EP0971904A1 - Nouveaux 1-amino-3-benzyluraciles - Google Patents

Nouveaux 1-amino-3-benzyluraciles

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Publication number
EP0971904A1
EP0971904A1 EP98916984A EP98916984A EP0971904A1 EP 0971904 A1 EP0971904 A1 EP 0971904A1 EP 98916984 A EP98916984 A EP 98916984A EP 98916984 A EP98916984 A EP 98916984A EP 0971904 A1 EP0971904 A1 EP 0971904A1
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EP
European Patent Office
Prior art keywords
alkyl
alkoxy
carbonyl
haloalkyl
phenyl
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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EP98916984A
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German (de)
English (en)
Inventor
Olaf Menke
Gerhard Hamprecht
Markus Menges
Michael Rack
Robert Reinhard
Peter Schäfer
Cyrill Zagar
Karl-Otto Westphalen
Ulf Misslitz
Helmut Walter
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BASF SE
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BASF SE
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Publication of EP0971904A1 publication Critical patent/EP0971904A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C07C281/02—Compounds containing any of the groups, e.g. carbazates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C07C281/06—Compounds containing any of the groups, e.g. semicarbazides

Definitions

  • the present invention relates to novel 1-amino-3-benzyluracils of the formula I.
  • R 1 is hydrogen, halogen or methyl
  • R 2, R 3 are independently hydrogen, cyano, thiocyanato, halogen, C ⁇ -C haloalkyl, C ⁇ ⁇ C 4 -haloalkoxy or C 1 -C 4 haloalkylthio;
  • R 4 is hydrogen, cyano, thiocyanato, halogen, C ⁇ -C 4 -alkyl, C 4 haloalkyl, C ⁇ -C 4 -alkoxy, C 4 haloalkoxy, C ⁇ -C 4 -haloalkylthio or (C ⁇ -C6 Alkylamino) carbonyl;
  • phenyl, phenoxy or phenylsulfonyl group which can be unsubstituted or can carry one to three substituents each selected from the group consisting of halogen, nitro, cyano, Ci-C ⁇ alkyl, Ci-C ⁇ haloalkyl, C ⁇ -C 6 Alkoxy and (-CC 6 alkoxy) carbonyl,
  • ⁇ is -C-C 3 alkylene which can carry a Ci-C ⁇ -alkyl substituent
  • R 11 is hydrogen, cyano, C 6 -alkyl, C 6 haloalkyl,
  • R 12 , R 13 independently of one another Ci-C ⁇ -alkyl, -C-C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, Cx-Ce-alkoxy-Ci-C ö -alkyl or
  • R 12 and R 13 together are a saturated or unsaturated
  • 2- to 4-membered carbon chain which can carry an oxo substituent, one link of this chain can be replaced by an oxygen, sulfur or nitrogen atom not adjacent to the variables Z 1 and Z 2 , and the carbon chain can still carry one to three residues , each selected from the group consisting of cyano, nitro, amino, halogen, Ci-Ce-alkyl, C 2 -C 6 alkenyl, Ci-Cg alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 - Alkynyloxy,
  • Ci-C ⁇ -haloalkyl cyano-C 6 -alkyl, hydroxy-C 5 -alkyl, C-C 6 -alkoxy-C 6 -alkyl, C 3 -C 6 -alkenyloxy-C 6 -alkyl, C 3 -C 6 alkynyloxy -CC 6 alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkoxy, carboxy, (-C 6 -alkoxy) carbonyl, (Ci-C ö -Alkyl) - carbonyloxy-Ci-C ß- alkyl and phenyl, which in turn can be unsubstituted or carry one to three substituents, each selected from the group consisting of cyano, nitro, amino, halogen, -C-C 6 alkyl , C ⁇ -C 6 haloalkyl, C ⁇ -C 6 -alkoxy and (C ⁇ -
  • R 14 is hydrogen, cyano, halogen, Ci-C ⁇ alkyl, Ci-C ⁇ haloalkyl, C ⁇ -C6 alkoxy, (Ci-C ⁇ -alkyl) carbonyl or carbonyl (C-C6 alkoxy!);
  • R 15 is hydrogen, OR 22 , SR 22 , -CC 6 alkyl, which may also carry one or two Ci-C ⁇ alkoxy substituents, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Ci-C ⁇ -Halogenalkyl, C 3 -C ⁇ -cycloalkyl, Cx-Ce-alkylthio-Ci-Ce-alkyl, -C-C 6 alkyliminooxy, -N (R 23 ) R 24 or phenyl, which may be unsubstituted or carry one to three substituents , each selected from the group consisting of cyano, nitro, halogen, Ci-C ⁇ - alkyl, C 2 ⁇ C 6 -alkenyl, Ci-C ß -haloalkyl, -C-C 6 alkoxy and (-C-C 6 alkoxy ) carbonyl,
  • R 22 is one of the meanings of R 19 ;
  • R 16 is hydrogen, cyano, halogen, Ci-C ⁇ - alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, -C-C 6 -alkoxy-C ⁇ -C 6 -alkyl, (-C ⁇ -C 6 -Alkyl) - carbonyl, (-C-C 6 -alkoxy) carbonyl, -N (R 5 ) R 26 , where R 25 and R 26 stand for one of the meanings of R 23 and R 24 , or phenyl, which in turn is another C ⁇ -C C ⁇ C ⁇ -C-C can carry one to three substituents each selected from the group consisting of cyano, nitro, halogen, 6 alkyl, 6 -haloalkyl, C 3 -C 6 -alkenyl, 6 -alkoxy and (C -0 6 -alkoxy) carbonyl;
  • R 17 is hydrogen, cyano, halogen, C ⁇ -C6 alkyl, Ci-C ⁇ -alkoxy, C ⁇ -C 6 haloalkyl, (C ⁇ -C6 alkyl) carbonyl or (Ci-C ⁇ alkoxy) carbonyl;
  • R 18 is hydrogen, cyano, -CC 6 alkyl or (-C 6 -alkoxy) carbonyl;
  • R 19 is hydrogen, Cx-Ce-alkyl, Cx-Ce-haloalkyl, C 2 -C 6 -alkenyl or C 2 - Ce -alkynyl, where the latter 4 groups can each carry one or two of the following radicals: cyano,
  • R 20 hydrogen, C ! -C 6 -alkyl, C 6 haloalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 -alkynyl, hydroxy-C ⁇ -C 6 alkyl, C ⁇ - C 6 -alkoxy-C 6 -C 6 -alkyl, -C-C 6 -alkylthio-C ⁇ -C 6 -alkyl, cyano-C ⁇ -C 6 -alkyl, (C ⁇ -C 6 -alkyl) carbonyl-C ⁇ -C 6 - alkyl, (Ci-C ⁇ -alkoxy) carbonyl -CC-C 6 -alkyl, (C ⁇ -C 6 -alkoxy) - carbonyl -C 2 -C6 -alkenyl, (Ci-C ö -alkyl) carbonyloxy-Ci-Cö- alkyl or
  • R 23 , R 24 independently of one another are hydrogen, -CC 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl,
  • Y is oxygen, sulfur or -N (R 27 ) -; Hydrogen, hydroxy, -CC 6 alkyl, C 3 -C 6 alkenyl,
  • R 30 is hydrogen, -CC 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, -C-C 6 -alkoxy-C ⁇ -C 6 -alkyl, ( -C-C 6 -alkoxy) - carbonyl-Ci-C ß- alkyl, (C 3 -C ß- alkenyloxy) carbonyl -Ci - C -alkyl,
  • Phenyl or phenyl-Ci-Cg-alkyl where the phenyl group and the phenyl ring of the phenylalkyl group can be unsubstituted or can carry one to three radicals, each selected from the group consisting of halogen, nitro, cyano, C 1 -C 6 -Al yl , -C-C 6 haloalkyl, -C-C 6 alkoxy and (Ci-C ⁇ - alkyl) carbonyl;
  • R 31 is hydrogen, hydroxy, -CC 6 -alkyl, C 3 -C 6 -cycloalkyl, -C-C 6 -alkoxy, (CI-C ⁇ -alkoxy) carbonyl -C -C ⁇ -alkoxy, C 3 - C - Alkenyl or C 3 - Ce alkenyloxy,
  • the heterocycle can be saturated, partially or completely unsaturated or aromatic and, if desired, can carry one to three substituents, each selected from the group consisting of halogen, nitro, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 - Alkoxy and (-C 6 alkyl) - carbonyl;
  • the invention also relates to the use of the compounds I as herbicides and / or for the desiccation and / or defoliation of plants, herbicidal compositions and agents for the desiccation and / or defoliation of plants which contain the compounds I as active substances, Process for the preparation of the compounds I and herbicidal agents and agents for desiccation and / or defoliation of plants using the compounds I, process for combating undesirable plant growth and for desiccation and / or defoliation of plants with the compounds I, and new intermediates of Formulas III and IV.
  • WO 95/04461 describes 3-benzyl-1-methyl-6-trif luormethyl-uracile of the formula II
  • R a is hydrogen, cyano, halogen, lower alkoxy
  • R b represents hydrogen, cyano, halogen, lower alkylaminocarbonyl or carboxy
  • the object of the present invention was therefore to provide new herbicidally active compounds which can be used to control undesirable plants better than before.
  • the task also extends to the provision of new desiccant / defoliant connections.
  • the compounds I are also suitable for defoliation and desiccation of parts of plants, for which crop plants such as cotton, potatoes, oilseed rape, sunflower, Soybeans or field beans, especially cotton, are suitable.
  • crops plants such as cotton, potatoes, oilseed rape, sunflower, Soybeans or field beans, especially cotton
  • agents for the desiccation and / or defoliation of plants, methods for producing these agents and methods for the desiccation and / or defoliation of plants with 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 are also possible if at least one substituent with a double bond is present.
  • 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.
  • 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, and the ammonium ion, which if desired one to four C ⁇ -C 4 alkyl and / or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, further phosphonium ions, sulfonium ions, preferably tri (-C 4 alkyl) sulfonium and sulfoxonium ions, preferably Tri (-C ⁇ C 4 alkyl)
  • 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 ⁇ -C-alkanoic acids, preferably Formate, acetate, propionate and butyrate.
  • the organic molecule parts mentioned in the definition of Alk, R 2 to R 31 and ⁇ represent collective terms for individual enumeration of the individual meanings. All carbon chains, that is, all against subst. Alkyl, alkylene, against subst. Alkoxy, alkylthio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkylamino, dialkylamino, alkyloximino, alkyliminooxy, alkylidenaminoxy, alkenyl, alkenyloxy, haloalkenyloxy, alkenylthio, alkynyl, alkynyl - Oxy and alkynylthio parts can be straight-chain or branched. Halogenated substituents preferably carry one to five identical or different halogen atoms. Halogen is fluorine, bromine, chlorine or iodine, in particular fluor
  • C 1 -C 4 alkyl for: CH 3 , C 2 H 5 , CH 2 -C 2 H 5 , CH (CH 3 ) 2 , n-butyl, 1-methylpropyl, CH 2 -CH (CH 3 ) 2 or C (CH 3 ) 3 , especially for CH 3 or C 2 H 5 ;
  • - C 1 -C 4 -haloalkyl a C ⁇ -4 alkyl C as mentioned above which is partially or fully substituted by fluorine, iodine, chlorine, bromine and / or substituted, eg CH 2 F, CHF 2, CF 3, CH 2 C1, CH (C1) 2 , 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 F 5 , 2 -Fluoropropyl, 3-fluoroprop
  • CF 2 -C 2 F 5 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or Nonafluorobutyl, in particular for CH 2 F, CHF 2 , CF 3 , CH 2 C1, 2-fluoroethyl, 2-chloroethyl or 2, 2, 2-trifluoroethyl;
  • C -C 6 alkyl for: C 1 -C 4 alkyl as mentioned above, and 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, 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-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2, 2-trimethylpropyl, 1-ethyl-l-methylpropyl or l -Ethyl-2-methylpropyl, especially for methyl, ethy
  • Ci-C ö -haloalkyl for: C ⁇ -Ce-alkyl as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, that is, for example, one of the radicals mentioned under -CC 4 -haloalkyl or for 5-fluoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1-pentyl, 5-iodo-1-pentyl, 5,5,5-trichloro-1-pentyl, undecafluoropentyl, 6- Fluoro-l-hexyl, 6-chloro-1-hexyl, 6-bromo-1-hexyl, 6-iodo-l-hexyl, 6, 6, 6-trichloro-l-hexyl or dodecafluorohexyl, especially for CH 2 F, CHF 2 , CF 3 , CH 2 C1, 2-fluoroethyl, 2-ch
  • Cyano-C ⁇ -C 6 alkyl for: for example CH 2 CN, 1-cyanoeth-l-yl, 2-cyanoeth-l-yl, 1-cyanoprop-l-yl, 2-cyanoprop-l-yl, 3-cyano - prop-1-yl, l-cyanoprop-2-yl, 2-cyanoprop-2-yl, 1-cyanobut-1-yl, 2-cyanobut-l-yl, 3-cyanobut-l-yl, 4-cyanobut -l-yl, l-cyanobut-2-yl, 2-cyanobut-2-yl, l-cyanobut-3-yl, 2-cyano-but-3-yl, l-cyano-2-methyl-prop-3 -yl, 2-cyano-2-methyl-prop-3-yl, 3-cyano-2-methyl-prop-3-yl or 2-cyanomethyl-prop-2-yl, in particular for CH 2 CN or 2-cyanoethyl ;
  • Phenyl-Ci-C ⁇ - alkyl for: e.g. benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-l-yl, 2-phenylprop-l-yl, 3-phenylprop-1-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-1-yl, 1- (benzyl) -1- (methyl) -eth-1-yl, 1- (benzyl) -prop-1 -yl or 2 -phenylhex-6 -yl, especially for benzyl or 2-phenylethyl;
  • Phenyl - (C -C 6 alkyl) carbonyloxy for: e.g. benzylcarbonyloxy, 1-phenylethylcarbonyloxy, 2-phenylethylcarbonyloxy, 1-phenylprop-1-ylcarbonyloxy, 2-phenylprop-l-ylcarbonyloxy, 3-phenylprop-1- ylcarbonyloxy, 1-phenylbut-l-ylcarbonyloxy, 2-phenylbut-1-ylcarbonyloxy, 3-phenylbut-l-ylcarbonyloxy, 4-phenylbut-1-ylcarbonyloxy, l-phenylbut-2-ylcarbonyloxy, 2-phenyl- but-2-ylcarbonyloxy, 3-phenylbut-2-ylcarbonyloxy, 4-phenyl-but-2-ylcarbonyloxy, 1- (benzyl) -eth-1-ylcarbonyloxy, 1- (benzyl) -1- (methyl)
  • Phenyl - (-C-C 6 -alkyl) sulfonyloxy for: e.g. benzylsulfonyloxy, 1-phenylethylsulfonyloxy, 2-phenylethylsulfonyloxy, 1-phenylprop-1-ylsulfonyloxy, 2-phenylprop-l-ylsulfonyloxy, 3-phenylprop-1- ylsulfonyloxy, 1-phenylbut-l-ylsulfonyloxy, 2-phenylbut-1-ylsulfonyloxy, 3-phenylbut-l-ylsulfonyloxy, 4-phenylbut-1-ylsulfonyloxy, l-phenylbut-2-ylsulfonyloxy, 2-phenyl- but-2-ylsulfonyloxy, 3-phenylbut-2-ylsulfonyloxy, 4-phen
  • (Ci-C ⁇ -alkyl) carbonyl for: methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl,
  • (-C-C 6 alkyl) carbonyl-C 6 -C 6 alkyl for: Ci-C ß -alkyl substituted by (Cx-Ce-alkyl) carbonyl as mentioned above, for example for methylcarbonylmethyl;
  • (Ci-C ß -haloalkyl) carbonyl for: a (CI-C ⁇ -alkyl) carbonyl radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example chloroacetyl, dichloroacetyl, Trichloroacetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl, chlorofluoracetyl, dichlorofluoroacetyl, chlorodifluoroacetyl, 2-fluoroethylcarbonyl, 2-chloroethylcarbonyl, 2-bromoethylcarbonyl, 2-iodoethylcarbonyl, 2, 2-trifluoromethylcarbonyl carbonyl, 2-chloro-2-fluoroethylcarbonyl, 2-chloro-2, 2-difluoroethylcarbonyl, 2, 2-d
  • (Ci-C ⁇ -alkyl) carbonyloxy for: acetyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, 1-methylethylcarbonyloxy, n-butylcarbonyloxy, 1-methylpropylcarbonyloxy, 2-methylpropylcarbonyloxy, 1, 1-dimethylethylcarbonyloxy, n-pentylcarbonyloxy, 1-methylbutylcarbonyloxy, 2-methylbutylcarbonyloxy, 3-methylbutylcarbonyloxy, 1, 1-dimethylpropylcarbonyloxy, 1, 2-dimethylpropylcarbonyloxy, 2, 2-dimethylpropylcarbonyloxy, 1-ethylpropylcarbonyloxy, n-hexylcarbonyloxy, 1-methylpentyl-methylpentylcarbonyloxy Methylpentyl - carbonyloxy, 4-methylpentylcarbonyloxy, 1, 1-dimethyl
  • (Ci-C ⁇ -haloalkyl) carbonyloxy for: a (Ci-C ⁇ - alkyl) carbonyloxy radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example chloroacetyloxy, dichloroacetyloxy , Trichloroacetyloxy, fluoroacetyloxy, difluoroacetyloxy, trifluoroacetyloxy, chlorofluoroacetyloxy, dichlorofluoroacetyloxy, chlorodifluoroacetyloxy, 2-fluoroethylcarbonyloxy, 2-chloroethylcarbonyloxy, 2-bromoethylcarbonyloxy, 2-iodoethylcarbonyloxy, 2,2, 2orethylcarbonyloxy, 2,2, 2orroxycarbonyloxy, 2,2, 2or 2-chloro-2-fluoro
  • Nonafluorobutylcarbonyloxy especially for trifluoroacetyl ⁇ oxy;
  • (Ci-C ß- alkyl) carbonylthio for acetylthio, ethylcarbonylthio, n-propylcarbonylthio, 1-methylethylcarbonylthio, n-butyl - carbonylthio, 1-methylpropylcarbonylthio, 2-methylpropylcarbonylthio, 1, 1-dimethylethylcarbonylthio, n-pentyl - n-pentyl 1-methylbutylcarbonylthio, 2-methylbutyl - carbonylthio, 3-methylbutylcarbonylthio, 1, 1-dimethylpropyl - carbonylthio, 1, 2-dimethylpropylcarbonylthio, 2, 2-dimethyl - propylcarbonylthio, 1-ethylpropylcarbonylthio, n-hexyl-carbonylthyl, carbonylthio 2-methylpentyl - carbonyl
  • (C 1 -C 6 haloalkyl) carbonylthio for: a (Ci -Ce alkyl) carbonylthio radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example chloroacetylthio, dichloroacetylthio , Trichloroacetylthio, fluoroacetylthio, difluoroacetylthio, tri-fluoroacetylthio, chlorofluoracetylthio, dichlorofluoroacetyl-thio, chlorodifluoroacetylthio, 2-fluoroethylcarbonylthio, 2-chloroethylcarbonylthio, 2-bromoethylcarbonylthio, 2-bromoethylcarbonylthio, 2-bromoethylcarbonylthio, 2-bromethylcarbonylthio, Tri
  • (Ci-C ⁇ -alkyl) carbamoyloxy for: methylcarbamoyloxy, ethyl-carbamoyloxy, n-propylcarbamoyloxy, 1-methylethylcarbamoyl-oxy, n-butylcarbamoyloxy, 1-methylpropylcarbamoyloxy, 2-methylpropylcarbamoyloxy, 1, 1-dimethyloyloxy, 1, 1-dimethyloyloxy, amyl Methylbutylcarbamoyloxy, 2-methylbutylcarbamoyloxy, 3-methylbutylcarbamoyloxy, 1,1-dimethylpropylcarbamoyloxy, 1, 2-dimethylpropylcarbamoyloxy, 2, 2-dimethylpropylcarbamoyloxy, 1-ethylpropylcarbamoyloxy, n-hexylcarbamoyl
  • (-C 6 -Halogenalkyl) carbamoyloxy for: a (-C 6 alkyl) - carbamoyloxy radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example chloromethylcarbamoyloxy, dichloro - methylcarbamoyloxy, trichloromethylcarbamoyloxy, fluoromethyl - carbamoyloxy, difluoromethylcarbamoyloxy, trifluoromethyl - carbamoyloxy, chlorofluoromethylcarbamoyloxy, dichlorofluoromethylcarbamoyloxy, chlorodifluoromethylcarbamoyloxy, oxy-2-oxyoxy, oxy-oxamoyloxy-2-oxy-oxamoyloxy-2-oxy-oxy-oxy-oxy-oxam-2-oxy-oxy-oxam-2-oxy-oxam
  • C 1 -C 4 alkoxy for: 0CH 3 , 0C 2 H 5 , 0CH 2 -C 2 H 5 , 0CH (CH 3 ) 2 , n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 0C (CH 3 ) 3 , especially for OCH 3 or 0C 2 H 5 ;
  • C 1 -C 6 alkoxy for: C 1 -C 4 alkoxy as mentioned above, and for example n-pentoxy, 1-methylbutoxy, 2-methylbutoxy,
  • C 1 -C 6 -haloalkoxy for: a C 1 -C 6 -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 1 -C 4 -haloalkoxy or for 5-fluoro-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-l-hexoxy or dodecafluorohexoxy, in particular for OCH 2 F, OCHF 2 , OCF 3 , OCH 2 Cl, 2-fluoroethoxy, 2-chloroethoxy
  • Hydroxy -CC 6 alkoxy for: for example OCH 2 OH, OCH (OH) -CH 3 , OCH 2 CH 2 OH, OCH (OH) -C 2 H 5 , OCH 2 -CH (OH) -CH 3 , OCH 2 CH 2 CH 2 OH, OCH (OH) -CH 2 -C 2 H 5 , OCH 2 -CH (OH) -C 2 H 5 , OCH 2 CH 2 -CH (OH) -CH 3 , OCH 2 CH 2 CH 2 CH 2 OH, l-hydroxybut-2-yloxy, 2-hydroxybut-2-yloxy, 3-hydroxybut-2-yloxy, 4-hydroxybut-2-yloxy, OCH (CH 3 ) -CH 2 OH, OC (CH 3 ) 2 -CH 2 OH, OCH (C 2 H 5 ) -CH 2 OH or 2-hydroxyhex-6-yloxy, in particular for OCH 2 OH or OCH 2 CH 2 OH;
  • Cyano-C ! -C 6 -alkoxy for: for example OCH 2 CN, OCH (CN) -CH 3 , OCH 2 CH 2 CN, OCH (CN) -C 2 H 5 , OCH 2 -CH (CN) -CH 3 , OCH 2 CH 2 CH 2 CN, OCH (CN) -CH 2 -C 2 H 5 , OCH 2 -CH (CN) -C 2 H 5 , OCH 2 CH 2 -CH (CN) -CH 3 , OCH 2 CH 2 CH 2 CHCN, 1-cyano-but-2-yloxy, 2-cyanobut-2-yloxy, 3-cyanobut-2-yloxy, 4-cyano-but-2-yloxy, OCH (CH 3 ) -CH 2 CN, OC ( CH 3 ) 2 -CH 2 CN, OCH (C 2 H 5 ) -CH 2 CN or 2-cyanohex-6-yloxy, in particular for OCH 2 CN or OCH 2
  • C 3 -C 6 -cycloalkyl-C ⁇ -C 6 -alkoxy for: eg cyclopropylmethoxy, 1- (cyclopropyl) ethoxy, 2- (cyclopropyl) ethoxy, l- (cyclopropyDprop-1-oxy, 2- (cyclopropyl) prop -l-oxy, 3- (cyclopropyl) prop-l-oxy, 1- (cyclopropyl) but-l-oxy, 2- (cyclopropyl) but-l-oxy, 3- (cyclopropyl) but-1-oxy, 4 - (Cyclopropyl) but-l-oxy, 1- (cyclopropyl) but-2-oxy, 2- (cyclopropyl) but-2-oxy, 3- (cyclopropyl) but-2-oxy, 4- (cyclopropyl) but-2-oxy, 1- (cyclopropylmethyl) -eth-1-oxy, l- (cyclopropylmethyl) -1- (methyl) -
  • Phenyl-Ci-C ⁇ - alkoxy for: e.g. benzyloxy, 1-phenylethoxy,
  • Heterocyclyl -CC 6 -alkoxy for: eg heterocyclyl methoxy, 1- (heterocyclyl) ethoxy, 2- (heterocyclyl) ethoxy, 1- (heterocyclyl) prop-l-yloxy, 2- (heterocyclyl) prop-l-yloxy , 3- (heterocyclic) prop-l-yloxy, 1- (heterocyclyl) but-l-yloxy, 2- (heterocyclic) but-l-yloxy, 3- (heterocyclyl) but-l-yloxy, 4 - (Heterocyclyl) but-l-yloxy, 1- (heterocyclyl) but-2-yloxy, 2- (heterocyclyl) but-2-yloxy, 3- (heterocyclyl) but-2-yloxy, 4- (heterocyclyl) but- 2-yloxy, 1- (heterocyclylmethyl) -eth
  • - phenyl-Ci-C ⁇ alkylthio for: for example, benzylthio, 1-phenylethylthio, 2-phenylethylthio, 1-phenylprop-l-ylthio, 2-phenylprop-1-ylthio, 3-phenylprop-l-ylthio, 1-phenylbut-l-ylthio, 2-phenylbut-l-ylthio, 3-phenylbut-l-ylthio, 4-phenylbut-l-ylthio, l-phenylbut-2-ylthio, 2-phenylbut-2-ylthio, 3- Phenylbut-2-ylthio, 3-phenylbut-2-ylthio, 4-phenylbut-2-ylthio,
  • - (-C-C 6 -alkoxy) carbonyl for: e.g. COOCH 3 , COOC 2 H 5 , COOCH 2 -C 2 H 5 , COOCH (CH 3 ) 2 , COO (nC 4 H 9 ), COOCH (CH 3 ) - C 2 H 5 , COOCH 2 -CH (CH 3 ) 2 , COOC (CH 3 ) 3 , COO (nC 5 Hn), 1-methylbutoxycarbonyl, 2-methyl- butoxycarbonyl, 3-methylbutoxycarbonyl, 2, 2-dimethylpropoxycarbonyl, 1-ethylpropoxycarbonyl, n-hexoxycarbonyl, 1,1-dimethylpropoxycarbonyl, 1, 2-dimethylpropoxycarbonyl, 1-methyl - pentoxycarbonyl, 2-methylpentoxycarbonyl, 3-methylpentoxy- carbonyl, 4-methylpentoxycarbonyl, 1, 1-dimethylbutoxycarbonyl, 1, 2-di
  • (Ci-C ⁇ -alkoxy) carbonyloxy for: methoxycarbonyloxy, ethoxycarbonyloxy, n-propoxycarbonyloxy, 1-methylethoxycarbonyloxy, n-butoxycarbonyloxy, 1-methylpropoxycarbonyloxy, 2-methylprooxycarbonyloxy, 1, 1-dimethylethoxycarbonyloxy, n-pentoxycarbonyloxy, 1-methylbutoxycarbonyloxy, 2-methylbutoxycarbonyloxy, 3-methylbutoxycarbonyloxy, 2, 2-dimethylpropoxycarbonyloxy, 1-ethylpropoxycarbonyloxy, n-hexoxycarbonyloxy, 1, 1-dimethylpropoxycarbonyloxy, 1, 2-dimethylpropoxycarbonyl - oxyyl, 1-methylpentoxycarbonyloxy, 1-methylpentoxy Methylpentoxycarbonyloxy, 3-methylpentoxycarbonyloxy, 4-methylpentoxycarbonyloxy, 1, 1-dimethylbutoxycarbonyl
  • (Ci-C ⁇ -alkoxy) carbonylthio for: methoxycarbonylthio, ethoxycarbonylthio, n-propoxycarbonylthio, 1-methylethoxycarbonylthio, n-butoxycarbonylthio, 1-methylpropoxycarbonylthio, 2-methylpropoxycarbonylthio, 1, 1-dimethylthoxycarbonylthio, n- Methylbutoxycarbonylthio, 2-methylbutoxycarbonylthio, 3-methylbutoxycarbonylthio, 2, 2-dimethylpropoxycarbonylthio, 1-ethylpropoxycarbonylthio, n-hexoxycarbonylthio, 1, 1-dimethylpropoxycarbonylthio, 1, 2-dimethylpropoxycarbonylthioyl, 1-methyl - pentoxycarbonylthio, 3-methylpentoxycarbonylthio, 4-methyl-pentoxycarbonylthio, 1, 1-dimethylbutoxycarbonylthio, 1,
  • C ⁇ -C 6 alkylthio for: methylthio, ethylthio, n-propylthio, 1-methylethylthio, n-butylthio, 1-methylpropylthio, 2-methylpropylthio, 1, 1-dimethylethylthio, n-pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2, 2-dimethylpropylthio, 1-ethylpropylthio, n-hexylthio, 1, 1-dimethylpropylthio, 1, 2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio , 1, 1-dimethylbutylthio, 1, 2-dimethylbutylthio, 1, 3-dimethylbutylthio, 2, 2-dimethylbutylthio, 2, 3-dimethyl
  • -C-C 4 -haloalkylthio for: partially or completely substituted by fluorine, chlorine and / or bromine -CC 4 -alkylthio such as methylthio, ethylthio, n-propylthio, 1-methylethylthio, n-butylthio, 1-methylpropylthio, 2-methylpropylthio and 1,1-dimethylethylthio, preferably methylthio or ethylthio, for example difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylhio, 2-bromoethylthio, 2-iodoethylthio, 2,2-di-fluoroethylthio 2, 2-trifluoroethylthio, 2, 2, 2-trichloroethyl
  • Ci-C ß -Alkylthio as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, for example one of the residues mentioned under -C-C 4 -haloalkylthio or for 5- Fluoropentylthio, 5-chloropentylthio, 5-bromopentylthio, 5-iodine pentylthio, undecaf luorpentylthio, 6-fluorohexylthio or 6-chlorohexylthio, especially for chloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio or 2, 2, 2-trifluorethylthio;
  • Ci-C ß- alkylsulfinyl for: methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1-methylethylsulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1, 1-dimethyl-ethylsulfinyl, n-pentylsulfinyl, 1-methylbutyl , 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 1, 1-dimethylpropylsulfinyl, 1, 2-dimethylpropylsulfinyl, 2, 2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, n-hexylsulfinyl, 1-methylpentylsulfinyl, 2- Methy
  • Ci-C ß- alkylsulfonyl for: methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 1-methylethylsulfonyl, n-butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1, 1-dimethyl - ethylsulfonyl, n-pentylsulfonyl, n-pentylsulfonyl Methylbutylsulfonyl, 3-methylbutylsulfonyl, 1, 1-dimethylpropylsulfonyl, 1, 2-dimethylpropylsulfonyl, 2, 2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, n-hexylsulfonyl, 1-methylpentyls
  • C ⁇ -C 6 alkylsulfonyloxy for: methylsulfonyloxy, ethylsulfonyl - oxy, n-propylsulfonyloxy, 1-methylethylsulfonyloxy, n-butylsulfonyloxy, 1-methylpropylsulfonyloxy, 2-methylpropyl - sulfonyloxy, 1, 1-dimethylsulfonyl - oxyl Methylbutylsulfonyloxy, 2-methylbutylsulfonyloxy, 3-methylbutylsulfonyloxy, 1, 1-dimethylpropylsulfonyloxy,
  • C -Cg-Haloalkylsulfonyloxy for: -C -C 6 alkylsulfonyloxy as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example ClCH 2 -S0 2 -0-, CH (Cl) 2 -S0 2 -0-, C (CI) 3 -S0 2 -0-, FCH 2 -S0 2 -0-, CHF 2 -S0 2 -0-, CF 3 -S0 2 -0-, chlorofluoromethyl-S0 2 -0-, dichlorofluoromethyl-S0 2 -0-, chlorodifluoromethyl-S0 2 -0-, 1-fluoroethyl-S0 2 -0-, 2-fluoroethyl-S0 2 -0-, 2-chloroethyl-S0 2 -0 -, 2-bromo-ethyl-S0
  • (-C-C 6 alkylamino) carbonyl for: e.g. CONH-CH3, CONH-C 2 H 5 , CONH-CH 2 -C 2 H 5 , CONH-C (CH 3 ) 2 , CONH- (nC 4 H 9 ) , CONH-CH (CH 3 ) -C 2 H 5 , CONH-CH 2 -CH (CH 3 ) 2 , CONH-C (CH 3 ) 3 , CONH- (n- C 5 H 11 ), 1-methylbutyl - aminocarbonyl, 2-methylbutylaminocarbonyl, 3-methylbutylaminocarbonyl, 2, 2-dimethylpropylaminocarbonyl, 1-ethylpropylaminocarbonyl, n-hexylaminocarbonyl, 1, 1-dimethylpropylaminocarbonyl, 1, 2-dimethylpropylaminocarbonyl, 1-methylpentyl 3-methylpentylaminocarbonyl, 4-methyl
  • Di- (-C 6 -alkyl) aminocarbonyl for: for example N, N-dimethylamino-carbonyl, N, N-diethylaminocarbonyl, N, -dipropylamino-carbonyl, N, N-di- (1-methylethyl) aminocarbonyl, N, N-dibutylaminocarbonyl, N, N-di- (1-methylpropyl) aminocarbonyl, N, N-di- (2-methylpropyl) aminocarbonyl, N, N-di- (1, 1-dimethylethyl) aminocarbonyl, N-ethyl-N-methylaminocarbonyl, N-methyl-N-propylaminocarbonyl, N-methyl-N- (1-methylethyl) - aminocarbonyl, N-butyl-N-methylaminocarbonyl, N-methyl-N-
  • (-CC 6 -alkyl) iminooxycarbonyl for: methyliminooxycarbonyl, ethyliminooxycarbonyl, n-propyliminooxycarbonyl, 1-methylethyliminooxycarbonyl, n-butyliminooxycarbonyl, 1-methyl-propyliminooxycarbonyl, 2-methylpropyliminooxycarbonyl,
  • C ⁇ -C 6 -Alkylidenaminoxy for: methylidenaminoxy, ethylidenaminoxy, 1-propylidenaminoxy, 2-propylidenaminoxy, 1-butylideneaminoxy, 2-butylidenaminoxy or 2 -hexylidenaminoxy, especially for methylidenaminoxy or 2 - propylidenaminoxy;
  • C ⁇ -C 6 -alkyliminooxy for: methyliminooxy, ethyliminooxy, n- propyliminooxy, 1-methylethyliminooxy, n-butyliminooxy, 1-methylpropyliminooxy, 2-methylpropyliminooxy, n-pentyl - iminooxy, n-hexyliminooxy, 1-methylpentyliminooxy, 2 -M pentyliminooxy, 3-methylpentyliminooxy or 4-methylpentyliminooxy, especially for methyliminooxy, ethyliminooxy or isopropyliminooxy;
  • Ci-C ⁇ -alkyloximino such as methoxyimino, ethoxyimino, 1-propoxyimino, 2-propoxyimino, 1-methylethoxyimino, n-butoxyimino, sec.
  • C 1 -C 6 -alkoxy-C 6 -C 6 -alkyl for: C -C 6 -alkoxy as mentioned above-substituted C 1 -C 6 -alkyl, for example for methoxymethyl, ethoxymethyl, n-propoxymethyl, (1-methyl-ethoxy ) methyl, n-butoxymethyl, (1-methylpropoxy) methyl, (2-methylpropoxy) methyl, (1, 1-dimethylethoxy) methyl, 2- (methoxy) ethyl, 2- (ethoxy) ethyl, 2- (n-propoxy ) ethyl, 2- (1-methylethoxy) ethyl, 2- (n-butoxy) ethyl, 2- (l-methylpropoxy) ethyl, 2- (2-methylpropoxy) ethyl, 2- (1, 1-dimethyl - ethoxy) ethyl, 2- (methoxy) propyl, 2- (ethoxy
  • Ci-Ce-Alkoxy-Cx-C ⁇ - alkoxy for: by C ! -C 6 -alkoxy as mentioned above -CC 6 -alkoxy, for example for methoxymethoxy, ethoxymethoxy, n-propoxymethoxy, (1-methylethoxy) methoxy, n-butoxymethoxy, (1-methylpropoxy) methoxy, (2- Methylpropoxy) methoxy, (1, 1-dimethylethoxy) methoxy, 2- (methoxy) ethoxy, 2- (ethoxy) ethoxy, 2- (n-propoxy) ethoxy, 2- (1-methylethoxy) ethoxy, 2- (n- Butoxy) ethoxy, 2- (l-methylpropoxy) ethoxy, 2- (2-methylpropoxy) ethoxy, 2- (1, 1-dimethyl - ethoxy) ethoxy, 2- (methoxy) ropoxy, 2- (ethoxy) propoxy,
  • C 1 -C 6 -alkylthio-C 1 -C 6 -alkoxy for: C 1 -C 6 -alkylthio substituted as above C 1 -C 6 -alkoxy, for example for methylthiomethoxy, ethylthiomethoxy, n-propylthio methoxy, (1-methylethylthio ) methoxy, n-butylthiomethoxy, (1-methylpropy1thio) methoxy, (2-methylpropy1thio) methoxy, (1, 1-dimethylethylthio) methoxy, 2- (methylthio) ethoxy, 2- (ethylthio) ethoxy, 2- (n-propylthio ) ethoxy, 2- (1-methylethylthio) ethoxy, 2- (n-butylthio) ethoxy, 2- (1-methylpropylthio) ethoxy, 2- (2-methylpropylthio)
  • (-C 6 -alkoxy) carbonyl -CC 6 -alkoxy for: Ci-C 6 -alkoxy substituted by (-C 6 -alkoxy) carbonyl as mentioned above, for example for methoxycarbonyl-methoxy, ethoxycarbonyl-methoxy, n-propoxycarbonyl-methoxy, n-butoxycarbonyl-methoxy, 1- (methoxycarbonyl) ethoxy, 2- (methoxycarbonyl) ethoxy, 2- (ethoxycarbonyl) ethoxy, 2- (n-propoxycarbonyl) ethoxy, 2- (n-butoxycarbonyl) ethoxy , 3- (methoxycarbonyl) propoxy, 3- (ethoxycarbonyl) ropoxy, 3- (n-propoxycarbonyl) propoxy, 3- (n-butoxycarbonyl) propoxy, 4- (methoxycarbonyl) butoxy, 4- (ethoxycarbonyl) butoxy, 4-
  • (C ⁇ -C 6 -alkoxy) carbonyl-Cx-Ce alkyl of: by (C ⁇ -C 6 alkoxy) - carbonyl as mentioned above substituted C ⁇ -alkyl, eg methoxycarbonylmethyl, ethoxycarbonylmethyl, 1 - (methoxycarbonyl ) ethyl, 2 - (methoxycarbonyl) ethyl, 2 - (ethoxycarbonyl) ethyl, 3 - (methoxycarbonyl) propyl, 4- (methoxycarbonyl) butyl, 5 - (methoxycarbonyl) pentyl or 6- (methoxycarbonyl) hexyl;
  • (Ci-C 6 -alkoxy) carbonyl-Ci-C ⁇ - alkylsulfonyl for: Ci-C ß- alkyl substituted by (Ci-C ⁇ - alkoxy) carbonyl as mentioned above, for example for methoxycarbonylmethylsulfonyl, ethoxycarbonylmethylsulfonyl, 1- (methoxycarbonyl ) ethylsulfonyl, 2 - (methoxycarbonyl) ethylsulfonyl, 2- (ethoxycarbonyl) ethylsulfonyl, 3- (methoxycarbonyl) propylsulfonyl, 4 - (methoxycarbonyl) butylsulfonyl, 5 - (methoxycarbonyl) pentylsulfonyl or 6 - (methoxycarbonyl) hexylsulfonyl;
  • C ⁇ -C 6 -alkylthio-C ⁇ -C 6 alkyl viewed by C ⁇ -C 6 -alkylthio as mentioned above substituted C ⁇ -alkyl, eg methylthiomethyl, ethylthiomethyl, n-propylthiomethyl, (1-methylethylthio) methyl , n-Butylthiomethyl, (1-methylpropylthio) methyl, (2-methylpropylthio) methyl, (1, 1-dimethylethylthio) methyl, 2-methylthioethyl, 2-ethylthioethyl, 2- (n-propylthio) ethyl, 2nd - (1-methylethylthio) ethyl, 2- (n-butylthio) ethyl, 2- (1-methylpropylthio) ethyl,
  • C 1 -C 6 -Alkylthio- (-C-C 6 -alkyl) carbonyl for: C 1 -C 6 -alkyl thio as mentioned above, preferably methylthio or ethylthio, substituted (C 1 -C 6 -alkyl) carbonyl, for example for methylthiomethylcarbonyl , Ethylthiomethylcarbonyl, 1- (methylthio) ethylcarbonyl, 2 - (methylthio) ethylcarbonyl, 3- (methylthio) propylcarbonyl, 4 - (methylthio) butylcarbonyl, 5- (methylthio) pentylcarbonyl or 6 - (methylthio) hexylcarbonyl, in particular for (methylthio) methylcarbonyl or 1- (methyl ⁇ thio) ethylcarbonyl; Di- (-C 6 -alkyl) amino-Ci-C ⁇ -alkoxy
  • C 3 -C 6 alkenyl for: e.g. B. Prop-2-en-l-yl, n-buten-4-yl, l-methyl-prop-2-en-l-yl, 2-methyl-prop-2-en-l-yl, 2-butene 1-yl, n-penten-3-yl, n-penten-4-yl, l-methyl-but-2-en-l-yl, 2-methyl-but-2-en-l-yl, 3- Methyl-but-2-en-l-yl, 1-methyl-but-3-en-l-yl, 2-methyl-but-3-en-l-yl, 3-methyl-but-3-en-en-l-yl,
  • C 2 -C 6 alkenyl for: ethenyl or one of the radicals mentioned under C 3 -C 6 alkenyl, in particular for ethenyl or prop-2-en-yl;
  • Phenyl-C 3 -C 6 -alkenyloxy for: eg 3-phenyl-allyloxy, 4-phenyl-but-2-enyloxy, 4-phenyl-but-3-enyloxy or 5-phenyl-pent-4-enyloxy, preferably 3 -Phenylallyloxy or 4-phenyl-but-2-enyloxy, especially for 3 -phenylallyloxy;
  • Heterocyclyl -C 3 -C 6 -alkenyloxy for: e.g. 3-heterocyclyl-allyl-oxy, 4-heterocyclyl-but-2-enyloxy, 4-heterocyclyl-but-3-enyloxy or 5-heterocyclyl-pent-4-enyloxy, preferably 3-heterocyclyl -allyloxy or 4-heterocyclyl-but-2-enyloxy, in particular for 3-heterocyclyl -allyloxy;
  • C 3 -C 6 alkenyloxy for: prop-1-en-l-yloxy, prop-2-en-l-yloxy, 1-methylethenyloxy, n-buten-1-yloxy, n-buten-2-yloxy, n -Butene-3-yloxy, 1-methyl-prop-1-en-1-yloxy, 2-methyl-prop-1-en-1-yloxy, 1-methyl-prop-2-en-1-yloxy, 2 Methyl prop-2-en-l-yloxy, n-penten-1-yloxy, n-penten-2-yloxy, n-penten-3-yloxy, n-penten-4-yloxy, 1-methyl-but-l-en-l-yl-oxy, 2-methyl-but-l-en-l-yloxy, 3-methyl- but-l-en-l-yloxy, l-methyl-but-2-en-l-yloxy, 2-methyl-but-2-en-yloxy, 3-methyl
  • C 2 -C 6 alkenyloxy for: ethenyloxy or one of the radicals mentioned under C 3 -C 6 alkenyloxy, in particular for ethenyloxy or prop-2-en-1-yloxy;
  • C 3 -C 6 haloalkenyloxy for: C 3 -C 6 alkenyloxy as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, for example 2-chloroallyloxy, 3-chloroallyloxy, 2, 3-dichloroallyloxy , 3, 3-dichloroallyloxy, 2, 3, 3-trichlorallyloxy, 2, 3-dichlorobut-2-enyloxy, 2-bromo-allyloxy, 3-bromoallyloxy, 2, 3-dibromoallyloxy, 3,3-dibromo-allyloxy, 2 , 3, 3-tribromoallyloxy or 2,3-dibromobut-2-enyloxy, in particular for 2 -chloroallyloxy or 3,3-dichloroallyloxy;
  • C 1 -C 6 -alkoxy-C 3 -C 6 -alkenyloxy for: C 3 -C 6 -alkoxy substituted by C ⁇ -C 6 -alkoxy as mentioned above, for example for 3- (methoxy) allyloxy, 3 - (ethoxy) allyloxy, 3 - (n-propoxy) allyl - oxy, 3- (n-butoxy) allyloxy, 3 - (n-pentoxy) allyloxy, 3- (n-hexoxy) allyloxy, 3- (methoxy) -1-methylallyloxy, 3- (methoxy) -2-methylallyloxy , 3- (methoxy) -3-methylallyloxy, 4 - (methoxy) but - 2-enyloxy, 4 - (ethoxy) but-2-enyloxy, 4 - (n-propoxy) but-2 -enyl - oxy, 4 - (n-butoxy) but -2 -enyloxy
  • C 2 -C 6 alkenylthio for: ethenylthio or C 3 -C 6 alkenylthio such as prop-1-en-l-ylthio, prop-2-en-l-ylthio, 1-methylethenylthio, n-butene-1- ylthio, n-buten-2-ylthio, n-buten-3-ylthio, 1-methyl-prop-1-en-l -ylthio, 2 -methyl-prop-1- en-l-yl thio, l- Methyl-prop-2-en-l-ylthio, 2-methyl-prop-2-en-l-ylthio, n-penten-1-ylthio, n-penten-2-ylthio, n-penten-3-yl thio , n-penten-4-ylthio, 1-methyl-but-l-en-l-ylthio, 2-methyl-but-1-en-l
  • C 3 -C 6 alkynyl for: prop-1-in-l-yl, prop-2-in-l-yl, n-but-1-in-l-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
  • C 2 -C 6 -alkynyl for: ethynyl or one of the radicals mentioned under C 3 -C 6 -alkynyl, in particular for ethynyl or prop-2-yn-1-yl;
  • Phenyl -C 3 -C 6 alkynyloxy for: e.g. 3 - phenylprop-2 - in 1 -yloxy, 4-phenylbut-2-in-1 -yloxy, 3-phenylbut-3 - in-2 -yloxy, 5- Phenylpent-3-ynoxy or 6-phenylhex-4-yn-1-yloxy, in particular for 3-phenylprop-2-yn-1-yloxy or 3-phenylbut-3-yn-2-yloxy; Heterocyclyl -C 3 -C 6 alkynyloxy for: e.g.
  • C3-C 6 -alkynylthio for: prop-1-in-l-ylthio, prop-2-in-l-ylthio, n-but-1-in-l-ylthio, n-but-l-in-3- ylthio, n-but-l-in-4-ylthio, n-but-2-in-l-ylthio, n-pent-1-in-l-ylthio, n-pent-l-in-3-ylthio, n-pent-l-in-4-ylthio, n-pent-l-in-5-ylthio, n-pent-2-in-l-ylthio, n-pent-2-in-4-ylthio, n- Pent-2-in-5-ylthio, 3-methyl-but-l-in-3-ylthio, 3-methylbut-l-in-4-ylthio, n-Hex-1-in-l-ylthi
  • C 2 -C 6 alkynylthio for: ethynylthio or one of the radicals mentioned under C 3 -C 6 -alkynylthio, in particular for ethynylthio or prop-2- in 1 -ylthio;
  • (C 3 -C 6 alkenyloxy) carbonyl for: prop-1-en-l-yloxycarbonyl, prop-2-en-l-yloxycarbonyl, 1-methylethenyloxycarbonyl, n-buten-1-yloxycarbonyl, n-buten-2- yloxycarbonyl, n-butene-3-yloxycarbonyl, 1-methyl-prop-l-en-l-yloxycarbonyl, 2-methyl-prop-1-en-l-yloxycarbonyl, l-methyl-prop-2-en-l- yloxycarbonyl, 2-methyl-prop-2-en-l-yloxycarbonyl, n-pentene-1-yloxycarbonyl, n-pentene-2-yloxycarbonyl, n-pentene-3-yloxycarbonyl, n-pentene-4- yloxycarbonyl, 1-methyl-but-l-en-l-yloxycarbonyl, 2-
  • (C 3 -C 6 alkenyloxy) carbonyl -CC 6 alkyl for: by (C 3 -C 6 alkenyloxy) carbonyl as mentioned above, preferably - as Prop-2-en-l-yl-oxycarbonyl, substituted Ci-C ö alkyl, for example prop-2-en-1-yl -oxycarbonyl -methyl;
  • (C -C 6 alkenyl) carbonyloxy for: ethenylcarbonyloxy or one of the radicals mentioned under (C 3 -C 6 alkenyl) carbonyloxy, in particular for ethenylcarbonyloxy or prop-2-en-1-ylcarbonyloxy;
  • (C 2 -C 6 alkenyl) carbonylthio for: ethenylcarbonylthio or one of the radicals mentioned under (C 3 -C 6 alkenyl) carbonylthio, in particular for prop-2-en-1-yl carbonylthio;
  • (C 2 -C 6 -alkynyl) carbonyloxy for: ethynylcarbonyloxy or one of the radicals mentioned under (C3-C 6 -alkynyl) carbonyloxy, in particular for ethynylcarbonyloxy or prop-2-yn-1-ylcarbonyloxy;
  • C 3 -C ⁇ alkynylsulfonyloxy for: prop-1-in-1-ylsulfonyloxy, prop-2-in-1-ylsulfonyloxy, n-but-1-in-1-ylsulfonyloxy, n-but-1-in-3 -ylsulfonyloxy, n-But-1-in-4-ylsulfonyloxy, n-But-2-in-1-ylsulfonyloxy, n-Pent-1-in-1-ylsulfonyloxy, n-Pent-1-in-3-ylsul
  • (C 2 -C 6 -alkynyl) carbonylthio for: ethynylcarbonylthio or one of the radicals mentioned under (C 3 -C 3 -alkynyl) carbonylthio, in particular for ethynylcarbonylthio or prop-2-yn-1-ylcarbonylthio;
  • C 3 -C 6 alkenyloxy -CC 6 alkyl for: by C 3 -C 6 alkenyloxy as mentioned above, preferably allyloxy, 2-methyl-prop-2-en-l-yloxy, but-l-ene -3-yloxy, but-l-en-4-yloxy or but-2-en-l-yloxy-substituted Ci-C ⁇ -alkyl, e.g. for allyloxymethyl, 2-allyloxyethyl or but-l-en-4- yloxymethyl;
  • C 3 -C 6 alkynyloxy -CC 6 alkyl for: by C 3 -C 6 -alkynyloxy as mentioned above, preferably propargyloxy, but-l-in-3-yl-oxy, but-l-in-4 -yloxy or but-2-yn-l-yloxy, substituted -CC 6 alkyl, for example for propargyloxymethyl or 2-propargyloxyethyl;
  • C 3 -C 7 cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl, in particular for cyclopentyl or cyclohexyl;
  • C 3 -C 6 cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
  • C 3 -C 6 cycloalkoxy for: cyclopropyloxy, cyclobutyloxy, cyclopentyloxy or cyclohexyloxy;
  • C 3 -C 6 cycloalkylthio for: cyclopropylthio, cyclobutylthio, cyclopentylthio or cyclohexylthio;
  • C 3 -C 6 cycloalkyl carbonyloxy for: cyclopropylcarbonyloxy, cyclobutylcarbonyloxy, cyclopentylcarbonyloxy or cyclohexylcarbonyloxy;
  • C 3 -C cycloalkylsulfonyloxy for: cyclopropylsulfonyloxy, cyclobutylsulfonyloxy, cyclopentylsulfonyloxy or cyclohexylsulfonyloxy;
  • C5-C7 cycloalkenyloxy for: cyclopent-1 -enyloxy, cyclopent-2 -enyloxy, Cylopent- 3 -enyloxy, cyclohex-1 -enyloxy, cyclo hex-2 -enyloxy, cyclohex-3 -enyloxy, cyclohept -1 - enyloxy,
  • -C -alkylene for: methylene, 1,1-ethylene, 1,2-ethylene, 1, 1-propylene, 1, 2-propylene, 1, 3-propylene, 2, 2-propylene, 1,1-butylene , 1,2-butylene, 1,3-butylene, 1,4-butylene, 2,2-butylene, 2,3-butylene, 2-methyl-1, 1-propylene, 2-methyl1-1, 2-propylene or 2 -methyl-1, 3-propylene, especially for -C-C 3 alkylene such as -CH 2 -, -CH (CH 3 ) -, -CH 2 CH 2 -, -CH (C 2 H 5 ) -, -CH 2 -CH (CH 3 ) -, -CH 2 CH 2 CH 2 - and -C (CH 3 ) 2 -.
  • 3- to 7-membered heterocyclyl is understood to mean both saturated, partially or completely unsaturated and aromatic heterocycles having one to three heteroatoms, selected from a group consisting of one to three nitrogen atoms, one or two oxygen atoms and one or two sulfur atoms .
  • 3- to 7-membered heterocycles are oxiranyl, aziridiny, oxetanyl, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl, isothiazolidinyl, pyrazolidinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, dioxolanyl and 1, 3-dioxanol such as 1,3-dioxanol Dioxolan-4-yl, dioxanyl such as
  • Furyl such as 2-furyl and 3-furyl
  • thienyl such as 2-thienyl
  • 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 2-0xazolyl, 4-oxazolyl 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,
  • the variables preferably have the following meanings, in each case individually or in combination:
  • R 1 is hydrogen or halogen, in particular hydrogen
  • R 2 is hydrogen
  • R 3 halogen, especially chlorine
  • R 6 is hydrogen, cyano, halo, C ⁇ -C 4 -alkoxy, C alkylthio, C 2 -C 4 alkenyloxy, C 2 -C alkenylthio, C 2 -C 4 alkynyloxy or C 2 -C 4 - Alkynylthio, especially hydrogen;
  • R 9 are hydrogen, C 6 alkyl, C 3 -C 6 alkenyl, (C ⁇ -C6 alkoxy) - carbonyl-Ci-C ⁇ alkyl or phenyl can be unsubstituted or which may carry one to three radicals, each selected from the group consisting of halogen, nitro, C 1 -C 6 -alkyl, C 1 -C 6 alkoxy and (C 1 -C 6 alkyl) carbonyl, in particular C 1 -C 3 alkyl, C 3 -C 4 alkenyl or (-C-C 3 alkoxy) carbonyl -C 1 -C 3 alkyl;
  • R 10 are hydrogen, C 3 alkyl, Ci -C3 alkoxy, (C 1 -C 3 alkoxy) carbonyl -C ⁇ -C 3 alkoxy or C 3 -C 4 alkenyloxy, in particular C ⁇ -C 3 - alkyl, C ⁇ -C3 alkoxy, (C 1 -C 3 alkoxy) carbonyl -C ⁇ -C 3 alkoxy or C 3 -C 4 alkenyloxy;
  • R 11 is hydrogen or methyl, especially hydrogen
  • R 12 , R 13 independently of one another C 1 -C 6 -alkyl, in particular C 1 -C 3 -alkyl or R 12 and R 13 together form a saturated or unsaturated, two- to four-membered carbon chain which can carry an oxo-substituent, the Carbon chain can still carry one or two radicals, each selected from the group consisting of Ci-C ⁇ -alkyl, C -C6 alkenyl, C 2 -C 6 alkenyloxy and (-C-C 6 alkoxy) carbonyl, especially a saturated two - or three-membered carbon chain, which can be unsubstituted or carry one or two radicals, each selected from the group consisting of C 1 -C 3 alkyl, C 2 -C 4 alkenyl and (Ci -C 3 alkoxy) carbonyl; R 14 is hydrogen, halogen or Ci-C ⁇ - alkyl, in particular hydrogen, chlorine or methyl; chlorine is particularly preferred;
  • R 15 OR 22 , -CC 4 alkyl, C 3 -C 4 -alkenyl, C 3 -C 4 -alkynyl, -C-C 6 alkyl iminooxy or -N (R 23 ) R 24 , in particular OR 22 or -N (R 23 ) R 24 ;
  • R 16 is hydrogen, halogen or Ci-C ⁇ -alkyl, especially hydrogen, chlorine or methyl;
  • R 17 is hydrogen, halogen or Ci-C ⁇ -alkyl, especially hydrogen, chlorine or methyl;
  • R 18 is hydrogen, -CC alkyl or (-C 4 alkoxy) carbonyl, especially hydrogen, methyl or (Ci -C 3 alkoxy) carbonyl,
  • R 19 is hydrogen, C 1 -C 3 -alkyl or C 3 -C 4 alkenyl, where the last two groups can each carry one of the following radicals: chlorine, (C 1 -C 6 -alkyl) carbonyl, (Ci-C ⁇ -alkoxy ) carbonyl or (C 3 -C 6 alkenyloxy) carbonyl; or (Ci-C ⁇ - alkylamino) carbonyl or di - (-C-C 6 alkyl) aminocarbonyl; in particular hydrogen, C 1 -C 3 alkyl or C 3 -C 4 alkenyl, where the last two groups can each carry one of the following radicals: chlorine, (C 1 -C 3 alkoxy) carbonyl or (C 3 - C 4 alkenyloxy) carbonyl; or (-CC 2 alkyl) aminocarbonyl or dimethylaminocarbonyl;
  • R 21 is hydrogen, methyl, -CC 6 alkoxy, C 3 -C 6 alkenyloxy or
  • (Ci-C ö -alkyl) carbonyloxy where the latter 4 radicals can carry one of the following substituents: (-C-C 6 -alkyl) carbonyl, (-C-C 6 -alkoxy) carbonyl, (C x -C 6 -alkyl) - amino) carbonyl or di - (Ci -C 6 alkyl) aminocarbonyl; or C 3 -C 6 alkynyloxy, (C 2 -C 6 alkynyl) carbonyloxy, phenoxy or benzoyloxy, where the phenyl rings of the latter two radicals may be unsubstituted or in turn may carry one to three substituents, each selected from the group consisting of halogen, -C 6 alkyl, C !
  • -C 6 halo alkyl and -CC 6 alkoxy in particular C 3 -C 4 alkynyloxy, C 1 -C 3 alkoxy or C 3 -Ce alkenyloxy, where the last two radicals can each carry one of the following substituents: (C 1 -C 3 alkoxy) carbonyl, (C 1 - C 3 alkyl) aminocarbonyl or dirnethylaminocarbonyl;
  • R 22 one of the preferred meanings of R 19, in particular are hydrogen, C 3 alkyl or C 3 -C 4 -alkenyl, where the last two groups to carry one of the following radicals, respectively: chlorine, (C 1 -C 3 alkoxy ) carbonyl or (C 3 -C 4 alkenyloxy) carbonyl; or (C 1 -C 2 alkyl) aminocarbonyl or dimethylaminocarbonyl;
  • R 23 , R 24 independently of one another hydrogen, C 1 -C 4 alkyl, C 3 -C 4 alkenyl, C 3 -C 6 cycloalkyl,
  • R 30 is hydrogen, -CC 6 -alkyl, C 3 -Cg-alkenyl, (Ci-Cg-alkoxy) - carbonyl-Ci-Cg-alkyl or phenyl, which in turn can carry one to three substituents, each selected from the group consisting of nitro, halogen, -C 6 alkyl, -C 6 alkoxy and (-C 6 alkoxy) carbonyl, in particular -C 6 alkoxy, C 3 -Cg -alkenyloxy or (-C 6 -Alkoxy) carbonyl -Ci -Cg alkoxy; C ⁇ -C 3 alkoxy, C 3 -C 4 alkenyloxy and (C ⁇ -C 3 alkoxy) carbonyl -C 1 -C 3 alkoxy are particularly preferred; R 30 is hydrogen, -CC 6 -alkyl, C 3 -Cg-alkenyl, (Ci-Cg-alkoxy) - carbon
  • R 31 are hydrogen, C 3 -alkyl, C 3 alkoxy, (Ci -C 3 alkoxy) - carbonyl -C 1 -C 3 alkoxy or C 3 -C 4 alkenyloxy, especially methyl, C ⁇ - C 3 alkoxy, (C 1 -C 3 alkoxy) carbonyl -C 1 -C 3 alkoxy or C 3 -C 4 alkenyloxy.
  • Alk trifluoromethyl
  • the l-amino-3-benzyluracils Ib.l to Ib.71 differ from the compounds Ia.l to la.71 only in that R 5 is in the ⁇ and R 6 in the ⁇ position:
  • the particularly preferred embodiments of the enamine esters III and the enamine carboxylates IV with respect to the substituents Alk and R 1 -R 31 correspond to those of the 1-amino-3-benzyluracile I.
  • the l-amino-3-benzyluracils of the formula I according to the invention can be obtained in various ways, in particular by one of the following processes:
  • L 1 means low molecular weight alkyl, preferably Ci-Cg-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 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 sodium alcoholates, alkali metal hydroxides, in particular sodium and potassium hydroxide, alkali metal carbonates, in particular sodium and potassium carbonate, and metal hydrides, in particular sodium hydride.
  • sodium hydride it has proven to be advantageous to work in an aliphatic or cyclic ether, in dimethylformamide or in dimethyl sulfoxide.
  • the 0.5 to twice the molar amount of base is sufficient for the reaction to succeed.
  • the reaction temperature is between (-78) ° C and the boiling point of the respective reaction mixture, in particular at (-60) to 60 ° C.
  • the process product is usually 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 III using acid.
  • 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.
  • 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. ⁇ (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).
  • Suitable bases are, for example, alkali metal alcoholates such as sodium methylate and potassium tert. -butanolate, alkali metal - carbonates such as sodium and potassium carbonate, or alkali metal hydrides such as sodium hydride and potassium hydride.
  • reaction is carried out in a polar solvent, e.g. in dimethylformamide, N-methylpyrrolidone, in a sulfoxide such as dimethyl sulfoxide or in a carboxylic acid ester such as ethyl acetate, which has so far been found to be particularly suitable.
  • a polar solvent e.g. in dimethylformamide, N-methylpyrrolidone
  • a sulfoxide such as dimethyl sulfoxide
  • carboxylic acid ester such as ethyl acetate
  • the amount of base and aminating agent is preferably 0.5 to twice the molar amount, based on the amount of III.
  • the process is carried out at (-10) ° C to the boiling point of the reaction mixture, in particular at 10 to 70 ° C.
  • the lH-3-Benzylurac ⁇ le V are in turn obtainable, for example, by cyclization of enamine esters VI or enamine carboxylates VII:
  • Suitable bases are, for example, alkali metal alcoholates such as sodium methylate, alkali metal carbonates such as sodium and potassium carbonate or alkali metal hydrides such as sodium and potassium hydride. There is also the possibility of first converting VIII into the alkali metal salt by means of base and then subsequently reacting it with IX.
  • an inert polar solvent or diluent e.g. in dimethylformamide, N-methylpyrrolidone, in a sulfoxide such as dimethyl sulfoxide, in a carboxylic acid ester such as ethyl acetate or in a ketone such as acetone.
  • reaction temperature is from 0 ° C to the boiling point of the reaction mixture.
  • OR c stands for the alcohol residues defined under R 6 .
  • the ether cleavage is usually carried out using an acid, for example using hydrogen bromide, hydrogen iodide or pyridinium hydrochloride, using a Lewis acid such as aluminum trichloride, tribromide, triiodide, boron trichloride, tribromide, trifluoride and iron trichloride, or using trimethylsilyl iodide.
  • a Lewis acid such as aluminum trichloride, tribromide, triiodide, boron trichloride, tribromide, trifluoride and iron trichloride
  • lithium salts such as lithium chloride or mixtures of an inorganic iodide and trimethylsilyl chloride can also be used to cleave the ether bond.
  • the bond can also be split under hydrogenation conditions using hydrogen in the presence of a hydrogenation catalyst such as platinum and palladium on activated carbon.
  • Diluents e.g. B. in an aliphatic, cyclic or aromatic hydrocarbon such as n-pentane, petroleum ether, cyclohexane, benzene, toluene or xylene, an aliphatic or cyclic ether such as diethyl ether, tert.
  • an aliphatic, cyclic or aromatic hydrocarbon such as n-pentane, petroleum ether, cyclohexane, benzene, toluene or xylene
  • an aliphatic or cyclic ether such as diethyl ether, tert.
  • reaction without a solvent can also be advantageous.
  • the alkylation can, for example, with the halide, preferably the chloride or bromide, the sulfate, sulfonate, preferably the methanesulfonate (mesylate), benzenesulfonate, p-toluenesulfonate (tosylate), p-bromobenzenesulfonate (brosylate), the trifluoromethanesulfonate (triflate) or the Diazo compound of an unsubstituted or substituted alkane, cycloalkane, haloalkane, alkene or alkyne.
  • the halide preferably the chloride or bromide
  • the sulfate, sulfonate preferably the methanesulfonate (mesylate), benzenesulfonate, p-toluenesulfonate (tosylate), p-bromobenzenesulfonate (
  • aprotic solvents in particular, for example aliphatic and cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, aliphatic ketones such as acetone, Amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, ureas such as tetramethylurea and 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone, carboxylic acid esters such as ethyl acetate, or halogenated aliphatic or aromatic hydrocarbons such as dichloromethane and chlorobenzene can be considered.
  • aliphatic and cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane
  • aliphatic ketones such as acetone
  • Amides such as dimethylformamide
  • sulfoxides such as dimethyl sulfoxide
  • ureas such
  • Both inorganic bases e.g. Alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrogen carbonates such as sodium and potassium hydrogen carbonate, or alkali metal hydrides such as sodium hydride and potassium hydride, as well as organic bases, e.g. Amines such as triethylamine, pyridine and N, N-diethylaniline, or alkali metal alcoholates such as sodium methoxide, ethanolate and potassium tert. -butanolate.
  • Alkali metal carbonates such as sodium carbonate and potassium carbonate
  • alkali metal hydrogen carbonates such as sodium and potassium hydrogen carbonate
  • alkali metal hydrides such as sodium hydride and potassium hydride
  • organic bases e.g. Amines such as triethylamine, pyridine and N, N-diethylaniline, or alkali metal alcoholates such as sodium methoxide, ethanolate and potassium tert. -butanolate.
  • reaction temperature 0 ° C to the boiling temperature of the reaction mixture is recommended, in particular from 0 to 60 ° C.
  • This method can also be used to make compounds I.
  • R 4 C 1 -C 4 alkoxy from the corresponding hydroxy precursors.
  • Suitable acylating agents are e.g. the acid halides, especially the acid chlorides, the anhydrides or isocyanates of alkane, cycloalkane, alkene, alkyne, phenyl or phenyl - alkane carboxylic acids.
  • the free acids or their anhydrides are also suitable, provided that a condensation agent such as carbonyldiimidazole and dicyclohexylcarbondiimide is used.
  • an inert organic solvent or diluent which is preferably aprotic, e.g. in an aliphatic or cyclic ether such as
  • ketone such as acetone
  • an amide such as dimethylformamide
  • a urea such as tetramethylurea and 1,3-dimethyl-tetrahydro2 (1H) -pyrimidinone
  • carboxylic acid ester such as ethyl acetate
  • an aliphatic or aromatic halogenated hydrocarbon such as dichloromethane and chlorobenzene.
  • Suitable cyanides are in particular metal cyanides, e.g. the alkali metal cyanides such as lithium, sodium and potassium cyanide, the alkaline earth metal cyanides such as magnesium cyanide, or also transition metal cyanides such as copper cyanide.
  • metal cyanides e.g. the alkali metal cyanides such as lithium, sodium and potassium cyanide, the alkaline earth metal cyanides such as magnesium cyanide, or also transition metal cyanides such as copper cyanide.
  • an ether such as tetrahydrofuran, dioxane and 1, 2-dimethoxyethane
  • an aprotic, polar solvent e.g. an alkyl nitrile such as aceto-, propio- and butyronitrile, an alkyl urea such as N, N, N ', N' -tetramethyl urea, an open-chain or cyclic dialkyl amide such as dimethylformamide, N-methyl-2-pyrrolidone, 1, 2-dimethyl-imidazolidine 2-one and 1, 2-dimethyl-3, 4, 5, 6-tetrahydro-2 (1H) -pyrimidinone, a dialkyl sulfoxide such as dimethyl sulfoxide, or in hexamethylphosphoric acid triamide.
  • an alkyl nitrile such as aceto-, propio- and butyronitrile
  • an alkyl urea such as N, N, N ', N' -
  • Useful catalysts are e.g. Transition metals and their complexes or salts, e.g. Compounds of copper such as copper (I) chloride, iodide, cyanide, or nickel such as nickel bis-triphenylphosphine dibromide.
  • a base in particular weakly nucleophilic bases, both inorganic bases, for example alkali metal carbonates such as sodium and potassium carbonate, Alkali metal bicarbonates such as sodium and potassium bicarbonate, or alkali metal hydrides such as sodium hydride and potassium hydride, as well as organic bases, for example amines such as triethylamine, pyridine and N, N-diethylaniline.
  • the proportions are usually not critical. In general, about one to ten times the amount of cyanide and base, based on the amount of starting compound I or V, is sufficient.
  • the reaction temperature is usually 50 to 250 ° C; To increase the selectivity of the reaction, it may also be advisable to work at lower temperatures, in particular at about 20 ° C.
  • the halogenation is usually carried out in an inert organic solvent or diluent.
  • aliphatic carboxylic acids such as acetic acid or chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride are suitable.
  • Low-boiling aliphatic carboxylic acids such as acetic acid are particularly preferred for iodination.
  • Elemental chlorine or bromine or sulfuryl chloride or sulfuryl bromide are particularly suitable for chlorination and bromination, at a reaction temperature of preferably 0 to 60 ° C., in particular 10 to 30 ° C. If desired, the chlorination and bromination can take place in the presence of an acid-binding agent, sodium acetate and tertiary amines such as triethylamine, dimethylaniline and pyridine being particularly preferred.
  • Elemental iodine is particularly preferred as the iodinating agent, in which case the reaction temperature is approximately 0 to 110 ° C., preferably 10 to 30 ° C.
  • the iodination proceeds particularly advantageously in the presence of a mineral acid such as fuming nitric acid.
  • the alcohol HOR d the alcoholate of which is used, or in an inert organic solvent or diluent, for example in an aromatic hydrocarbon such as toluene and the xylenes, in an ether such as diethyl ether, tetrahydrofuran and 1,2- Dimeth oxyethane, or in a halogenated hydrocarbon such as dichloromethane and chlorobenzene.
  • an aromatic hydrocarbon such as toluene and the xylenes
  • an ether such as diethyl ether, tetrahydrofuran and 1,2- Dimeth oxyethane
  • a halogenated hydrocarbon such as dichloromethane and chlorobenzene.
  • the reaction temperature is generally from 0 to 150 ° C, preferably at room temperature (about 20 ° C) up to the boiling point of the reaction mixture.
  • the acetalization is generally carried out in an inert aprotic organic solvent, for example in an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aromatic hydrocarbon such as benzene, toluene, o-, m-, p-xylene and Mesitylene, or in a chlorinated hydrocarbon such as methylene chloride, chloroform and chlorobenzene, unless it is carried out without solvent in an excess of HZ ⁇ -R 12 , HZ 2 R 13 or HZ 1 (R 12 R 13 ) Z 2 -H.
  • an inert aprotic organic solvent for example in an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane
  • aromatic hydrocarbon such as benzene, toluene,
  • Resulting water of reaction can be removed from the reaction mixture as usual, e.g. by means of water separation.
  • the acetalization is preferably carried out in the presence of an organic acid such as p-toluenesulfonic acid and / or a Lewis acid such as tin tetrachloride, tin II chloride, iron III chloride, tellurium tetrachloride and boron trifluoroetherate or a suitable catalyst such as montmorillonite K 10 , the amount of acid normally being between 0.5 and 100 mol%, based on the amount of starting material to be acetalized.
  • the proportions are not critical. For a complete reaction, all reactants are used in approximately stoichiometric amounts, but an excess of HZ ⁇ -R 12 and HZ 2 R 13 or HZ 1 (R 12 R 1 ) Z -H is preferably used.
  • temperatures from (-78) to 180 ° C, preferably (-40) to 150 ° C.
  • R 12 and R 13 do not form a common radical and Z i R 12 and Z 2 R 13 are not the same, they can, if desired, be purified and separated by methods known per se, such as crystallization and chromatography.
  • acetalization via a detour to acetalization to dialkyl acetal, preferably dimethylacetal, and subsequent transacetalization in the presence of a suitable catalyst.
  • a suitable catalyst preferably dimethylacetal
  • the solvents, catalysts and other reaction conditions used for the transacetalization correspond to those already listed above for the acetalization.
  • the acetal can be used without the addition of acid, in the presence of an acid, eg a mineral acid such as hydrochloric acid and sulfuric acid, an organic carboxylic acid such as, luoressigklare formic acid, acetic acid, oxalic acid and Trif, in the presence of an acidic ion exchanger such as Amberlite ® (trademark of the company. "Aldrich”) IR120 or IRC84, or in the presence of a
  • Transition metal salt such as mercury (II) oxide, copper (I) oxide and iron (III) chloride can be performed.
  • solvents or diluents examples include aromatics such as benzene, toluene and o-, m-, p-xylene, aliphatic or cyclic ethers such as 1,2-dimethoxyethane, diethyl ether, tetrahydrofuran and dioxane, alcohols such as methanol, ethanol and isopropanol , polar organic solvents such as dimethylformamide, dimethyl sulfoxide and acetonitrile, ketones such as acetone and butanone, or water. It is preferred to work without a solvent in an excess of the acid used for the acetal cleavage, formic acid being particularly preferred.
  • the starting materials I and V, where R 6 is a group —C (R 11 ) (Z ⁇ -R 12 ) (Z 2 R i3 ), and H 2 Y are used in at least stochiometric amounts, however an excess of H 2 Y, up to about 200 mol%, is also possible.
  • the amount of acid, ion exchanger or transition metal salt is not critical. In general, an amount of up to about 300 mol%, based on the amount of H 2 Y, is sufficient.
  • reaction temperature is (-78) to 180 ° C, preferably 0 ° C to the boiling point of the respective diluent.
  • the reaction can be carried out with the following phosphorylides Xa to Xd, phosphonium salts XIa to Xld and phosphonates Xlla to Xlld:
  • R 3 P C (R 14 ) -CO-R 15 Xa
  • R 3 P C (R 14 ) -CH 2 -CO-R 15 Xb
  • R 3 P®-CH (R 14 ) -CH 2 -CO-R 15 Hal ⁇ Xlb, R 3 P®-CH (R 14 ) -C (R 16 ) C (R 17 ) -CO-R 15 shark ® XIc, R 3 P®-CH (R 14 ) -CH 2 -CH (R 18 ) -CO-R 15 Hai® Xld;
  • the radicals R on the phosphorus may be the same or different and are, for example, branched or unbranched C -Cs-alkyl groups, C 5 - or Cg -cycloalkyl groups and in particular phenyl, the further (for the implementation of inert substituents, for example C ⁇ .C-alkyl such as methyl, ethyl and tert-butyl, -CC 4 alkoxy such as methoxy or halogen such as fluorine, chlorine and bromine) can wear.
  • triphenylphosphine is particularly inexpensive and the reactions are also very reactive and easy to separate, solid triphenylphosphine oxide.
  • Inert organic solvents e.g. Aromatics such as toluene and o-, m-, p-xylene, ethers such as 1,2-dimethoxyethane, diethyl ether, tetrahydrofuran and dioxane, polar organic solvents such as dimethylformamide and dimethyl sulfoxide, or alcohols such as methanol, ethanol and isopropanol, into consideration.
  • all reactants are used in approximately stochiometric amounts; however, an excess of base is preferably used, up to about 10 mol%.
  • reaction temperature is (-40) to 150 ° C.
  • the compounds of the formulas X, XI and XII are known or can be prepared in a known manner (see, for example, Houben-Weyl, Methods of Org. Chemistry, Vol. El, p. 636 ff., Georg Thieme Verlag, Stuttgart 1982 , Chem. Ber. £ 5, 3993 1962) or Houben-Weyl, Methods d. Org. Chemie, Vol. E2, pp. 345ff., Georg Thieme Verlag, Stuttgart 1982).
  • R 15 is -SR 22 or -N (R 23 ) R 24
  • R 15 is -SR 22 or -N (R 23 ) R 24
  • R 15 is -SR 22 or -N (R 23 ) R 24
  • R 15 is hydroxyl to their acid halides (halogen instead of of R 15 ) and the process products are then reacted with an amine HN (R 23 ) R 24 , thiol H-SR 22 or with a reactive derivative of these compounds.
  • V ⁇ R 6 CO R 11 ⁇ V ⁇ R 6 C (NR 27 ) R 11 ⁇
  • the reaction is usually carried out in an inert organic solvent or diluent, e.g. in an aromatic such as toluene and xylene, in a chlorinated hydrocarbon such as dichloromethane, chloroform and chlorobenzene, in an ether such as diethyl ether, 1, 2-dimethoxyethane and tetrahydrofuran, in an alcohol such as methanol and ethanol, or in a mixture of the solvents mentioned.
  • an inert organic solvent or diluent e.g. in an aromatic such as toluene and xylene, in a chlorinated hydrocarbon such as dichloromethane, chloroform and chlorobenzene, in an ether such as diethyl ether, 1, 2-dimethoxyethane and tetrahydrofuran, in an alcohol such as methanol and ethanol, or in a mixture of the solvents mentioned.
  • amines HN-R 27 are present as salts, for example as hydrochlorides or oxalates, the addition of a base such as preferably sodium carbonate, potassium carbonate, sodium hydrogen carbonate, triethylamine and pyridine is recommended for their release.
  • a base such as preferably sodium carbonate, potassium carbonate, sodium hydrogen carbonate, triethylamine and pyridine is recommended for their release.
  • the water of reaction formed can optionally be removed from the reaction mixture by distillation or with the aid of a water separator.
  • the reaction temperature is usually from (-30) to 150 ° C., preferably 0 to 130 ° C.
  • V ⁇ R 6 C (NR 27 )
  • R 11 ⁇ ⁇ V ⁇ R 6 CO R 11 ⁇
  • the cleavage is carried out without solvent or in an inert solvent or diluent with water or a reactive derivative of water.
  • the reaction can be carried out hydrolytically or under oxidative conditions, a reaction temperature from (-78) to 180 ° C., preferably 0 ° C. to the boiling point of the diluent, being recommended.
  • solvents or diluents examples include Aromatics such as benzene, toluene and o-, m-, p-xylene, chlorinated hydrocarbons such as dichloromethane, chloroform and chlorobenzene, ethers such as dialkyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, alcohols such as methanol and ethanol, ketones such as acetone, ester organic acids such as ethyl acetate or water and mixtures of the solvents mentioned.
  • Aromatics such as benzene, toluene and o-, m-, p-xylene, chlorinated hydrocarbons such as dichloromethane, chloroform and chlorobenzene, ethers such as dialkyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, alcohols such as methanol and ethanol, ketones such as ace
  • a mineral acid such as hydrochloric acid, hydrobromic acid and sulfuric acid
  • a carboxylic acid such as acetic acid and trifluoroacetic acid
  • a sulfonic acid such as p-toluenesulfonic acid
  • oxidizing agents such as lead tetraacetate, sodium hypochlorite and hydrogen peroxide are particularly suitable.
  • the reaction can also be carried out in the presence of a catalyst such as copper (II) sulfate, titanium tetrachloride and boron trifluoroetherate.
  • a catalyst such as copper (II) sulfate, titanium tetrachloride and boron trifluoroetherate.
  • the amounts of acid, oxidizing agent and catalyst can be varied within a wide range. Normally, both the amount of acid and the catalyst are from 5 to 200 mol%, and the amount of oxidizing agent is from 25 to 400 mol%, based on the amount of the compound to be oxidized; but they can also be used in a considerably larger excess.
  • the reaction is conveniently carried out in an inert organic solvent, e.g. an aromatic such as toluene and o-, m-, p-xylene, an aliphatic or cyclic ether such as diethyl ether, tert. -Butyl methyl ether, tetrahydrofuran and dioxane, a chlorinated hydrocarbon such as methylene chloride, chloroform and chlorobenzene, or in an organic carboxylic acid such as formic acid.
  • an inert organic solvent e.g. an aromatic such as toluene and o-, m-, p-xylene, an aliphatic or cyclic ether such as diethyl ether, tert. -Butyl methyl ether, tetrahydrofuran and dioxane, a chlorinated hydrocarbon such as methylene chloride, chloroform and chlorobenzene, or in an organic carboxylic acid such as
  • Suitable reducing agents are, for example, hydrogen or metal salts such as tin (II) chloride, metal hydrides such as diisobutyl aluminum hydride, diisopropyl aluminum hydride,
  • Lithium trisethoxy aluminum hydride and lithium bisethoxy aluminum hydride or triethylsilane Lithium trisethoxy aluminum hydride and lithium bisethoxy aluminum hydride or triethylsilane.
  • diisobutylaluminum hydride, formic acid or hydrogen is preferred.
  • the reduction can be carried out in the presence of a catalyst, e.g. Triethyloxonium tetrafluoroborate or Raney nickel can be performed.
  • a catalyst e.g. Triethyloxonium tetrafluoroborate or Raney nickel can be performed.
  • reaction temperature depends on the particular reducing agent, but is generally between (-78) and 150 ° C.
  • the enamine esters of formula III are new. Their preparation and that of the enamine esters VI can be carried out by methods known per se, for example by one of the following processes: Procedure U)
  • R e stands for hydrogen or amino.
  • the ethyl ester has so far proven particularly useful as the 3-aminoalk-2-enoic acid ester XIV, but any other ester, preferably an alkyl ester, can also be used.
  • 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 the xylenes, a halogenated, aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1, 2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric acid 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-dimethoxyethane, tetrahydr
  • 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 tertiary 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 tertiary base such as triethylamine and pyridine
  • the starting compounds are expediently used in stoichiometric amounts or one works with a slight excess of one or the other component up to about 10 mol%. When working without solvent in the presence of an organic base, it is advisable to use the latter in a larger excess.
  • the enamine ester obtained is converted with excess base directly (i.e. "in situ") into the corresponding product of value I or V, the purification of which can then be carried out by means of customary separation processes such as crystallization and chromatography.
  • Suitable solvents or diluents are, in particular, azeotropically miscible organic solvents, for example aromatics such as benzene, toluene and the xylenes, 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.
  • aromatics such as benzene, toluene and the xylenes
  • 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
  • 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" (from Fluka).
  • Suitable basic catalysts are e.g. Metal hydrides such as sodium hydride and particularly preferably metal alcoholates such as sodium methoxide and ethanolate.
  • ß-ketoester XVI and the benzylurea XVII are reacted in approximately stochiometric amounts or one works with a slight excess of one or the other component, up to about 10 mol%. It is usually sufficient to use half to twice the molar amount of catalyst, based on the amount of one of the starting compounds.
  • reaction is carried out at a
  • L 2 represents Ci-Cg-alkyl or phenyl.
  • This reaction can be 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 being normally from 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 being normally from 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 the xylenes, 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 is recommended.
  • the reaction temperature is normally 50 to 100 ° C., but preferably 60 to 80 ° C.
  • the enamine carboxylates of formula IV are also new; They too - and the enamine carboxylates VII - can be prepared in a manner known per se, for example from a benzylamine of the formula XIX according to the following general reaction scheme ⁇ >:
  • reaction of XIX with XX 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 the xylenes, 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 the xylenes
  • an aliphatic or cyclic ether such as diethyl ether, dibutyl ether , 1, 2-dimethoxyethane, tetrahydrofuran
  • the reaction temperature in this reaction is generally around 70 to 140 ° C., in particular 100 to 120 ° C.
  • reaction of XVI with XIX is an aminolysis, which is usually either without a solvent [cf. e.g. J. Soc. Dyes Col. 42, 81 (1926), Ber. 64. # 970 (1931);
  • Solvent / diluent especially in an aprotic solvent, for example in an aromatic such as toluene and
  • Xylenes or a halogenated aromatic such as chlorobenzene, is carried out.
  • a basic catalyst for example a higher boiling amine [see e.g. B. Helv. Chim. Acta H, 779 (1928) and U.S. 2,416,738] or pyridine.
  • the reaction temperature is preferably from about 20 to 160 ° C., in particular from 80 ° C. to the boiling point of the reaction mixture or of the basic catalyst.
  • the starting compounds are each reacted in approximately stochiometric amounts or one works with a slight excess of one or the other component, up to about 10 mol%. If one works in the presence of a basic catalyst, this is normally used in half to twice the molar amount, based on the amount of one of the starting materials.
  • Suitable solvents / diluents are, in particular, azeotropically miscible organic liquids, for example aromatics such as benzene, toluene and the xylenes, 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-toluenesulfonic acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid or acidic cation exchangers such as "Amberlyst 15" (from Fluka).
  • reaction temperature is about 70 to 150 ° C; however, to rapidly remove the reaction water formed, it is advisable to work at the boiling point of the reaction mixture in question.
  • reaction mixtures are generally worked up by methods known per se, for example by diluting the reaction mixture with water and then isolating the product of value by means of filtration, crystallization or solvent extraction, or by removing the solvent, distributing the residue in a mixture of water and a suitable organic solvent and working up the organic phase for the product of value.
  • the 1-amino-3-benzyluracils I can be prepared by one of the synthesis methods mentioned above.
  • the l-amino-3-benzyluracils I can be obtained in the preparation as isomer mixtures which, if desired, can, however, be separated into the largely pure isomers by the customary methods such as crystallization or chromatography, including on an optically active adsorbate. Pure optically active isomers can advantageously be prepared from corresponding optically active starting products.
  • Salts of the compounds I which can be used commercially can be formed by reaction with a base of the corresponding cation, preferably an alkali metal hydroxide or hydride, or by reaction with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • a base of the corresponding cation preferably an alkali metal hydroxide or hydride
  • an acid of the corresponding anion preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • Salts of I can also be prepared in a conventional manner by salting the corresponding alkali metal salt, as can ammonium, phosphonium, sulfonium and sulfoxonium salts using ammonia, phosphonium, sulfonium or sulfoxonium hydroxides.
  • 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, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. 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: Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec, altissima, Beta vulgaris spec, rapa, Brassica napus var. Napus, Brassica napus var. Napos-brassica, Brassica rapa var.
  • europaea Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, S accharum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (see vulgar), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.
  • the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • l-amino-3-benzyluracils I are also suitable for the desiccation and / or defoliation of plants.
  • desiccants are particularly suitable for drying out the above-ground parts of crops such as potatoes, rapeseed, sunflower and soybeans. This enables a fully mechanical harvesting of these important crops.
  • the compounds I or the compositions comprising them can be sprayed, for example in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprays or granules. Nebulization, 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.
  • mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, e.g. 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 and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives,
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • emulsions, pastes or oil dispersions the l-amino-3-benzyluracils 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, adhesive, dispersant or emulsifier and possibly solvent or oil can also be prepared which are suitable for dilution with water.
  • the surface-active substances are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa- , Hepta- and octadecanols as well as fatty alcohol glycol ether, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenyl glycolphenyl, alkylphen ary
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules e.g. Coated, impregnated and homogeneous granules can be produced 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 generally 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).
  • Wettol ® EM 31 nonionic emulsifier based on ethoxylated castor oil.
  • a stable emulsion concentrate is obtained.
  • the active ingredients I or the herbicidal compositions can be applied pre- or post-emergence. If the active ingredients are less compatible for 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 wherever 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).
  • the application rates of active ingredient I are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a.S.) depending on the control target, the season, the target plants and the growth stage.
  • the l-amino-3-benzyluracils I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
  • 1,2,4-thiazadiols, 1,3,4-thiadiazoles, amides, aminophosphoric acid and their derivatives, aminotriazoles, anilides, aryloxy- / heteroaryloxyalkanoic acids and their derivatives, benzoic acid and their derivatives, benzoic acid come as mixing partners.
  • thiadiazinone 2 - (hetaroyl / aroyl) -1, 3-cyclohexanedione, hetero-aryl-aryl-ketones, benzylisoxazolidinones, meta-CF 3 -phenyl derivatives, carba ate, quinoline carboxylic acid and its derivatives, chloroacetanilides, cyclohexane-1,3 -dione derivatives, diazines, dichloropropionic acid and their derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyl-uracils, imidazoles, imidazylones, 3-one , 4, 5, 6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy and
  • 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 by means of finely distributing nozzles.
  • the vessels were lightly sprinkled to promote germination and growth, and then covered with clear plastic covers until the plants grew
  • test plants For the purpose of post-emergence treatment, the test plants, depending on the growth habit, were first 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 for post-emergence treatment was 3.9 or 1.9 g / ha a.S. (active substance).
  • the plants were kept in a species-specific manner at temperatures of 10 to 15 25 ° C and 20 to 35 ° C.
  • the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated.
  • the young cotton plants were dripping wet with aqueous preparations of the sheet-treated active ingredients (with an addition of 0.15 wt .-% of the fatty alcohol alkoxylate Plurafac LF ® 700 1), based on the spray mixture).
  • the amount of water applied was the equivalent of 1000 l / ha. After 13 days, the number of leaves dropped and the degree of defoliation in% were determined.

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Abstract

L'invention concerne des 1-amino-3-benzyluraciles de formule (I) et leurs sels, formule dans laquelle R1 représente H, halogène, CH¿3?; R?2, R3¿ représentent H, CN, SCN, halogène, halogènure d'alkyle C¿1?-C4, halogénure d'alcoxy C1-C4, halogénure d'alkylthio C1-C4; R?4¿ représente R3 + alkyle C¿1?-C4, alcoxy C1-C4, alkyle C1-C6 NH-CO; R?5¿ représente alcylène C¿1?-C4 lié en position α ou β via O ou S et portant un groupe C(=NOR?7)-R8, R7¿ ayant la même signification que R?20 et R8¿ représentant H, alkyle C¿1?-C3, CHO éventuellement substitué, COOH, COSH ou aminocarbonyle; R?6¿ en position α ou β. L'invention concerne également leur procédé de production et leur utilisation en tant qu'herbicides et/ou pour la dessiccation/défoliation de plantes.
EP98916984A 1997-03-24 1998-03-18 Nouveaux 1-amino-3-benzyluraciles Withdrawn EP0971904A1 (fr)

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DE19712312 1997-03-24
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DE19523372A1 (de) * 1995-06-29 1997-01-09 Basf Ag Neue 1-Amino-3-benzyluracile

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