction is advantageously carried out in an aprotic, polar solvent or diluent such as dimethylformamide, 2-butanone, dimethyl sulfoxide and acetonitrile, advantageously in the presence of a base, for example an alkali metal or alkaline earth metal alcoholate, in particular a sodium alcoholate such as sodium methoxide, an alkali metal or alkaline earth metal carbonates, in particular sodium carbonate, or an alkali metal hydride such as lithium and sodium hydride.
Normalerweise ist die 1- bis 2 -fache molare Menge an Base, bezogen auf die Menge an XVII oder XIX, ausreichend. Die Reaktionstemperatur liegt im allgemeinen bei 80 bis 180°C, vorzugsweise bei der Siedetemperatur des Reaktions - gemisches .Normally 1 to 2 times the molar amount of base, based on the amount of XVII or XIX, is sufficient. The reaction temperature is generally 80 to 180 ° C, preferably at the boiling point of the reaction mixture.
Bezüglich der Mengenverhältnisse der AusgangsVerbindungen gelten die Angaben für Methode G) .With regard to the quantitative ratios of the original connections, the information for method G) applies.
In einer besonders bevorzugten Ausführungsform verwendet man ein Natriumalkoholat als Base und destilliert den im Laufe der Reaktion entstehenden Alkohol kontinuierlich ab. Die auf diese Weise hergestellten Enaminester IV können ohne Isolierung aus der Reaktionsmischung gemäß Verfahren D) zu einem Salz der substituierten Benzthiazole I (mit R1 = H) cyclisiert werden.In a particularly preferred embodiment, a sodium alcoholate is used as the base and the alcohol formed in the course of the reaction is distilled off continuously. The enamine esters IV prepared in this way can be cyclized to a salt of the substituted benzothiazoles I (with R 1 = H) without isolation from the reaction mixture according to process D).
Die Urethane XIX sind ihrerseits z.B. aus Kohlensäurechloriden XX und Anilinen XXI herstellbar:For their part, the urethanes XIX are e.g. can be produced from carbonic acid chlorides XX and anilines XXI:
Um einen Überschuß an Anilin zu vermeiden muß in der Regel eine Hilfsbase wie Triethylamin, Pyridin oder die Alkalimetallcarbo- nate zum Abfangen des bei der Reaktion entstehenden Chlorwasserstoffs zugesetzt werden. Pyridin eignet sich besonders, da es gleichzeitig als Lösungsmittel benutzt werden kann.In order to avoid excess aniline, an auxiliary base such as triethylamine, pyridine or the alkali metal carbonates must generally be added to trap the hydrogen chloride formed in the reaction. Pyridine is particularly suitable because it can also be used as a solvent.
Neben Pyridin kommen als Lösungs -/Verdünnungsmittel insbesondere aromatische Kohlenwasserstoffe wie Benzol, Toluol und o-, m- , p- Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Dichlorethan, niedere Alkohole wie Methanol und Etha- nol, aliphatische oder cyclische Ether wie Dimethoxyethan, Tetra- hydrofuran und Dioxan, Carbonsäureester wie Essigsäureethylester, oder aprotisch polare Solventien wie Dimethylformamid und Di- methylsulfoxid in Betracht.In addition to pyridine, the solvents / diluents used are in particular aromatic hydrocarbons such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, lower alcohols such as methanol and ethanol, aliphatic or cyclic ethers such as dimethoxyethane , Tetrahydrofuran and dioxane, carboxylic acid esters such as ethyl acetate, or aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide.
Die Reaktionstemperatur liegt allgemein bei 0°C bis Rückflußtempe- ratur des jeweiligen Reaktionsgemisches. Zweckmäßig setzt man die Edukte entweder in ca. stöchiometrischen Mengen ein oder man wählt einen Überschuß an Kohlensäurechlorid von höchstens 10 Molprozenten.The reaction temperature is generally from 0 ° C. to the reflux temperature of the respective reaction mixture. The starting materials are expediently used either in approximately stoichiometric amounts or an excess of carbonic acid chloride of at most 10 mol percent is chosen.
Die Hilfsbase wird üblicherweise in etwa äquimolarer Menge - bezogen auf die Menge an XX oder XXI - verwendet, oder im Überschuß bis zur ca. 2fachen molaren Menge. Bei Verwendung von Pyridin als Hilfsbase empfiehlt sich ein noch größerer Überschuß, wobei dann ohne zusätzliches Lösungsmittel gearbeitet werden kann.The auxiliary base is usually used in an approximately equimolar amount, based on the amount of XX or XXI, or in excess up to about 2 times the molar amount. If pyridine is used as the auxiliary base, an even larger excess is recommended, in which case it is possible to work without additional solvent.
Verfahren L)Procedure L)
Reaktion eines Isocyanats XXII mit einem Anilinderivat XXI:Reaction of an isocyanate XXII with an aniline derivative XXI:
XXII XXI III (R1 = H)XXII XXI III (R 1 = H)
L2 steht für niedermolekulares Alkyl, vorzugsweise Cχ-C4 -Alkyl, oder Phenyl.L 2 stands for low molecular weight alkyl, preferably Cχ-C 4 alkyl, or phenyl.
Diese Umsetzung erfolgt zweckmäßig in einem im wesentlichen wasserfreien, aprotischen, organischen Lösungs- oder Verdünnungsmittel, beispielsweise in Gegenwart eines aliphatischen oder cyclischen Ethers wie Diethylether, 1, 2 -Dimethoxyethan, Tetrahydrofuran und Dioxan, eines aliphatischen oder aromatischen Kohlenwasserstoffs wie n-Hexan, Benzol, Toluol und o-, m- , p-Xylol, eines halogenierten, aliphatischen Kohlenwasserstoffs wie Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, 1, 2 -Dichlorethan und Chlorbenzol, eines aprotischen, polaren Lösungsmittels wie Dimethylformamid, Hexamethylphosphorsäuretriamid und Dimethylsulfoxid, oder eines Gemisches aus den genannten Solventien.This reaction is expediently carried out in an essentially anhydrous, aprotic, organic solvent or diluent, for example in the presence of an aliphatic or cyclic ether such as diethyl ether, 1, 2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene , Toluene and o-, m-, p-xylene, a halogenated, aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1, 2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide, or a mixture of the mentioned solvents.
Gewünschtenfalls kann in Gegenwart einer Metallhydridbase wie Natrium- und Kaliumhydrid, eines Alkalimetall- oder Erd- alkalimetallalkoholates wie Natriummethanσlat, -ethanolat und Kalium- tert. -butanolat, oder einer organischen Stickstoffbase wie Triethylamin und Pyridin gearbeitet werden, wobei die organische Base gleichzeitig als Lösungsmittel dienen kann. Zweckmäßig setzt man die Edukte in etwa stöchiometrischen Mengen ein oder man verwendet eine der Komponenten im Überschuß, bis etwa 20 mol-%. Arbeitet man ohne Lösungsmittel in Gegenwart einer organischen Base, so liegt diese vorteilhaft in einem noch größeren Überschuß vor.If desired, in the presence of a metal hydride base such as sodium and potassium hydride, an alkali metal or alkaline earth metal alcoholate such as sodium methoxide, ethanolate and potassium tert. -butanolate, or an organic nitrogen base such as triethylamine and pyridine, where the organic base can simultaneously serve as a solvent. The starting materials are expediently used in approximately stoichiometric amounts or one of the components is used in excess, up to approximately 20 mol%. If one works without solvent in the presence of an organic base, this is advantageously present in an even larger excess.
Die Reaktionstemperatur liegt im allgemeinen bei (-80) bis 150°C, vorzugsweise bei (-30)°C bis zur Siedetemperatur des jeweiligen Reaktionsgemisches.The reaction temperature is generally from (-80) to 150 ° C, preferably from (-30) ° C to the boiling point of the reaction mixture.
Die Arylanilide der Formel IV sind ebenfalls neu; auch sie können auf an sich bekannte Weise hergestellt werden, beispielsweise durch Umsetzung eines Amids XXIII mit einem Urethan XXIV gemäß Verfahren M) :The arylanilides of formula IV are also new; they too can be prepared in a manner known per se, for example by reacting an amide XXIII with a urethane XXIV according to process M):
XXIII XXIII
L2 steht für niedermolekulares Alkyl, vorzugsweise C1-C4-Alkyl, oder Phenyl.L 2 stands for low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
Die Umsetzung erfolgt vorteilhaft in einem weitgehend wasserfreien Lösungs -/Verdünnungsmittel bei Normaldruck, besonders bevorzugt in Gegenwart eines sauren Katalysators .The reaction is advantageously carried out in a largely anhydrous solvent / diluent at atmospheric pressure, particularly preferably in the presence of an acid catalyst.
Zur Herstellung von Enamincarboxylaten IV mit R1 = Amino empfiehlt es sich, Verbindungen XXIV mit geschützter Amino- gruppe (z.B. als Hydrazon) einzusetzen.To prepare enamine carboxylates IV with R 1 = amino, it is advisable to use compounds XXIV with a protected amino group (for example as a hydrazone).
Als Lösungs -/Verdünnungsmittel kommen insbesondere mit Wasser azeotrop mischbare organische Flüssigkeiten, beispielsweise Aromaten wie Benzol, Toluol und o-, m-, p-Xylol oder halogenierte Kohlenwasserstoffe wie Tetrachlorkohlenstoff und Chlorbenzol, in Betracht.Suitable solvents / diluents are, in particular, water which is azeotropically miscible with water, for example aromatics such as benzene, toluene and o-, m-, p-xylene or halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene.
Geeignete Katalysatoren sind insbesondere starke Mineral - säuren wie Schwefelsäure, organische Säuren wie p-Toluol - sulfonsäure, Phosphor enthaltende Säuren wie Orthophosphor- säure und Polyphosphorsäure oder saure Kationenaustauscher wie "Amberlyst 15" (Firma Fluka) .Suitable catalysts are, in particular, strong mineral acids such as sulfuric acid, organic acids such as p-toluene sulfonic acid, acids containing phosphorus such as orthophosphoric acid and polyphosphoric acid or acidic cation exchangers such as "Amberlyst 15" (from Fluka).
Im allgemeinen ist eine Reaktionstemperatur von etwa 70 bis 150°C ausreichend; zur raschen Entfernung des entstehenden Reaktionswassers arbeitet man jedoch zweckmäßigerweise bei der Siedetemperatur des jeweiligen Reaktionsgemisches.In general, a reaction temperature of about 70 to 150 ° C is sufficient; To rapidly remove the water of reaction formed, however, it is expedient to work at the boiling point of the respective reaction mixture.
XXIII und XXIV werden üblicherweise in etwa stöchiometrischen Mengen eingesetzt; vorzugsweise verwendet man XXIV im leichten Überschuß bis etwa 20 mol-%.XXIII and XXIV are usually used in approximately stoichiometric amounts; XXIV is preferably used in a slight excess of up to about 20 mol%.
Das Amid XXIII kann wie folgt hergestellt werden (Verfahren N) ) :The amide XXIII can be prepared as follows (process N)):
XXIII (R3 = H) XXV XXIXXIII (R 3 = H) XXV XXI
Die Umsetzung erfolgt vorzugsweise in einem wasserfreien inerten aprotischen Lösungsmittel, beispielsweise in einem halogenierten Kohlenwasserstoff wie Methylenchlorid, Chloroform, Tetrachlorkohlenstoff und Chlorbenzol, einem aromatischen Kohlenwasserstoff wie Benzol, Toluol und o-, m- , p- Xylol, oder einem aliphatischen oder cyclischen Ether wie Diethylether, Dibutylether, 1, 2 -Dimethoxyethan, Tetrahydrofuran und Dioxan.The reaction is preferably carried out in an anhydrous, inert aprotic solvent, for example in a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, an aromatic hydrocarbon such as benzene, toluene and o-, m-, p-xylene, or an aliphatic or cyclic ether such as Diethyl ether, dibutyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane.
Die Reaktionstemperatur liegt im allgemeinen bei etwa 70 bis 140°C, insbesondere bei 100 bis 120°C.The reaction temperature is generally about 70 to 140 ° C, especially 100 to 120 ° C.
XXV und XXI werden üblicherweise in etwa stöchiometrischen Mengen eingesetzt, oder man verwendet eine der Komponenten im Überschuß, bis etwa 10 mol-%. Die Isocyanate XVIII sind z.B. aus den Anilinderivaten XXI gemäß Verfahren 0) erhältlich:XXV and XXI are usually used in approximately stoichiometric amounts, or one of the components is used in excess, up to about 10 mol%. The isocyanates XVIII can be obtained, for example, from the aniline derivatives XXI according to process 0):
Das Verfahren kann in einem inerten, im wesentlichen wasserfreien Lösungs- oder Verdünnungsmittel oder ohne Lösungsmittel durchgeführt werden, wobei die Anilinderivate XXI bevorzugt mit Phosgen, einem "Phosgenäquivalent" wie Diphosgen, Triphosgen und Carbonyldiimidazol oder mit Chlorameisensäuretrichlormethylester umgesetzt werden.The process can be carried out in an inert, essentially anhydrous solvent or diluent or without solvent, the aniline derivatives XXI preferably being reacted with phosgene, a "phosgene equivalent" such as diphosgene, triphosgene and carbonyldiimidazole or with chloroformic acid trichloromethyl ester.
Als Lösungs- oder Verdünnungsmittel kommen insbesondere aprotische, organische Lösungsmittel, beispielsweise Dimethylformamid oder Aromaten wie Toluol und o-, m- , p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform, 1, 2 -Dichlorethan und Chlorbenzol, aliphatische oder cyclische Ether wie 1, 2 -Dimethoxyethan, Tetrahydrofuran und Dioxan, oder Ester wie Essigsäureethylester, sowie Gemische dieser Lösungsmittel, in Betracht.Suitable solvents or diluents are, in particular, aprotic, organic solvents, for example dimethylformamide or aromatics such as toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene, aliphatic or cyclic ethers such as 1 , 2-dimethoxyethane, tetrahydrofuran and dioxane, or esters such as ethyl acetate, and mixtures of these solvents.
Zweckmäßig setzt man die Edukte in etwa stöchiometrischen Mengen ein, oder eine der Komponenten im Überschuß, bis ca. 200 mol-%.The starting materials are expediently used in approximately stoichiometric amounts, or one of the components in excess, up to approximately 200 mol%.
Je nach eingesetztem Anilinderivat XXI kann der Zusatz einer Base wie Triethylamin vorteilhaft sein, beispielsweise in 0,5- bis 2-facher molarer Menge, bezogen auf die Menge an XXI.Depending on the aniline derivative XXI used, the addition of a base such as triethylamine may be advantageous, for example in 0.5 to 2 times the molar amount, based on the amount of XXI.
Die Reaktionstemperatur liegt allgemein bei (-20)°C bis zur Rückflußtemperatur des jeweiligen Lösungsmittels oder Reaktionsgemisches .The reaction temperature is generally from (-20) ° C to the reflux temperature of the particular solvent or reaction mixture.
Die Anilinderivate XXI sind ihrerseits auf an sich bekannte Weise (vgl. z.B. Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag Stuttgart, Bd. XI/1, 4. Auflage 1957, S. 431ff.) durch Reduktion der entsprechenden Nitroderivate XXVI erhältlich: The aniline derivatives XXI are, in turn, in a manner known per se (see, for example, Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag Stuttgart, Vol. XI / 1, 4th edition 1957, p. 431ff.) By reducing the corresponding nitroderivate XXVI available:
Bezüglich Reduktionsmittel, Lösungsmittel, Reaktionstemperaturen und Mengenverhältnissen sei auf die Angaben bei Verfahren F) verwiesen.With regard to reducing agents, solvents, reaction temperatures and quantitative ratios, reference is made to the information given in process F).
Auch die Verbindungen XXVIII und XXI können ein oder mehrere Chiralitätszentren enthalten und fallen dann üblicherweise als Enantiomeren- oder Diastereomerengemische an. Die Mischungen können gewünschtenfalls nach den hierfür üblichen Methoden, z.B. mittels Kristallisation oder Chromatographie an einem optisch aktiven Adsorbat, in die weitgehend reinen Isomeren getrennt werden. Reine optisch aktive Isomere lassen sich beispielsweise auch aus entsprechenden optisch aktiven Ausgangsmaterialien herstellen.Compounds XXVIII and XXI can also contain one or more centers of chirality and are then usually obtained as mixtures of enantiomers or diastereomers. If desired, the mixtures can be prepared by the usual methods, e.g. by means of crystallization or chromatography on an optically active adsorbate into which the largely pure isomers are separated. Pure optically active isomers can also be produced, for example, from corresponding optically active starting materials.
Sofern nicht anders angegeben werden alle vorstehend beschriebenen Verfahren zweckmäßigerweise bei Atmosphärendruck oder unter dem Eigendruck des jeweiligen Reaktionsgemisches vorgenommen. Im allgemeinen setzt man die Reaktionspartner in einem Molverhältnis von 0,95:1 bis 5:1 ein.Unless otherwise stated, all of the processes described above are expediently carried out at atmospheric pressure or under the autogenous pressure of the respective reaction mixture. In general, the reactants are used in a molar ratio of 0.95: 1 to 5: 1.
Die Aufarbeitung der Reaktionsgemische erfolgt in der Regel nach an sich bekannten Methoden, beispielsweise durch Verdünnen derThe reaction mixtures are generally worked up by methods known per se, for example by diluting the
Reaktionslösung mit Wasser und anschließender Isolierung desReaction solution with water and subsequent isolation of the
Produktes mittels Filtration, Kristallisation oder Lösungs - mittelextraktion, oder durch Entfernen des Lösungsmittels, Verteilen des Rückstandes in einem Gemisch aus Wasser und einem geeigneten organischenProduct by filtration, crystallization or solvent extraction, or by removing the solvent, distributing the residue in a mixture of water and a suitable organic
Lösungsmittel und Aufarbeiten der organischen Phase auf dasSolvent and working up the organic phase on the
Produkt hin.Product out.
Die Verbindungen I und deren landwirtschaftlich brauchbaren Salze eignen sich - sowohl als Isomerengemische als auch in Form der reinen Isomeren - als Herbizide. Die I enthaltenden herbiziden 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 Schad- gräser, ohne die Kulturpflanzen nennenswert zu schädigen. Dieser Effekt tritt vor allem bei niedrigen Aufwandmengen auf. In Abhängigkeit von der jeweiligen Applikationsmethode können die Verbindungen 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:The compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides. The herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly when high amounts are applied. In crops such as wheat, rice, maize, soybeans and cotton, they work against weeds and grass weeds without causing any significant damage to crops. This effect occurs especially at low application rates. Depending on the particular application method, the compounds I or herbicidal compositions comprising them can also be used in a further number of crop plants for eliminating undesired plants. The following crops are considered, for example:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus offici- nalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus , Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica) , Cucumis sati- vus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium) , Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Ly- copersicon lycopersicum, Malus spec, Manihot esculenta, Medicago sativa, Musa spec, Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharu officina- rum, 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. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica) v, Cucumis sati Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Lens humus lupulus, I Linum usitatissimum, Lycopersicon lycopersicum, Malus spec, Manihot esculenta, Medicago sativa, Musa spec, Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec, Pisus sativum, Prun avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharu officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (see vulgar), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.
Darüber hinaus können die Verbindungen I auch in Kulturen, die durch Züchtung einschließlich gentechnischer Methoden gegen die Wirkung von Herbiziden tolerant sind, verwandt werden.In addition, the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
Die Verbindungen I bzw. die sie enthaltenden herbizide Mittel können beispielsweise in Form von direkt versprühbaren wäßrigen Lösungen, Pulvern, Suspensionen, auch hochprozentigen wäßrigen, öligen oder sonstigen Suspensionen oder Dispersionen, Emulsionen, Öldispersionen, Pasten, Stäubemitteln, Streumitteln oder Granula- ten 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 I or the herbicidal compositions comprising them can be sprayed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents or granules , Atomizing, dusting, scattering or pouring can be used. The application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
Als inerte Hilfsstoffe kommen im Wesentlichen in Betracht: Mineralölfraktionen von mittlerem bis hohem Siedepunkt wie Kerosin und Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Paraffine, Tetrahydronaphthalin, alky- lierte Naphthaline und deren Derivate, alkylierte Benzole und deren Derivate, Alkohole wie Methanol, Ethanol, Propanol, Butanol und Cyclohexanol , Ketone wie Cyclohexanon, stark polare Lösungsmittel, z.B. Amine wie N-Methylpyrrolidon und Wasser.The following are essentially considered as inert auxiliaries: mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated Benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, for example amines such as N-methylpyrrolidone and water.
Wäßrige Anwendungsformen können aus Emulsionskonzentraten, Sus- Pensionen, Pasten, netzbaren Pulvern oder wasserdispergierbaren Granulaten durch Zusatz von 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.Aqueous use forms can be prepared from emulsion concentrates, Sus pensions, pastes, wettable powders or water-dispersible granules by adding water. 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, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
Als oberflächenaktive Stoffe kommen die Alkali-, Erdalkali-, Ammoniumsalze von aromatischen Sulfonsäuren, z.B. Lignin-, Phenol-, Naphthalin- und Dibutylnaphthalinsulfonsäure, sowie von Fettsäuren, Alkyl- und Alkylarylsulfonaten, Alkyl-, Laurylether- und Fettalkoholsulfaten, sowie Salze sulfatierter Hexa-, Hepta- und Octadecanolen sowie von Fettalkoholglykolether, Kondensationsprodukte von sulfoniertem Naphthalin und seiner Derivate mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphthalinsulfonsäuren mit Phenol und Formaldehyd, Polyoxyethylenoc- tylphenolether, ethoxyliertes Isooctyl-, Octyl- oder Nonylphenol, Alkylphenyl-, Tributylphenylpolyglykolether, Alkylarylpolyether- alkohole, Isotridecylalkohol, Fettalkoholethylenoxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylen- oder Polyoxypropylen- alkylether, Laurylalkoholpolyglykoletheracetat, Sorbitester, Lignin-Sulfitablaugen oder Methylcellulose in Betracht.The alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols as well as of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives Formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl polyethylenethoxyethylene, fatty alcohol, ethylene alcohol, fatty alcohol, ethylene alcohol alkyl ether, lauryl alcohol polyglycol ether acetate, sorbitol ester, lignin sulfite waste liquor or methyl cellulose.
Pulver-, Streu- und Stäubemittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden.Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
Granulate, z.B. Umhüllungs-, Imprägnierungs- und Homogengranulate können durch Bindung der Wirkstoffe an feste Trägerstoffe hergestellt werden. Feste Trägerstoffe sind Mineralerden wie Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Produkte wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver oder andere feste Trägerstoffe. Die Konzentrationen der Wirkstoffe I in den anwendungsfertigen Zubereitungen können in weiten Bereichen variiert werden. Im allgemeinen enthalten 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.Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral soils such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urea and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers. The concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range. In general, the formulations contain from about 0.001 to 98% by weight, preferably 0.01 to 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 the NMR spectrum).
Die folgenden Formulierungsbeispiele verdeutlichen die Her- Stellung solcher Zubereitungen:The following formulation examples illustrate the preparation of such preparations:
I. 20 Gewichtsteile der Verbindung Nr. 1 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 Gewichtsteilen Calciumsalz der Dodecylbenzolsulfonsäure und 5 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Rizinusöl besteht. Durch Ausgießen und feines Verteilen der Lösung in 100000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew. -% des Wirkstoffs enthält.I. 20 parts by weight of compound no. 1 are dissolved in a mixture consisting of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of Addition product of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
II. 20 Gewichtsteile der Verbindung Nr. 2 werden in einer Mischung gelöst, die aus 40 Gewichtsteilen Cyclohexanon, 30 Gewichtsteilen Isobutanol, 20 Gewichtsteilen des Anlagerungsproduktes von 7 Mol Ethylenoxid an 1 Mol Isooctyl- phenol und 10 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Rizinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100000 Gewichts - teilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew.-% des Wirkstoffs enthält.II. 20 parts by weight of compound no. 2 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 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide on 1 Mole of castor oil consists. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.
III. 20 Gewichtsteile des Wirkstoffs Nr. 4 werden in einer Mischung gelöst, die aus 25 Gewichtsteilen Cyclohexanon, 65 Gewichtsteilen einer Mineralölfraktion vom Siedepunkt 210 bis 280°C 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 enthält.III. 20 parts by weight of active ingredient no. 4 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.
IV. 20 Gewichtsteile des Wirkstoffs Nr. 6 werden mitIV. 20 parts by weight of active ingredient No. 6 are with
3 Gewichtsteilen des Natriumsalzes der Diisobutyl- naphthalin-α-sulfonsäure, 17 Gewichtsteilen des Natrium- salzes einer Ligninsulfonsäure aus einer Sulfit-Ablauge und 60 Gewichtsteilen pulverförmigem Kieselsäuregel gut vermischt und in einer Hammermühle vermählen. Durch feines Verteilen der Mischung in 20 000 Gewichtsteilen Wasser enthält man eine Spritzbrühe, die 0,1 Gew. -% des Wirkstoffs enthält.3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel are mixed well and ground in a hammer mill. By fine Distributing the mixture in 20,000 parts by weight of water contains a spray mixture which contains 0.1% by weight of the active ingredient.
V. 3 Gewichtsteile des Wirkstoffs Nr. 8 werden mitV. 3 parts by weight of active ingredient No. 8 are with
97 Gewichtsteilen feinteiligem Kaolin vermischt. Man erhält auf diese Weise ein Stäubemittel, das 3 Gew.-% des Wirkstoffs enthält.97 parts by weight of finely divided kaolin mixed. In this way, a dust is obtained which contains 3% by weight of the active ingredient.
VI. 20 Gewichtsteile des Wirkstoffs Nr. 12 werden mitVI. 20 parts by weight of active ingredient No. 12 are with
2 Gewichtsteilen Calciumsalz der Dodecylbenzolsulfonsäure, 8 Gewichtsteilen Fettalkohol-polyglykolether, 2 Gewichtsteilen Natriumsalz eines Phenol-Harnstoff-Formaldehyd- Kondensates und 68 Gewichtsteilen eines paraffinischen Mineralöls innig vermischt. Man erhält eine stabile ölige Dispersion.2 parts by weight of calcium 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 condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
VII. 1 Gewichtsteil der Verbindung Nr. 14 wird in einer Mischung gelöst, die aus 70 Gewichtsteilen Cyclohexanon, 20 Gewichtsteilen ethoxyliertem Isooctylphenol undVII. 1 part by weight of compound no. 14 is dissolved in a mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and
10 Gewichtsteilen ethoxyliertem Rizinusöl besteht. Anschließend kann mit Wasser auf die gewünschte Wirkstoff - konzentration verdünnt werden. Man erhält ein stabiles Emulsionskonzentrat.There are 10 parts by weight of ethoxylated castor oil. It can then be diluted with water to the desired active ingredient concentration. A stable emulsion concentrate is obtained.
VIII. 1 Gewichtsteil der Verbindung Nr. 19 wird in einer Mischung gelöst, die aus 80 Gewichtsteilen Cyclohexanon und 20 Gewichtsteilen Wettol® EM 31 (= nichtionischer Emulgator auf der Basis von ethoxyliertem Rizinusöl; BASF AG) be- steht. Danach kann mit Wasser auf die gewünschte Wirkstoff - konzentration verdünnt werden. Man erhält ein stabiles Emulsionskonzentrat ... VIII 1 part by weight of Compound No. 19 is dissolved in a mixture containing 31 (= nonionic emulsifier based on ethoxylated castor oil; BASF AG) 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol ® EM is sawn. Then it can be diluted with water to the desired active ingredient concentration. A stable emulsion concentrate is obtained.
Die Applikation der Wirkstoffe I bzw. der herbiziden Mittel kann im Vorauflauf- 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 active ingredients I or the herbicidal compositions can be applied pre- or post-emergence. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit as far as possible, while the active ingredients are applied to the leaves of undesirable plants growing below them or the uncovered floor area (post-directed, lay-by).
Die Aufwandmengen an Wirkstoff I betragen je nach Bekämpfungs- ziel, Jahreszeit, Zielpflanzen und WachstumsStadium 0,001 bis 3,0, vorzugsweise 0,01 bis 1,0 kg/ha aktive Substanz (a.S.). Zur Verbreiterung des WirkungsSpektrums und zur Erzielung synergistischer Effekte können die 3 - (Benzazol -4 -yl) pyrimidindion- Derivate I mit zahlreichen Vertretern anderer herbizider oder Wachstumsregulierender Wirkstoffgruppen gemischt und gemeinsam ausgebracht werden. Beispielsweise kommen als Mischungspartner 1,2, 4-Thiadiazole, 1, 3, 4-Thiadiazole, Amide, Aminophosphorsäure und deren Derivate, Aminotriazole, Anilide, Aryloxy-/Heteroaryl- oxyalkansäuren und deren Derivate, Benzoesäure und deren Derivate, Benzothiadiazinone, 2- (Hetaroyl/Aroyl) -1, 3 -cyclohexan- dione, Heteroaryl-Aryl-Ketone, Benzylisoxazolidinone, meta-CF3-Phenylderivate, Carbamate, Chinolincarbonsäure und deren Derivate, Chloracetanilide, Cyclohexan-1, 3-dionderivate, Diazine, Dichlorpropionsäure und deren Derivate, Dihydrobenzofurane, Dihydrofuran-3-one, Dinitroaniline, Dinitrophenole, Diphenyl- ether, Dipyridyle, Halogencarbonsäuren und deren Derivate, Harnstoffe, 3-Phenyluracile, Imidazole, Imidazolinone, N-Phenyl- 3 , 4, 5, 6-tetrahydrophthalimide, Oxadiazole, Oxirane, Phenole, Aryloxy- und Heteroaryloxyphenoxypropionsäureester, Phenylessig- säure und deren Derivate, 2-Phenylpropionsäure und deren Derivate, Pyrazole, Phenylpyrazole, Pyridazine, Pyridincarbon- säure und deren Derivate, Pyrimidylether, Sulfonamide, Sulfonyl - harnstoffe, Triazine, Triazinone, Triazolinone, Triazolcarbox- amide und Uracile in Betracht.The application rates of active ingredient I are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (as), depending on the control target, season, target plants and growth stage. To broaden the spectrum of activity and to achieve synergistic effects, the 3 - (benzazole -4 -yl) pyrimidinedione derivatives I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups and applied together. For example, 1,2, 4-thiadiazoles, 1, 3, 4-thiadiazoles, amides, aminophosphoric acid and their derivatives, aminotriazoles, anilides, aryloxy / heteroaryloxyalkanoic acids and their derivatives, benzoic acid and their derivatives, benzothiadiazinones, 2- (Hetaroyl / aroyl) -1, 3 -cyclohexanediones, heteroaryl-aryl-ketones, benzylisoxazolidinones, meta-CF 3 -phenyl derivatives, carbamates, quinolinecarboxylic acid and their derivatives, chloroacetanilides, cyclohexane-1, 3-dione derivatives, diazine acid and dichloropropane their derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3, 4, 5, 6-tetrahydrophthalide Oxadiazoles, oxiranes, phenols, aryloxy- and heteroaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid e and their derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.
Außerdem kann es von Nutzen sein, die Verbindungen I allein 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 Mineralsalzlösungen, welche zur Behebung von Ernährungs- und Spurenelementmängeln eingesetzt werden. Es können auch nichtphytotoxische Öle und Ölkonzentrate zugesetzt werden.It may also be useful to apply the compounds I alone or in combination with other herbicides, mixed with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.
Herstellungsbeispiele:Preparation Examples:
Beispiel 1example 1
3- [7-Chlor-5-fluor-l-methyl-lH-benzotriazol-4-yl] -l-methyl-6-tri- fluormethyl-2,4 (1H,3H) -pyrimidindion (Verb. 2)3- [7-chloro-5-fluoro-l-methyl-1H-benzotriazol-4-yl] -l-methyl-6-trifluoromethyl-2,4 (1H, 3H) -pyrimidinedione (Verb. 2)
Zu einer Mischung aus 0,25 g 3- [7-Chlor-5-fluor-1-methyl-lH-ben- zotriazol-4-yl] -6-trifluormethyl-2, 4 (IH, 3H) -pyrimidindion, 0, 12 g Kaliumcarbonat und 20 ml absolutem Dimethylformamid wurden bei 20°C 0,12 g Methyliodid getropft. Anschließend rührte man noch 18 Stunden, wonach das Reaktionsgemisch mit 50 ml Wasser versetzt wurde. Dann extrahierte man dreimal mit je 20 ml Ethylacetat. Die vereinigten organischen Phasen wurden mit Wasser gewaschen, über Natriumsulfat getrocknet und schließlich eingeengt. Die Reinigung des Rohprodukts erfolgte chromatographisch an Kieselgel (Eluent: Cyclohexan/Ethylacetat = 1:1). Ausbeute: 0,07 g; iH-N R (270 MHz, in CDC13) : δ tppm] = 7.45 (d, IH) , 6.45 (s,lH), 4.55 (s,3H) , 3.60 (s,3H) .To a mixture of 0.25 g of 3- [7-chloro-5-fluoro-1-methyl-1H-benzotriazol-4-yl] -6-trifluoromethyl-2,4 (IH, 3H) -pyrimidinedione, 0 , 12 g of potassium carbonate and 20 ml of absolute dimethylformamide were added dropwise at 20 ° C. 0.12 g of methyl iodide. The mixture was then stirred for a further 18 hours, after which 50 ml of water were added to the reaction mixture. Then extracted three times with 20 ml of ethyl acetate. The combined organic phases were washed with water, over Dried sodium sulfate and finally concentrated. The crude product was purified chromatographically on silica gel (eluent: cyclohexane / ethyl acetate = 1: 1). Yield: 0.07 g; iH-N R (270 MHz, in CDC1 3 ): δ tppm] = 7.45 (d, IH), 6.45 (s, lH), 4.55 (s, 3H), 3.60 (s, 3H).
Beispiel 2Example 2
3- [7-Chlor-5-fluor-l-methyl-lH-benzotriazol-4-yl] -6-trifluor- methyl-2, 4 (1H,3H) -pyrimidindion (Verb. 1)3- [7-chloro-5-fluoro-l-methyl-1H-benzotriazol-4-yl] -6-trifluoromethyl-2, 4 (1H, 3H) -pyrimidinedione (Verb. 1)
0,13 g Natriummethylat in 7 ml absolutem Dimethylformamid unter Stickstoffatmosphäre wurden bei 0°C innerhalb von 15 Minuten mit 0,43 g 3-Amino-4, 4, 4-trifluorbut-2-ensäureethylester in 3 ml Dimethylformamid versetzt. Man rührte zunächst eineinhalb Stunden bei 10°C, wonach innerhalb von 15 Minuten eine Lösung von 0,57 g 7-Chlor-5-fluor-l-methyl-lH-benzotriazol-4-yl-carbaminsäure- et ylester in 20 ml Dimethylformamid zu dem Reaktionsgemisch getropft wurde. Anschließend erwärmte man auf 20°C und rührte noch 5 Minuten. Dann wurde die Mischung auf 60°C erwärmt und mit 0,35 g 1, 8-Diazabicyclo [5.4.0] undec-7-en (DBU) versetzt. Abschließend rührte man noch 4 Stunden bei 120°C und 18 Stunden bei 20°C. Zur Aufarbeitung wurde die Mischung auf 100 ml einer 10 gew.-%igen wässrigen Kaliumcarbonat-Lösung gegossen. Das Wertprodukt extrahierte man mittels Diethylether (zweimal 50 ml) und, nachdem die verbliebene wäßrige Phase mit Salzsäure auf einen pH- Wert von 1 gebracht worden war, mittels Ethylacetat (dreimal 30 ml) .0.13 g of sodium methylate in 7 ml of absolute dimethylformamide under a nitrogen atmosphere were mixed with 0.43 g of 3-amino-4,4,4,4-trifluorobut-2-enoate in 3 ml of dimethylformamide at 0 ° C. within 15 minutes. The mixture was first stirred at 10 ° C. for one and a half hours, after which a solution of 0.57 g of 7-chloro-5-fluoro-1-methyl-1H-benzotriazol-4-yl-carbamic acid etyl ester in 20 ml of dimethylformamide was found within 15 minutes was added dropwise to the reaction mixture. The mixture was then warmed to 20 ° C. and stirred for a further 5 minutes. The mixture was then heated to 60 ° C. and 0.35 g of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) was added. Finally, stirring was continued for 4 hours at 120 ° C and 18 hours at 20 ° C. For working up, the mixture was poured onto 100 ml of a 10% by weight aqueous potassium carbonate solution. The product of value was extracted using diethyl ether (twice 50 ml) and, after the remaining aqueous phase had been brought to pH 1 with hydrochloric acid, using ethyl acetate (three times 30 ml).
Die vereinigten organischen Phasen wurden noch mit ca. 20 ml gesättigter wässriger Natriumchlorid-Lösung und 30 ml 10 gew.%iger wässriger Lithiumchlorid-Lösung gewaschen, dann über Natriumsulfat getrocknet und schließlich eingeengt. Ausbeute: 0,25 g; !H-NMR (250 MHz, in CDC13) : δ [ppm] = 10.25 (br,lH), 7.45 (d,lH), 6.30 (s,lH) , 4.60 (s,3H) .The combined organic phases were washed with about 20 ml of saturated aqueous sodium chloride solution and 30 ml of 10% by weight aqueous lithium chloride solution, then dried over sodium sulfate and finally concentrated. Yield: 0.25 g; ! H-NMR (250 MHz, in CDC1 3 ): δ [ppm] = 10.25 (br, lH), 7.45 (d, lH), 6.30 (s, lH), 4.60 (s, 3H).
Vorstufe 2.1Preliminary stage 2.1
2-Chlor-4-fluor-N-trifluoracetylanilin2-chloro-4-fluoro-N-trifluoroacetylaniline
Zu 100 g 2-Chlor-4-fluoranilin in 800 ml absolutem Diethylether wurden bei 0°C 144,3 g Trifluoressigsäureanhydrid in 150 ml Diethylether getropft. Nach erwärmen auf 20°C versetzte man die Mischung mit 500 ml Wasser. Die organische Phase wurde abgetrennt, dreimal mit Wasser gewaschen, dann über Natriumsulfat getrocknet und schließlich eingeengt. Ausbeute: 151,5 g; XH-NMR (270 MHz, in CDC13) : δ [ppm] = 8.35 (br,lH), 8.25 (dd,lH), 7.20 (dd,lH), 7.05 (dt,lH). Vorstufe 2 . 2144.3 g of trifluoroacetic anhydride in 150 ml of diethyl ether were added dropwise to 100 g of 2-chloro-4-fluoroaniline in 800 ml of absolute diethyl ether at 0 ° C. After heating to 20 ° C., the mixture was mixed with 500 ml of water. The organic phase was separated, washed three times with water, then dried over sodium sulfate and finally concentrated. Yield: 151.5 g; X H-NMR (270 MHz, in CDC1 3 ): δ [ppm] = 8.35 (br, lH), 8.25 (dd, lH), 7.20 (dd, lH), 7.05 (dt, lH). Preliminary stage 2. 2
3-Chlor-5-fluor-2-N-trifluoracetylamino-nitrobenzol3-chloro-5-fluoro-2-N-trifluoroacetylamino-nitrobenzene
Zu 75 g 2-Chlor-4-fluor-N-trifluoracetylanilin in 753 ml Essig- 5 säureanhydrid wurden bei (-5)°C langsam 375 ml 98 %ige Salpetersäure getropft. Danach rührte man eine Stunde bei (-5)°C, wonach die Mischung auf 20°C erwärmt wurde. Den Reaktionsverlauf verfolgte man dabei mittels Hochdruckflüssigkeitschromatographie an einer RpD-18-Säule (Eluent: Acetonitril/Wasser = 7:3). Sobald375 ml of 98% nitric acid were slowly added dropwise at (-5) ° C. to 75 g of 2-chloro-4-fluoro-N-trifluoroacetylaniline in 753 ml of acetic 5-anhydride. The mixture was then stirred at (-5) ° C for one hour, after which the mixture was heated to 20 ° C. The course of the reaction was followed by high pressure liquid chromatography on an RpD-18 column (eluent: acetonitrile / water = 7: 3). As soon as
10 kein Edukt mehr nachzuweisen war, goß man das Reaktionsgemisch auf eine eiskalte, gesättigte wässrige Natriumchlorid-Lösung. Anschließend wurde das feste Wertprodukt abgetrennt, mit Wasser gewaschen und mehrere Stunden lang im Trockenschrank unter reduziertem Druck bei 20°C getrocknet. Ausbeute: 62,3 g;10 no more educt could be detected, the reaction mixture was poured onto an ice-cold, saturated aqueous sodium chloride solution. The solid product of value was then separated off, washed with water and dried in a drying cabinet at 20 ° C. under reduced pressure for several hours. Yield: 62.3 g;
15 iH-NMR (270 MHz, in CDC13) : δ [ppm] = 8.50 (br,lH), 7.80 (dd,lH), 7.60 (dd,lH) .15 i H-NMR (270 MHz, in CDC1 3 ): δ [ppm] = 8.50 (br, lH), 7.80 (dd, lH), 7.60 (dd, lH).
Vorstufe 2.3Preliminary stage 2.3
3-Chlor-5-fluor-2- (N-methyl-N-trifluoracetylamino) -nitrobenzol3-chloro-5-fluoro-2- (N-methyl-N-trifluoroacetylamino) nitrobenzene
2020th
Zu einer Mischung aus 16,1 g 3-Chlor-5-fluor-2-N-trifluoracetylamino-nitrobenzol, 11,6 g Kaliumcarbonat und 100 ml absolutem Dimethylformamid wurden 12 , 0 g Methyliodid gegeben. Anschließend rührte man 18 Stunden bei 20°C, wonach die Reaktionsmischung mit12.0 g of methyl iodide were added to a mixture of 16.1 g of 3-chloro-5-fluoro-2-N-trifluoroacetylamino-nitrobenzene, 11.6 g of potassium carbonate and 100 ml of absolute dimethylformamide. The mixture was then stirred at 20 ° C. for 18 hours, after which the reaction mixture was also added
25 500 ml Wasser versetzt wurde. Dann extrahierte man dreimal mit je 100 ml Ethylacetat. Die vereinigten organischen Phasen wurden noch über Natriumsulfat getrocknet und schließlich eingeengt. Ausbeute: 16,3 g; iH-NMR (270 MHz, in CDC13) : δ [ppm] = 7.80 (m, IH) , 7.60 (m,lH),25 500 ml of water was added. Then extracted three times with 100 ml of ethyl acetate. The combined organic phases were dried over sodium sulfate and finally concentrated. Yield: 16.3 g; i H-NMR (270 MHz, in CDC1 3 ): δ [ppm] = 7.80 (m, IH), 7.60 (m, lH),
30 3.40 (s,3H) .30 3.40 (s, 3H).
Vorstufe 2.4Preliminary stage 2.4
3-Chlor-5-fluor-2-methylamino-nitrobenzol3-chloro-5-fluoro-2-methylamino-nitrobenzene
35 Zu einer Lösung von 16,3 g 3-Chlor-5-fluor-2- (N-methyl-N-tri- fluoracetylamino) -nitrobenzol in 173 ml Ethanol wurden 173 ml einer 1-normalen wässrigen Natriumhydroxid-Lösung gegeben. Anschließend rührte man 1 Stunde, wonach die Mischung mit 500 ml Wasser verdünnt wurde. Dann extrahierte man dreimal mit 80 ml 0 Ethylacetat. Die vereinigten organischen Phasen wurden noch mit Wasser gewaschen, über Natriumsulfat getrocknet und schließlich eingeengt. Ausbeute: 10,1 g; iH-NMR (270 MHz, in CDC13) : δ [ppm] = 7.70 (dd,lH), 7.35 (dd, IH) , 6.70-6.50 (br,lH), 3.10 (d,3H). 535 To a solution of 16.3 g of 3-chloro-5-fluoro-2- (N-methyl-N-trifluoroacetylamino) nitrobenzene in 173 ml of ethanol was added 173 ml of a 1 normal aqueous sodium hydroxide solution. The mixture was then stirred for 1 hour, after which the mixture was diluted with 500 ml of water. Then it was extracted three times with 80 ml of 0 ethyl acetate. The combined organic phases were washed with water, dried over sodium sulfate and finally concentrated. Yield: 10.1 g; i H-NMR (270 MHz, in CDC1 3 ): δ [ppm] = 7.70 (dd, lH), 7.35 (dd, IH), 6.70-6.50 (br, lH), 3.10 (d, 3H). 5
11 reversed phase, auf Kieselgel Vorstufe 2 . 5 11 reversed phase, on silica gel Preliminary stage 2. 5
2-Amino-6-chlor-4-fluor-N-methylanilin2-amino-6-chloro-4-fluoro-N-methylaniline
Zu 10,1 g 3-Chlor-5-fluor-2-methylamino-nitrobenzol in 207 ml ab- solutem Ethanol wurden 55,94 g Zinndichlorid-Dihydrat gegeben. Anschließend erwärmte man auf 50°C und tropfte 0,94 g Natrium- boranat in 55 ml absolutem Ethanol so zu, daß die Mischung nicht heißer als 60°C wurde. Zur Aufarbeitung goß man auf 1 1 Eiswasser, wonach das Gemisch mit Natronlauge auf einen pH-Wert von 14 ge- bracht wurde. Dann extrahierte man dreimal mit 100 ml tert. -Butyl -methylether. Die vereinigten organischen Phasen wurden noch mit Wasser gewaschen, über Natriumsulfat getrocknet und schließlich eingeengt. Ausbeute: 7,5 g; 3-H-NMR (270 MHz, in CDC13) : δ [ppm] = 6.50 (dd, IH) , 6.35 (dd,lH), 3.90-3.60 (br,3H), 2.65 (s,3H).55.94 g of tin dichloride dihydrate were added to 10.1 g of 3-chloro-5-fluoro-2-methylamino-nitrobenzene in 207 ml of absolute ethanol. The mixture was then heated to 50 ° C. and 0.94 g of sodium boranate in 55 ml of absolute ethanol were added dropwise in such a way that the mixture did not get hotter than 60 ° C. For working up, 1 liter of ice water was poured into the mixture, after which the mixture was brought to pH 14 with sodium hydroxide solution. Then extracted three times with 100 ml of tert. Butyl methyl ether. The combined organic phases were washed with water, dried over sodium sulfate and finally concentrated. Yield: 7.5 g; 3 H NMR (270 MHz, in CDC1 3 ): δ [ppm] = 6.50 (dd, IH), 6.35 (dd, lH), 3.90-3.60 (br, 3H), 2.65 (s, 3H).
Vorstufe 2.6Preliminary stage 2.6
7-Chlor-5-fluor-1-methylbenzotriazol7-chloro-5-fluoro-1-methylbenzotriazole
Zu 7,5 g 2-Amino-6-chlor-4-fluor-N-methylanilin in 117 mlTo 7.5 g of 2-amino-6-chloro-4-fluoro-N-methylaniline in 117 ml
10 %iger Salzsäure wurde bei 5°C eine Lösung von 3,25 g Natriumnitrit in 19 ml Wasser gegeben. Nach einer Stunde rühren bei 5°C verdünnte man die Reaktionsmischung mit 200 ml Wasser. Danach wurde der Feststoffanteil abgetrennt, mit 3x50 ml Wasser gewaschen und im Vakuumtrockenschrank bei 20°C getrocknet. Ausbeute: 7,2 g; iH-NMR (270 MHz, in CDC13) : δ [ppm] = 7.60 (dd,lH), 7.30 (dd,lH), 4.55 (s,3H) .A solution of 3.25 g of sodium nitrite in 19 ml of water was added to 10% hydrochloric acid at 5 ° C. After stirring for one hour at 5 ° C., the reaction mixture was diluted with 200 ml of water. The solids content was then separated off, washed with 3 × 50 ml of water and dried in a vacuum drying cabinet at 20 ° C. Yield: 7.2 g; i H-NMR (270 MHz, in CDC1 3 ): δ [ppm] = 7.60 (dd, lH), 7.30 (dd, lH), 4.55 (s, 3H).
Vorstufe 2.7Preliminary stage 2.7
7-Chlor-5-fluor-l-methyl-4-nitrobenzotriazol7-chloro-5-fluoro-l-methyl-4-nitrobenzotriazole
Zu 1,5 g 7-Chlor-5-fluor-1-methylbenzotriazol in 28 ml konzentrierter Schwefelsäure wurden bei (-20)°C langsam 0,65 ml 98 %ige Salpetersäure getropft. Dann rührte man eine Stunde bei 0°C, wonach die Mischung auf 20°C erwärmt wurde. Anschließend rührte man noch 18 Stunden und goß das Reaktionsgemisch dann auf 500 ml Eis- wasser. Der Feststoffanteil wurde abgetrennt, mit Wasser gewaschen und im Vakuumtrockenschrank bei 20°C getrocknet. Ausbeute: 1,66 g; iH-NMR ( 270 MHz , in CDC13 ) : δ [ppm] = 7 . 50 ( d, IH) , 4 . 65 ( s , 3H) . Vors tufe 2 . 80.65 ml of 98% nitric acid were slowly added dropwise at (-20) ° C. to 1.5 g of 7-chloro-5-fluoro-1-methylbenzotriazole in 28 ml of concentrated sulfuric acid. The mixture was then stirred at 0 ° C. for one hour, after which the mixture was heated to 20 ° C. The mixture was then stirred for a further 18 hours and the reaction mixture was then poured onto 500 ml of ice water. The solids content was separated off, washed with water and dried at 20 ° C. in a vacuum drying cabinet. Yield: 1.66 g; i H-NMR (270 MHz, in CDC1 3 ): δ [ppm] = 7. 50 (d, IH), 4. 65 (s, 3H). Step 2. 8th
4-Amino-7-chlor-5-fluor-1-methylbenzotriazol4-amino-7-chloro-5-fluoro-1-methylbenzotriazole
1,66 g 7-Chlor-5-fluor-l-methyl-4-nitrobenzotriazol wurden analog zu Vorstufe 2.5 mit Zinndichlorid/Natriumboranat reduziert. Ausbeute: 1,27 g; iH-NMR (250 MHz, in (CD3)2SO): δ [ppm] = 7.45 (d, IH) , 6.25 (br.,2H), 4.45 (s,3H), 4.30 (q,2H), 1.35 (t,3H).1.66 g of 7-chloro-5-fluoro-l-methyl-4-nitrobenzotriazole were reduced analogously to precursor 2.5 with tin dichloride / sodium boranate. Yield: 1.27 g; iH-NMR (250 MHz, in (CD 3 ) 2 SO): δ [ppm] = 7.45 (d, IH), 6.25 (br., 2H), 4.45 (s, 3H), 4.30 (q, 2H), 1.35 (t, 3H).
Vorstufe 2.9Preliminary stage 2.9
7-Chlor-5-fluor-l-methyl-lH-benzotriazol-4-yl-carbaminsäure- ethylester7-chloro-5-fluoro-l-methyl-1H-benzotriazol-4-yl-carbamic acid ethyl ester
Zu 13 ml absolutem Pyridin wurden bei 0°C 2,28 g Chlorameisen- säureethylester langsam zugetropft, wonach man für 15 Minuten bei dieser Temperatur rührte. Dann wurden bei 0°C 1,27 g 4-Arrino-7-chlor-5-fluor-1-methylbenzotriazol in 20 ml Pyridin zugetropft. Anschließend rührte man zunächst weitere 30 Minuten bei 0°C, erwärmte dann auf 20°C und rührte nochmals 18 Stunden. Schließlich wurde die Reaktionsmischung auf 100 ml 10 %ige Salzsäure gegossen. Danach extrahierte man dreimal mit 50 ml tert.- Butyl-methylether. Die vereinigten organischen Phasen wurden noch mit 100 ml Wasser gewaschen und dann eingeengt.2.28 g of ethyl chloroformate were slowly added dropwise to 13 ml of absolute pyridine at 0 ° C., and the mixture was then stirred at this temperature for 15 minutes. Then 1.27 g of 4-arrino-7-chloro-5-fluoro-1-methylbenzotriazole in 20 ml of pyridine were added dropwise at 0.degree. The mixture was then stirred at 0 ° C. for a further 30 minutes, then warmed to 20 ° C. and stirred again for 18 hours. Finally the reaction mixture was poured onto 100 ml of 10% hydrochloric acid. The mixture was then extracted three times with 50 ml of tert-butyl methyl ether. The combined organic phases were washed with 100 ml of water and then concentrated.
Den Rückstand versetzte man mit 50 ml Diethylether. Der ungelöste Anteil wurde abgetrennt und mit 3x30 ml Diethylether gewaschen. Die vereinigten Etherphasen engte man ein. Ausbeute: 0,37 g; iH-NMR (250 MHz, in CDC13) : δ [ppm] = 7.35 (d,lH), 6.90 (br.,lH), 4.55 (s,3H) .The residue was mixed with 50 ml of diethyl ether. The undissolved portion was separated and washed with 3x30 ml diethyl ether. The combined ether phases were concentrated. Yield: 0.37 g; i H-NMR (250 MHz, in CDC1 3 ): δ [ppm] = 7.35 (d, lH), 6.90 (br., lH), 4.55 (s, 3H).
Beispiel 3Example 3
3- [7-Chlor-5-fluor-l-methyl-2-trifluormethyl-lH-benzimid- azol-4-yl] -l-methyl-6-trifluormethyl-2, 4 (IH, 3H) -pyrimidindion (Verb. 1.5)3- [7-chloro-5-fluoro-l-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl] -l-methyl-6-trifluoromethyl-2, 4 (IH, 3H) -pyrimidinedione (Verb 1.5)
2,46 g 3- [7-Chlor-5-fluor-l-methyl-2-trifluormethyl-lH-benzimid- azol-4-yl] -6-trifluormethyl-2, 4 (IH, 3H) -pyrimidindion wurden analog zu Beispiel 1 mit Methyliodid alkyliert. Die Reinigung des Rohproduktes erfolgte chromatographisch an Kieselgel (Eluent: Cyclohexan/Ethylacetat = 2:1). Ausbeute: 1,4 g; iH-NMR (250 MHz, in CDC13) : δ [ppm] = 7.35 (d,lH), 6.40 (s,lH), 4.30 (s,3H) , 3.55 (s,3H) .2.46 g of 3- [7-chloro-5-fluoro-l-methyl-2-trifluoromethyl-1H-benzimide-azol-4-yl] -6-trifluoromethyl-2, 4 (IH, 3H) -pyrimidinedione were analogous to Example 1 alkylated with methyl iodide. The crude product was purified by chromatography on silica gel (eluent: cyclohexane / ethyl acetate = 2: 1). Yield: 1.4 g; i H-NMR (250 MHz, in CDC1 3 ): δ [ppm] = 7.35 (d, 1H), 6.40 (s, 1H), 4.30 (s, 3H), 3.55 (s, 3H).
Beispiel 4Example 4
3- [7-Chlor-5-fluor-l-methyl-2-trifluormethyl-lH-benzimid- azol-4-yl] -l-amino-6-trifluormethyl-2, 4 (IH, 3H) -pyrimidindion (Verb. 6) Zu einer Mischung aus 0,5 g 3- [7-Chlor-5-fluor-l-methyl-2-tri- fluormethyl-lH-benzimidazol-4-yl] -6-trifluormethyl-2, 4 (1H,3H) - -pyrimidindion, 2,35 g Kaliumcarbonat und 5 ml Ethylacetat wurden 0,25 g 2, 4-Dinitro-O-aminophenol gegeben. Nach 18 Stunden rühren bei 20°C verdünnte man mit 50 ml Ethylacetat. Die erhaltene Mischung wurde noch mit 3x30 ml Wasser gewaschen, über Natriumsulfat getrocknet und schließlich eingeengt. Die Reinigung des Rohproduktes erfolgte mittels einer Mitteldruckflüssigkeitschro- matographie (MPLC; Eluent: Cyclohexan/Ethylacetat = 2:1). Ausbeute: 0,4 g; iH-NMR (250 MHz, in CDC13) : δ [ppm] = 7.35 (d,lH), 6.30 (s,lH), 4.65 (s,2H) , 4.25 (s,3H) .3- [7-chloro-5-fluoro-l-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl] -l-amino-6-trifluoromethyl-2, 4 (IH, 3H) -pyrimidinedione (Verb 6) To a mixture of 0.5 g of 3- [7-chloro-5-fluoro-l-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl] -6-trifluoromethyl-2, 4 (1H, 3H) - Pyrimidinedione, 2.35 g of potassium carbonate and 5 ml of ethyl acetate were added to 0.25 g of 2,4-dinitro-O-aminophenol. After stirring for 18 hours at 20 ° C., the mixture was diluted with 50 ml of ethyl acetate. The mixture obtained was washed with 3 × 30 ml of water, dried over sodium sulfate and finally concentrated. The crude product was purified by means of medium pressure liquid chromatography (MPLC; eluent: cyclohexane / ethyl acetate = 2: 1). Yield: 0.4 g; i H-NMR (250 MHz, in CDC1 3 ): δ [ppm] = 7.35 (d, 1H), 6.30 (s, 1H), 4.65 (s, 2H), 4.25 (s, 3H).
Beispiel 5 3- [7-Chlor-5-fluor-l-methyl-2-trifluormethyl-lH-benzimid- azol-4-yl] -6-trifluormethyl-2, 4 (1H,3H) -pyrimidindion (Verb. 4)Example 5 3- [7-chloro-5-fluoro-l-methyl-2-trifluoromethyl-1H-benzimidazol-4-yl] -6-trifluoromethyl-2, 4 (1H, 3H) -pyrimidinedione (comp. 4 )
Zu 0,82 g Natriumhydrid in 50 ml absolutem Dimethylformamid wurden bei 0 bis 5°C 4,31 g 3-Amino-4, 4, 4-trifluorbut-2-ensäure- ethylester in 20 ml Dimethylformamid getropft. Dann rührte man eine Stunde bei gleicher Temperatur, wonach die Mischung bei (-30) °C mit 7-Chlor-5-fluor-4-isocyanato-l-methyl-2-trifluor- methylbenzimidazol (aus Vorstufe 5.4) in 40 ml Dimethylformamid versetzt wurde. Anschließend rührte man noch eine Stunde bei (-30) °C und eine weitere Stunde bei 20°C.4.31 g of 3-amino-4,4,4,4-trifluorobut-2-enoic acid ethyl ester in 20 ml of dimethylformamide were added dropwise at 0.8 to 5 ° C. to 0.82 g of sodium hydride in 50 ml of absolute dimethylformamide. Then the mixture was stirred for one hour at the same temperature, after which the mixture at (-30) ° C. with 7-chloro-5-fluoro-4-isocyanato-l-methyl-2-trifluoromethylbenzimidazole (from precursor 5.4) in 40 ml of dimethylformamide was transferred. The mixture was then stirred for a further hour at (-30) ° C. and for a further hour at 20 ° C.
Zur Aufarbeitung wurde das Reaktionsgemisch vorsichtig auf 200 ml Eiswasser gegossen. Durch ansäuern mit 10 %iger Salzsäure erhielt man einen Feststoff, der abfiltriert, mit Wasser gewaschen und bei 20°C im Vakuumtrockenschrank getrocknet wurde. Nach Reinigung mittels Flash-Chromatographie (Eluens: Cyclohexan/Ethylacetat = 2:1) erhielt man 5,08 g Wertprodukt.For working up, the reaction mixture was carefully poured onto 200 ml of ice water. Acidification with 10% hydrochloric acid gave a solid which was filtered off, washed with water and dried at 20 ° C. in a vacuum drying cabinet. After purification by means of flash chromatography (eluent: cyclohexane / ethyl acetate = 2: 1), 5.08 g of valuable product were obtained.
Nach Abtrennen des Feststoffanteils noch im Filtrat verbliebenes Wertprodukt (2,46 g) wurde durch dreimalige Extraktion mit 200 ml tert. -Butyl-methylether, waschen der vereinigten Etherphasen, trocknen über Natriumsulfat und einengen isoliert. Gesamtausbeute: 7,54 g;After the solids had been separated off, the product of value still remaining in the filtrate (2.46 g) was tert-extracted three times with 200 ml. -Butyl methyl ether, wash the combined ether phases, dry over sodium sulfate and concentrate isolated. Overall yield: 7.54 g;
XH-NMR (250 MHz, in CDC13) : δ [ppm] = 7.40 (d,lH), 6.30 (s,lH), 4.30 (s,3H) . X H-NMR (250 MHz, in CDC1 3 ): δ [ppm] = 7.40 (d, 1H), 6.30 (s, 1H), 4.30 (s, 3H).
Vorstufe 5.1Preliminary stage 5.1
7-Chlor-5-fluor-l-methyl-2-trifluormethylbenzimidazol7-chloro-5-fluoro-l-methyl-2-trifluoromethylbenzimidazole
15, 5 g 3-Chlor-5-fluor-2- (N-methyl-N-trifluoracetylamino) -nitrobenzol (aus Vorstufe 2.3) wurden analog zu Vorstufe 2.5 mit Zinn- dichlorid/Natriumboranat ohne Zwischenisolierung zur entsprechenden Aminoverbindung reduziert, die dann unter Wasserabspaltung spontan zum Wertprodukt cyclisierte. Ausbeute: 9,32 g; iH-NMR (250 MHz, in CDC13) : δ [ppm] = 7.45 (d,lH), 7.20 (d,lH), 4.25 (s,3H) .15.5 g of 3-chloro-5-fluoro-2- (N-methyl-N-trifluoroacetylamino) nitrobenzene (from precursor 2.3) were reduced analogously to precursor 2.5 with tin dichloride / sodium boranate without intermediate isolation to give the corresponding amino compound, which then spontaneously cyclized to the product of value with elimination of water. Yield: 9.32 g; iH-NMR (250 MHz, in CDC1 3 ): δ [ppm] = 7.45 (d, lH), 7.20 (d, lH), 4.25 (s, 3H).
Vorstufe 5.2 7-Chlor-5-fluor-1-methyl-4-nitro-2-trifluormethylbenzimidazolPrecursor 5.2 7-chloro-5-fluoro-1-methyl-4-nitro-2-trifluoromethylbenzimidazole
Zu 9,65 g 7-Chlor-5-fluor-l-methyl-2-trifluormethylbenzimidazol in 96,5 ml Essigsäureanhydrid wurden bei 0°C langsam 46,3 mlTo 9.65 g of 7-chloro-5-fluoro-l-methyl-2-trifluoromethylbenzimidazole in 96.5 ml of acetic anhydride was slowly added to 46.3 ml at 0 ° C.
98 %ige Salpetersäure getropft. Nach einer Stunde Rühren bei 0°C erwärmte man das Gemisch vorsichtig auf 20°C. (Wenn dabei exotherme Reaktion einsetzte, wurde die Temperatur mittels Eisbad unter 25°C gehalten.) Anschließend rührte man zunächst noch zwei Stunden bei 20°C und goß die Reaktionsmischung dann in eiskalte, gesättigte wässrige Kochsalz-Lösung. Der entstandene Feststoff - anteil wurde abgetrennt, mit Wasser gewaschen und bei 20°C im Vakuumtrockenschrank getrocknet. Ausbeute: 8,5 g; !H-NMR (400 MHz, in CDC13) : 5 [ppm] = 7.40 (d,lH), 4.35 (s,3H).98% nitric acid dropped. After stirring for 1 hour at 0 ° C, the mixture was carefully warmed to 20 ° C. (If an exothermic reaction started, the temperature was kept below 25 ° C. by means of an ice bath.) Subsequently, the mixture was initially stirred for a further two hours at 20 ° C. and the reaction mixture was then poured into ice-cold, saturated aqueous sodium chloride solution. The resulting solid fraction was separated off, washed with water and dried at 20 ° C. in a vacuum drying cabinet. Yield: 8.5 g; ! H NMR (400 MHz, in CDC1 3 ): 5 [ppm] = 7.40 (d, 1H), 4.35 (s, 3H).
Vorstufe 5.3 4-Amino-7-chlor-5-fluor-1-methyl-2-trifluormethylbenzimidazolPrecursor 5.3 4-amino-7-chloro-5-fluoro-1-methyl-2-trifluoromethylbenzimidazole
8,71 g 7-Chlor-5-fluor-l-methyl-4-nitro-2-trifluormethylbenzimidazol wurden analog Vorstufe 2.5 mittels Zinndichlorid/Natrium- boranat reduziert. Ausbeute: 6,3 g; !H-NMR (270 MHz, in CDC13) : δ [ppm] = 7.05 (d,lH), 4.45 (br,2H), 4.20 (s,3H) .8.71 g of 7-chloro-5-fluoro-l-methyl-4-nitro-2-trifluoromethylbenzimidazole were reduced analogously to precursor 2.5 using tin dichloride / sodium boranate. Yield: 6.3 g; ! H-NMR (270 MHz, in CDC1 3 ): δ [ppm] = 7.05 (d, 1H), 4.45 (br, 2H), 4.20 (s, 3H).
Vorstufe 5.4Preliminary stage 5.4
7-Chlor-5-fluor-4-isocyanato-l-methyl-2-trifluormethylbenzimid- azol7-chloro-5-fluoro-4-isocyanato-l-methyl-2-trifluoromethylbenzimide-azole
Zu 6,3 g 4-Amino-7-chlor-5-fluor-l-methyl-2-trifluormethylbenzimidazol in 100 ml absolutem Toluol wurden 23,32 g Diphosgen gegeben. Anschließend erhitzte man 6 Stunden auf Rückfluß - temperatur. Nach weiteren 18 Stunden rühren bei 20°C wurde die Reaktionsmischung eingeengt. Das erhaltene Rohprodukt wurde ohne Reinigung direkt zum Endprodukt 1.4 umgesetzt.23.32 g of diphosgene were added to 6.3 g of 4-amino-7-chloro-5-fluoro-l-methyl-2-trifluoromethylbenzimidazole in 100 ml of absolute toluene. The mixture was then heated to the reflux temperature for 6 hours. After stirring for a further 18 hours at 20 ° C., the reaction mixture was concentrated. The crude product obtained was converted directly to the end product 1.4 without purification.
Beispiel 6 3- [7-Chlor-l,2-dimethyl-5-fluor-lH-benzimidazol-4-yl] -1- methyl-6-trifluormethyl-2, 4 (IH, 3H) -pyrimidindion (Verb. 8)Example 6 3- [7-chloro-1,2-dimethyl-5-fluoro-1H-benzimidazol-4-yl] -1-methyl-6-trifluoromethyl-2,4 (IH, 3H) -pyrimidinedione (comp. 8 )
0,33 g 3- [7-Chlor-l,2-dimethyl-5-fluor-lH-benzimidazol-4-yl]- 6-trifluormethyl-2, 4 (IH, 3H) -pyrimidindion wurden analog Beispiel 1 mit Methyliodid alkyliert. Ausbeute: 0,04 g; iH-NMR (250 MHz, in CDC13) : δ [ppm] = 7.10 (d, IH) , 6.40 (s,lH), 4.00 (s,3H), 3.55 (s,3H), 2.55 (s,3H).0.33 g of 3- [7-chloro-l, 2-dimethyl-5-fluoro-1H-benzimidazol-4-yl] - 6-trifluoromethyl-2, 4 (IH, 3H) -pyrimidinedione were analogous to Example 1 with methyl iodide alkylated. Yield: 0.04 g; iH-NMR (250 MHz, in CDC1 3 ): δ [ppm] = 7.10 (d, IH), 6.40 (s, lH), 4.00 (s, 3H), 3.55 (s, 3H), 2.55 (s, 3H) ).
Beispiel 7 5 3- [7-Chlor-l,2-dimethyl-5-fluor-lH-benzimidazol-4-yl] -6-trifluor- methyl-2 , 4 ( IH, 3H) -pyrimidindion (Verb . 7 )Example 7 5 3- [7-chloro-l, 2-dimethyl-5-fluoro-1H-benzimidazol-4-yl] -6-trifluoromethyl-2, 4 (IH, 3H) -pyrimidinedione (comp. 7)
Das 7-Chlor-l, 2-dimethyl-5-fluor-4-isocyanatobenzimidazol ausThe 7-chloro-l, 2-dimethyl-5-fluoro-4-isocyanatobenzimidazole from
Vorstufe 7.4 wurde analog Beispiel 5 mit 3-Amino-4, 4, 4-trifluor- 10 but-2-ensäureethylester umgesetzt. Die Reinigung des Rohproduktes erfolgte mittels Mitteldruckflüssigkeitschromatographie (Eluens:Precursor 7.4 was reacted analogously to Example 5 with 3-amino-4,4,4,4-trifluoro-10-but-2-enoic acid ethyl ester. The crude product was purified by means of medium pressure liquid chromatography (eluent:
Ethylacetat/Methanol = 15:1). Ausbeute: 0,7 g;Ethyl acetate / methanol = 15: 1). Yield: 0.7 g;
^-H-NMR (270 MHz, in CDC13) : δ [ppm] = 7.15 (d, IH) , 6.20 (s,lH),^ H NMR (270 MHz, in CDC1 3 ): δ [ppm] = 7.15 (d, IH), 6.20 (s, lH),
4.05 (s,3H) , 2.55 (s,3H) . 154.05 (s, 3H), 2.55 (s, 3H). 15
Vorstufe 7.1Preliminary stage 7.1
7-Chlor-l, 2-dimethyl-5-fluorbenzimidazol7-chloro-1,2-dimethyl-5-fluorobenzimidazole
Zu 6,96 g 2-Amino-6-chlor-4-fluor-N-methylanilin (aus Vorstufe 20 2.5) in 4,1 g Essigsäureanhydrid wurden 100 ml 10 %ige Salzsäure gegeben. Anschließend erhitzte man 4 Stunden auf Rückfluß - temperatur. Nach dem Abkühlen wurde die Mischung in Eiswasser aufgenommen. Dann neutralisierte man vorsichtig mit einer wässri- gen Natriumcarbonat-Lösung. Das entstandene feste Rohprodukt 25 wurde abgetrennt, mit Wasser gewaschen und bei 20°C im Vakuumtrockenschrank getrocknet. Ausbeute: 7,92 g; iH-NMR (270 MHz, in CDC13) : δ [ppm] = 7.25 (dd, IH) , 6.95 (dd,lH), 4.00 (s,3H) , 2.55 (s,3H) .100 ml of 10% hydrochloric acid were added to 6.96 g of 2-amino-6-chloro-4-fluoro-N-methylaniline (from precursor 20 2.5) in 4.1 g of acetic anhydride. The mixture was then heated to reflux temperature for 4 hours. After cooling, the mixture was taken up in ice water. Then it was carefully neutralized with an aqueous sodium carbonate solution. The resulting solid crude product 25 was separated off, washed with water and dried at 20 ° C. in a vacuum drying cabinet. Yield: 7.92 g; i H-NMR (270 MHz, in CDC1 3 ): δ [ppm] = 7.25 (dd, IH), 6.95 (dd, lH), 4.00 (s, 3H), 2.55 (s, 3H).
30 Vorstufe 7.230 Preliminary stage 7.2
7-Chlor-l , 2-dimethyl-5-fluor-4-nitrobenzimidazol7-chloro-l, 2-dimethyl-5-fluoro-4-nitrobenzimidazole
Zu 7,92 g 7-Chlor-l,2-dimethyl-5-fluorbenzimidazol in 139 ml konzentrierter Schwefelsäure wurden bei (-5) bis maximal 0°C 98 %ige98.9% of 7.92 g of 7-chloro-1,2-dimethyl-5-fluorobenzimidazole in 139 ml of concentrated sulfuric acid were obtained at (-5) to a maximum of 0 ° C
35 Salpetersäure getropft, wobei man den Reaktionsverlauf mittels Hochdruckflüssigkeitschromatographie (HPLC) auf einer RP-18-Säule (Eluens: Acetonitril/Wasser = 1:1) kontrollierte. Sobald kein Edukt mehr nachzuweisen war, wurde das Reaktionsgemisch auf Eis- wasser gegossen, wonach man den pH-Wert mittels Natronlauge auf35 nitric acid was added dropwise, the course of the reaction being checked by means of high pressure liquid chromatography (HPLC) on an RP-18 column (eluent: acetonitrile / water = 1: 1). As soon as there was no longer any starting material to be detected, the reaction mixture was poured onto ice water, after which the pH was raised using sodium hydroxide solution
40 14 einstellte. Der Feststoffanteil wurde abgetrennt, mit Wasser gewaschen und bei 20°C im Vakuumtrockenschrank getrocknet. Die Trennung der beiden entstandenen regioisomeren Nitroverbindungen erfolgte mittels Flash-Chromatographie auf Kieselgel (Eluent: Ethylacetat; das zuerst eluierte Produkt war das gewünschte40 14 set. The solids content was separated off, washed with water and dried at 20 ° C. in a vacuum drying cabinet. The two regioisomeric nitro compounds formed were separated by means of flash chromatography on silica gel (eluent: ethyl acetate; the product eluted first was the desired one
45 Regioisomer) . Ausbeute: 5,6 g; 4I-NMR (400 MHz, in CDC13) : δ [ppm] = 7.05 (d, IH) , 4.10 (s,3H), 2.65 (s,3H) .45 regioisomer). Yield: 5.6 g; 4I-NMR (400 MHz, in CDC1 3 ): δ [ppm] = 7.05 (d, IH), 4.10 (s, 3H), 2.65 (s, 3H).
Vorstufe 7.3 4-Amino-7-chlor-l, 2-dimethyl-5-fluorbenzimidazolPrecursor 7.3 4-amino-7-chloro-l, 2-dimethyl-5-fluorobenzimidazole
5,6 g 7-Chlor-l, 2-dimethyl-5-fluor-4-nitrobenzimidazol wurden analog Vorstufe 2.5 mittels Zinndichlorid/Natriumboranat reduziert. Das erhaltene Rohprodukt wurde ohne Reinigung direkt in Vorstufe 7.4 eingesetzt. Ausbeute: 4,1 g.5.6 g of 7-chloro-l, 2-dimethyl-5-fluoro-4-nitrobenzimidazole were reduced analogously to precursor 2.5 using tin dichloride / sodium boranate. The crude product obtained was used directly in preliminary stage 7.4 without purification. Yield: 4.1 g.
Vorstufe 7.4Preliminary stage 7.4
7-Chlor-l, 2-dimethyl-5-fluor-4-isocyanatobenzimidazol7-chloro-1,2-dimethyl-5-fluoro-4-isocyanatobenzimidazole
4,1 g 4-Amino-7-chlor-l,2-dimethyl-5-fluorbenzimidazol wurden analog Vorstufe 5.4 mit Diphosgen umgesetzt. Das erhaltene Rohprodukt wurde, wiederum ohne Reinigung, direkt zum Endprodukt 1.7 umgesetzt.4.1 g of 4-amino-7-chloro-l, 2-dimethyl-5-fluorobenzimidazole were reacted with diphosgene analogously to precursor 5.4. The crude product obtained was converted directly to the end product 1.7, again without purification.
Beispiel 8Example 8
3- [7-Chlor-2-dimethylamino-5-fluorbenzoxazol-4-yl] -1-methyl- 6-trifluormethyl-2, 4- (1H,3H) -pyrimidindion (Verb. 19)3- [7-chloro-2-dimethylamino-5-fluorobenzoxazol-4-yl] -1-methyl-6-trifluoromethyl-2,4- (1H, 3H) -pyrimidinedione (Verb. 19)
1,0 g 3- [2-Amino-4-chlor-6-fluor-3-hydroxyphenyl] -l-methyl-6-tri- fluormethyl-2, 4- (1H,3H) -pyrimidindion wurden in 100 ml 1,2-Di- chlorethan mit 0,5 g Dichlormethylenimmoniumchlorid gemischt, wonach man die Mischung in einen Glaseinsatz für Druckbehälter füllte und im verschlossenen Druckbehälter 5 Stunden auf 120°C erhitzte. Der Eigendruck des Behälters stieg dabei auf ca. 5 bar. Anschließend kühlte man den Behälter ab. Die klare Produkt-Lösung wurde mit verdünnter wässriger Kaliumcarbonat-Lösung gewaschen. Die organische Phase wurde noch über Natriumsulfat getrocknet und schließlich eingeengt. Die Reinigung des Rohproduktes erfolgte mittels Flash-Chromatographie unter Verwendung einer kurzen Säule (Eluent: Cyclohexan/tert. -Butyl -methylether = 8:2). Ausbeute: 0,5 g; iH-NMR (270 MHz, in CDC13) : δ [ppm] = 6.85 (d,lH), 6.4 (s,lH), 3.6 (s,3H) , 3.25 (s,6H) .1.0 g of 3- [2-amino-4-chloro-6-fluoro-3-hydroxyphenyl] -l-methyl-6-trifluoromethyl-2, 4- (1H, 3H) -pyrimidinedione were dissolved in 100 ml of 1 , 2-dichloroethane mixed with 0.5 g dichloromethyleneimmonium chloride, after which the mixture was poured into a glass insert for pressure vessels and heated to 120 ° C. in the sealed pressure vessel for 5 hours. The internal pressure of the container rose to approx. 5 bar. Then the container was cooled. The clear product solution was washed with dilute aqueous potassium carbonate solution. The organic phase was dried over sodium sulfate and finally concentrated. The crude product was purified by means of flash chromatography using a short column (eluent: cyclohexane / tert-butyl methyl ether = 8: 2). Yield: 0.5 g; i H-NMR (270 MHz, in CDC1 3 ): δ [ppm] = 6.85 (d, 1H), 6.4 (s, 1H), 3.6 (s, 3H), 3.25 (s, 6H).
Vorstufe 8.1Preliminary stage 8.1
3- [4-Chlor-6-fluor-3-methoxy-2-nitrophenyl] -1-methyl-6-trifluor- methyl-2,4- (1H,3H) -pyrimidindion3- [4-chloro-6-fluoro-3-methoxy-2-nitrophenyl] -1-methyl-6-trifluoromethyl-2,4- (1H, 3H) pyrimidinedione
Zu 51,0 g 3- [4-Chlor-6-fluor-3-methoxyphenyl] -l-methyl-6-tri- fluormethyl-2, 4- (IH, 3H) -pyrimidindion in 1 1 konzentrierter Schwefelsäure tropfte man unter Kühlung auf (-20) °C langsam Nitriersäure, bestehend aus 20,4 ml konzentrierter Schwefelsäure und 25,5 ml 98 %iger Salpetersäure. Nach beendeter Zugabe wurde noch 30 Minuten bei (-20) °C gerührt. Dann rührte man die Reaktionsmischung in 1 1 Eiswasser ein. Der entstandene Feststoff - anteil wurde abgetrennt, mit Wasser gewaschen und im Vakuum- 5 trockenschrank bei 20°C getrocknet. Ausbeute: 57,0 g; iH-NMR (270 MHz, in CDC13) : δ [ppm] = 7.55 (d,lH), 6.35 (s,lH), 4.05 (s,3H) , 3.55 (s,3H) .51.0 g of 3- [4-chloro-6-fluoro-3-methoxyphenyl] -1-methyl-6-trifluoromethyl-2,4, (IH, 3H) -pyrimidinedione in 1 l of concentrated sulfuric acid were added dropwise Cooling to (-20) ° C slowly nitrating acid, consisting of 20.4 ml concentrated sulfuric acid and 25.5 ml of 98% nitric acid. After the addition had ended, the mixture was stirred at (-20) ° C. for a further 30 minutes. Then the reaction mixture was stirred into 1 liter of ice water. The resulting solid portion was separated, washed with water and dried in a vacuum drying oven at 20 ° C. Yield: 57.0 g; iH-NMR (270 MHz, in CDC1 3 ): δ [ppm] = 7.55 (d, lH), 6.35 (s, lH), 4.05 (s, 3H), 3.55 (s, 3H).
Vorstufe 8.2 10 3- [4-Chlor-6-fluor-3-hydroxy-2-nitrophenyl] -l-methyl-6-trifluor- methyl-2, 4- (IH, 3H) -pyrimidindionPrecursor 8.2 10 3- [4-chloro-6-fluoro-3-hydroxy-2-nitrophenyl] -l-methyl-6-trifluoromethyl-2, 4- (IH, 3H) -pyrimidinedione
Zu 57,0 g 3- [4-Chlor-6-fluor-3-methoxy-2-nitrophenyl] -l-methyl-6- trifluormethyl-2, 4- (IH, 3H) -pyrimidindion in ca. 500 ml absolutemTo 57.0 g of 3- [4-chloro-6-fluoro-3-methoxy-2-nitrophenyl] -l-methyl-6-trifluoromethyl-2, 4- (IH, 3H) -pyrimidinedione in approx. 500 ml of absolute
15 Dimethylformamid wurden 19,0 g Lithiumchlorid gegeben. Anschließend rührte man 3 Stunden bei 80-90°C. Nach dem Abkühlen wurde die Reaktionsmischung mit 1 1 Walser versetzt. Das Wertprodukt extrahierte man mit 3x200 ml Methyl-tert. -butylether . Die Ether-Phase wurde noch mehrmals mit Wasser gewaschen, dann getrocknet und15 dimethylformamide were given 19.0 g of lithium chloride. The mixture was then stirred at 80-90 ° C for 3 hours. After cooling, the reaction mixture was mixed with 1 1 Walser. The valuable product was extracted with 3x200 ml of methyl tert. -butyl ether. The ether phase was washed several times with water, then dried and
20 schließlich eingeengt. Ausbeute: 46,1 g; l-H-NMR (250 MHz, in CDC13) : δ [ppm] = 7.65 (d,lH), 6.35 (s,lH), 3.60 (s,3H) .20 finally narrowed. Yield: 46.1 g; 1 H NMR (250 MHz, in CDC1 3 ): δ [ppm] = 7.65 (d, 1H), 6.35 (s, 1H), 3.60 (s, 3H).
Vorstufe 8.3 25 3- [2-Amino-4-chlor-6-fluor-3-hydroxyphenyl] -l-methyl-6-trifluor- methyl-2, 4- (IH, 3H) -pyrimidindionPrecursor 8.3 25 3- [2-Amino-4-chloro-6-fluoro-3-hydroxyphenyl] -l-methyl-6-trifluoromethyl-2, 4- (IH, 3H) -pyrimidinedione
Zu 46,0 g 3- [4-Chlor-6-fluor-3-hydroxy-2-nitrophenyl] -l-methyl-6- trifluormethyl-2, 4- (IH, 3H) -pyrimidindion in 423 ml Wasser und 30 36,8 ml konzentrierter Salzsäure wurden bei 65°C portionsweiseTo 46.0 g of 3- [4-chloro-6-fluoro-3-hydroxy-2-nitrophenyl] -l-methyl-6-trifluoromethyl-2, 4- (IH, 3H) -pyrimidinedione in 423 ml of water and 30 36.8 ml of concentrated hydrochloric acid were added in portions at 65 ° C
34 g Eisenpulver gegeben. Anschließend erhitzte man 3 Stunden aufGiven 34 g of iron powder. The mixture was then heated for 3 hours
Rückflußtemperatur. Nach dem Abkühlen wurde die Mischung mitReflux temperature. After cooling, the mixture became with
500 ml Ethylacetat geschüttelt. Mittels Filtration über Celite® Shaken 500 ml of ethyl acetate. By filtration through Celite ®
(Fa. Manville Corporation) befreite man die organische Phase von 35 den Resten an anorganischem Material. Das Filtrat wurde noch über(Manville Corporation), the organic phase was freed from 35 residues of inorganic material. The filtrate was still over
Natriumsulfat getrocknet und schließlich eingeengt. Ausbeute:Dried sodium sulfate and finally concentrated. Yield:
37,5 g; iH-NMR ( 270 MHz , in CDC13 ) : δ [ppm] = 6 . 65 ( d, IH) , 6 . 40 ( s , lH) ,37.5 g; iH-NMR (270 MHz, in CDC1 3 ): δ [ppm] = 6. 65 (d, IH), 6. 40 (s, lH),
3 . 60 ( s , 3H) . 403rd 60 (s, 3H). 40
Beispiel 9Example 9
3- [7-Chlor-5-fluorbenzoxazol-4-yl] -l-methyl-6-trifluor- methyl-2, 4- (1H,3H) -pyrimidindion (Verb. 12)3- [7-chloro-5-fluorobenzoxazol-4-yl] -l-methyl-6-trifluoromethyl-2, 4- (1H, 3H) -pyrimidinedione (Verb. 12)
45 Zu einer Lösung von 0,5 g 3- [2-Amino-4-chlor-6-fluor-3-hydroxy- phenyl] -l-methyl-6-trifluormethyl-2 , 4- (IH, 3H) -pyrimidindion (aus Vorstufe 8.3) in 30 ml absolutem Methanol wurden 0,5 g Trimethyl- orthoformiat gegeben. Danach erhitzte man 20 Stunden auf Rück- flußtemperatur. Anschließend wurden Lösungsmittel und überschüssiger Orthoester bei reduziertem Druck entfernt. Den Rückstand löste man in Ethylacetat. Die organische Phase wurde noch mit Wasser gewaschen, dann über Natriumsulfat getrocknet und schließlich eingeengt. Die Reinigung des Rohproduktes erfolgte mittels Flash-Chromatographie (Eluent : Cyclohexan/tert . -Butyl-methylether = 3:1). Ausbeute: 0,26 g; iH-NMR ( 250 MHz , in CDC13 ) : δ [ppm] = 8 . 20 ( s , lH) , 7 . 40 (d, lH) , 6 . 40 ( s , lH) , 3 . 60 ( s , 3H) .45 To a solution of 0.5 g of 3- [2-amino-4-chloro-6-fluoro-3-hydroxyphenyl] -l-methyl-6-trifluoromethyl-2, 4- (IH, 3H) pyrimidinedione (from precursor 8.3) in 30 ml of absolute methanol, 0.5 g of trimethyl given orthoformate. The mixture was then heated to the reflux temperature for 20 hours. Then solvent and excess orthoester were removed at reduced pressure. The residue was dissolved in ethyl acetate. The organic phase was washed with water, then dried over sodium sulfate and finally concentrated. The crude product was purified by means of flash chromatography (eluent: cyclohexane / tert-butyl methyl ether = 3: 1). Yield: 0.26 g; iH-NMR (250 MHz, in CDC1 3 ): δ [ppm] = 8. 20 (s, lH), 7. 40 (d, lH), 6. 40 (s, lH), 3. 60 (s, 3H).
Beispiel 10Example 10
3- [7-Chlor-5-fluor-2-methoxybenzoxazol-4-yl] -1-methyl-6-trifluor- methyl-2, 4- (1H,3H) -pyrimidindion (Verb. 14)3- [7-chloro-5-fluoro-2-methoxybenzoxazol-4-yl] -1-methyl-6-trifluoromethyl-2, 4- (1H, 3H) -pyrimidinedione (Verb. 14)
1,0 g 3- [2-Amino-4-chlor-6-fluor-3-hydroxyphenyl] -l-methyl-6-tri- fluorrr.ethyl-2, 4- (IH, 3H) -pyrimidindion (aus Vorstufe 8.3) wurden analog Beispiel 9 mit Tetramethylorthocarbonat umgesetzt.1.0 g of 3- [2-amino-4-chloro-6-fluoro-3-hydroxyphenyl] -l-methyl-6-trifluororrr.ethyl-2, 4- (IH, 3H) -pyrimidinedione (from precursor 8.3) were reacted with tetramethyl orthocarbonate analogously to Example 9.
Ausbeute: 0,7 g; !H-NMR (250 MHz, in CDC13) : δ [ppm] = 7.10 (d,lH), 6.40 (s,lH),Yield: 0.7 g; ! H-NMR (250 MHz, in CDC1 3 ): δ [ppm] = 7.10 (d, lH), 6.40 (s, lH),
4.20 (s,3H), 3.60 (s,3H).4.20 (s, 3H), 3.60 (s, 3H).
In der nachfolgenden Tabelle 2 sind neben den vorstehend beschriebenen noch weitere 3- (Benzazol-4-yl)pyrimidindion-Derivate der Formel I aufgeführt, die auf analoge Weise hergestellt wurden oder herstellbar sind: In addition to those described above, Table 2 below also lists further 3- (benzazol-4-yl) pyrimidinedione derivatives of the formula I which were prepared or can be prepared in an analogous manner:
Tabelle 2Table 2
AnwendungsbeispieleExamples of use
Die herbizide Wirkung der 3 - (Benzazol -4 -yl) pyrimidindion-DerivateThe herbicidal activity of the 3 - (benzazole -4 -yl) pyrimidinedione derivatives
1 ließ sich durch die folgenden Gewächshausversuche zeigen:1 was shown 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.Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels. The seeds of the test plants were sown separately according to species.
Bei Vorauflaufbehandlung wurden die in Wasser suspendierten oder emulgierten Wirkstoffe direkt nach Einsaat mittels fein verteilender Düsen aufgebracht. Die Gefäße wurden leicht beregnet, um Keimung und Wachstum zu fördern, und anschließend mit durchsich tigen Plastikhauben abgedeckt, bis die Pflanzen angewachsen waren. Diese Abdeckung bewirkt ein gleichmäßiges Keimen der Test- pflanzen, sofern dies nicht durch die Wirkstoffe beeinträchtigt wurde.In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles. The vessels were sprinkled lightly to promote germination and growth, and then pervaded plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.
Zum Zweck der Nachauflauf ehandlung wurden die Testpflanzen je nach Wuchsform erst bis zu einer Wuchshöhe von 3 bis 15 cm angezogen und erst dann mit den in Wasser suspendierten oder emulgierten Wirkstoffen behandelt. Die Testpflanzen 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 Nachauflaufbehandlung betrug 15,6 oder 7,8 g/ha a.S. (aktive Substanz) . For the purpose of post-emergence, the test plants were each according to the growth habit, only grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. 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 post-emergence treatment was 15.6 or 7.8 g / ha aS (active substance).
Die Pflanzen wurden artenspezifisch bei Temperaturen von 10 - 25°C bzw. 20 - 35°C gehalten. Die Versuchsperiode erstreckte sich überThe plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species. The trial period spanned
2 bis 4 Wochen. Während dieser Zeit wurden die Pflanzen gepflegt, und ihre Reaktion auf die einzelnen Behandlungen wurde ausgewer 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated
Bei Aufwandmengen von 15,6 und 7,8 g/ha a.S. zeigte die Verbindung Nr. 18 im Nachauflaufverfahren eine sehr gute herbizide Wirkung gegen die o.g. Unkräuter. At application rates of 15.6 and 7.8 g / ha a.S. Compound No. 18 showed a very good herbicidal activity against the above in the post-emergence process. Weeds.

Claims

Patentansprüche claims
1. 3- (Benzazol-4-yl) pyrimidindion-Derivate der Formel I1. 3- (Benzazol-4-yl) pyrimidinedione derivatives of the formula I.
in der die Variablen folgende Bedeutungen haben:in which the variables have the following meanings:
X Sauerstoff oder Schwefel;X oxygen or sulfur;
Rl Wasserstoff, Amino, Ci-Cg-Alkyl oder Cι-C6-Halogenalkyl;R l is hydrogen, amino, Ci-Cg-alkyl or -C-C 6 haloalkyl;
R2 Wasserstoff, Halogen, Cι-C6-Alkyl, Cι-C6-Halogenalkyl , Cι-C6-Alkylthio, Cι-C6-Alkylsulfinyl oder Cι-C6-Alkyl- sulfonyl;R 2 is hydrogen, halogen, Cι-C 6 -alkyl, C 6 haloalkyl, Cι-C 6 alkylthio, Cι-C 6 alkylsulfinyl or Cι-C6 alkyl sulfonyl;
R3 Wasserstoff, Halogen oder Ci-Cg-Alkyl;R 3 is hydrogen, halogen or Ci-Cg-alkyl;
R4 Wasserstoff oder Halogen;R 4 is hydrogen or halogen;
R5 Cyano, Halogen, Ci-Cβ-Alkyl, Cι-C6-Halogenalkyl , Cι-C6-Alkoxy oder Cι-C6-Halogenalkoxy;R 5 cyano, halogen, Ci-Cβ-alkyl, -CC 6 -haloalkyl, -C-C 6 alkoxy or -C-C 6 -haloalkoxy;
=Y- eine Gruppe =N-N(R6)-, =C (ZR7) -N(R6) -, =C(ZR7)-0- oder =C(ZR7)-S-;= Y- a group = NN (R 6 ) -, = C (ZR 7 ) -N (R 6 ) -, = C (ZR 7 ) -0- or = C (ZR 7 ) -S-;
R6 Cι-C6-Alkyl, Ci -C4 -Halogenalkyl, C3-C6-Cycloalkyl, C3-C6-Alkenyl, C3-C6-Alkinyl , Cι-C6-Alkylsulfonyl,R 6 Cι-C6 alkyl, Ci -C 4 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, Cι-C 6 alkylsulfonyl,
(Ci-Ce-Alkyl) carbonyl, (Cj -C6 -Halogenalkyl) carbonyl, (Ci-Cß-Alkyl) thiocarbonyl, (Cι-C6-Alkoxy) carbonyl, (Ci-Cg-Alkoxy) thiocarbonyl oder(Ci-Ce-alkyl) carbonyl, (Cj -C 6 haloalkyl) carbonyl, (Ci-C ß- alkyl) thiocarbonyl, (Cι-C 6 -alkoxy) carbonyl, (Ci-Cg-alkoxy) thiocarbonyl or
Ci-Cß-Alkyl, das durch Cyano, Cχ-C6-Alkoxy, Cι-C6-Alkyl- thio, (Cι-C6-Alkoxy) carbonyl, (Ci-Cö-Alkylamino) carbonyl ,Ci-C ß- alkyl by cyano, Cχ-C 6 -alkoxy, Cι-C 6 -alkyl thio, (Cι-C 6 -alkoxy) carbonyl, (Ci-Cö-alkylamino) carbonyl,
Di (Ci-Cδ-alkyl) aminocarbonyl oder (Cι-C5-Alkyl) carbonyloxy substituiert sein kann;Di (Ci-C δ- alkyl) aminocarbonyl or (-C-C 5 alkyl) carbonyloxy may be substituted;
Z eine chemische Bindung, Sauerstoff, Schwefel, -S(O)-, -S(0)2-, - H- oder -N(R8)-;Z is a chemical bond, oxygen, sulfur, -S (O) -, -S (0) 2 -, - H- or -N (R 8 ) -;
R7 und R8 unabhängig voneinander Cι-C6-Alkyl, Ci-Cε-Halogenalkyl , Hydroxy-Cι-C -alkyl , Cyano-Cι-C -alkyl, Cι-C4-Alkoxy-Cι-C4-alkyl, Cι-C4-Halo- genalkoxy-Cι-C4-alkyl , C3-C4-Alkenyloxy-Cι-C -alkyl , C3-C4-Alkinyloxy-Cι-C4-alkyl , C3-C8-Cycloalk- oxy-Cι-C4-alkyl,R 7 and R 8 are independent of one another -C-C 6 alkyl, Ci-Cε-haloalkyl, hydroxy-Cι-C -alkyl, cyano-Cι-C -alkyl, Cι-C 4 -alkoxy-Cι-C 4 -alkyl, Cι-C 4 -halo genalkoxy -CC 4 -alkyl, C 3 -C 4 -alkenoxy-CC -alkyl, C 3 -C 4 -alkynyloxy -CC 4 -alkyl, C 3 -C 8 -cycloalk- oxy-Cι- C 4 alkyl,
Amino-Cι-C4-alkyl , Cι-C4-Alkylamino-Cι-C4-alkyl , Di (Cχ-C4-alkyl) amino-C1-C4-alkyl, C!-C -Alkyl- thio-Cι-C -alkyl, Cι-C4-Halogenalkylthio-Cι-C4-alkyl , C3-C4-Alkenylthio-Cι-C -alkyl, C3-C4-Alkinyl - thio-Cι-C4-alkyl , Cι-C4-Alkylsulfinyl-Cι~C4-alkyl , Cι-C4-Halogenalkylsulfinyl-Cι-C4-alkyl , C3-C4~Alkenyl - sulfinyl-Cι-C4-alkyl , C3-C4-Alkinylsulfinyl-Cι-C4-alkyl , Cι-C4-Alkylsulfonyl-Cι-C4-alkyl , Cι-C4-Halogenalkylsul - fonyl-Cι-C4-alkyl, C3-C4-Alkenylsulfonyl-Cι-C4-alkyl,Amino -CC 4 -alkyl, -C 4 -alkylamino -CC 4 -alkyl, di (Cχ-C 4 -alkyl) amino-C 1 -C 4 -alkyl, C ! -C -alkyl- thio -CC -alkyl, -CC 4 -haloalkylthio -CC-C 4 -alkyl, C 3 -C 4 -alkenylthio -CC -alkyl, C 3 -C 4 -alkynyl - thio -C-C 4 -alkyl, -C-C 4 -alkylsulfinyl-Cι ~ C 4 -alkyl, Cι-C 4 -haloalkylsulfinyl-Cι-C 4 -alkyl, C 3 -C 4 ~ alkenyl - sulfinyl-Cι-C 4 -alkyl, C 3 -C 4 -alkynylsulfinyl -CC 4 -alkyl, -C-C 4 -alkylsulfonyl -CC-C 4 -alkyl, -C-C 4 -haloalkylsul - fonyl -CC-C 4 -alkyl, C 3 -C 4 alkenylsulfonyl -CC 4 alkyl,
C3-C -Alkinylsulfonyl-Cι-C4-alkyl , C -C6-Alkenyl , Cyano-C3-C6-alkenyl, C3-Cg-Halogenalkenyl , C3- 6-Alkinyl , Cyano-C3-C6-alkinyl, C -Cs-Halogenalkinyl , Hydroxycar- bonyl-C1-C4-alkyl , (Cχ-C4-Alkoxy) carbonyl-Cι-C4-alkyl , (Cι-C -Alkylthio) carbonyl-Cι-C4-alkyl, Aminocarbo- nyl-Cι-C4-alkyl , (C1-C4-Alkylanu.no) carbonyl-Cι-C4-alkyl , Di (Cι-C -alkyl) aminocarbonyl-C -C4-alkyl, Di (Cι-C4-al- kyl) phosphonyl -C1-C4 -alkyl, C3-C8-Cycloalkyl, C3-C8-Cycloalkyl-Cι-C4-alkyl, Phenyl, Phenyl-Cι~C4-alkyl, 3- bis 7-gliedriges Heterocyclyl oderC 3 -C -alkynylsulfonyl -CC-C 4 alkyl, C -C 6 alkenyl, cyano-C 3 -C 6 -alkenyl, C 3 -Cg-haloalkenyl, C 3 - 6 alkynyl, cyano-C 3 - C 6 -alkynyl, C -Cs-haloalkynyl, hydroxycarbonyl-C 1 -C 4 -alkyl, (Cχ-C 4 -alkoxy) carbonyl -CC-C 4 -alkyl, (-C -C-alkylthio) carbonyl -CC -C 4 -alkyl, aminocarbonyl -CC 4 -alkyl, (C 1 -C 4 -alkylanu.no) carbonyl -CC 4 -alkyl, di (-C -alkyl) aminocarbonyl-C -C 4- alkyl, di (-CC 4 -alkyl) phosphonyl-C 1 -C 4 -alkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyl -CC 4 -alkyl, phenyl, Phenyl-C ~ C 4 alkyl, 3- to 7-membered heterocyclyl or
Heterocyclyl-Cι-C4-alkyl, wobei jeder Heterocyclyl-Ring ein Carbonyl- oder Thiocarbonyl-Ringglied enthalten kann, und wobei jeder Cycloalkyl-, Phenyl- und Heterocyclylring unsubstituiert sein oder ein bis vier Substituenten tra- gen kann, jeweils ausgewählt aus der Gruppe bestehend ausHeterocyclyl -CC 4 -alkyl, where each heterocyclyl ring can contain a carbonyl or thiocarbonyl ring member, and where each cycloalkyl, phenyl and heterocyclyl ring can be unsubstituted or can carry one to four substituents, each selected from the group Group consisting of
Cyano, Nitro, Amino, Hydroxy, Carboxy, Halogen, Cι~C4-Alkyl, Cι-C4-Halogenalkyl, Cι-C4-Alkoxy, Cι-C4-Halogenalkoxy, Cι-C4-Alkylthio, Cι-C -Halogenalkyl- thio, Cι-C4-Alkylsulfonyl, C].-C4-Halogenalkylsulfonyl , (Cι~C4-Alkoxy) carbonyl, (Cι-C4-Alkyl) carbonyl,Cyano, nitro, amino, hydroxy, carboxy, halogen, Cι ~ C 4 -alkyl, C 4 haloalkyl, Cι-C 4 -alkoxy, C 4 haloalkoxy, Cι-C 4 alkylthio, Cι-C -Halogenalkyl- thio, -C-C 4 -alkylsulfonyl, C] .- C 4 -Halogenalkylsulfonyl, (-C-C 4 -alkoxy) carbonyl, (-C-C 4 -alkyl) carbonyl,
(Cι-C4-Halogenalkyl) carbonyl, (Cι-C4-Alkyl) carbonyloxy, (Cι-C4-Halogenalkyl) carbonyloxy und Di (Cι-C4-alkyl) amino,(Cι-C 4 haloalkyl) carbonyl, (Cι-C4 alkyl) carbonyloxy, (Cι-C 4 -haloalkyl) carbonyloxy and di (Cι-C4 alkyl) amino,
oder, sofern Z eine chemische Bindung bedeutet, R7 ge- wünschtenfalls auch Wasserstoff, Hydroxy, Cyano,or, if Z is a chemical bond, R 7 if desired also hydrogen, hydroxy, cyano,
Mercapto, Amino, Halogen, -CH (OH) -CH2-R9 , -CH (Halogen) -CH2-R9, -CH2-CH (Halogen) -R9 , -CH=CH-R9 oder -CH=C (Halogen) -R9 , wobeiMercapto, amino, halogen, -CH (OH) -CH 2 -R 9 , -CH (halogen) -CH 2 -R 9 , -CH 2 -CH (halogen) -R 9 , -CH = CH-R 9 or -CH = C (halogen) -R 9 , where
R9 für Hydroxycarbonyl , (C].-C4-Alkoxy) carbonyl, (Cι-C4-Alkylthio) carbonyl, Aminocarbonyl, (Cι~C4-Alkyl - amino) carbonyl oder Di (Cι-C4~alkyl) aminocarbonyl steht, oder R7 und R8 zusammen eine 1, 3-Propylen-, Tetra - methylen-, Pentamethylen- oder Ethylenoxyethylen-Kette, die jeweils unsubstituiert sein oder ein bis vier Cι~C4-Alkylgruppen oder ein oder zwei (Cι~C4-Alkoxy) carbonylgruppen tragen kann;R 9 for hydroxycarbonyl, (C] .- C 4 -alkoxy) carbonyl, (Cι-C 4 -alkylthio) carbonyl, aminocarbonyl, (Cι ~ C 4 -alkyl-amino) carbonyl or di (Cι-C 4 ~ alkyl) aminocarbonyl, or R 7 and R 8 together form a 1,3-propylene, tetra-methylene, pentamethylene or ethyleneoxyethylene chain, each of which is unsubstituted or one to four C 1 -C 4 -alkyl groups or one or two (C 1 -C 4 -Alkoxy) can carry carbonyl groups;
sowie die landwirtschaftlich brauchbaren Salze der Verbindungen I .and the agriculturally useful salts of the compounds I.
2. 3- (Benzazol-4-yl) pyrimidindion-Derivate der Formel I nach Anspruch 1, wobei X für Sauerstoff,2. 3- (benzazol-4-yl) pyrimidinedione derivatives of the formula I according to claim 1, where X is oxygen,
Rl für Wasserstoff, Amino oder Ci-Cg-Alkyl, R2 für Wasserstoff, Halogen, Ci-Cg-Alkyl, Cι-C5-Halogenalkyl oder Ci-Cg-Alkylsulfonyl,R 1 for hydrogen, amino or Ci-Cg-alkyl, R 2 for hydrogen, halogen, Ci-Cg-alkyl, Cι-C 5 haloalkyl or Ci-Cg-alkylsulfonyl,
R3 für Wasserstoff,R 3 for hydrogen,
R4 für Wasserstoff, Fluor cder Chlor, R5 für Cyano oder Halogen und R6 für Ci-Cg-Alkyl, C3-Cg-Alkinyl , Ci-Cg-Alkylsulfonyl oder (Ci-Cg-Alkoxy) carbonyl stehen.R 4 is hydrogen, fluorine or chlorine, R 5 is cyano or halogen and R 6 is Ci-Cg-alkyl, C 3 -Cg-alkynyl, Ci-Cg-alkylsulfonyl or (Ci-Cg-alkoxy) carbonyl.
3. Verwendung der 3- (Benzazol-4-yl) pyrimidindion-Derivate I und ihrer landwirtschaftlich brauchbaren Salze, gemäß Anspruch 1, als Herbizide.3. Use of the 3- (benzazol-4-yl) pyrimidinedione derivatives I and their agriculturally useful salts, according to claim 1, as herbicides.
4. Herbizide Mittel, enthaltend eine herbizid wirksame Menge mindestens eines 3- (Benzazol-4-yl)pyrimidindion-Derivates der Formel I oder eines Salzes von I, gemäß Anspruch 1, und min- destens einen flüssigen und/oder festen Trägerstoff sowie gewünschtenfalls mindestens einen oberflächenaktiven Stoff.4. Herbicidal compositions containing a herbicidally effective amount of at least one 3- (benzazol-4-yl) pyrimidinedione derivative of the formula I or a salt of I, according to claim 1, and at least one liquid and / or solid carrier and, if desired at least one surfactant.
5. Verfahren zur Herstellung von herbizid wirksamen Mitteln, dadurch gekennzeichnet, daß man eine herbizid wirksame Menge mindestens eines 3- (Benzazol-4-yl)pyrimidindion-Derivates der Formel I oder eines Salzes von I, gemäß Anspruch 1, und mindestens einen inerten flüssigen und/oder festen Trägerstoff sowie gewünschtenfalls mindestens einen oberflächenaktiven Stoff mischt.5. A process for the preparation of herbicidally active agents, characterized in that a herbicidally effective amount of at least one 3- (benzazol-4-yl) pyrimidinedione derivative of the formula I or a salt of I, according to claim 1, and at least one inert mixes liquid and / or solid carrier and, if desired, at least one surface-active substance.
6. Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs, dadurch gekennzeichnet, daß man eine herbizid wirksame Menge mindestens eines 3- (Benzazol-4-yl)pyrimidindion-Derivates der Formel I oder eines Salzes von I, gemäß Anspruch 1, auf Pflanzen, deren Lebensraum oder auf Saatgut einwirken läßt. 6. A method for controlling unwanted vegetation, characterized in that a herbicidally effective amount of at least one 3- (benzazol-4-yl) pyrimidinedione derivative of the formula I or a salt of I, according to claim 1, on plants, their habitat or can act on seeds.
Arylharnstoffe der Formel III Arylureas of the formula III
wobei L2 für Cι-C4-Alkyl oder Phenyl steht und Ri-R5 sowie Y die in Anspruch 1 angegebenen Bedeutungen haben.where L 2 is -CC 4 alkyl or phenyl and R i -R 5 and Y have the meanings given in claim 1.
8. Arylamilide der Formel IV8. Arylamilides of formula IV
wobei L2 für C1-C4 -Alkyl oder Phenyl steht und Ri-R5 sowie Y die in Anspruch 1 angegebenen Bedeutungen haben.where L 2 is C 1 -C 4 alkyl or phenyl and R 1 -R 5 and Y have the meanings given in claim 1.
9. Substituierte 2 -Aminophenole, -thiophenole und -aniline der Formel V9. Substituted 2-aminophenols, thiophenols and anilines of the formula V
wobei die Variablen X und Ri-R6 die in Anspruch 1 angegebenen Bedeutungen haben. where the variables X and R i -R 6 have the meanings given in claim 1.
EP98963564A 1997-12-17 1998-12-11 Herbicides 3-(benzazol-4-yl)pyrimidine-dione-derivatives Withdrawn EP1047693A1 (en)

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