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WO1998007720A1 - Substituted 2-arylpyridine as herbicide - Google Patents

Substituted 2-arylpyridine as herbicide Download PDF

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Publication number
WO1998007720A1
WO1998007720A1 PCT/EP1997/004421 EP9704421W WO9807720A1 WO 1998007720 A1 WO1998007720 A1 WO 1998007720A1 EP 9704421 W EP9704421 W EP 9704421W WO 9807720 A1 WO9807720 A1 WO 9807720A1
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WIPO (PCT)
Prior art keywords
alkyl
alkoxy
butyl
substituted
cooch
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PCT/EP1997/004421
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German (de)
French (fr)
Inventor
Peter Schäfer
Gerhard Hamprecht
Markus Menges
Olaf Menke
Michael Rack
Cyrill Zagar
Helmut Walter
Karl-Otto Westphalen
Ulf Misslitz
Original Assignee
Basf Aktiengesellschaft
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Priority to AU42049/97A priority Critical patent/AU4204997A/en
Publication of WO1998007720A1 publication Critical patent/WO1998007720A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to new substituted 2-aryl pyridines of the formula I.
  • n zero or 1;
  • R 1 mercapto, hydroxysulfonyl, chlorosulfonyl, aminosulfonyl, C ⁇ -C 6 -alkylthio, C ⁇ -C 6 -alkylsulfinyl, Ci -C 6 -alkylsulfonyl, Ci -C 6 -alkylaminosulfonyl or di- (Ci-C ⁇ -alkyl) aminosulfonyl, -
  • R 2 , R 3 independently of one another are hydrogen or halogen
  • R 4 is hydrogen, Cx-Ce-alkyl, Ci -C 6 -haloalkyl, cyano-C ⁇ -C 6 -alkyl, C ⁇ -C 6 -alkoxy, CI-C ⁇ -alkoxy-Ci-C ⁇ -alkyl, Ci -C -halogen - Alkoxy -CC-alkyl, -CC 6 -alkylthio -CC 6 -alkyl, -C-C 6 -alkyl-sulfinyl -CC-C 6 - alkyl, -C-C 6 -alkylsulfonyl -C ⁇ -C 6 -alkyl, -C-C 4 -alkoxy-C ⁇ -C 4 -alkoxy-C ⁇ -C 4 -alkyl, (Cj .
  • X is oxygen, sulfur, -NH-, -N (CH 3 ) - or methylene; Y is a chemical bond, carbonyl or C (R 5 , R 6 ), where
  • R 5 , R 6 independently of one another for hydrogen, nitro
  • the invention also relates to the use of the compounds I as herbicides or for
  • WO 95/02590 describes a large number of herbicidally active 2-phenylpyridines.
  • the present invention was based on new herbicidally active compounds as a task with which undesired plants can be controlled more effectively than before.
  • the task also extends to the provision of new desiccant / defoliant connections.
  • substituted 2-arylpyridines of the formula I defined at the outset with herbicidal activity and new intermediates X, XVI, XXXIa, XXXIb, XXXIIa, XXXIIc, XXVIa, XXXVIb, XXXVIIa and XXXVIIb for their preparation were found.
  • herbicidal compositions have been found which contain the compounds I and have a very good herbicidal action.
  • processes for the preparation of these compositions and processes for controlling unwanted vegetation using the compounds I have been found.
  • the compounds I are also suitable for the desiccation / defoliation of parts of plants, for which crop plants such as cotton, potato, rapeseed, sunflower, soybean or field beans, in particular cotton and potato, are suitable.
  • crops plants such as cotton, potato, rapeseed, sunflower, soybean or field beans, in particular cotton and potato
  • 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.
  • the invention relates both to the pure enantiomers or diastereomers and to their mixtures.
  • Particularly suitable salts are those of the alkali metals, preferably sodium and potassium salts, of the alkaline earth metals, preferably calcium and magnesium salts, those of the transition metals, preferably zinc and iron salts, and also ammonium salts in which the ammonium ion, if desired, has one to four C 1 -C 4 -Alkyl-, hydroxy-C-C-alkyl substituents and / or can carry a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylamium, triethylbenzylammonium and trimethyl (2-hydroxyethyl) ammonium salts , furthermore phosphonium salts, sulfonium salts such as preferably tri- (C 1 -C 4 -alkyl) sulfonium salts, and sulfoxonium salts such as preferably tri- (C ⁇ -C-al
  • the organic molecule parts mentioned for the substituents R 1 and R 4 to R 6 or as residues on a phenyl ring represent collective terms for individual enumeration of the individual groups - members.
  • Halogenated substituents preferably carry one to five identical or different halogen atoms.
  • Halogen is in each case fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine.
  • C 1 -C 4 alkyl fr CH 3 , C 2 H 5 , n-propyl, CH (CH 3 ) 2 , n-butyl, 1-methylpropyl, 2-methylpropyl or C (CH) 3 , in particular for CH 3 , C 2 H 5 , CH (CH 3 ) 2 or C (CH 3 ) 3 ;
  • -C 1 -C 6 alkyl for: for example CH 3 , C 2 H 5 , n-propyl, CH (CH 3 ) 2 , n-butyl, 1-methylpropyl, 2-methylpropyl, C (CH 3 ) 3 , 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-diethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl,
  • -C-C 4 haloalkyl for: a C ⁇ -C 4 alkyl radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example for CH 2 F, CHF 2 , CF 3 , CH 2 C1, CH (C1) 2 , C (C1) 3 , CHFC1, CF (C1) 2 , CF 2 C1, CF 2 Br,
  • Ci-C ö haloalkyl for: a Ci-Ce alkyl radical as mentioned above, which is partially or completely replaced by fluorine, chlorine,
  • Bromine and / or iodine is substituted, for example for CH 2 F, CHF 2 , CF 3 , CH 2 C1, CH (C1) 2 , C (C1) 3 , CHFC1, CF (C1) 2 , CF 2 C1, CF.
  • Cyano-C ⁇ -C 6 alkyl for: for example CH 2 CN, 1-cyanoethyl, 2-cyanoethyl, 1-cyanoprop-l-yl, 2-cyanoprop-l-yl, 3-cyanoprop-l-yl, 1-cyanobut -l-yl, 2-cyanobut-l-yl, 3-cyanobut-l-yl, 4-cyano-but-l-yl, l-cyanobut-2-yl, 2-cyanobut-2-yl, 3-cyanobut -2-yl, 4-cyanobut-2-yl, 1- (CH 2 CN) -eth-1-yl, 1- (CH 2 CN) -1- (CH 3 ) -eth- 1-yl, 1- (CH 2 CN) prop-1-yl or 2-cyano-hex-6-yl, in particular for CH 2 CN or 2-cyanoethyl;
  • C 3 -C 7 cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl, in particular for cyclopentyl or cyclohexyl;
  • cycloalkyl-C 6 -C 6 alkyl for: cyclopropyl -CH 2 , 1-cyclopropyl-ethyl, 2-cyclopropyl-ethyl, 1-cyclopropyl-prop-l-yl, 2-cyclopropyl-prop -l-yl, 3-cyclopropyl-prop-l-yl, 1-cyclopropyl-but-1-yl, 2-cyclopropyl-but-l-yl, 3-cyclopropyl-but-l-yl, 4-cyclopropyl -but-1-yl, 1-cyclopropyl-but-2-yl, 2-cyclopropyl-but-2-yl, 3-cyclopropyl-but-2-yl, 4-cyclopropyl-but-2-yl, 1 - (Cyclopropyl -CH 2 ) eth-l-yl, 1- (cyclopropyl -CH 2 ) -1- (CH 3
  • (-C-C 6 alkyl) carbonyl for: for example CO-CH 3 , CO-C 2 H 5 , CO-CH 2 -C 2 H 5 , CO-CH (CH 3 ) 2 . n-butylcarbonyl, CO-CH (CH 3 ) -C 2 H 5 , 2-methylpropylcarbonyl, CO-C (CH 3 ) 3 , n-pentylcarbonyl, 1-methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 1, 1-dimethylpropylcarbonyl, 1, 2-dimethylpropylcarbonyl, 2, 2-dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, n-hexylcarbonyl, 1-methylpentylcarbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentylcarbonyl, 1, 1- Dimethylbutyl - carbonyl, 1, 2-di
  • -C-C 6 alkoxy for: for example 0CH 3 , OC 2 H 5 , n-propoxy, OCH (CH 3 ) 2 , n-butoxy, OCH (CH 3 ) -C 2 H 5 , 0CH 2 -CH (CH 3 ) 2 , OC (CH 3 ) 3 , n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2, 2-dimethylpropoxy, 1-ethyl- propoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2, 2-dimethylbutoxy, 2, 3- Dimethylbutoxy, 3, 3-dimethylbutoxy, 1-ethylbutoxy,
  • 2-ethylbutoxy 1, 1, 2-trimethylpropoxy, 1, 2, 2-trimethylprop oxy, 1-ethyl-l-methylpropoxy or l-ethyl-2-methylpropoxy, in particular 0CH 3 , OC 2 H 5 , 0CH (CH 3 ) 2 or OC (CH 3 ) 3 ;
  • C 1 -C 6 -alkoxy-C 6 -C 6 -alkyl for: C 1 -C 6 -alkoxy as mentioned above substituted C 1 -C 6 -alkyl, for example for
  • CH 2 OCH 3 CH 2 OC 2 H 5 , CH 2 OCH 2 -C 2 H 5 , CH 2 OCH (CH 3 ) 2 , CH 2 OCH 2 CH 2 -C 2 H 5 , (l-methylpropoxy) methyl, (2-Methylpropoxy) methyl, CH 2 OC (CH) 3 , CH 2 0 (CH 2 ) 3 -C 2 H 5 , CH 2 0 (CH 2 ) 4 -C 2 H 5 , CH (CH 3 ) OCH 3 , CH (CH 3 ) OC 2 H 5 , CH 2 CH 2 OCH 3 , CH 2 CH 2 0C 2 H 5 , CH 2 CH 2 0CH 2 -C 2 H5, CH 2 CH 2 0CH (CH 3 ) 2 , CH 2 CH 2 OCH 2 CH 2 -C 2 H 5 , 2- (1-methylpropoxy) ethyl, 2- (2-methylpropoxy) ethyl, CH 2 CH 2 OC (CH 3 ) 3 , 2-
  • C 1 -C 4 -alkoxy-C 4 -alkoxy-C 4 -C 4 -alkyl for: by 0CH 3 , OC 2 H 5 , n-propoxy, OCH (CH 3 ) 2 , n-butoxy, 1-methylpropoxy, 2-methyl-propoxy or OC (CH 3 ) 3 , preferably OCH 3 , substituted C 1 -C 4 -alkoxy-C 4 -C 4 -alkyl, that is, for example, for CH 2 OCH OCH 3 , CH 2 OCH 2 OC 2 H 5 , CH 2 OCH 2 OCH (CH 3 ) 2 or CH 2 OCH 2 OC (CH 3 ) 3 ;
  • Ci -C-C 4 haloalkoxy -CC 4 - alkyl for: by Ci -C 4 haloalkoxy such as OCH 2 F, OCHF 2 , 0CF 3 , 0CH 2 C1, 0CH (C1) 2 , 0C (C1) 3 , 0CHFC1 , 0CF (C1) 2 , 0CF 2 C1, 0CF 2 Br, 1-fluoroethoxy, 2-fluoroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2, 2-difluoroethoxy, 2, 2, 2-trifluoro ethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2, 2-difluoroethoxy, 2, 2-dichloro-2-fluoroethoxy, 2, 2, 2-trichloroethoxy, OC 2 F 5 , 2-fluoropropoxy, 3-fluoropropoxy , 2-chloropropoxy, 3-chloropropoxy,
  • C 3 -C Cycloalkyloxy -CC 6 alkyl for: by C 3 -C cycloalkyloxy such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy and cycloheptyloxy, preferably cyclopropyloxy, substituted -CC 6 alkyl, for example for cyclopropyl -OCH 2 , 1-cyclopropyloxy-ethyl, 2-cyclopropyloxy-ethyl, 1-cyclopropyloxy-prop-l-yl, 2-cyclopropyloxy-prop-1-yl, 3-cyclopropyloxy-prop-l-yl, 1- Cyclopropyloxy-but-1-yl, 2-cyclopropyloxy-but-l-yl, 3-cyclopropyloxy-but-1-yl, 4-cyclopropyloxy-but-l-yl, 1-cyclopropyloxy-but-2- y
  • (C ⁇ -C 4 -alkoxy) carbonyl for: COOCH 3 , COOC 2 H 5 , n-propoxycarbonyl, OCH (CH 3 ) 2 , n-butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl or OC (CH 3 ) 3 , in particular for C00CH 3 , COOC 2 H 5 or COOC (CH 3 ) 3 ;
  • (Ci-C ö -alkoxy) carbonyl for: C00CH 3 , COOC 2 H 5 , n-propoxycarbonyl, OCH (CH 3 ), n-butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl, OC (CH 3 ) 3 , n-pentoxycarbonyl, 1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2, 2-dimethylpropoxycarbonyl, 1-ethyl-propoxycarbonyl, n-hexoxycarbonyl, 1, 1-dimethylpropoxycarbonyl, 1, 2-dimethylpropoxycarbonyl, 1-methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4-methylpentoxycarbonyl, 1, 1-dimethylbutoxycarbonyl, 1,2-diethylbutoxycarbonyl, 1, 3-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl, 2, 3-
  • (C 1 -C 4 alkoxy) carbonyl -C ⁇ -C 4 alkyl by (C 1 -C 4 alkoxy) - carbonyl - as mentioned above - substituted C 1 -C 4 alkyl, eg CH 2 COOCH 3 , CH 2 COOC 2 H 5 , CH 2 COOCH 2 -C 2 H 5 , CH 2 COOCH (CH 3 ) 2 , CH 2 COOCH 2 CH 2 -C 2 H 5 , (1-methylpropoxycarbonyl) - ethyl, ( 2-Methylpropoxy-carbonyDmethyl, CH 2 COOC (CH 3 ) 3 , CH 2 COO (CH 2 ) 3 -C 2 H 5 , CH 2 COO (CH 2 ) 4 -C 2 H 5 , CH (CH 3 ) COOCH 3 , CH (CH 3 ) COOC 2 H 5 , CH 2 CH 2 COOCH 3 , CH 2 CH COOC 2 H 5 , CH CH COOCH 2 H
  • C ! -C 6 alkylthio for: e.g. SCH 3 , SC 2 H 5 , n-propylthio, SCH (CH 3 ) 2 , n-butylthio, SCH (CH 3 ) -CH 5 , SCH 2 -CH (CH 3 ) 2 , SC (CH 3 ) 3 , n-pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2, 2-dimethylpropylthio, 1-ethylpropylthio, n-hexylthio, 1, 1-dimethylpropylthio, 1, 2 -Dimethylpropylthio, l-methyl-pentylthio, 2-methylpentylthio, 3-methylpentylthio, 4 -methyl - pentylthio, 1, 1-dimethylbutylthio, 1, 2-dimethylbutylthio, 1, 3-dimethyl
  • C 1 -C 6 -alkylthio-C 1 -C 6 -alkyl for: C 1 -C 6 -alkyl-substituted by C 1 -C 6 -alkylthio as mentioned above, for example for CH 2 SCH 3 , CH 2 SC 2 H 5 , CH 2 SCH 2 -C 2 H 5 , CH 2 SCH (CH 3 ) 2 , CH 2 SCH 2 CH 2 -C 2 H 5 , (l-methylpropylthio) methyl, (2-methylpropylthio) methyl, CH 2 SC (CH 3 ) 3 , CH 2 S (CH 2 ) 3- 2 H5, CH 2 S (CH 2 ) 4- 2H5, CH ( CH 3 ) SCH 3 , CH (CH 3 ) SC 2 H 5 , CH 2 CH SCH 3 , CH 2 CH 2 SC 2 H 5 , CH 2 CH 2 SCH 2 -C 2 H 5 , CH 2 CH 2 SCH (CH 3 ) 2 , CH 2 CH 2
  • C 3 -C 7 cycloalkylthio-C 6 -C 6 alkyl for: by C 3 -C 7 cycloalkyl thio such as cyclopropylthio, cyclobutylthio, cyclopentyl thio, cyclohexylthio and cycloheptylthio, preferably cyclopropylthio, substituted C 1 -C 6 alkyl, that is e.g.
  • cyclopropyl-SCH 2 1-cyclopropylthio-ethyl, 2-cyclopropylthio-ethyl, 1-cyclopropylthio-prop-l-yl, 2-cyclopropylthio-prop-l-yl, 3-cyclopropylthio-prop-l-yl, 1 -Cyclopropylthio-but-l-yl, 2-cyclopropylthio-but-l-yl, 3-cyclopropylthio-but-l-yl, 4-cyclopropylthio-but-l-yl, l-cyclopropylthio-but-2-yl, 2 -Cyclopropylthio-but-2-yl, 3-cyclopropylthio-but-2-yl 4-cyclopropyl thio-but-2-yl, 1- (cyclopropyl-SCH 2 -) -eth-l-yl, 1- (cyclopropyl- SCH 2
  • C -Cg-alkylsulfinyl for: e.g. SOCH 3 , S0C 2 H 5 , n-propylsulfinyl, SOCH (CH 3 ) 2 , n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, SOC (CH 3 ) 3 , n-pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2, 2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, n-hexylsulfinyl, 1, 1-dimethylpropylsulfinyl, 1, 2-dimethylpropylsulfinyl, 1 -Methylpentylsulfinyl, 2-methylpentyls
  • Ci-Ce-alkylsulfonyl for: e.g. S0 2 CH 3 , S0 2 C 2 H 5 , n-propylsulfonyl, S0CH (CH 3 ) 2 , n-butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, S0 2 C (CH 3 ) 3 , n-pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl,
  • C 6 -C 6 -alkylsulfonyl-C 6 -C 6 -alkyl for: Cx-Cg-alkylsulfonyl substituted as C above ! -C 6 alkyl, e.g.
  • CH 2 S0 2 - (CH 2 ) 4 -C 2 H 5 CH (CH 3 ) S0 2 -CH 3 , CH (CH 3 ) S0 2 -C 2 H 5 , CH 2 CH 2 S0 2 -CH 3 , CH 2 CH 2 S0 2 -C 2 H 5 , CH 2 CH 2 S0 2 -CH 2 -C 2 H 5 , CH 2 CH 2 S0 2 -CH (CH 3 ) 2 , CH 2 CH 2 S0 2 -CH 2 CH -C 2 H 5 , 2- (1-methylpropylsulfonyl) ethyl, 2- (2-methylpropylsulfonyl) ethyl, CH 2 CH 2 S0 2 -C (CH 3 ) 3 , CH 2 CH 2 S0 2 - ( CH 2 ) 3 -C 2 H 5 , CH 2 CH 2 S0 2 - (CH 2 ) 4 -C 2 H 5 ,
  • Di- (Ci-Ce-alkyaminosulfonyl for: e.g. (CH 3 ) 2 N-S0 2 -, (C 2 H 5 > 2 N-S0 2 -, N, N-Dipropylamino-S0 2 -, N, N- Di (1-methyl-ethyl) amino-S0-, N, N-dibutylamino-S0 2 -, N, N-Di (1-methyl-propyl) amino-S02-, N, N-Di (2-methylpropyl) amino-S02-, N, N-Di (1, l-dimethylethyl) amino-S0 2 -, N-ethyl-N-methyl - amino-S0 2 -, N-methyl-N-propylamino-S0-, N- Methyl-N- (1-methylethyl) amino-S02-, N-butyl-N-methylamino-S ⁇ 2-, N-methyl-
  • C 3 -C 8 alkenyl for: C 3 -C ⁇ alkenyl as mentioned above, or for example for n-hept-2-en-1-yl, n-hept-3 -en- 1-yl, n-oct- 2 -en- 1-yl, n-oct-3-en-l-yl, especially for allyl;
  • C 3 -C 8 haloalkenyl for: C 3 -C 8 alkenyl as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example for 2-chloroallyl, 3-chloroallyl, 2, 3-dichlorallyl, 3, 3-dichlorallyl, 2,3,3-trichlorallyl, 2,3-dichlorobut-2-enyl, 2-bromoallyl, 3-bromoallyl, 2, 3-dibromoallyl, 3, 3-dibromoallyl, 2, 3, 3-tribromoallyl or 2,3-dibromobut-2-enyl, in particular for 3 -chloroallyl;
  • C 1 -C 6 -alkoxy-C 3 -C 8 -alkenyl for: C 3 -C 8 -alkoxy substituted by -C-C 6 -alkoxy as mentioned above, for example for 3- (methoxy) allyl; C 3 -C 6 alkenyloxy for: e.g. B.
  • C 2 -C 4 -Alkenyloxy-C ⁇ -C 4 alkyl for: by C 3 -C 4 ⁇ alkenyloxy such as vinyloxy, allyloxy, but-l-en-3-yloxy, but-l-en-4 -yloxy, but -2-en-l-yloxy, l-methylprop-2-enyloxy or 2-methyl-prop-2-enyloxy substituted C 1 -C 4 -alkyl, for example for vinyloxymethyl, allyloxymethyl, 2-allyloxyethyl or but-l- en-4-yloxymethyl, especially for 2-allyloxyethyl;
  • C 3 -C 6 alkynyl for: e.g. B. Prop-1-in-l-yl, propargyl, n-but-1 - in-l-yl, n-but-l-in-3-yl, n-but-l-in-4-yl, n- But-2-in-1-yl, n-pent-1-in-1-yl, n-pent-1-in-3-yl, n-pent-1-in-4-yl, n-pent l-in-5-yl, n-pent-2-in-l-yl, n-pent-2 -in-4-yl, n-pent-2-in- 5-yl, 3-methyl-but-l-in-3-yl, 3-methyl-but-l-in-4-yl, n-hex-1-in-l-yl, n-hex-l- in-3-yl, n-hex-1-in-4-yl, n-hex-1
  • haloalkynyl C 3 -C ⁇ alkynyl as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example for 1,1-difluoroprop-2- in-l-yl, 4-fluorobut-2-in-l-yl, 4-chlorobut-2-in-l-yl, 1, 1-difluorobut-2-in-l-yl, 5-fluoropent-3- in-l-yl or 6-fluoro-hex-4-in-l-yl;
  • C 1 -C 6 -alkoxy-C 3 -C 8 -alkynyl for: C 3 -C 8 -alkynyl substituted by C ⁇ -C 6 -alkoxy as mentioned above, for example for 3-methoxy-prop-2 - in-1- yl;
  • C 3 -C 8 alkynyloxy for: for example propargyloxy, prop-2-in-1-yloxy, n-but-1-in-1-yloxy, n-but-1-in-3-yloxy, n-but- l-in-4-yloxy, n-but-2-in-l-yloxy, n-pent-1-in-l-yloxy, n-pent-l-in-3-yloxy, n-pent-l- in-4-yloxy, n-pent-1-in-5-yloxy, n-pent-2-in-1-yl-oxy, n-pent-2-in-4-yloxy, n-pent-2- in-5-yloxy, 3-methyl-but-l-in-3-yloxy, 3-methyl-but-l-in-4-yloxy, n-hex-1-in-l-yl-oxy, n- Hex-l-in-3-yloxy, n-hex-
  • C 3 -C 4 alkynyloxy -CC -alkyl for: by C 3 -C 4 -alkynyloxy such as propargyloxy, but-l-in-3-yloxy, but-l-in-4-yloxy, but-2- in-l-yloxy, l-methylprop-2-inyloxy and 2-methylprop-2-inyloxy, preferably propargyloxy, substituted C 1 -C 4 -alkyl, for example for propargyloxymethyl or 2-propargoxyethyl, in particular for 2-propargyloxyethyl;
  • the benzyl group (as one of the meanings of R 4 ) is preferably unsubstituted or carries a nitro, halogen, Cx -C 4 alkyl, Ci -C 4 alkoxy or (Ci -C 4 alkoxy) carbonyl substituent .
  • the variables preferably have the following meanings, individually or in combination:
  • R 1 mercapto, hydroxysulfonyl, chlorosulfonyl, aminosulfonyl,
  • Ci-C ⁇ -alkylthio Ci-C ⁇ -alkylsulfinyl or -C-C 6 -alkylsulfonyl, in particular Ci-C 6 -alkylsulfonyl;
  • R 2 halogen, especially chlorine
  • R 3 is hydrogen or halogen, preferably halogen, especially fluorine or chlorine;
  • R 4 is hydrogen, C 1 -C 6 -alkyl, cyano-C 1 -C 6 -alkyl, C ⁇ -C 6 -alkoxy, Ci -C 6 -alkoxy-C ⁇ -C 6 - alkyl, Ci -C 6 -alkylthio-Ci - C 6 - alkyl, (Ci -C 6 alkoxy) carbonyl -C ⁇ -C 6 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 6 alkenyloxy or C3-C6 - Alkynyloxy, especially hydrogen, -C 6 alkyl, cyano -C 6 alkyl, (-C 6 alkoxy) carbonyl -C] . -C 6 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl;
  • R 5 , R 6 independently of one another are hydrogen, C 1 -C 4 alkyl or (C] .- C 4 alkoxy) carbonyl, in particular a chemical bond or Methylene.
  • substituted 2-arylpyridines of the formulas Ib, Ic, Id, le, If, Ig, Ih, Ii, Ik, Im and In are particularly preferred, in particular
  • the substituted 2-arylpyridines of the formula I can be obtained in various ways, for example by one of the following processes:
  • oxidizing agents customary for the oxidation of the pyridine ring are peracetic acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid, monopermaleic acid, magnesium onoperphthalate, sodium perborate and oxones
  • Suitable solvents are e.g. Water, sulfuric acid, carboxylic acids such as acetic acid and trifluoroacetic acid and halogenated hydrocarbons such as dichloromethane and chloroform.
  • the oxidation is usually successful at temperatures from 0 ° C to the boiling point of the reaction mixture.
  • the oxidizing agent is normally used in at least equimolar amounts, based on the starting compound. In general, an excess of oxidizing agent has proven to be particularly advantageous.
  • IIIIIVM 1 stands for B (OH) 2 , Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br, Zn-J, lithium, copper or tin tri (C 1 -C 4 alkyl), preferably for B (OH) 2 , Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br or Zn-J.
  • Palladium catalysts such as tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium (II) chloride, 1,4-bis (diphenylphosphino) butane-palladium (II) chloride come in particular as catalysts , 1,2-bis (diphenylphosphino) ethane-palladium (II) chloride, palladiu (II) acetate + triphenylphosphine, palladium (II) acetate + tri - (o-tolyl) -phosphine or palladium on activated carbon, and nickel catalysts such as bis (triphenylphosphine) nickel (II) chloride, 1,3-bis (diphenylphosphino) propane nickel (II) chloride or nickel (II) acetylacetonate.
  • nickel catalysts such as bis (triphenylphosphine) nickel (I
  • aminophenol VIII can also be reacted with oxalic acid (derivatives) XI such as oxalic acid chloride and (if desired substituted) maleic anhydride:
  • Sulfur, -NH- or -N (CH 3 ) - means can be prepared according to synthesis scheme (3):
  • X ' represents oxygen, sulfur, -NH- or -N (CH 3 ) -;
  • R 4 ' represents one of the meanings of R 4 with the exception of hydrogen.
  • the p-fluorophenylpyridines of the formula XII are, for example, analogously to process C) by transition metal-catalyzed cross-coupling reaction of II with XVII
  • R 4 represents one of the meanings of R 4 with the exception of hydrogen.
  • Synthesis scheme (3) ⁇ is obtained by nucleophilic aromatic substitution of the fluorine by a malonic ester residue and subsequent acid hydrolysis with decarboxylation to give the phenylacetic acid derivative XX. With its reduction occurs ⁇ as in the case of XVI; see.
  • Such implementations are also known per se, for example from the following literature:
  • CH 2 can be prepared according to synthesis scheme (5):
  • Alkyl is preferably
  • R 4 represents one of the meanings of R 4 with the exception of hydrogen.
  • Transition metal-catalyzed cross-coupling reaction of the halopyridine II with a boronic acid or trialkyltin compound of the formula XXIII leads to the aldehyde XXIV.
  • XXIV can also be obtained by reacting II with the metal organyl XXI and hydrolysis of the reaction product XXII.
  • the nitro group on the pyridine can be reduced both before and after the alkylation of the benzoxazinone XXXIIa.
  • XXIX one first obtains XXXa or XXXb depending on the reducing agent, its amount and the reduction conditions.
  • O-alkyl preferably Ci-Cg
  • X ' represents oxygen, sulfur, -NH-, -N (CH 3 ) -;
  • R 4 represents one of the meanings of R 4 with the exception of hydrogen.
  • D the literature cited for methods D
  • G the literature cited for methods D
  • the 2 - (-Fluoro-3-nitrophenyl) - 5-nitropyridines XXXV can be obtained by nitrating the corresponding 2 - (4-fluorophenyl) - 5-nitropyridines ⁇ cf. refer to the literature ⁇ listed in Method D ( Figure 2 -. (4-fluorophenyl) - 5 -nitropyridine in turn are, for example analogously to Process C> by cross-coupling reaction of the 2-halo-5-nitropyridine XXXIV with XVII accessible.
  • the substituted 2-arylpyridines I can normally be prepared by one of the synthesis processes mentioned above. For economic or procedural reasons, however, it may be more expedient to prepare some compounds I from similar 2-arylpyridines, but which differ in the meaning of a radical.
  • reaction mixtures are generally worked up by methods known per se, for example by diluting the reaction solution with water and subsequent
  • 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 on the
  • the substituted 2-arylpyridines I can be obtained as isomer mixtures which, however, can be separated, if desired, by customary methods such as crystallization or chromatography, also on an optically active adsorbate, in the far ⁇ continuously pure isomers in the production. Pure optically active isomers can advantageously be prepared from corresponding optically active starting products.
  • Agricultural salts of the compounds I can be formed by reaction with a base of the corresponding cation, preferably an alkali metal hydroxide or hydride.
  • Salts of I, the metal ion of which is not an alkali metal ion, 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:
  • the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • the substituted 2-arylpyridines I are also suitable for the desiccation and / or defoliation of plants.
  • the compounds I or the compositions containing them can be, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions,
  • Old dispersions, pastes, dusts, sprinkles or granules by spraying, atomizing, dusting, scattering or pouring can be used.
  • the application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • inert auxiliaries mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tarols as well as 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 tarols as well as oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e.g. Paraffins, tetrahydronaphthalene, alky
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • emulsions, pastes or old dispersions can be carried out as such or dissolved in a substrate or solvent, can be homogenized in water using wetting agents, adhesives, dispersants or emulsifiers.
  • wetting agents adhesives, dispersants or emulsifiers.
  • concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols as well as of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives Formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl poly
  • 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 contain from about 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • the following formulation examples illustrate the preparation of such preparations:
  • Benzene 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide in 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide in 1 mole of castor oil.
  • an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
  • Wettol ® EM 31 nonionic emulsifier based on ethoxylated castor oil; BASF AG.
  • 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 as far as possible, while the active ingredients are applied to the leaves of undesirable plants growing below them or the uncovered floor area (post-directed, lay-by).
  • 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 substituted 2-arylpyridines I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups and applied together.
  • a suspension of 55.4 g 3 was added in portions at 15 to 20 ° C. to a solution of 24.3 g of 3-chlorine -2 - (4-methoxyphenyl) -5-methyl-thiopyridine (from stage 1) in 150 ml of trichloromethane -Chlorper- benzoic acid (from Aldrich; content 56 to 87 wt .-%) in 250 ml trichloromethane. After the addition was complete, stirring was continued for 45 minutes. The resulting 3-chlorobenzoic acid was then filtered off and washed with trichloromethane.
  • Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels.
  • the seeds of the test plants were sown separately according to species.
  • the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles.
  • the tubes were lightly sprinkled to promote germination and growth, and then covered with clear plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, provided that this has not been impaired by the active ingredients.
  • 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. 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 vessels a few days before the treatment.
  • the application rate for the post-emergence treatment was 15.6 or 7.8 g / ha aS (active substance).
  • the plants were kept in a species-specific manner at temperatures of 10 to 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.
  • Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
  • the plants used in the greenhouse experiments are composed of the following types:
  • the young cotton plants were dripping wet with aqueous preparations of the active ingredients (with an addition of 0.15 wt -.% Of the fatty alcohol alkoxylate Plurafac LF ® 700 1), based on the
  • Spray broth treated with leaves.
  • 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

Substituted 2-arylpyridine of formula (I) and salts thereof. In said formula (I), R1 = SH, SO¿2?OH, SO2C1, SO2NH2, C1-C6-Alkylthio, C1-C6-Alkyl sulfinyl, C1-C6-alkylsulfonyl, C1-C6-alkylamino-sulfonyl, Di(C1-C6-alkyl)aminosulfonyl; R?2, R3¿ = H, halogen; R4 = H, C¿1?-C6-alkyl, C1-C6-halogenalkyl, cyano-C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkoxy-C1-C6-alkyl, C1-C4-halogen-alkoxy-C1-C4-alkyl, C1-C6-alkylthio-C1-C6-alkyl, C1-C6 alkyl sulfinyl-C1-C6-alkyl, C1-C6-alkylsulfonyl-C1-C6-alkyl, C1-C4-alkoxy-C1-C4-alkoxy-C1-C4-alkyl, C1-C6-alkoxycarbonyl-C1-C6-alkyl, C1-C3-alkoxy-C1-C3-alkoxycarbonyl-C1-C6-alkyl, C2-C4-alkenyloxy-C1-C4-alkyl, C3-C4-alkinyloxy-C1-C4-alkyl, C3-C7-cycloalkyl, C3-C7-cycloalkyl-C1-C6-alkyl, C3-C7-cycloalkyloxy-C1-C6-alkyl, C3-C7-cycloalkylthio-C1-C6-alkyl, C3-C8-alkenyl, C3-C8-alkinyl, C3-C8-halogenalkenyl, C3-C8-halogenalkinyl, C1-C6-alkoxy-C3-C8-alkenyl, C1-C6-alkoxy-C3-C8-alkinyl, C1-C6-alkylcarbonyl, C1-C6-alkylsulfonyl, C3-C6-alkenyloxy, C3-C6-alkinyloxy or eventually substituted benzyl; X = -O-, -S-, -NH-, -N(CH3)-, -CH2-; Y = chemical bond, -CO-, C(R?5,R6); R5,R6¿ = H, NO¿2?, CN, OCH3, SCH3, halogen, C1-C4-alkyl, C1-C4-halogenalkyl, C1-C4-alkoxycarbonyl, C2-C6-alkenyl, C3-C6-alkinyl, C1-C4-alkoxycarbonyl-C1-C4-alkyl. Application as herbicide; for plant desiccation/defoliation.

Description

Substituierte 2-arylpyridine als herbizlde Substituted 2-arylpyridines as herbicides
Beschreibungdescription
Die vorliegende Erfindung betrifft neue substituierte 2-Aryl pyridine der Formel IThe present invention relates to new substituted 2-aryl pyridines of the formula I.
Figure imgf000003_0001
in der die Variablen folgende Bedeutungen haben:
Figure imgf000003_0001
in which the variables have the following meanings:
n Null oder 1;n zero or 1;
R1 Mercapto, Hydroxysulfonyl, Chlorsulfonyl, Aminosulfonyl , Cχ-C6 -Alkylthio, Cι-C6-Alkylsulfinyl, Ci -C6 -Alkylsulfonyl, Ci -C6 -Alkylaminosulfonyl oder Di- (Ci-Cβ-alkyl) aminosulfonyl ,-R 1 mercapto, hydroxysulfonyl, chlorosulfonyl, aminosulfonyl, Cχ-C 6 -alkylthio, Cι-C 6 -alkylsulfinyl, Ci -C 6 -alkylsulfonyl, Ci -C 6 -alkylaminosulfonyl or di- (Ci-Cβ-alkyl) aminosulfonyl, -
R2 , R3 unabhängig voneinander Wasserstoff oder Halogen;R 2 , R 3 independently of one another are hydrogen or halogen;
R4 Wasserstoff, Cx-Ce-Alkyl, Ci -C6-Halogenalkyl, Cyano-Cι-C6- alkyl, Cι-C6-Alkoxy, CI-CΘ -Alkoxy-Ci-Cβ -alkyl, Ci -C -Halogen- alkoxy-Cι-C - alkyl, Cι-C6-Alkylthio-Cι-C6-alkyl, Cι-C6-Alkyl- sulfinyl-Cι-C6- alkyl, Cι-C6 -Alkylsulfonyl -Cι-C6-alkyl , Cι-C4-Alkoxy-Cι-C4-alkoxy-Cι-C4-alkyl, (Cj.-C6 -Alkoxy) - carbonyl -C -C6 -alkyl, Ci -C3 -Alkoxy- (Ci -C3 -alkoxy) carbonyl - Cι-C6- alkyl, C2 -C -Alkenyloxy-Cι-C -alkyl, C3-C -Alkinyl - oxy-Cχ-C - alkyl, C3-C -Cycloalkyl, C3-C7-Cycloalkyl -Ci -C6 - alkyl, C3-C7-Cycloalkyloxy-Cι-C6 -alkyl, C3-C7-Cycloalkyl- thio-Cι-C6- alkyl, C3-C8-Alkenyl, C3-C8 -Alkinyl,R 4 is hydrogen, Cx-Ce-alkyl, Ci -C 6 -haloalkyl, cyano-Cι-C 6 -alkyl, Cι-C 6 -alkoxy, CI-CΘ-alkoxy-Ci-Cβ-alkyl, Ci -C -halogen - Alkoxy -CC-alkyl, -CC 6 -alkylthio -CC 6 -alkyl, -C-C 6 -alkyl-sulfinyl -CC-C 6 - alkyl, -C-C 6 -alkylsulfonyl -Cι-C 6 -alkyl, -C-C 4 -alkoxy-Cι-C 4 -alkoxy-Cι-C 4 -alkyl, (Cj . -C 6 -alkoxy) - carbonyl -C -C 6 -alkyl, Ci -C 3 -alkoxy- (Ci -C 3 alkoxy) carbonyl - -C-C 6 - alkyl, C 2 -C -alkenyloxy-Cι-C -alkyl, C 3 -C -alkynyl - oxy-Cχ-C - alkyl, C 3 -C - Cycloalkyl, C 3 -C 7 cycloalkyl -Ci -C 6 alkyl, C 3 -C 7 cycloalkyloxy -CC 6 alkyl, C 3 -C 7 cycloalkyl-thio -CC 6 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl,
C3-C8-Halogenalkenyl, C -Cβ-Halogenalkinyl, Cx-Ce-Alkoxy- C3-C8-alkenyl, Ci -C6 -Alkoxy-C3-C8- alkinyl, (Ci -C6-Alkyl) - carbonyl, Cι-C6 -Alkylsulfonyl, C3-C6 -Alkenyloxy, C3-C6-Alkinyloxy oder Benzyl, das unsubstituiert sein oder am Phenylring ein bis drei Substituenten tragen kann, jeweils ausgewählt aus der Gruppe bestehend aus Nitro, Halogen, Cι-C6 -Alkyl, Ci-Ce -Alkoxy und (Cι-C6 -Alkoxy) carbonyl;C 3 -C 8 haloalkenyl, C -Cβ-haloalkynyl, Cx-Ce alkoxy- C 3 -C 8 alkenyl, Ci -C 6 alkoxy-C 3 -C 8 alkynyl, (Ci -C 6 alkyl ) - carbonyl, -CC 6 alkylsulfonyl, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy or benzyl, which may be unsubstituted or may carry one to three substituents on the phenyl ring, each selected from the group consisting of nitro , Halogen, -CC 6 alkyl, Ci-Ce alkoxy and (-C 6 alkoxy) carbonyl;
X Sauerstoff, Schwefel, -NH-, -N(CH3)- oder Methylen; Y eine chemische Bindung, Carbonyl oder C(R5,R6), wobeiX is oxygen, sulfur, -NH-, -N (CH 3 ) - or methylene; Y is a chemical bond, carbonyl or C (R 5 , R 6 ), where
R5,R6 unabhängig voneinander für Wasserstoff, Nitro,R 5 , R 6 independently of one another for hydrogen, nitro,
Cyano, Methoxy, Methylthio, Halogen, Cι-C4 -Alkyl, Cχ-C4-Halogenalkyl, (C -C4 -Alkoxy) carbonyl,Cyano, methoxy, methylthio, halo, Cι-C4-alkyl, Cχ-C 4 haloalkyl, (C -C 4 alkoxy) carbonyl,
C2-C6-Alkenyl, C3 -C6 -Alkinyl oder (Ci -C4 -Alkoxy) - carbonyl -Cx -C4 -alkyl stehen,C 2 -C 6 alkenyl, C 3 -C 6 alkynyl or (Ci -C 4 alkoxy) carbonyl -Cx -C 4 alkyl,
sowie die landwirtschaftlich brauchbaren Salze der Verbindungen I mit R1 = Hydroxysulfonyl .as well as the agriculturally useful salts of the compounds I with R 1 = hydroxysulfonyl.
Außerdem betrifft die Erfindung die Verwendung der Verbindungen I als Herbizide oder zurThe invention also relates to the use of the compounds I as herbicides or for
Desikkation/Defoliation von Pflanzen, - herbizide Mittel und Mittel zur Desikkation und/oderDesiccation / defoliation of plants, herbicidal agents and agents for desiccation and / or
Defoliation von Pflanzen, welche die Verbindungen I als wirksame Substanzen enthalten,Defoliation of plants which contain the compounds I as active substances,
Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs und zur Desikkation und/oder Defoliation von Pflanzen mit den Verbindungen I,Process for combating undesired plant growth and for desiccating and / or defoliation of plants with the compounds I,
Verfahren zur Herstellung der Verbindungen I und von herbiziden Mitteln und Mitteln zur Desikkation und/oderProcess for the preparation of the compounds I and herbicidal agents and agents for desiccation and / or
Defoliation von Pflanzen unter Verwendung der Verbindungen I sowie - Zwischenprodukte der Formeln X, XVI, XXXIa, XXXIb, XXXIIa,Defoliation of plants using the compounds I and intermediate products of the formulas X, XVI, XXXIa, XXXIb, XXXIIa,
XXXIIc, XXXVIa, XXXVIb und XXXVII.XXXIIc, XXXVIa, XXXVIb and XXXVII.
In der WO 95/02590 wird eine Vielzahl von herbizid wirksamen 2 - Phenylpyridinen beschrieben. Unter deren allgemeine Formel fallen zwar auch einige der vorliegenden Verbindungen I mit R1 = Cι-C4-Alkylthio, doch werden in der Druckschrift als Einzelverbindungen nur solche mit einer Trifluormethylgruppe in 5 -Position des Pyridinringes genannt.WO 95/02590 describes a large number of herbicidally active 2-phenylpyridines. Some of the present compounds I with R 1 = C 1 -C 4 -alkylthio also fall under their general formula, but only single compounds with a trifluoromethyl group in the 5-position of the pyridine ring are mentioned in the publication as individual compounds.
Da die herbizide Wirkung der aus der WO 95/02590 bekannten Verbindungen bezuglich der Schadpflanzen nicht immer völlig befriedigend ist, lagen der vorliegenden Erfindung neue herbizid wirksame Verbindungen als Aufgabe zugrunde, mit denen sich unerw nschte Pflanzen noch besser als bisher gezielt bekämpfen lassen. Die Aufgabe erstreckt sich auch auf die Bereitstellung neuer desikkant/defoliant wirksamer Verbindungen.Since the herbicidal action of the compounds known from WO 95/02590 is not always completely satisfactory in relation to the harmful plants, the present invention was based on new herbicidally active compounds as a task with which undesired plants can be controlled more effectively than before. The task also extends to the provision of new desiccant / defoliant connections.
Demgemäß wurden die eingangs definierten substituierten 2-Aryl- pyridine der Formel I mit herbizider Wirkung sowie neue Zwischen- Produkte X, XVI, XXXIa, XXXIb, XXXIIa, XXXIIc, XXXVIa, XXXVIb, XXXVIIa und XXXVIIb zu deren Herstellung gefunden. Ferner wurden herbizide Mittel gefunden, die die Verbindungen I enthalten und eine sehr gute herbizide Wirkung besitzen. Außerdem wurden Verfahren zur Herstellung dieser Mittel und Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs mit den Verbindungen I gefunden.Accordingly, the substituted 2-arylpyridines of the formula I defined at the outset with herbicidal activity and new intermediates X, XVI, XXXIa, XXXIb, XXXIIa, XXXIIc, XXXVIa, XXXVIb, XXXVIIa and XXXVIIb for their preparation were found. Furthermore, herbicidal compositions have been found which contain the compounds I and have a very good herbicidal action. In addition, processes for the preparation of these compositions and processes for controlling unwanted vegetation using the compounds I have been found.
Des weiteren wurde gefunden, daß die Verbindungen I auch zur Desikkation/Defoliation von Pflanzenteilen geeignet sind, wofür Kulturpflanzen wie Baumwolle, Kartoffel, Raps, Sonnenblume, Soja- bohne oder Ackerbohnen, insbesondere Baumwolle und Kartoffel, in Betracht kommen. Diesbezüglich wurden Mittel zur Desikkation und/ oder Defoliation von Pflanzen, Verfahren zur Herstellung dieser Mittel und Verfahren zur Desikkation und/oder Defoliation von Pflanzen mit den Verbindungen I gefunden.Furthermore, it was found that the compounds I are also suitable for the desiccation / defoliation of parts of plants, for which crop plants such as cotton, potato, rapeseed, sunflower, soybean or field beans, in particular cotton and potato, are suitable. In this regard, 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.
Die Verbindungen der Formel I können je nach Substitutionsmuster ein oder mehrere Chiralitätszentren enthalten und liegen dann als Enantiomeren- oder Diastereomerengemische vor. Gegenstand der Erfindung sind sowohl die reinen Enantiomere oder Diastereomere als auch deren Gemische.Depending on the substitution pattern, the compounds of the formula I can contain one or more centers of chirality and are then present as mixtures of enantiomers or diastereomers. The invention relates both to the pure enantiomers or diastereomers and to their mixtures.
Die substituierten 2-Arylpyridine I mit R1 = Hydroxysulfonyl können in Form ihrer landwirtschaf lich brauchbaren Salze vorliegen, wobei es auf die Art des Salzes in der Regel nicht ankommt. Im allgemeinen kommen die Salze von solchen Basen in Betracht, bei denen die herbizide Wirkung im Vergleich zu der freien Verbindung I nicht negativ beeinträchtigt ist.The substituted 2-arylpyridines I with R 1 = hydroxysulfonyl can be present in the form of their agriculturally useful salts, the type of salt generally not being important. In general, the salts of such bases come into consideration in which the herbicidal action is not adversely affected in comparison with the free compound I.
Als Salze eignen sich besonders diejenigen der Alkalimetalle, vorzugsweise Natrium- und Kaliumsalze, der Erdalkalimetalle, vorzugsweise Calcium- und Magnesiumsalze, die der Übergangs - metalle, vorzugsweise Zink- und Eisensalze, sowie Ammoniumsalze, bei denen das Ammoniumion gewünschtenfalls ein bis vier Cι-C4-Alkyl-, Hydroxy-Cι-C-alkylsubstituenten und/oder einen Phenyl- oder Benzylsubstituenten tragen kann, vorzugsweise Diiso - propylammonium-, Tetramethylammonium-, Tetrabutylam onium-, Tri- ethylbenzylammonium- und Trimethyl- (2-hydroxyethyl) -ammoniumsalze, des weiteren Phosphoniumsalze, Sulfoniumsalze wie vorzugsweise Tri- (Cι-C4-alkyl) sulfonium-salze, und Sulfoxoniumsalze wie vorzugsweise Tri- (Cχ-C-alkyl) sulfoxoniumsalze.Particularly suitable salts are those of the alkali metals, preferably sodium and potassium salts, of the alkaline earth metals, preferably calcium and magnesium salts, those of the transition metals, preferably zinc and iron salts, and also ammonium salts in which the ammonium ion, if desired, has one to four C 1 -C 4 -Alkyl-, hydroxy-C-C-alkyl substituents and / or can carry a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylamium, triethylbenzylammonium and trimethyl (2-hydroxyethyl) ammonium salts , furthermore phosphonium salts, sulfonium salts such as preferably tri- (C 1 -C 4 -alkyl) sulfonium salts, and sulfoxonium salts such as preferably tri- (Cχ-C-alkyl) sulfoxonium salts.
Die für die Substituenten R1 und R4 bis R6 oder als Reste an einem Phenylring genannten organischen Molekülteile stellen Sammelbegriffe für individuelle Aufzählungen der einzelnen Gruppen - mitglieder dar. Sämtliche Kohlenstoffketten, also alle Alkyl-, Halogenalkyl-, Cyanoalkyl-, Alkylcarbonyl- , Alkoxy-, Halogen - alkoxy-, Alkoxycarbonyl - , Alkylthio-, Alkylsulfinyl-, Alkyl- sulfonyl-, Alkylamino-, Alkenyl-, Halogenalkenyl- , Alkenyloxy-, Alkinyl-, Halogenalkinyl - und Alkinyloxy-Teile können geradkettig oder verzweigt sein. Halogenierte Substi uenten tragen vorzugsweise ein bis fünf gleiche oder verschiedene Halogenatome.The organic molecule parts mentioned for the substituents R 1 and R 4 to R 6 or as residues on a phenyl ring represent collective terms for individual enumeration of the individual groups - members. All carbon chains, ie all alkyl, haloalkyl, cyanoalkyl, alkylcarbonyl, Alkoxy, halogen - alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl, alkyl Sulfonyl, alkylamino, alkenyl, haloalkenyl, alkenyloxy, alkynyl, haloalkynyl and alkynyloxy parts can be straight-chain or branched. Halogenated substituents preferably carry one to five identical or different halogen atoms.
Die Bedeutung Halogen steht jeweils für Fluor, Chlor, Brom oder lod, insbesondere für Fluor oder Chlor.Halogen is in each case fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine.
Ferner stehen beispielsweise:Furthermore, for example:
C1-C -Alkyl f r: CH3 , C2H5, n-Propyl, CH(CH3)2, n-Butyl, 1-Methylpropyl, 2-Methylpropyl oder C(CH )3, insbesondere für CH3, C2H5, CH(CH3)2 oder C(CH3)3;C 1 -C 4 alkyl fr: CH 3 , C 2 H 5 , n-propyl, CH (CH 3 ) 2 , n-butyl, 1-methylpropyl, 2-methylpropyl or C (CH) 3 , in particular for CH 3 , C 2 H 5 , CH (CH 3 ) 2 or C (CH 3 ) 3 ;
- Cι-C6-Alkyl für: z.B. CH3 , C2H5, n-Propyl, CH(CH3)2, n-Butyl, 1-Methylpropyl, 2-Methylpropyl, C(CH3)3, n-Pentyl, 1-Methyl - butyl, 2-Methylbutyl, 3-Methylbutyl , 2, 2-Dimethylpropyl , 1-Ethylpropyl, n-Hexyl, 1 , 1-Dimethylpropyl, 1 , 2-Dimethyl - propyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1, 1-Dimethylbutyl, 1 , 2-Dimethylbutyl , 1,3-Di- ethylbutyl, 2, 2-Dimethylbutyl, 2 , 3-Dimethylbutyl , 3,3-Di- methylbutyl, 1-Ethylbutyl , 2-Ethylbutyl, 1, 1, 2-Trimethyl- propyl, 1, 2 , 2-Trimethylpropyl, 1-Ethyl-l-methylpropyl oder l-Ethyl-2-methylpropyl, insbesondere für CH3 , C2H5, n-Propyl, CH(CH3)2, n-Butyl, C(CH3)3, n-Pentyl oder n-Hexyl ,--C 1 -C 6 alkyl for: for example CH 3 , C 2 H 5 , n-propyl, CH (CH 3 ) 2 , n-butyl, 1-methylpropyl, 2-methylpropyl, C (CH 3 ) 3 , 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-diethylbutyl, 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, in particular for CH 3 , C 2 H 5 , n-propyl, CH (CH 3 ) 2 , n-butyl, C (CH 3 ) 3 , n-pentyl or n-hexyl,
Cι-C4 -Halogenalkyl für: einen Cχ-C4 -Alkylrest wie vorstehend genannt, der partiell oder vollständig durch Fluor, Chlor, Brom und/oder lod substituiert ist, also z.B. für CH2F, CHF2, CF3, CH2C1, CH(C1)2, C(C1)3, CHFC1, CF(C1)2, CF2C1, CF2Br,-C-C 4 haloalkyl for: a Cχ-C 4 alkyl radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example for CH 2 F, CHF 2 , CF 3 , CH 2 C1, CH (C1) 2 , C (C1) 3 , CHFC1, CF (C1) 2 , CF 2 C1, CF 2 Br,
1-Fluorethyl, 2-Fluorethyl , 2-Chlorethyl , 2-Bromethyl, 2-Iod- ethyl, 2, 2-Difluorethyl, 2, 2 , 2-Trifluorethyl, 2-Chlor-2- fluorethyl, 2-Chlor-2 , 2-dif luorethyl, 2 , 2-Dichlor-2-fluorethyl, 1, 2-Dichlorethyl, 2 , 2 , 2-Trichlorethyl , C2F5, 2-Fluor- propyl, 3-Fluorpropyl, 2, 2-Difluorpropyl , 2 , 3-Dif luorpropyl , 2-Chlorpropyl, 3-Chlorpropyl, 2 , 3-Dichlorpropyl , 2-Brom- propyl, 3-Brompropyl, 3 , 3 , 3-Trifluorpropyl , 3 , , 3-Trichlor - propyl, 2 , 2 , 3, 3 , 3-Pentafluorpropyl, Heptafluorpropyl , 1- (Fluormethyl )-2-fluorethyl, 1- (Chlormethyl) -2-chlorethyl , 1- (Brommethyl) -2-bromethyl , 4-Fluorbutyl, 4-Chlorbutyl , 4-Brombutyl oder Nonafluorbutyl, insbesondere für CHF, CHF2, CF3, CH2C1 oder 2 -Fluorethyl;1-fluoroethyl, 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, 1, 2-dichloroethyl, 2, 2, 2-trichloroethyl, C 2 F 5 , 2-fluoropropyl, 3-fluoropropyl, 2, 2-difluoropropyl, 2, 3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2, 3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3, 3, 3-trifluoropropyl, 3,, 3-trichloropropyl, 2, 2, 3, 3, 3-pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl, especially for CHF, CHF 2 , CF 3 , CH 2 C1 or 2 -fluoroethyl;
Ci-Cö-Halogenalkyl für: einen Ci-Ce-Alkylrest wie vorstehend genannt, der partiell oder vollständig durch Fluor, Chlor,Ci-C ö haloalkyl for: a Ci-Ce alkyl radical as mentioned above, which is partially or completely replaced by fluorine, chlorine,
Brom und/oder lod substituiert ist, also z.B. für CH2F, CHF2, CF3, CH2C1, CH(C1)2, C(C1)3, CHFC1, CF(C1)2, CF2C1, CF2Br, 1-Fluorethyl, 2-Fluorethyl, 2-Chlorethyl , 2-Bromethyl, 2-Iod- ethyl, 2, 2-Difluorethyl, 2 , 2, 2-Trifluorethyl, 2-Chlor-2- fluorethyl, 2-Chlor-2 , 2-difluorethyl, 2 , 2-Dichlor-2-fluorethyl, 1, 2-Dichlorethyl, 2 , 2 , 2-Trichlorethyl, C2F5, 2-Fluor- propyl, 3-Fluorpropyl, 2 , 2-Dif luorpropyl , 2 , 3-Difluorpropyl , 2-Chlorpropyl, 3-Chlorpropyl, 2 , 3-Dichlorpropyl , 2-Brom- propyl, 3-Brompropyl, 3, 3 , 3-Trifluorpropyl, 3 , 3 , 3-Trichlor- propyl, 2, 2, 3 , 3 , 3-Pentafluorpropyl, Heptafluorpropyl, 1- (Fluormethyl) -2-fluorethyl, 1- (Chlormethyl) -2-chlorethyl, 1- (Brommethyl) -2-bromethyl, 4-Fluorbutyl, 4-Chlorbutyl,Bromine and / or iodine is substituted, for example for CH 2 F, CHF 2 , CF 3 , CH 2 C1, CH (C1) 2 , C (C1) 3 , CHFC1, CF (C1) 2 , CF 2 C1, CF. 2 Br, 1-fluoroethyl, 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, 1, 2-dichloroethyl, 2, 2, 2-trichloroethyl, C 2 F 5 , 2-fluoropropyl, 3-fluoropropyl, 2, 2-difluoropropyl, 2, 3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2, 3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3, 3, 3-trifluoropropyl, 3, 3, 3-trichloropropyl, 2, 2, 3, 3, 3-pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromethyl, 4-fluorobutyl, 4-chlorobutyl,
4-Brotnbutyl, Nonafluorbutyl, 5-Fluorpentyl, 5-Chlorpentyl , 5-Brompentyl, 5-Iodpentyl, 5, 5, 5-Trichlorpentyl, Undecafluor- pentyl, 6-Fluorhexyl, 6-Chlorhexyl, 6-Bromhexyl, 6-Iodhexyl, 6, 6, 6-Trichlorhexyl oder Dodecafluorhexyl , insbesondere für CH2F, CHF2, CF3, CH2C1 , 2-Fluorethyl, 2-Chlorethyl , 1,2-Di- chlorethyl, 2, 2, 2-Trifluorethyl oder C2F5;4-Brotnbutyl, Nonafluorbutyl, 5-Fluorpentyl, 5-Chlorpentyl, 5-Brompentyl, 5-Iodpentyl, 5, 5, 5-Trichlorpentyl, Undecafluoropentyl, 6-Fluorhexyl, 6-Chlorhexyl, 6-Bromhexyl, 6-Iodhexyl, 6, 6, 6-trichlorhexyl or dodecafluorohexyl, in particular for CH 2 F, CHF 2 , CF 3 , CH 2 C1, 2-fluoroethyl, 2-chloroethyl, 1,2-di-chloroethyl, 2, 2, 2-trifluoroethyl or C 2 F 5 ;
Cyano-Cι-C6-alkyl für: z.B. CH2CN, 1-Cyanoethyl , 2-Cyanoethyl, 1-Cyanoprop-l-yl, 2-Cyanoprop-l-yl, 3-Cyanoprop-l-yl , 1-Cyanobut-l-yl, 2-Cyanobut-l-yl, 3-Cyanobut-l-yl , 4-Cyano- but-l-yl, l-Cyanobut-2-yl, 2-Cyanobut-2-yl , 3-Cyanobut-2-yl, 4-Cyanobut-2-yl, 1- (CH2CN) -eth-l-yl, 1- (CH2CN) -1- (CH3) -eth- 1-yl, 1- (CH2CN) -prop-1-yl oder 2-Cyano-hex-6-yl , insbesondere für CH2CN oder 2-Cyanoethyl ;Cyano-Cι-C 6 alkyl for: for example CH 2 CN, 1-cyanoethyl, 2-cyanoethyl, 1-cyanoprop-l-yl, 2-cyanoprop-l-yl, 3-cyanoprop-l-yl, 1-cyanobut -l-yl, 2-cyanobut-l-yl, 3-cyanobut-l-yl, 4-cyano-but-l-yl, l-cyanobut-2-yl, 2-cyanobut-2-yl, 3-cyanobut -2-yl, 4-cyanobut-2-yl, 1- (CH 2 CN) -eth-1-yl, 1- (CH 2 CN) -1- (CH 3 ) -eth- 1-yl, 1- (CH 2 CN) prop-1-yl or 2-cyano-hex-6-yl, in particular for CH 2 CN or 2-cyanoethyl;
C3-C7-Cycloalkyl für: Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl oder Cycloheptyl, insbesondere für Cyclopentyl oder Cyclohexyl ;C 3 -C 7 cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl, in particular for cyclopentyl or cyclohexyl;
c3-C7-Cycloalkyl-Cι-C6-alkyl für: Cyclopropyl -CH2, 1-Cyclo- propyl-ethyl, 2-Cyclopropyl-ethyl, 1-Cyclopropyl-prop-l-yl , 2-Cyclopropyl-prop-l-yl, 3-Cyclopropyl-prop-l-yl, 1-Cyclo- propyl-but-1-yl, 2-Cyclopropyl-but-l-yl, 3-Cyclopropyl- but-l-yl, 4-Cyclopropyl-but-l-yl, l-Cyclopropyl-but-2-yl, 2-Cyclopropyl-but-2-yl, 3-Cyclopropyl-but-2-yl, 4-Cyclo- propyl-but-2-yl, 1- (Cyclopropyl -CH2) eth-l-yl, 1- (Cyclopropyl -CH2) -1- (CH3) -eth-l-yl, 1- (Cyclopropyl -CH2) prop-1-yl, Cyclobutyl -CH2, 1-Cyclobutyl-ethyl, 2-Cyclobutyl-ethyl , 1-Cyclobutyl-prop-l-yl , 2-Cyclobutyl-prop-l-yl, 3-Cyclobutyl- prop-1-yl, 1-Cyclobutyl-but-l-yl, 2-Cyclobutyl-but-l-yl ,c 3 -C 7 cycloalkyl-C 6 -C 6 alkyl for: cyclopropyl -CH 2 , 1-cyclopropyl-ethyl, 2-cyclopropyl-ethyl, 1-cyclopropyl-prop-l-yl, 2-cyclopropyl-prop -l-yl, 3-cyclopropyl-prop-l-yl, 1-cyclopropyl-but-1-yl, 2-cyclopropyl-but-l-yl, 3-cyclopropyl-but-l-yl, 4-cyclopropyl -but-1-yl, 1-cyclopropyl-but-2-yl, 2-cyclopropyl-but-2-yl, 3-cyclopropyl-but-2-yl, 4-cyclopropyl-but-2-yl, 1 - (Cyclopropyl -CH 2 ) eth-l-yl, 1- (cyclopropyl -CH 2 ) -1- (CH 3 ) -eth-l-yl, 1- (cyclopropyl -CH 2 ) prop-1-yl, cyclobutyl -CH 2 , 1-cyclobutyl-ethyl, 2-cyclobutyl-ethyl, 1-cyclobutyl-prop-l-yl, 2-cyclobutyl-prop-l-yl, 3-cyclobutyl-prop-1-yl, 1-cyclobutyl- but-l-yl, 2-cyclobutyl-but-l-yl,
3-Cyclobutyl-but-l-yl, 4-Cyclobutyl-but-l-yl, 1-Cyclobutyl- but-2-yl, 2-Cyclobutyl-but-2-yl, 3-Cyclobutyl-but-2-yl, 4-Cyclobutyl-but-2-yl, 1- (Cyclobutyl -CH2) eth-l-yl, 1- (Cyclo- butyl-CH2)-l- (CH3) -eth-l-yl, 1- (Cyclobutyl -CH2) prop-1-yl , Cyclopentyl -CH2, 1-Cyclopentyl-ethyl, 2-Cyclopentyl-ethyl, 1-Cyclopentyl-prop-l-yl, 2-Cyclopentyl-prop-l-yl, 3-Cyclo- pentyl-prop-1-yl, 1-Cyclopentyl-but-l-yl , 2-Cyclopentyl- but-l-yl, 3-Cyclopentyl-but-l-yl, 4-Cyclopentyl-but-l-yl, l-Cyclopentyl-but-2-yl, 2-Cyclopentyl-but-2-yl, 3-Cyclo- pentyl-but-2-yl, 4-Cyclopentyl-but-2-yl , 1- (Cyclopentyl - CH2) eth-l-yl, 1- (Cyclopentyl -CH2) -1- (CH3 ) -eth-l-yl , l-(Cyclo- pentyl-CH2)prop-l-yl, Cyclohexyl -CH2, 1-Cyclohexyl-ethyl , 2-Cyclohexyl-ethyl, 1-Cyclohexyl-prop-l-yl , 2-Cyclohexyl- prop-1-yl, 3-Cyclohexyl-prop-l-yl, 1-Cyclohexyl-but-l-yl, 2-Cyclohexyl-but-l-yl , 3-Cyclohexyl-but-l-yl , 4-Cyclohexyl- but-l-yl, l-Cyclohexyl-but-2-yl, 2-Cyclohexyl-but-2-yl, 3-Cyclohexyl-but-2-yl, 4-Cyclohexyl-but-2-yl, l-(Cyclo- hexyl-CH2)eth-l-yl, 1- (Cyclohexyl -CH ) -1- (CH3) -eth-l-yl, 1- (Cyclohexyl -CH2)prop-l-yl, Cycloheptyl-CH2, 1-Cycloheptyl- ethyl, 2-Cycloheptyl-ethyl, 1-Cycloheptyl-prop-l-yl, 2-Cyclo- heptyl-prop-1-yl, 3-Cycloheptyl-prop-l-yl, 1-Cycloheptyl- but-l-yl, 2-Cycloheptyl-but-l-yl, 3-Cycloheptyl-but-l-yl, 4-Cycloheptyl-but-l-yl, l-Cycloheptyl-but-2-yl , 2-Cyclo- heptyl-but-2-yl, 3-Cycloheptyl-but-2-yl , 4-Cycloheptyl- but-2-yl, 1- (Cycloheptyl-CH2) eth-l-yl, 1- (Cycloheptyl- CH2) -1- (CH3) -eth-l-yl oder 1- (Cycloheptyl -CH2)prop-l-yl , insbesondere für C3 -Ce-Cycloalkyl -CH2;3-cyclobutyl-but-l-yl, 4-cyclobutyl-but-l-yl, 1-cyclobutyl-but-2-yl, 2-cyclobutyl-but-2-yl, 3-cyclobutyl-but-2-yl, 4-cyclobutyl-but-2-yl, 1- (cyclobutyl -CH 2 ) eth-l-yl, 1- (cyclobutyl-CH 2 ) -l- (CH 3 ) -eth-l-yl, 1- (Cyclobutyl -CH 2 ) prop-1-yl, cyclopentyl -CH 2 , 1-cyclopentyl-ethyl, 2-cyclopentyl-ethyl, 1-cyclopentyl-prop-l-yl, 2-cyclopentyl-prop-l-yl, 3 -Cyclopentyl-prop-1-yl, 1-cyclopentyl-but-l-yl, 2-cyclopentyl- but-l-yl, 3-cyclopentyl-but-l-yl, 4-cyclopentyl-but-l-yl, l-cyclopentyl-but-2-yl, 2-cyclopentyl-but-2-yl, 3-cyclo- pentyl-but-2-yl, 4-cyclopentyl-but-2-yl, 1- (cyclopentyl-CH 2 ) eth-l-yl, 1- (cyclopentyl -CH 2 ) -1- (CH 3 ) -eth- l-yl, l- (cyclopentyl-CH 2 ) prop-l-yl, cyclohexyl -CH 2 , 1-cyclohexyl-ethyl, 2-cyclohexyl-ethyl, 1-cyclohexyl-prop-l-yl, 2-cyclohexyl - prop-1-yl, 3-cyclohexyl-prop-l-yl, 1-cyclohexyl-but-l-yl, 2-cyclohexyl-but-l-yl, 3-cyclohexyl-but-l-yl, 4-cyclohexyl - but-l-yl, l-cyclohexyl-but-2-yl, 2-cyclohexyl-but-2-yl, 3-cyclohexyl-but-2-yl, 4-cyclohexyl-but-2-yl, l- ( Cyclohexyl-CH 2 ) eth-l-yl, 1- (cyclohexyl -CH) -1- (CH 3 ) -eth-l-yl, 1- (cyclohexyl -CH 2 ) prop-l-yl, cycloheptyl- CH 2 , 1-cycloheptyl-ethyl, 2-cycloheptyl-ethyl, 1-cycloheptyl-prop-l-yl, 2-cyclo-heptyl-prop-1-yl, 3-cycloheptyl-prop-l-yl, 1-cycloheptyl - but-l-yl, 2-cycloheptyl-but-l-yl, 3-cycloheptyl-but-l-yl, 4-cycloheptyl-but-l-yl, l-cycloheptyl-but-2-yl, 2-cyclo - heptyl-but-2-yl, 3-cyclohe ptyl-but-2-yl, 4-cycloheptyl-but-2-yl, 1- (cycloheptyl-CH 2 ) eth-l-yl, 1- (cycloheptyl-CH 2 ) -1- (CH 3 ) -eth- l-yl or 1- (cycloheptyl -CH 2 ) prop-l-yl, especially for C 3 -Ce-cycloalkyl -CH 2 ;
(Cι-C6-Alkyl) carbonyl für: z.B. CO-CH3, CO-C2H5, CO-CH2-C2H5, CO-CH(CH3)2. n-Butylcarbonyl, CO-CH(CH3) -C2H5, 2-Methylpropyl - carbonyl, CO-C(CH3)3, n-Pentylcarbonyl, 1-Methylbutylcarbonyl , 2-Methylbutylcarbonyl, 3-Methylbutylcarbonyl, 1 , 1-Dimethyl - propylcarbonyl, 1, 2-Dimethylpropylcarbonyl, 2, 2-Dimethyl- propylcarbonyl, 1-Ethylpropylcarbonyl, n-Hexylcarbonyl , 1-Methylpentylcarbonyl, 2-Methylpentylcarbonyl, 3-Methyl- pentylcarbonyl, 4-Methylpentylcarbonyl, 1 , 1-Dimethylbutyl - carbonyl, 1 , 2-Dimethylbutylcarbonyl, 1, 3-Dimethylbutyl - carbonyl, 2 , 2-Dimethylbutylcarbonyl , 2 , 3-Dimethylbutyl - carbonyl, 3 , 3-Dimethylbutylcarbonyl , 1-Ethylbutylcarbonyl , 2-Ethylbutylcarbonyl, 1,1, 2-Trimethylpropylcarbonyl, 1, 2,2-Trimethylpropylcarbonyl, 1-Ethyl-l-methylpropylcarbonyl oder l-Ethyl-2-methylpropylcarbonyl, insbesondere für CO-CH3 oder CO-C2H5;(-C-C 6 alkyl) carbonyl for: for example CO-CH 3 , CO-C 2 H 5 , CO-CH 2 -C 2 H 5 , CO-CH (CH 3 ) 2 . n-butylcarbonyl, CO-CH (CH 3 ) -C 2 H 5 , 2-methylpropylcarbonyl, CO-C (CH 3 ) 3 , n-pentylcarbonyl, 1-methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 1, 1-dimethylpropylcarbonyl, 1, 2-dimethylpropylcarbonyl, 2, 2-dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, n-hexylcarbonyl, 1-methylpentylcarbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentylcarbonyl, 1, 1- Dimethylbutyl - carbonyl, 1, 2-dimethylbutylcarbonyl, 1, 3-dimethylbutyl - carbonyl, 2, 2-dimethylbutylcarbonyl, 2, 3-dimethylbutyl - carbonyl, 3, 3-dimethylbutylcarbonyl, 1-ethylbutylcarbonyl, 2-ethylbutylcarbonyl, 1,1, 2-trimethylpropylcarbonyl, 1, 2,2-trimethylpropylcarbonyl, 1-ethyl-l-methylpropylcarbonyl or l-ethyl-2-methylpropylcarbonyl, in particular for CO-CH 3 or CO-C 2 H 5 ;
Cι-C6-Alkoxy für: z.B. 0CH3, OC2H5, n-Propoxy, OCH(CH3)2, n-Butoxy, OCH(CH3) -C2H5, 0CH2 -CH (CH3) 2, OC(CH3)3, n-Pentoxy, 1-Methylbutoxy, 2-Methylbutoxy, 3-Methylbutoxy, 1 , 1-Dimethyl- propoxy, 1 , 2-Dimethylpropoxy, 2 , 2-Dimethylpropoxy, 1-Ethyl- propoxy, n-Hexoxy, 1-Methylpentoxy, 2-Methylpentoxy, 3-Methylpentoxy, 4-Methylpentoxy, 1, 1-Dirnethylbutoxy, 1, 2-Dimethylbutoxy, 1, 3-Dimethylbutoxy, 2 , 2-Dimethylbutoxy, 2, 3-Dimethylbutoxy, 3 , 3-Dimethylbutoxy, 1-Ethylbutoxy,-C-C 6 alkoxy for: for example 0CH 3 , OC 2 H 5 , n-propoxy, OCH (CH 3 ) 2 , n-butoxy, OCH (CH 3 ) -C 2 H 5 , 0CH 2 -CH (CH 3 ) 2 , OC (CH 3 ) 3 , n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2, 2-dimethylpropoxy, 1-ethyl- propoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2, 2-dimethylbutoxy, 2, 3- Dimethylbutoxy, 3, 3-dimethylbutoxy, 1-ethylbutoxy,
2-Ethylbutoxy, 1, 1, 2-Trimethylpropoxy, 1, 2 , 2-Trimethylprop- oxy, 1-Ethyl-l-methylpropoxy oder l-Ethyl-2-methylpropoxy, insbesondere 0CH3 , OC2H5, 0CH(CH3)2 oder OC(CH3)3;2-ethylbutoxy, 1, 1, 2-trimethylpropoxy, 1, 2, 2-trimethylprop oxy, 1-ethyl-l-methylpropoxy or l-ethyl-2-methylpropoxy, in particular 0CH 3 , OC 2 H 5 , 0CH (CH 3 ) 2 or OC (CH 3 ) 3 ;
Cι-C6-Alkoxy-Cι-C6-alkyl für: durch Cι-C6-Alkoxy wie vor- stehend genannt substituiertes Ci-Cβ-Alkyl, also z.B. fürC 1 -C 6 -alkoxy-C 6 -C 6 -alkyl for: C 1 -C 6 -alkoxy as mentioned above substituted C 1 -C 6 -alkyl, for example for
CH2OCH3, CH2OC2H5, CH2OCH2-C2H5, CH2OCH (CH3 ) 2 , CH2OCH2CH2-C2H5 , (l-Methylpropoxy)methyl, (2-Methylpropoxy)methyl , CH2OC(CH )3, CH20(CH2)3-C2H5, CH20(CH2)4-C2H5, CH(CH3)OCH3, CH (CH3 ) OC2H5 , CH2CH2OCH3, CH2CH20C2H5, CH2CH20CH2-C2H5, CH2CH20CH (CH3) 2 , CH2CH2OCH2CH2-C2H5, 2- (1-Methylpropoxy) ethyl, 2-(2-Methyl- propoxy)ethyl, CH2CH2OC (CH3) 3, CH2CH20 (CH2) 3-C2H5, CH2CH20(CH2) -C2H5, 2- (OCH3) propyl, 2- (OC2H5) propyl, 2- (OCH2-C2H5) propyl, 2- [OCH (CH3) 2] propyl, 2- (OCH2CH2-C2H5) - propyl, 2- (1-Methylpropoxy) propyl, 2- (2-Methylpropoxy) propyl , 2- [OC(CH3)3] propyl, 3- (OCH3) ropyl, 3- (OC2H5) propyl ,CH 2 OCH 3 , CH 2 OC 2 H 5 , CH 2 OCH 2 -C 2 H 5 , CH 2 OCH (CH 3 ) 2 , CH 2 OCH 2 CH 2 -C 2 H 5 , (l-methylpropoxy) methyl, (2-Methylpropoxy) methyl, CH 2 OC (CH) 3 , CH 2 0 (CH 2 ) 3 -C 2 H 5 , CH 2 0 (CH 2 ) 4 -C 2 H 5 , CH (CH 3 ) OCH 3 , CH (CH 3 ) OC 2 H 5 , CH 2 CH 2 OCH 3 , CH 2 CH 2 0C 2 H 5 , CH 2 CH 2 0CH 2 -C 2 H5, CH 2 CH 2 0CH (CH 3 ) 2 , CH 2 CH 2 OCH 2 CH 2 -C 2 H 5 , 2- (1-methylpropoxy) ethyl, 2- (2-methylpropoxy) ethyl, CH 2 CH 2 OC (CH 3 ) 3 , CH 2 CH 2 0 ( CH 2 ) 3 -C 2 H 5 , CH 2 CH 2 0 (CH 2 ) -C 2 H 5 , 2- (OCH 3 ) propyl, 2- (OC 2 H 5 ) propyl, 2- (OCH 2 -C 2 H 5 ) propyl, 2- [OCH (CH 3 ) 2 ] propyl, 2- (OCH 2 CH 2 -C 2 H 5 ) propyl, 2- (1-methylpropoxy) propyl, 2- (2-methylpropoxy) propyl, 2- [OC (CH 3 ) 3 ] propyl, 3- (OCH 3 ) ropyl, 3- (OC 2 H 5 ) propyl,
3- (OCH2-C2H5) propyl, 3- [OCH (CH3) 2] propyl, 3- (OCH2CH2-C2H5) - propyl, 3- (1-Methylpropoxy) propyl , 3- (2-Methylpropoxy) - propyl, 3- [OC (CH3) 3j propyl, 3- [0(CH2) 3-C2H5] propyl, 3- [0(CH2)4-C2H5] propyl, 2- (OCH3)butyl, 2- (OC2H5)butyl, 2- (OCH -C2H5)butyl, 2- [OCH(CH3) 2] butyl, 2- (OCH2CH2-C2H5) - butyl, 2- (1-Methylpropoxy) butyl, 2- (2-Methylpropoxy) butyl , 2-[OC(CH3)3]butyl, 3- (OCH3)butyl , 3- (OC2H5) butyl, 3-(OCH2-C2H5)butyl, 3-[OCH(CH3)2]butyl, 3- (OCH2CH2-C2H5) - butyl, 3- (1-Methylpropoxy) butyl, 3- (2-Methylpropoxy) butyl , 3-[OC(CH3)3]butyl, 4- (OCH3)butyl , 4- (OC2H5)butyl ,3- (OCH 2 -C 2 H 5 ) propyl, 3- [OCH (CH 3 ) 2 ] propyl, 3- (OCH 2 CH 2 -C 2 H 5 ) propyl, 3- (1-methylpropoxy) propyl, 3- (2-Methylpropoxy) propyl, 3- [OC (CH 3 ) 3 i propyl, 3- [0 (CH 2 ) 3 -C 2 H 5 ] propyl, 3- [0 (CH 2 ) 4-C2H 5 ] propyl, 2- (OCH 3 ) butyl, 2- (OC 2 H 5 ) butyl, 2- (OCH -C 2 H 5 ) butyl, 2- [OCH (CH 3 ) 2 ] butyl, 2- (OCH 2 CH 2 -C 2 H 5 ) - butyl, 2- (1-methylpropoxy) butyl, 2- (2-methylpropoxy) butyl, 2- [OC (CH 3 ) 3 ] butyl, 3- (OCH 3 ) butyl, 3- (OC 2 H 5 ) butyl, 3- (OCH 2 -C 2 H 5 ) butyl, 3- [OCH (CH 3 ) 2 ] butyl, 3- (OCH 2 CH 2 -C 2 H 5 ) - butyl , 3- (1-Methylpropoxy) butyl, 3- (2-Methylpropoxy) butyl, 3- [OC (CH 3 ) 3 ] butyl, 4- (OCH 3 ) butyl, 4- (OC 2 H 5 ) butyl,
4-(OCH2-C2H5)butyl, 4- [OCH (CH3) 2] butyl, 4- (OCH2CH2-C2H5) - butyl, 4- (1-Methylpropoxy) butyl, 4- (2-Methylpropoxy)butyl , 4-[OC(CH3)3]butyl, 4- [0 (CH2) 3-C2H5] butyl , 4- [0 (CH2) 4-C H5] - butyl, 5- (OCH3) pentyl, 5- (OC2H5) pentyl , 5- (OCH2-C2H5) pentyl, 5- [OCH (CH3) 2] pentyl, 5- (OCH2CH2-C2H5) pentyl , 5-(l-Methyl- propoxy) pentyl, 5- (2-Methylpropoxy) pentyl , 5- [OC (CH3) 3] pentyl , 5- [0(CH2)3-C2H5] pentyl, 5- [0(CH2) 4-C2H5] pentyl, 6- (0CH3) hexyl , 6-(OC2H5)hexyl, 6- (OCH2-C2H5) hexyl , 6- [OCH(CH3) 2] hexyl, 6- (OCH2CH2-C2H5) hexyl, 6- (1-Methylpropoxy) hexyl , 6-(2-Methyl- propoxy) hexyl, 6- [OC (CH3) 3] hexyl, 6- [0(CH2) 3-C2H5] hexyl oder 6- [0(CH2)4-C2H5] hexyl, insbesondere für CH2OCH3 oder CH2OC H5;4- (OCH 2 -C 2 H 5 ) butyl, 4- [OCH (CH 3 ) 2 ] butyl, 4- (OCH 2 CH 2 -C 2 H 5 ) butyl, 4- (1-methylpropoxy) butyl, 4- (2-methylpropoxy) butyl, 4- [OC (CH 3 ) 3 ] butyl, 4- [0 (CH 2 ) 3 -C 2 H 5 ] butyl, 4- [0 (CH 2 ) 4 -CH 5 ] - butyl, 5- (OCH 3 ) pentyl, 5- (OC 2 H 5 ) pentyl, 5- (OCH 2 -C 2 H 5 ) pentyl, 5- [OCH (CH 3 ) 2 ] pentyl, 5- ( OCH 2 CH 2 -C 2 H 5 ) pentyl, 5- (1-methylpropoxy) pentyl, 5- (2-methylpropoxy) pentyl, 5- [OC (CH 3 ) 3 ] pentyl, 5- [0 (CH 2 ) 3 -C 2 H 5 ] pentyl, 5- [0 (CH 2 ) 4 -C 2 H 5 ] pentyl, 6- (0CH 3 ) hexyl, 6- (OC 2 H 5 ) hexyl, 6- (OCH 2 -C 2 H 5 ) hexyl, 6- [OCH (CH 3 ) 2 ] hexyl, 6- (OCH 2 CH 2 -C 2 H 5 ) hexyl, 6- (1-methylpropoxy) hexyl, 6- (2- Methyl propoxy) hexyl, 6- [OC (CH 3 ) 3 ] hexyl, 6- [0 (CH 2 ) 3 -C 2 H 5 ] hexyl or 6- [0 (CH 2 ) 4 -C 2 H 5 ] hexyl, especially for CH 2 OCH 3 or CH 2 OC H 5 ;
Cι-C4-Alkoxy-Cι-C4-alkoxy-Cι-C4-alkyl für: durch 0CH3, OC2H5, n-Propoxy, OCH(CH3)2, n-Butoxy, 1-Methylpropoxy, 2-Methyl- propoxy oder OC(CH3)3, vorzugsweise OCH3, substituiertes Cι.-C4-Alkoxy-Cι-C4-alkyl, also z.B. für CH2OCH OCH3, CH2OCH2OC2H5, CH2OCH2OCH(CH3)2 oder CH2OCH2OC (CH3) 3;C 1 -C 4 -alkoxy-C 4 -alkoxy-C 4 -C 4 -alkyl for: by 0CH 3 , OC 2 H 5 , n-propoxy, OCH (CH 3 ) 2 , n-butoxy, 1-methylpropoxy, 2-methyl-propoxy or OC (CH 3 ) 3 , preferably OCH 3 , substituted C 1 -C 4 -alkoxy-C 4 -C 4 -alkyl, that is, for example, for CH 2 OCH OCH 3 , CH 2 OCH 2 OC 2 H 5 , CH 2 OCH 2 OCH (CH 3 ) 2 or CH 2 OCH 2 OC (CH 3 ) 3 ;
Cι-C4 -Halogenalkoxy-Cι-C4- alkyl für: durch Ci -C4 -Halogenalkoxy wie OCH2F, OCHF2 , 0CF3, 0CH2C1, 0CH(C1)2, 0C(C1)3, 0CHFC1, 0CF(C1)2, 0CF2C1, 0CF2Br, 1-Fluorethoxy, 2-Fluorethoxy, 2-Bromethoxy, 2-Iodethoxy, 2 , 2-Dif luorethoxy, 2 , 2 , 2-Trifluor- ethoxy, 2-Chlor-2-fluorethoxy, 2-Chlor-2, 2-difluorethoxy, 2, 2-Dichlor-2-fluorethoxy, 2, 2, 2-Trichlorethoxy, OC2F5, 2-Fluorpropoxy, 3-Fluorpropoxy, 2-Chlorpropoxy, 3-Chlor- propoxy, 2-Brompropoxy, 3-Brompropoxy, 2 , 2-Difluorpropoxy, 2, 3-Difluorpropoxy, 2 , 3-Dichlorpropoxy, 3 , 3, 3-Trif luorpropoxy, 3, 3, 3-Trichlorpropoxy, 2 , 2 , 3 , 3 , 3-Pentafluorpropoxy, Heptaf luorpropoxy, 1- (CH2F) -2-fluorethoxy, 1- (CH2C1) -2-chlor- ethoxy, 1- (CHBr) -2-bromethoxy, 4-Fluorbutoxy, 4-Chlorbutoxy, 4-Brombutoxy und Nonafluorbutoxy substituiertes C1-C4 -Alkyl, also z.B. für 2 - (OCHF2) ethyl, 2 - (OCF3) ethyl oder 2- (OC2F5) -ethyl;-C-C 4 haloalkoxy -CC 4 - alkyl for: by Ci -C 4 haloalkoxy such as OCH 2 F, OCHF 2 , 0CF 3 , 0CH 2 C1, 0CH (C1) 2 , 0C (C1) 3 , 0CHFC1 , 0CF (C1) 2 , 0CF 2 C1, 0CF 2 Br, 1-fluoroethoxy, 2-fluoroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2, 2-difluoroethoxy, 2, 2, 2-trifluoro ethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2, 2-difluoroethoxy, 2, 2-dichloro-2-fluoroethoxy, 2, 2, 2-trichloroethoxy, OC 2 F 5 , 2-fluoropropoxy, 3-fluoropropoxy , 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2, 2-difluoropropoxy, 2, 3-difluoropropoxy, 2, 3-dichloropropoxy, 3, 3, 3-trifluoropropoxy, 3, 3, 3-trichloropropoxy, 2, 2, 3, 3, 3-pentafluoropropoxy, heptafluoropropoxy, 1- (CH 2 F) -2-fluoroethoxy, 1- (CH 2 C1) -2-chloroethoxy, 1- (CHBr) -2-bromethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy and nonafluorobutoxy substituted C 1 -C 4 alkyl, e.g. for 2 - (OCHF 2 ) ethyl, 2 - (OCF 3 ) ethyl or 2- (OC 2 F 5 ) ethyl;
C3-C -Cycloalkyloxy-Cι-C6-alkyl für: durch C3-C -Cycloalkyloxy wie Cyclopropyloxy, Cyclobutyloxy, Cyclopentyloxy, Cyclo- hexyloxy und Cycloheptyloxy, vorzugsweise Cyclopropyloxy, substituiertes Cι-C6-Alkyl, also z.B. für Cyclopropyl-OCH2, 1-Cyclopropyloxy-ethyl , 2-Cyclopropyloxy-ethyl, 1-Cyclopropyloxy-prop-l-yl, 2-Cyclo- propyloxy-prop-1-yl, 3-Cyclopropyloxy-prop-l-yl, 1-Cyclo- propyloxy-but-1-yl, 2-Cyclopropyloxy-but-l-yl, 3-Cyclopropyl- oxy-but-1-yl, 4-Cyclopropyloxy-but-l-yl, 1-Cyclopropyloxy- but-2-yl, 2-Cyclopropyloxy-but-2-yl, 3-Cyclopropyloxy-but- 2-yl, 4-Cyclopropyloxy-but-2-yl, 1- (Cyclopropyl-OCH -) -eth- l-yl, 1- (Cyclopropyl-OCH2)-1- (CH3) -eth-l-yl, 1- (Cyclopropyl- OCH2) -prop-1-yl, 2-Cyclopropyloxy-hex-6-yl, Cyclobutyl-OCH2, 1-Cyclobutyloxy-ethyl, 2-Cyclobutyloxy-ethyl, 1-Cyclobutyl - oxy-prop-1-yl, 2-Cyclobutyloxy-prop-l-yl, 3-Cyclobutyloxy- prop-1-yl, 1-Cyclobutyloxy-but-l-yl , 2-Cyclobutyloxy-but- 1-yl, 3-Cyclobutyloxy-but-l-yl, 4-Cyclobutyloxy-but-l-yl , l-Cyclobutyloxy-but-2-yl, 2-Cyclobutyloxy-but-2-yl , 3-Cyclo- butyloxy-but-2-yl, 4-Cyclobutyloxy-but-2-yl , 1- (Cyclobutyl- OCH2) -eth-l-yl, 1- (Cyclobutyl-OCH2) -1- (CH3) -eth-l-yl , 1- (Cyclobutyl-OCH2) -prop-1-yl, 2-Cyclobutyloxy-hex-6-yl, Cyclopentyl-OCH2, 1-Cyclopentyloxy-ethyl , 2-Cyclopentyloxy- ethyl, 1-Cyclopentyloxy-prop-l-yl, 2-Cyclopentyloxy-prop-C 3 -C Cycloalkyloxy -CC 6 alkyl for: by C 3 -C cycloalkyloxy such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy and cycloheptyloxy, preferably cyclopropyloxy, substituted -CC 6 alkyl, for example for cyclopropyl -OCH 2 , 1-cyclopropyloxy-ethyl, 2-cyclopropyloxy-ethyl, 1-cyclopropyloxy-prop-l-yl, 2-cyclopropyloxy-prop-1-yl, 3-cyclopropyloxy-prop-l-yl, 1- Cyclopropyloxy-but-1-yl, 2-cyclopropyloxy-but-l-yl, 3-cyclopropyloxy-but-1-yl, 4-cyclopropyloxy-but-l-yl, 1-cyclopropyloxy-but-2- yl, 2-cyclopropyloxy-but-2-yl, 3-cyclopropyloxy-but-2-yl, 4-cyclopropyloxy-but-2-yl, 1- (cyclopropyl-OCH -) -eth-l-yl, 1- ( Cyclopropyl-OCH 2 ) -1- (CH 3 ) -eth-1-yl, 1- (cyclopropyl-OCH 2 ) -prop-1-yl, 2-cyclopropyloxy-hex-6-yl, cyclobutyl-OCH 2 , 1 -Cyclobutyloxy-ethyl, 2-cyclobutyloxy-ethyl, 1-cyclobutyl-oxy-prop-1-yl, 2-cyclobutyloxy-prop-l-yl, 3-cyclobutyloxy-prop-1-yl, 1-cyclobutyloxy-but-l -yl, 2-cyclobutyloxy-but-1-yl, 3-cyclobutyloxy-but-l-yl, 4-cyclobutyloxy-b ut-l-yl, l-cyclobutyloxy-but-2-yl, 2-cyclobutyloxy-but-2-yl, 3-cyclobutyloxy-but-2-yl, 4-cyclobutyloxy-but-2-yl, 1- (Cyclobutyl-OCH 2 ) -eth-l-yl, 1- (cyclobutyl-OCH 2 ) -1- (CH 3 ) -eth-l-yl, 1- (cyclobutyl-OCH 2 ) -prop-1-yl, 2-cyclobutyloxy-hex-6-yl, cyclopentyl-OCH 2 , 1-cyclopentyloxy-ethyl, 2-cyclopentyloxy-ethyl, 1-cyclopentyloxy-prop-l-yl, 2-cyclopentyloxy-prop-
1-yl, 3-Cyclopentyloxy-prop-l-yl, 1-Cyclopentyloxy-but-l-yl, 2-Cyclopentyloxy-but-l-yl, 3-Cyclopentyloxy-but-l-yl , 4-Cyclopentyloxy-but-l-yl, l-Cyclopentyloxy-but-2-yl , 2-Cyclopentyloxy-but-2-yl, 3-Cyclopentyloxy-but-2-yl 4-Cyclo- pentyloxy-but-2-yl, 1- (Cyclopentyl-OCH2) -eth-l-yl , l-(Cyclo- pentyl-OCH2)-l- (CH3) -eth-l-yl, 1- (Cyclopentyl-OCH2) -prop-1-yl , 2-Cyclopentyloxy-hex-6-yl, Cyclohexyl-OCH2, 1-Cyclohexyloxy- ethyl, 2-Cyclohexyloxy-ethyl, 1-Cyclohexyloxy-prop-l-yl , 2-Cyclohexyloxy-prop-l-yl, 3-Cyclohexyloxy-prop-l-yl , 1-Cyclohexyloxy-but-l-yl, 2-Cyclohexyloxy-but-l-yl , 3-Cyclo- hexyloxy-but-1-yl, 4-Cyclohexyloxy-but-l-yl, 1-Cyclohexyloxy- but-2-yl, 2-Cyclohexyloxy-but-2-yl, 3-Cyclohexyloxy-but-2-yl, 4-Cyclohexyloxy-but-2-yl, 1- (Cyclohexyl-OCH2) -eth-l-yl , 1- (Cyclohexyl-OCH2) -1- (CH3) -eth-l-yl, 1- (Cyclohexyl-OCH2) - prop-1-yl, 2-Cyclohexyloxy-hex-6-yl , Cycloheptyl-OCH2, 1-Cycloheptyloxy-ethyl, 2-Cycloheptyloxy-ethyl, 1-Cyclo- heptyloxy-prop-1-yl, 2-Cycloheptyloxy-prop-l-yl, 3-Cyclo- heptyloxy-prop-1-yl, 1-Cycloheptyloxy-but-l-yl , 2-Cyclo- heptyloxy-but-1-yl, 3-Cycloheptyloxy-but-l-yl, 4-Cyclo- heptyloxy-but-1-yl, l-Cycloheptyloxy-but-2-yl , 2-Cyclo- heptyloxy-but-2-yl, 3-Cycloheptyloxy-but-2-yl , 4-Cyclo- heptyloxy-but-2-yl, 1- (Cycloheptyl-OCH2) -eth-l-yl, l-(Cyclo- heptyl-OCH2) -1- (CH3) -eth-l-yl, 1- (Cycloheptyl-OCH2) -prop-1-yl oder 2-Cycloheptyloxy-hex-6-yl;1-yl, 3-cyclopentyloxy-prop-l-yl, 1-cyclopentyloxy-but-l-yl, 2-cyclopentyloxy-but-l-yl, 3-cyclopentyloxy-but-l-yl, 4-cyclopentyloxy-but- l-yl, l-cyclopentyloxy-but-2-yl, 2-cyclopentyloxy-but-2-yl, 3-cyclopentyloxy-but-2-yl 4-cyclopentyloxy-but-2-yl, 1- (cyclopentyl- OCH 2) eth-l-yl, l- (cyclopentyl-OCH 2) -l- (CH3) eth-l-yl, 1- (cyclopentyl-OCH 2) -prop-1-yl, 2 -Cyclopentyloxy-hex-6-yl, cyclohexyl-OCH 2 , 1-cyclohexyloxy-ethyl, 2-cyclohexyloxy-ethyl, 1-cyclohexyloxy-prop-l-yl, 2-cyclohexyloxy-prop-l-yl, 3-cyclohexyloxy- prop-l-yl, 1-cyclohexyloxy-but-l-yl, 2-cyclohexyloxy-but-l-yl, 3-cyclohexyloxy-but-1-yl, 4-cyclohexyloxy-but-l-yl, 1- Cyclohexyloxy-but-2-yl, 2-cyclohexyloxy-but-2-yl, 3-cyclohexyloxy-but-2-yl, 4-cyclohexyloxy-but-2-yl, 1- (cyclohexyl-OCH 2 ) -eth-l-yl, 1- (cyclohexyl-OCH 2 ) -1- (CH 3 ) -eth-l-yl, 1- ( Cyclohexyl-OCH 2 ) - prop-1-yl, 2-cyclohexyloxy-hex-6-yl, cycloheptyl-OCH 2 , 1-cycloheptyloxy-ethyl, 2-cycloheptyloxy-ethyl, 1-cyclo-heptyloxy-prop-1-yl , 2-cycloheptyloxy-prop-l-yl, 3-cycloheptyloxy-prop-1-yl, 1-cycloheptyloxy-but-l-yl, 2-cycloheptyloxy-but-1-yl, 3-cycloheptyloxy-but -l-yl, 4-cycloheptyloxy-but-1-yl, l-cycloheptyloxy-but-2-yl, 2-cycloheptyloxy-but-2-yl, 3-cycloheptyloxy-but-2-yl, 4 -Cyclo-heptyloxy-but-2-yl, 1- (cycloheptyl-OCH 2 ) -eth-l-yl, l- (cyclo-heptyl-OCH 2 ) -1- (CH 3 ) -eth-l-yl, 1- (cycloheptyl-OCH 2 ) prop-1-yl or 2-cycloheptyloxy-hex-6-yl;
(Cχ-C4 -Alkoxy) carbonyl für: COOCH3, COOC2H5, n- Propoxy- carbonyl, OCH(CH3)2, n-Butoxycarbonyl, 1-Methylpropoxy- carbonyl, 2-Methylpropoxycarbonyl oder OC(CH3)3, insbesondere für C00CH3, COOC2H5 oder COOC(CH3)3;(Cχ-C 4 -alkoxy) carbonyl for: COOCH 3 , COOC 2 H 5 , n-propoxycarbonyl, OCH (CH 3 ) 2 , n-butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl or OC (CH 3 ) 3 , in particular for C00CH 3 , COOC 2 H 5 or COOC (CH 3 ) 3 ;
(Ci-Cö-Alkoxy) carbonyl für: C00CH3 , COOC2H5, n-Propoxy- carbonyl, OCH(CH3) , n-Butoxycarbonyl, 1-Methylpropoxy- carbonyl, 2-Methylpropoxycarbonyl, OC(CH3)3, n-Pentoxy- carbonyl , 1-Methylbutoxycarbonyl, 2-Methylbutoxycarbonyl, 3-Methylbutoxycarbonyl, 2, 2-Dimethylpropoxycarbonyl, 1-Ethyl- propoxycarbonyl , n-Hexoxycarbonyl , 1, 1-Dimethylpropoxy- carbonyl, 1, 2-Dimethylpropoxycarbonyl , 1-Methylpentoxy- carbonyl, 2-Methylpentoxycarbonyl, 3-Methylpentoxycarbonyl, 4-Methylpentoxycarbonyl, 1, 1-Dimethylbutoxycarbonyl , 1,2-Di- ethylbutoxycarbonyl, 1, 3-Dimethylbutoxycarbonyl, 2,2-Di- methylbutoxycarbonyl, 2 , 3-Dimethylbutoxycarbonyl, 3,3-Di- methylbutoxycarbonyl, 1-Ethylbutoxycarbonyl, 2-Ethylbutoxy- carbonyl, 1, 1, 2-Trimethylpropoxycarbonyl, 1, 2 , 2-Trimethyl - propoxycarbonyl , l-C2Hs-l-CH3-propoxycarbonyl oder l-C2H5-2-CH3-propoxycarbonyl , insbesondere für COOCH3, COOC2H5 oder COOC(CH3)3;(Ci-C ö -alkoxy) carbonyl for: C00CH 3 , COOC 2 H 5 , n-propoxycarbonyl, OCH (CH 3 ), n-butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl, OC (CH 3 ) 3 , n-pentoxycarbonyl, 1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2, 2-dimethylpropoxycarbonyl, 1-ethyl-propoxycarbonyl, n-hexoxycarbonyl, 1, 1-dimethylpropoxycarbonyl, 1, 2-dimethylpropoxycarbonyl, 1-methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4-methylpentoxycarbonyl, 1, 1-dimethylbutoxycarbonyl, 1,2-diethylbutoxycarbonyl, 1, 3-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl, 2, 3- Dimethylbutoxycarbonyl, 3,3-dimethylbutoxycarbonyl, 1-ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl, 1, 1, 2-trimethylpropoxycarbonyl, 1, 2, 2-trimethylpropoxycarbonyl, 1C 2 Hs-1-CH 3 -propoxycarbonyl or 1C 2 H 5 -2-CH 3 -propoxycarbonyl, especially for COOCH 3 , COOC 2 H 5 or COOC (CH 3 ) 3 ;
(C1-C4 -Alkoxy) carbonyl -Cι-C4-alkyl für: durch (C1-C4 -Alkoxy) - carbonyl - wie vorstehend genannt - substituiertes C1-C4 -Alkyl, also z.B. für CH2COOCH3, CH2COOC2H5, CH2COOCH2-C2H5, CH2COOCH(CH3)2, CH2COOCH2CH2 -C2H5, (1-Methylpropoxycarbonyl) - ethyl, (2-Methylpropoxy- carbonyDmethyl, CH2COOC(CH3) 3 , CH2COO (CH2) 3-C2H5, CH2COO(CH2)4-C2H5, CH(CH3)COOCH3, CH (CH3 ) COOC2H5, CH2CH2COOCH3 , CH2CH COOC2H5, CH CH COOCH2-C2H5, CH2CH2COOCH (CH3) 2, CH2CH2COOCH2CH2-C2H5 , 2- ( 1-Methylpropoxycarbonyl ) ethyl , 2- (2-Methylpropoxycarbonyl)ethyl, CH2CH2COOC (CH3) 3,(C 1 -C 4 alkoxy) carbonyl -Cι-C 4 alkyl: by (C 1 -C 4 alkoxy) - carbonyl - as mentioned above - substituted C 1 -C 4 alkyl, eg CH 2 COOCH 3 , CH 2 COOC 2 H 5 , CH 2 COOCH 2 -C 2 H 5 , CH 2 COOCH (CH 3 ) 2 , CH 2 COOCH 2 CH 2 -C 2 H 5 , (1-methylpropoxycarbonyl) - ethyl, ( 2-Methylpropoxy-carbonyDmethyl, CH 2 COOC (CH 3 ) 3 , CH 2 COO (CH 2 ) 3 -C 2 H 5 , CH 2 COO (CH 2 ) 4 -C 2 H 5 , CH (CH 3 ) COOCH 3 , CH (CH 3 ) COOC 2 H 5 , CH 2 CH 2 COOCH 3 , CH 2 CH COOC 2 H 5 , CH CH COOCH 2 -C 2 H 5 , CH 2 CH 2 COOCH (CH 3 ) 2 , CH 2 CH 2 COOCH 2 CH 2 -C 2 H 5 , 2- (1-methylpropoxycarbonyl) ethyl, 2- (2-methylpropoxycarbonyl) ethyl, CH 2 CH 2 COOC (CH 3 ) 3 ,
CH2CH2COO(CH2)3-C2H5, CH2CH2COO (CH2) 4-C2H5, 2-(COOCH3)- propyl, 2- (COOC2H5) propyl, 2- (COOCH2-C2H5) propyl, 2- [COOCH(CH3)2] propyl, 2- (COOCH2CH2-C2H5) propyl , 2- (1 -Methyl - propoxycarbonyl ) propyl , 2- ( 2-Methylpropoxycarbonyl) propyl , 2- [COOC(CH3)3] propyl, 3- (COOCH3) propyl , 3- (COOC2H5) propyl , 3- (COOCH2-C2H5) propyl, 3- [COOCH(CH3) 2] propyl , 3- (COOCH2CH2- C2H5) propyl, 3- (1-Methylpropoxycarbonyl ) propyl , 3-(2-Methyl- propoxycarbonyl) propyl, 3- [COOC (CH3) 3] propyl , 3- [COO (CH2) 3- C2H5] propyl, 3- [COO (CH2) 4-C2H5] propyl, 2- (C00CH3) butyl , 2-(C00C2H5)butyl, 2- (C00CH2-C2H5) butyl , 2- [COOCH (CH3 ) 2] butyl , 2- (COOCH2CH2-C2H5) butyl , 2 - ( 1-Methylpropoxycarbonyl ) butyl , 2- (2-Methylpropoxycarbonyl) butyl, 2- [COOC (CH3) 3] butyl, 3- (COOCH3)butyl, 3-(COOC2H5)butyl, 3- (COOCH2-C2H5) butyl, 3- [COOCH (CH3) 2] butyl, 3- (COOCH2CH2-C2H5) butyl, 3- (l-Methyl - propoxycarbonyl) butyl, 3- (2-Methylpropoxycarbonyl ) butyl , 3- [COOC (CH3) 3] butyl, 4-(COOCH3)butyl, 4- (COOC2H5)butyl , 4- (COOCH2-C2H5) butyl, 4- [COOCH (CH3) 2] butyl, 4- (COOCH2CH2-CH 2 CH 2 COO (CH 2 ) 3 -C 2 H 5 , CH 2 CH 2 COO (CH 2 ) 4 -C 2 H 5 , 2- (COOCH 3 ) propyl, 2- (COOC 2 H 5 ) propyl , 2- (COOCH 2 -C 2 H 5 ) propyl, 2- [COOCH (CH 3 ) 2 ] propyl, 2- ( COOCH 2 CH 2 -C 2 H5) propyl, 2- (1-methylpropoxycarbonyl) propyl, 2- (2-methylpropoxycarbonyl) propyl, 2- [COOC (CH 3 ) 3 ] propyl, 3- (COOCH 3 ) propyl, 3- (COOC 2 H 5 ) propyl, 3- (COOCH 2 -C 2 H 5 ) propyl, 3- [COOCH (CH 3 ) 2 ] propyl , 3- (COOCH 2 CH 2 - C 2 H 5 ) propyl, 3- (1-methylpropoxycarbonyl) propyl, 3- (2-methylprooxycarbonyl) propyl, 3- [COOC (CH 3 ) 3 ] propyl, 3- [COO (CH 2 ) 3 - C 2 H 5 ] propyl, 3- [COO (CH 2 ) 4 -C 2 H 5 ] propyl, 2- (C00CH 3 ) butyl, 2- (C00C 2 H 5 ) butyl, 2- (C00CH 2 -C 2 H 5 ) butyl, 2- [COOCH (CH 3 ) 2 ] butyl, 2- (COOCH 2 CH 2 -C 2 H 5 ) butyl, 2 - (1-methylpropoxycarbonyl) butyl, 2 - (2-Methylpropoxycarbonyl) butyl, 2- [COOC (CH 3 ) 3 ] butyl, 3- (COOCH 3 ) butyl, 3- (COOC 2 H 5 ) butyl, 3- (COOCH 2 -C 2 H 5 ) butyl , 3- [COOCH (CH 3 ) 2 ] butyl, 3- (COOCH 2 CH 2 -C 2 H 5 ) butyl, 3- (l-methylpropoxycarbonyl) butyl, 3- (2-methylpropoxycarbonyl) butyl, 3- [COOC (CH 3 ) 3 ] butyl, 4- (COOCH 3 ) butyl, 4- (COOC 2 H 5 ) butyl, 4- (COOCH 2 -C 2 H 5 ) butyl, 4- [COOCH (CH 3 ) 2 ] butyl, 4- (COOCH 2 CH 2 -
C2H5)butyl, 4- (1-Methylpropoxycarbonyl) butyl, 4-(2-Methyl- propoxycarbonyl) butyl oder 4- [COOC (CH3) 3] butyl ;C 2 H 5 ) butyl, 4- (1-methylpropoxycarbonyl) butyl, 4- (2-methylpropoxycarbonyl) butyl or 4- [COOC (CH 3 ) 3 ] butyl;
(Ci-Cö-AlkoxyJcarbonyl-Ci-Ce-alkyl für: durch (Cχ~C6-Alkoxy) - carbonyl wie vorstehend genannt substituiertes Cι-C6-Alkyl, also z.B. für CH2COOCH3, CH2COOC2H5, CH2COOCH2-C H5, CH2COOCH(CH3)2- CH2COOCH2CH2-C2H5, ( 1-Methylpropoxycarbonyl ) - methyl, (2-Methylpropoxycarbonyl )methyl, CH2COOC (CH3) 3, CH2COO(CH2)3-C2H5, CH2COO(CH2)4-C2H5, CH (CH3) COOCH3 , CH(CH3)COOC2H5, CH2CH2COOCH3 , CH2CH2COOC2H5, CH2CH2COOCH2-C2H5, CH2CHCOOCH(CH3)2, CH2CH2COOCH2CH2-C2H5 , 2- (1-Methylpropoxy - carbonyl) ethyl , 2- (2-Methylpropoxycarbonyl) ethyl , CH2CH2COOC(CH3)3, CH2CH2COO(CH2)3-C2H5, CH2CH2COO (CH2) 4-C2H5, 2- (COOCH3) ropyl, 2- (COOC2H5) propyl , 2- (COOCH2-C2H5) propyl , 2- [COOCH (CH3)2] propyl, 2- (COOCH2CH2-C2H5) propyl, 2- (l-Methyl - propoxycarbonyl ) propyl , 2- ( 2-Methylpropoxycarbony1 ) ropyl , 2- [COOC (CH3)3] propyl, 3- (COOCH3) propyl , 3- (COOC2H5) propyl, 3- (COOCH2-C2H5) propyl, 3- [COOCH (CH3) 2] propyl, 3- (COOCH2CH2- C2H5) propyl, 3- (1-Methylpropoxycarbonyl) propyl, 3- (2 -Methyl - propoxycarbonyl) propyl, 3- [COOC (CH3) 3] propyl, 3- [COO (CH2) 3- C2H5] propyl, 3- [COO (CH2)4-C2H5] propyl, 2- (COOCH3)butyl , 2- (COOC2H5) butyl, 2-(COOCH2-C H5)butyl, 2- [COOCH (CH3) 2] butyl , 2- (COOCH2CH2-C2H5 ) butyl , 2- ( 1-Methylpropoxycarbonyl ) butyl , 2- (2-Methylpropoxycarbonyl) butyl, 2- [COOC(CH3) 3] butyl, 3-(COOCH3)butyl, 3- (COOC2H5) butyl, 3- (COOCH2-C2H5) butyl ,(Ci-Cö-AlkoxyJcarbonyl-Ci-Ce-alkyl for: by (Cχ ~ C 6 -alkoxy) - carbonyl as substituted above -CC-C 6 alkyl, so for example for CH 2 COOCH 3 , CH 2 COOC 2 H 5 , CH 2 COOCH 2 -CH 5 , CH 2 COOCH (CH 3 ) 2 - CH 2 COOCH 2 CH 2 -C 2 H 5 , (1-methylpropoxycarbonyl) - methyl, (2-methylpropoxycarbonyl) methyl, CH 2 COOC (CH 3 ) 3 , CH 2 COO (CH 2 ) 3 -C 2 H 5 , CH 2 COO (CH 2 ) 4 -C 2 H 5 , CH (CH 3 ) COOCH 3 , CH (CH 3 ) COOC 2 H 5 , CH 2 CH 2 COOCH 3 , CH 2 CH 2 COOC 2 H 5 , CH 2 CH 2 COOCH 2 -C 2 H 5 , CH 2 CHCOOCH (CH 3 ) 2 , CH 2 CH 2 COOCH 2 CH 2 -C 2 H5, 2- (1-methylpropoxycarbonyl) ethyl, 2- (2-methylpropoxycarbonyl) ethyl, CH 2 CH 2 COOC (CH 3 ) 3 , CH 2 CH 2 COO (CH 2 ) 3-C2H5, CH 2 CH 2 COO ( CH 2 ) 4 -C 2 H 5 , 2- (COOCH 3 ) ropyl, 2- (COOC 2 H 5 ) propyl, 2- (COOCH 2 -C 2 H 5 ) propyl, 2- [COOCH (CH 3 ) 2 ] propyl, 2- (COOCH 2 CH 2 -C 2 H 5 ) propyl, 2- (1-methylpropoxycarbonyl) propyl, 2- (2-methylpropoxycarbonyl) ropyl, 2- [COOC (CH 3 ) 3 ] propyl, 3- (CO OCH 3 ) propyl, 3- (COOC 2 H 5 ) propyl, 3- (COOCH 2 -C 2 H 5 ) propyl, 3- [COOCH (CH 3 ) 2 ] propyl, 3- (COOCH 2 CH 2 - C 2 H 5 ) propyl, 3- (1-methylpropoxycarbonyl) propyl, 3- (2-methylpropoxycarbonyl) propyl, 3- [COOC (CH 3 ) 3 ] propyl, 3- [COO (CH 2 ) 3 - C 2 H 5 ] propyl, 3- [COO (CH 2 ) 4 -C 2 H 5 ] propyl, 2- (COOCH 3 ) butyl, 2- (COOC 2 H 5 ) butyl, 2- (COOCH 2 -CH 5 ) butyl, 2- [COOCH (CH 3 ) 2 ] butyl, 2- (COOCH 2 CH 2 -C 2 H 5 ) butyl, 2- (1-methylpropoxycarbonyl) butyl, 2- (2-methylpropoxycarbonyl) butyl, 2- [COOC ( CH 3 ) 3 ] butyl, 3- (COOCH 3 ) butyl, 3- (COOC 2 H 5 ) butyl, 3- (COOCH 2 -C 2 H 5 ) butyl,
3- [COOCH(CH3)2]butyl, 3- (COOCH2CH2-C2H5) butyl, 3- (l-Methyl - propoxycarbonyl) butyl, 3- ( 2-Methylpropoxycarbonyl) butyl , 3- [COOC (CH3)3] butyl, 4- (COOCH3)butyl , 4- (COOC2H5) butyl , 4- (COOCH -C H5) butyl, 4- [COOCH (CH3) 2] butyl , 4- (COOCH2CH2- C2H5)butyl, 4- (1-Methylpropoxycarbonyl) butyl, 4-{2-Methyl- propoxycarbonyl) butyl, 4- [COOC (CH3) 3] butyl, 4- [COO (CH2) 3- C2H5] butyl, 4-[COO(CH2)4-C2H5]butyl, 5- (COOCH3) pentyl , 5- (COOC2H5) pentyl, 5- (COOCH2-C2H5) pentyl, 5- [COOCH(CH3) 2] - pentyl, 5- (COOCH2CH2-C2H5) pentyl , 5- (1 -Methylpropoxycarbonyl ) pentyl , 5- ( 2 -Methylpropoxycarbonyl ) pentyl , 5- [COOC (CH3) 3] pentyl, 5- [COO (CH2) 3-C2H5] pentyl, 5- [COO (CH2) 4- C2H5] pentyl, 6- (COOCH3) hexyl, 6- (COOC2H5) hexyl, 6-(COOCH2-3- [COOCH (CH 3 ) 2 ] butyl, 3- (COOCH 2 CH 2 -C 2 H 5 ) butyl, 3- (l-methylpropoxycarbonyl) butyl, 3- (2-methylpropoxycarbonyl) butyl, 3- [ COOC (CH 3 ) 3 ] butyl, 4- (COOCH 3 ) butyl, 4- (COOC 2 H 5 ) butyl, 4- (COOCH -CH 5 ) butyl, 4- [COOCH (CH 3 ) 2 ] butyl, 4 - (COOCH 2 CH 2 - C 2 H 5 ) butyl, 4- (1-methylpropoxycarbonyl) butyl, 4- {2-methylprooxycarbonyl) butyl, 4- [COOC (CH 3 ) 3 ] butyl, 4- [COO (CH 2 ) 3 - C 2 H 5 ] butyl, 4- [COO (CH 2 ) 4 -C 2 H 5 ] butyl, 5- (COOCH 3 ) pentyl, 5- (COOC2H5) pentyl, 5- (COOCH 2 -C 2 H 5 ) pentyl, 5- [COOCH (CH 3 ) 2 ] - pentyl, 5- (COOCH 2 CH 2 -C 2 H 5 ) pentyl, 5- (1-Methylpropoxycarbonyl) pentyl, 5- (2-Methylpropoxycarbonyl) pentyl, 5- [COOC (CH 3 ) 3] pentyl, 5- [COO (CH 2 ) 3-C 2 H5] pentyl, 5- [COO (CH 2 ) 4 - C 2 H 5 ] pentyl, 6- (COOCH 3 ) hexyl, 6- (COOC 2 H 5 ) hexyl, 6- (COOCH 2 -
C2H5) hexyl, 6- [COOCH (CH3)2] hexyl, 6- (COOCH2CH2-C2H5) hexyl , 6- (1 -Methylpropoxycarbonyl) hexyl, 6- (2 -Methylpropoxycarbonyl) hexyl, 6- [COOC (CH3)3] hexyl, 6- [COO (CH2) 3-C2H5] hexyl oder 6- [COO(CH2)4-C2H5] hexyl, insbesondere für CH2COOCH3 oder CH2COOC2H5;C 2 H 5 ) hexyl, 6- [COOCH (CH 3 ) 2 ] hexyl, 6- (COOCH 2 CH 2 -C 2 H 5 ) hexyl, 6- (1-methylpropoxycarbonyl) hexyl, 6- (2-methylpropoxycarbonyl) hexyl, 6- [COOC (CH 3 ) 3 ] hexyl, 6- [COO (CH 2 ) 3 -C 2 H 5 ] hexyl or 6- [COO (CH 2 ) 4 -C 2 H 5 ] hexyl, especially for CH 2 COOCH 3 or CH 2 COOC 2 H 5 ;
C!-C3-Alkoxy- (Cι-C3-alkoxy) carbonyl-Ci-Cö-alkyl für: durch OCH3, OC2H5, OCH2-C2H5 oder OCH(CH3)2 substituiertes (Cι-C3-Alkoxy)carbonyl-Cι-C6-alkyl wie CH2COOCH3 , CH COOC2H5, CH2COOCH2-C2H5, CH2COOCH (CH3 ) 2 , CH (CH3 ) COOCH3 , CH (CH3 ) COOC2H5,C! -C 3 alkoxy- (-C-C 3 -alkoxy) carbonyl-Ci-Cö-alkyl for: (Cι- substituted by OCH3, OC 2 H 5 , OCH 2 -C 2 H5 or OCH (CH 3 ) 2 C 3 -alkoxy) carbonyl -CC 6 -alkyl such as CH 2 COOCH 3 , CH COOC 2 H 5 , CH 2 COOCH 2 -C 2 H 5 , CH 2 COOCH (CH 3 ) 2 , CH (CH 3 ) COOCH 3 , CH (CH 3 ) COOC 2 H 5 ,
CH2CH2COOCH3, CH2CH2COOC2H5, CH CH2COOCH2-C2H5, CH2CH2COOCH(CH3)2, 2- (COOCH3 ) propyl , 2- (COOC2H5) propyl , 2- (COOCH2-C2H5) propyl, 2- [COOCH (CH3) 2] propyl , 3- (COOCH3) propyl, 3- (COOC2H5) propyl, 3- (COOCH2-C2H5) propyl , 3- [COOCH (CH3)2] propyl, 2- (COOCH3) butyl, 2- (COOC2H5) butyl,CH 2 CH 2 COOCH 3 , CH 2 CH 2 COOC 2 H 5 , CH CH 2 COOCH 2 -C 2 H 5 , CH 2 CH 2 COOCH (CH 3 ) 2 , 2- (COOCH 3 ) propyl, 2- (COOC 2 H 5 ) propyl, 2- (COOCH 2 -C 2 H 5 ) propyl, 2- [COOCH (CH 3 ) 2 ] propyl, 3- (COOCH3) propyl, 3- (COOC 2 H 5 ) propyl, 3- (COOCH 2 -C 2 H 5 ) propyl, 3- [COOCH (CH 3 ) 2 ] propyl, 2- (COOCH 3 ) butyl, 2- (COOC 2 H 5 ) butyl,
2- (COOCH2-C H5) butyl, 2- [COOCH (CH3) 2] butyl , 3- (COOCH3) butyl ,2- (COOCH 2 -CH 5 ) butyl, 2- [COOCH (CH 3 ) 2 ] butyl, 3- (COOCH 3 ) butyl,
3- (COOC2H5) butyl, 3- (COOCH2-C2H5) butyl , 3- [COOCH (CH3) 2] butyl , 4-(COOCH3)butyl, 4- (COOC2H5) butyl , 4- (COOCH2-C2H5) butyl ,3- (COOC 2 H 5 ) butyl, 3- (COOCH 2 -C 2 H 5 ) butyl, 3- [COOCH (CH 3 ) 2 ] butyl, 4- (COOCH 3 ) butyl, 4- (COOC 2 H 5 ) butyl, 4- (COOCH 2 -C 2 H 5 ) butyl,
4- [COOCH (CH3)2] butyl, 5- (COOCH3) pentyl , 5- (COOC2H5) pentyl , 5- (COOCH2-C2H5) pentyl, 5- [COOCH (CH3) 2] pentyl , 6- (COOCH3) hexyl,4- [COOCH (CH 3 ) 2 ] butyl, 5- (COOCH 3 ) pentyl, 5- (COOC 2 H 5 ) pentyl, 5- (COOCH 2 -C 2 H 5 ) pentyl, 5- [COOCH (CH 3 ) 2 ] pentyl, 6- (COOCH 3 ) hexyl,
6- (COOC2H5) hexyl, 6- (COOCH2-C2H5) hexyl oder6- (COOC 2 H 5 ) hexyl, 6- (COOCH 2 -C 2 H 5 ) hexyl or
6- [COOCH (CH3)2] hexyl, vorzugsweise CH2COOCH3 oder CH2COOC2H , also z.B. für CH2COOCH2OCH3, CH2COOCH2OC2H5, CH2COOCH2OCH (CH3 ) 2 oder CH2COOCH OC(CH3)3;6- [COOCH (CH 3 ) 2 ] hexyl, preferably CH 2 COOCH 3 or CH 2 COOC 2 H, e.g. for CH 2 COOCH 2 OCH 3 , CH 2 COOCH 2 OC 2 H 5 , CH 2 COOCH 2 OCH (CH 3 ) 2 or CH 2 COOCH OC (CH 3 ) 3 ;
(Ci-Cβ-AlkoxyJcarbonyl-Ci-Ce-alkoxy für: durch (Cι-C6-Alkoxy) - carbonyl wie vorstehend genannt substituiertes Cι-C6-Alkoxy, also z.B. für OCH COOCH3, OCH2COOC2H5, OCH COOCH2-C2H5 , OCH2COOCH(CH3)2, OCH COOCH2CH2-C2H5, (1-Methylpropoxycarbonyl ) - methoxy, (2-Methylpropoxycarbonyl) ethoxy, OCH2COOC (CH ) 3,(Ci-Cβ-AlkoxyJcarbonyl-Ci-Ce-alkoxy for: by (-C-C 6 alkoxy) - carbonyl substituted as above -CC-C 6 alkoxy, for example for OCH COOCH 3 , OCH 2 COOC 2 H 5 , OCH COOCH 2 -C 2 H 5 , OCH 2 COOCH (CH 3 ) 2 , OCH COOCH 2 CH 2 -C 2 H5, (1-methylpropoxycarbonyl) methoxy, (2-methylpropoxycarbonyl) ethoxy, OCH 2 COOC (CH) 3 ,
OCH2COO(CH2)3-C2H5, OCH2COO(CH2)4-C2H5, OCH (CH3) COOCH3 , OCH(CH3)COOC2H5, OCH2CH2COOCH3, OCH2CH2COOC2H5, OCH2CH2COOCH2-C2H5, OCH2CH2COOCH (CH3) 2 , OCH2CH2COOCH2CH2-C2H5, 2- (l-Methylpropoxycarbonyl)ethoxy, 2- (2-Methylpropoxy- carbonyl )ethoxy, OCH2CH2COOC (CH3) 3, OCH2CH2COO (CH2) 3-C2H5,OCH 2 COO (CH 2 ) 3-C 2 H5, OCH 2 COO (CH 2 ) 4 -C 2 H 5 , OCH (CH 3 ) COOCH 3 , OCH (CH 3 ) COOC 2 H 5 , OCH 2 CH 2 COOCH 3 , OCH 2 CH 2 COOC 2 H 5 , OCH 2 CH 2 COOCH2-C 2 H 5 , OCH 2 CH 2 COOCH (CH 3 ) 2 , OCH 2 CH 2 COOCH 2 CH 2 -C 2 H 5 , 2- ( l-methylpropoxycarbonyl) ethoxy, 2- (2-methylpropoxycarbonyl) ethoxy, OCH 2 CH 2 COOC (CH 3 ) 3 , OCH 2 CH 2 COO (CH 2 ) 3 -C 2 H 5 ,
OCH2CH2COO(CH2)4-C2H5, 2- (COOCH3) propoxy, 2- (COOC2H5) ropoxy,OCH 2 CH 2 COO (CH 2 ) 4 -C 2 H 5 , 2- (COOCH3) propoxy, 2- (COOC 2 H 5 ) ropoxy,
2- (COOCH2-C2H5) propoxy, 2- [COOCH (CH3 ) 2] propoxy,2- (COOCH 2 -C 2 H 5 ) propoxy, 2- [COOCH (CH 3 ) 2 ] propoxy,
2- (COOCH2CH2-C2H5) propoxy, 2- ( 1 -Methylpropoxycarbonyl) propoxy ,2- (COOCH 2 CH 2 -C 2 H 5 ) propoxy, 2- (1-methylpropoxycarbonyl) propoxy,
2- (2 -Methylpropoxycarbonyl) propoxy, 2- [COOC (CH3) 3] propoxy, 3- (COOCH3) propoxy, 3- (COOC2H5) propoxy, 3- (COOCH2-C2H5) propoxy,2- (2-methylpropoxycarbonyl) propoxy, 2- [COOC (CH3) 3] propoxy, 3- (COOCH 3 ) propoxy, 3- (COOC 2 H 5 ) propoxy, 3- (COOCH 2 -C 2 H 5 ) propoxy ,
3- [COOCH (CH3)2] propoxy, 3- (COOCH2CH2-C2H5) propoxy,3- [COOCH (CH 3 ) 2 ] propoxy, 3- (COOCH 2 CH 2 -C 2 H 5 ) propoxy,
3- (1 -Methylpropoxycarbonyl) propoxy, 3- (2-Methylpropoxy- carbonyl) propoxy, 3- [COOC (CH ) 3] propoxy, 3- [COO (CH2)3-C2H5] propoxy, 3- [COO (CH2) 4-C2H5] propoxy, 2- (COOCH3)butoxy, 2- (COOC2H5)butoxy, 2- (COOCH2-C2H5) butoxy , 2- [COOCH(CH3)2]butoxy, 2- (COOCH2CH2-C2H5) butoxy, 2- (l-Methyl - propoxycarbonyl )butoxy, 2- (2-Methylpropoxycarbonyl) butoxy , 2- [COOC(CH3)3]butoxy, 3- (COOCH3) butoxy, 3- (COOC2H5) butoxy, 3- (COOCH2-C2H5) butoxy, 3- [COOCH (CH3 ) 2] butoxy, 3- (COOCH2CH2-C2H5) butoxy, 3- ( 1-Methylpropoxycarbonyl ) butoxy,3- (1-methylpropoxycarbonyl) propoxy, 3- (2-methylpropoxy- carbonyl) propoxy, 3- [COOC (CH) 3 ] propoxy, 3- [COO (CH 2 ) 3 -C 2 H 5 ] propoxy, 3- [COO (CH 2 ) 4 -C 2 H 5 ] propoxy, 2 - (COOCH 3 ) butoxy, 2- (COOC 2 H 5 ) butoxy, 2- (COOCH 2 -C 2 H 5 ) butoxy, 2- [COOCH (CH 3 ) 2 ] butoxy, 2- (COOCH 2 CH 2 - C 2 H 5 ) butoxy, 2- (1-methylpropoxycarbonyl) butoxy, 2- (2-methylpropoxycarbonyl) butoxy, 2- [COOC (CH 3 ) 3 ] butoxy, 3- (COOCH 3 ) butoxy, 3- ( COOC 2 H 5 ) butoxy, 3- (COOCH 2 -C 2 H 5 ) butoxy, 3- [COOCH (CH 3 ) 2 ] butoxy, 3- (COOCH 2 CH2-C 2 H 5 ) butoxy, 3- (1 -Methylpropoxycarbonyl) butoxy,
3- (2-Methylpropoxycarbonyl) butoxy, 3- [COOC (CH3) 3] butoxy, 4- (COOCH3) butoxy, 4- (COOC2H5) butoxy, 4- (COOCH2-C2H5) butoxy,3- (2-methylpropoxycarbonyl) butoxy, 3- [COOC (CH 3 ) 3 ] butoxy, 4- (COOCH 3 ) butoxy, 4- (COOC 2 H 5 ) butoxy, 4- (COOCH 2 -C 2 H 5 ) butoxy,
4- [COOCH (CH3)2] butoxy, 4- (COOCH2CH2-C2H5) butoxy, 4- (l-Methyl - propoxycarbonyl) butoxy, 4- (2-Methylpropoxycarbonyl)butoxy,4- [COOCH (CH 3 ) 2 ] butoxy, 4- (COOCH 2 CH 2 -C 2 H 5 ) butoxy, 4- (l-methylpropoxycarbonyl) butoxy, 4- (2-methylpropoxycarbonyl) butoxy,
4- [COOC (CH3) 3] butoxy, 4- [COO (CH2) 3-C2H5] butoxy,4- [COOC (CH 3 ) 3 ] butoxy, 4- [COO (CH 2 ) 3 -C 2 H 5 ] butoxy,
4- [COO (CH )4- 2H5] butoxy, 5- (COOCH3) pentoxy , 5-(COOC2H5)- pentoxy, 5- (COOCH2-C H5) pentoxy, 5- [COOCH (CH3) 2] pentoxy,4- [COO (CH) 4 - 2 H5] butoxy, 5- (COOCH 3) pentoxy, 5- (COOC 2 H 5) - pentoxy, 5- (COOCH 2 -CH 5) pentoxy, 5- [COOCH (CH 3 ) 2 ] pentoxy,
5- (COOCH2CH2-C2H5) pentoxy, 5- (1-Methylpropoxycarbonyl) pentoxy, 5- (2-Methylpropoxycarbonyl) pentoxy, 5- [COOC (CH3) 3] pentoxy,5- (COOCH 2 CH 2 -C 2 H 5 ) pentoxy, 5- (1-methylpropoxycarbonyl) pentoxy, 5- (2-methylpropoxycarbonyl) pentoxy, 5- [COOC (CH 3 ) 3 ] pentoxy,
5- [COO (CH2)3-C2H5] pentoxy, 5- [COO (CH2) 4-C2H5] pentoxy,5- [COO (CH 2 ) 3 -C 2 H 5 ] pentoxy, 5- [COO (CH 2 ) 4 -C 2 H 5 ] pentoxy,
6- (COOCH3)hexoxy, 6- (COOC2H5) hexoxy, 6- (COOCH2-C2H5) hexoxy, 6- [COOCH (CH3)2] hexoxy, 6- (COOCH2CH2-C2H5) hexoxy, 6- (l-Methyl - propoxycarbonyl) hexoxy, 6- (2-Methylpropoxycarbonyl) hexoxy, 6- [COOC (CH3) 3] hexoxy, 6- [COO (CH2) 3-C2H5] hexoxy oder 6- [COO (CH2) 4-C2H5] hexoxy, insbesondere für OCHCOOCH3 oder OCH2COOC2H5;6- (COOCH 3 ) hexoxy, 6- (COOC 2 H 5 ) hexoxy, 6- (COOCH 2 -C 2 H 5 ) hexoxy, 6- [COOCH (CH 3 ) 2 ] hexoxy, 6- (COOCH 2 CH 2 -C 2 H 5 ) hexoxy, 6- (l-methylpropoxycarbonyl) hexoxy, 6- (2-methylpropoxycarbonyl) hexoxy, 6- [COOC (CH 3 ) 3 ] hexoxy, 6- [COO (CH 2 ) 3 - C 2 H 5 ] hexoxy or 6- [COO (CH 2 ) 4 -C 2 H 5 ] hexoxy, in particular for OCHCOOCH 3 or OCH 2 COOC 2 H 5 ;
C!-C6-Alkylthio für: z.B. SCH3, SC2H5, n-Propylthio, SCH(CH3)2, n-Butylthio, SCH (CH3) -C H5, SCH2 -CH (CH3) 2, SC(CH3)3, n-Pentyl - thio, 1-Methylbutylthio, 2-Methylbutylthio, 3-Methylbutyl - thio, 2, 2-Dimethylpropylthio, 1-Ethylpropylthio, n-Hexylthio, 1, 1-Dimethylpropylthio, 1 , 2-Dimethylpropylthio, l-Methyl - pentylthio, 2-Methylpentylthio, 3-Methylpentylthio, 4 -Methyl - pentylthio, 1, 1-Dimethylbutylthio, 1, 2-Dimethylbutylthio, 1, 3-Dimethylbutylthio, 2, 2-Dimethylbutylthio, 2 , 3-Dimethyl - butylthio, 3 , 3-Dimethylbutylthio, 1-Ethylbutylthio, 2-Ethyl- butylthio, 1, 1, 2-Trimethylpropylthio, 1, 2 , 2-Trimethylpropyl - thio, 1-Ethyl-l-methylpropylthio oder l-Ethyl-2-methylpropyl- thio, insbesondere für SCH3 oder SC2H5;C ! -C 6 alkylthio for: e.g. SCH 3 , SC 2 H 5 , n-propylthio, SCH (CH 3 ) 2 , n-butylthio, SCH (CH 3 ) -CH 5 , SCH 2 -CH (CH 3 ) 2 , SC (CH 3 ) 3 , n-pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2, 2-dimethylpropylthio, 1-ethylpropylthio, n-hexylthio, 1, 1-dimethylpropylthio, 1, 2 -Dimethylpropylthio, l-methyl-pentylthio, 2-methylpentylthio, 3-methylpentylthio, 4 -methyl - pentylthio, 1, 1-dimethylbutylthio, 1, 2-dimethylbutylthio, 1, 3-dimethylbutylthio, 2, 2-dimethylbutylthio, 2, 3 -Dimethyl - butylthio, 3, 3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1, 1, 2-trimethylpropylthio, 1, 2, 2-trimethylpropylthio, 1-ethyl-l-methylpropylthio or l-ethyl -2-methylpropyl- thio, especially for SCH 3 or SC 2 H5;
Cι-C6-Alkylthio-Cι-C6-alkyl für: durch Ci-Cö-Alkylthio wie vorstehend genannt substituiertes Cχ-C6-Alkyl, also z.B. für CH2SCH3, CH2SC2H5, CH2SCH2-C2H5, CH2SCH (CH3) 2 , CH2SCH2CH2-C2H5, (l-Methylpropylthio)methyl, (2-Methylpropylthio) methyl , CH2SC(CH3)3, CH2S(CH2)3- 2H5, CH2S (CH2 ) 4- 2H5, CH(CH3)SCH3, CH(CH3)SC2H5, CH2CH SCH3, CH2CH2SC2H5, CH2CH2SCH2-C2H5, CH2CH2SCH(CH3)2, CH2CH2SCH2CH2-C2H5, 2- ( 1-Methylpropyl - thio)ethyl, 2- (2-Methylpropylthio) ethyl, CH2CH2SC (CH3) 3, CH2CH2S(CH2)3-C2H5, CH2CH2S(CH2)4-C2H5, 2- (SCH3) propyl , 2- (SC2H5) propyl, 2- (SCH2-C2H5) propyl , 2- [SCH (CH3) 2] propyl , 2- (SCH2CH2-C2H5) propyl, 2- (1-Methylpropylthio) propyl , 2- (2-Methylpropylthio) propyl, 2- [SC (CH3 ) 3] propyl , 3- (SCH3) propyl, 3- (SC2H5) propyl, 3- (SCH2-C2H5) propyl, 3- [SCH (CH3)21 propyl, 3- (SCH2CH2-C2H5) propyl , 3- { l-Methyl - propylthio) propyl, 3- (2-Methylpropylthio) propyl , 3-[SC(CH3)3]propyl, 3- [S (CH2) 3-C2H5] propyl, 3- [S(CH2)4-C2H5] propyl, 2- (SCH3)butyl, 2- (SC2H5)butyl, 2-(SCH2-C2H5)butyl, 2-[SCH(CH3)2]butyl, 2- (SCH2CH2-C2H5)butyl , 2- (1-Methylpropylthio) butyl, 2- (2-Methylpropylthio) butyl , 2- [SC(CH3)3]butyl, 3-(SCH3)butyl, 3- (SC2H5)butyl, 3-(SCH2-C2H5)butyl, 3- [SCH (CH3) 2] butyl, 3- (SCH2CH2-C2H5) butyl , 3- (1-Methylpropylthio) butyl, 3- (2-Methylpropylthio) butyl, 3- [SC(CH3)3)butyl, 4- (SCH3)butyl, 4- (SC2H5)butyl, 4-(SCH -C2H5)butyl, 4- [SCH (CH3) 21 butyl , 4- (SCH2CH2-C2H5)butyl , 4- (1-Methylpropylthio) butyl, 4- (2-Methylpropylthio) butyl, 4- [SC(CH3)3]butyl, 4- [S(CH2)3-C2H5]butyl,C 1 -C 6 -alkylthio-C 1 -C 6 -alkyl for: C 1 -C 6 -alkyl-substituted by C 1 -C 6 -alkylthio as mentioned above, for example for CH 2 SCH 3 , CH 2 SC 2 H 5 , CH 2 SCH 2 -C 2 H 5 , CH 2 SCH (CH 3 ) 2 , CH 2 SCH 2 CH 2 -C 2 H 5 , (l-methylpropylthio) methyl, (2-methylpropylthio) methyl, CH 2 SC (CH 3 ) 3 , CH 2 S (CH 2 ) 3- 2 H5, CH 2 S (CH 2 ) 4- 2H5, CH ( CH 3 ) SCH 3 , CH (CH 3 ) SC 2 H 5 , CH 2 CH SCH 3 , CH 2 CH 2 SC 2 H 5 , CH 2 CH 2 SCH 2 -C 2 H 5 , CH 2 CH 2 SCH (CH 3 ) 2 , CH 2 CH 2 SCH 2 CH 2 -C 2 H 5 , 2- (1-methylpropyl - thio) ethyl, 2- (2-methylpropylthio) ethyl, CH 2 CH 2 SC (CH 3 ) 3 , CH 2 CH 2 S (CH 2 ) 3 -C 2 H5, CH 2 CH 2 S (CH 2 ) 4 - C 2 H5, 2- (SCH 3 ) propyl, 2- (SC 2 H 5 ) propyl, 2- (SCH 2 -C 2 H 5 ) propyl, 2- [SCH (CH 3 ) 2 ] propyl, 2- (SCH 2 CH 2 -C 2 H 5 ) propyl, 2- (1-methylpropylthio) propyl, 2- (2-methylpropylthio) propyl, 2- [SC (CH 3 ) 3 ] propyl, 3- (SCH 3 ) propyl, 3- (SC 2 H 5 ) propyl, 3- (SCH 2 -C 2 H 5 ) propyl, 3- [SCH (CH 3 ) 2 1 propyl, 3- (SCH 2 CH 2 -C 2 H 5 ) propyl, 3- {l-methylpropylthio) propyl, 3 - (2-Methylpropylthio) propyl, 3- [SC (CH 3 ) 3 ] propyl, 3- [S (CH 2 ) 3 -C 2 H 5 ] propyl, 3- [S (CH 2 ) 4 -C 2 H 5 ] propyl, 2- (SCH 3 ) butyl, 2- (SC 2 H 5 ) butyl, 2- (SCH 2 -C 2 H 5 ) butyl, 2- [SCH (CH 3 ) 2 ] butyl, 2- ( SCH 2 CH 2 -C 2 H 5 ) butyl, 2- (1-methylpropylthio) butyl, 2- (2-methylpropylthio) butyl, 2- [SC (CH 3 ) 3 ] butyl, 3- (SCH 3 ) butyl, 3- (SC 2 H 5 ) butyl, 3- (SCH 2 -C 2 H 5 ) butyl, 3- [SCH (CH 3 ) 2 ] butyl, 3- (SCH 2 CH 2 -C 2 H 5 ) butyl, 3- (1-methylpropylthio) butyl, 3- (2-methylpropylthio) butyl, 3- [SC (CH 3 ) 3 ) butyl, 4- (SCH 3 ) butyl, 4- (SC 2 H 5 ) butyl, 4- (SCH -C 2 H 5 ) butyl, 4- [SCH (CH 3 ) 2 1 butyl, 4- (SCH 2 CH 2 -C 2 H 5 ) butyl, 4- (1-methylpropylthio) butyl, 4- (2-methylpropylthio) butyl, 4- [SC (CH 3 ) 3 ] butyl , 4- [S (CH 2 ) 3 -C 2 H 5 ] butyl,
4- [S(CH2)4-C2H5] butyl, 5- (SCH3) pentyl, 5- (SC2H5) pentyl, 5- (SCH2-C2H5)pentyl, 5- [SCH (CH3) 2] pentyl, 5- (SCH2CH2-C2H5) pentyl, 5- (1-Methylpropylthio) entyl,4- [S (CH 2 ) 4 -C 2 H 5 ] butyl, 5- (SCH 3 ) pentyl, 5- (SC 2 H 5 ) pentyl, 5- (SCH 2 -C 2 H 5 ) pentyl, 5- [SCH (CH 3 ) 2 ] pentyl, 5- (SCH 2 CH 2 -C 2 H 5 ) pentyl, 5- (1-methylpropylthio) entyl,
5- (2-Methylpropylthio) pentyl, 5- [SC (CH3) 3] pentyl ,5- (2-methylpropylthio) pentyl, 5- [SC (CH 3 ) 3 ] pentyl,
5- [S(CH2)3-C2H5] pentyl, 5- [S (CH2) 4-C2H5] pentyl , 6- (SCH3) hexyl, 6-(SC2H5)hexyl, 6- (SCH2-C2H5) hexyl, 6- [SCH (CH3) 23 hexyl ,5- [S (CH 2 ) 3 -C 2 H 5 ] pentyl, 5- [S (CH 2 ) 4 -C 2 H 5 ] pentyl, 6- (SCH 3 ) hexyl, 6- (SC 2 H 5 ) hexyl, 6- (SCH 2 -C 2 H 5 ) hexyl, 6- [SCH (CH 3 ) 2 3 hexyl,
6- (SCH2CH2-C2H5) hexyl, 6- (1-Methylpropylthio) hexyl, 6- (2-Methylpropylthio) hexyl, 6- [SC (CH3) 3] hexyl ,6- (SCH 2 CH 2 -C 2 H 5 ) hexyl, 6- (1-methylpropylthio) hexyl, 6- (2-methylpropylthio) hexyl, 6- [SC (CH 3 ) 3 ] hexyl,
6- [S (CH2) 3-C2H5] hexyl oder 6- [S (CH2) 4-C2H5] hexyl, insbesondere für CH2SCH3 oder CH2SC2H5;6- [S (CH 2 ) 3 -C 2 H 5 ] hexyl or 6- [S (CH 2 ) 4 -C 2 H 5 ] hexyl, especially for CH 2 SCH 3 or CH 2 SC 2 H 5 ;
C3-C7-Cycloalkylthio-Cι-C6-alkyl für: durch C3-C7-Cycloalkyl- thio wie Cyclopropylthio, Cyclobutylthio, Cyclopentyl thio, Cyclohexylthio und Cycloheptylthio, vorzugsweise Cyclopropylthio, substituiertes Cι-C6-Alkyl, also z.B. für Cyclopropyl-SCH2, 1-Cyclopropylthio-ethyl, 2-Cyclopropylthio-ethyl, 1-Cyclopropylthio-prop-l-yl, 2-Cyclopropylthio-prop-l-yl, 3-Cyclopropylthio-prop-l-yl, 1-Cyclopropylthio-but-l-yl , 2-Cyclopropylthio-but-l-yl , 3-Cyclopropylthio-but-l-yl, 4-Cyclopropylthio-but-l-yl, l-Cyclopropylthio-but-2-yl, 2-Cyclopropylthio-but-2-yl , 3-Cyclopropylthio-but-2-yl 4-Cyclopropyl thio-but-2-yl, 1- (Cyclopropyl-SCH2-) -eth-l-yl, 1- (Cyclopropyl-SCH2) -1- (CH3) - eth-l-yl, 1- (Cyclopropyl-SCH2) -prop-1-yl, 2-Cyclopropylthio- hex-6-yl, Cyclobutyl-SCH2, 1-Cyclobutylthio-ethyl , 2-Cyclo- butylthio-ethyl, 1-Cyclobutylthio-prop-l-yl, 2-Cyclobutyl - thio-prop-1-yl, 3-Cyclobutylthio-prop-l-yl, 1-Cyclobutylthio- but-l-yl, 2-Cyclobutylthio-but-l-yl, 3-Cyclobutylthio-but- 1-yl, 4-Cyclobutylthio-but-l-yl, l-Cyclobutylthio-but-2-yl, 2-Cyclobutylthio-but-2-yl, 3-Cyclobutylthio-but-2-yl, 4-Cyclobutylthio-but-2-yl, 1- (Cyclobutyl-SCH2) -eth-l-yl, 1- (Cyclobutyl-SCH2) -1- (CH3) -eth-l-yl , 1- (Cyclobutyl-SCH2) - prop-1-yl, 2-Cyclobutylthio-hex-6-yl, Cyclopentyl-SCH2 , 1-Cyclopentylthio-ethyl, 2-Cyclopentylthio-ethyl, 1-Cyclo- pentylthio-prop-1-yl, 2-Cyclopentylthio-prop-l-yl , 3-Cyclo- pentylthio-prop-1-yl, 1-Cyclopentylthio-but-l-yl, 2-Cyclo- pentylthio-but-1-yl, 3-Cyclopentylthio-but-l-yl, 4-Cyclo- pentylthio-but-1-yl, l-Cyclopentylthio-but-2-yl , 2-Cyclo- pentylthio-but-2-yl, 3-Cyclopentylthio-but-2-yl 4-Cyclo- pentylthio-but-2-yl, 1- (Cyclopentyl-SCH2) -eth-l-yl, l-(Cyclo- pentyl-SCH2)-l- (CH3) -eth-l-yl, 1- (Cyclopentyl-SCH2) -prop-1-yl, 2-Cyclopentylthio-hex-6-yl, Cyclohexyl-SCH2, 1-Cyclohexyl - thio-ethyl, 2-Cyclohexylthio-ethyl, 1-Cyclohexylthio-prop- 1-yl, 2-Cyclohexylthio-prop-l-yl , 3-Cyclohexylthio-prop-l-yl , 1-Cyclohexylthio-but-l-yl, 2-Cyclohexylthio-but-l-yl , 3-Cyclohexylthio-but-l-yl, 4-Cyclohexylthio-but-l-yl , l-Cyclohexylthio-but-2-yl, 2-Cyclohexylthio-but-2-yl, 3-Cyclohexylthio-but-2-yl, 4-Cyclohexylthio-but-2-yl, 1- (Cyclohexyl-SCH2) -eth-l-yl, 1- (Cyclohexyl-SCH2) -1- (CH3)- eth-l-yl, 1- (Cyclohexyl-SCH2) -prop-1-yl, 2-Cyclohexylthio- hex-6-yl, Cycloheptyl-SCH2, 1-Cycloheptylthio-ethyl , 2-Cyclo- heptylthio-ethyl, 1-Cycloheptylthio-prop-l-yl, 2-Cycloheptyl - thio-prop-1-yl, 3-Cycloheptylthio-prop-l-yl , 1-Cycloheptyl- thio-but-1-yl, 2-Cycloheptylthio-but-l-yl, 3-Cycloheptylthio- but-l-yl, 4-Cycloheptylthio-but-l-yl, 1-Cycloheptylthio-but- 2-yl, 2-Cycloheptylthio-but-2-yl, 3-Cycloheptylthio-but-2-yl , 4-Cycloheptylthio-but-2-yl, 1- (Cycloheptyl-SCH2) -eth-l-yl, 1- (Cycloheptyl-SCH2)-l-(CH3) -eth-l-yl, 1- (Cycloheptyl-SCH2) - prop-1-yl oder 2-Cycloheptylthio-hex-6-yl;C 3 -C 7 cycloalkylthio-C 6 -C 6 alkyl for: by C 3 -C 7 cycloalkyl thio such as cyclopropylthio, cyclobutylthio, cyclopentyl thio, cyclohexylthio and cycloheptylthio, preferably cyclopropylthio, substituted C 1 -C 6 alkyl, that is e.g. for cyclopropyl-SCH 2 , 1-cyclopropylthio-ethyl, 2-cyclopropylthio-ethyl, 1-cyclopropylthio-prop-l-yl, 2-cyclopropylthio-prop-l-yl, 3-cyclopropylthio-prop-l-yl, 1 -Cyclopropylthio-but-l-yl, 2-cyclopropylthio-but-l-yl, 3-cyclopropylthio-but-l-yl, 4-cyclopropylthio-but-l-yl, l-cyclopropylthio-but-2-yl, 2 -Cyclopropylthio-but-2-yl, 3-cyclopropylthio-but-2-yl 4-cyclopropyl thio-but-2-yl, 1- (cyclopropyl-SCH 2 -) -eth-l-yl, 1- (cyclopropyl- SCH 2 ) -1- (CH 3 ) - eth-l-yl, 1- (cyclopropyl-SCH 2 ) -prop-1-yl, 2-cyclopropylthio-hex-6-yl, cyclobutyl-SCH 2 , 1-cyclobutylthio -ethyl, 2-cyclobutylthio-ethyl, 1-cyclobutylthio-prop-l-yl, 2-cyclobutyl-thio-prop-1-yl, 3-cyclobutylthio-prop-l-yl, 1-cyclobutylthio-but-l -yl, 2-cyclobutylthio-but-l-yl, 3-cyclobuty lthio-but-1-yl, 4-cyclobutylthio-but-l-yl, l-cyclobutylthio-but-2-yl, 2-cyclobutylthio-but-2-yl, 3-cyclobutylthio-but-2-yl, 4-cyclobutylthio-but-2-yl, 1- (cyclobutyl-SCH 2 ) -eth-l-yl, 1- (cyclobutyl-SCH 2 ) -1- (CH 3 ) -eth-l-yl, 1- ( Cyclobutyl-SCH 2 ) - prop-1-yl, 2-cyclobutylthio-hex-6-yl, cyclopentyl-SCH 2 , 1-cyclopentylthio-ethyl, 2-cyclopentylthio-ethyl, 1-cyclopentylthio-prop-1-yl , 2-Cyclopentylthio-prop-l-yl, 3-cyclopentylthio-prop-1-yl, 1-cyclopentylthio-but-l-yl, 2-cyclopentylthio-but-1-yl, 3-cyclopentylthio-but -l-yl, 4-cyclopentylthio-but-1-yl, l-cyclopentylthio-but-2-yl, 2-cyclopentylthio-but-2-yl, 3-cyclopentylthio-but-2-yl 4- Cyclopentylthio-but-2-yl, 1- (cyclopentyl-SCH 2 ) -eth-l-yl, l- (Cyclopentyl-SCH 2 ) -l- (CH 3 ) -eth-l-yl, 1 - (Cyclopentyl-SCH 2 ) -prop-1-yl, 2-cyclopentylthio-hex-6-yl, cyclohexyl-SCH 2 , 1-cyclohexyl-thio-ethyl, 2-cyclohexylthio-ethyl, 1-cyclohexylthio-prop-1 -yl, 2-cyclohexylthio-prop-l-yl, 3-cyclohexylthio-prop-l-yl, 1-cyclohexylthio-but-l-yl, 2-cyclohexylthio-but-l-yl, 3-cyclohexylthio-but-l -yl, 4-cyclohexylthio-but-l-yl, l-cyclohexylthio-but-2 -yl, 2-cyclohexylthio-but-2-yl, 3-cyclohexylthio-but-2-yl, 4-cyclohexylthio-but-2-yl, 1- (cyclohexyl-SCH 2 ) -eth-l-yl, 1- (Cyclohexyl-SCH 2 ) -1- (CH 3 ) - eth-l-yl, 1- (cyclohexyl-SCH 2 ) -prop-1-yl, 2-cyclohexylthio-hex-6-yl, cycloheptyl-SCH 2 , 1-cycloheptylthio-ethyl, 2-cycloheptylthio-ethyl, 1-cycloheptylthio-prop-l-yl, 2-cycloheptyl-thio-prop-1-yl, 3-cycloheptylthio-prop-l-yl, 1-cycloheptyl- thio-but-1-yl, 2-cycloheptylthio-but-l-yl, 3-cycloheptylthio-but-l-yl, 4-cycloheptylthio-but-l-yl, 1-cycloheptylthio-but-2-yl, 2- Cycloheptylthio-but-2-yl, 3-cycloheptylthio-but-2-yl, 4-cycloheptylthio-but-2-yl, 1- (cycloheptyl-SCH 2 ) -eth-1-yl, 1- (cycloheptyl-SCH 2 ) -l- (CH 3 ) -eth-1-yl, 1- (cycloheptyl-SCH 2 ) -prop-1-yl or 2-cycloheptylthio-hex-6-yl;
C -Cg-Alkylsulfinyl für: z.B. SOCH3, S0C2H5, n-Propylsulf inyl , SOCH(CH3)2, n-Butylsulfinyl, 1-Methylpropylsulfinyl , 2-Methyl- propylsulf inyl, SOC(CH3)3, n-Pentylsulfinyl, 1-Methylbutyl - sulfinyl, 2-Methylbutylsulf inyl , 3-Methylbutylsulfinyl , 2, 2-Dimethylpropylsulfinyl, 1-Ethylpropylsulfinyl, n-Hexyl- sulfinyl, 1 , 1-Dimethylpropylsulfinyl, 1, 2-Dimethylpropyl - sulfinyl, 1-Methylpentylsulfinyl, 2-Methylpentylsulfinyl, 3-Methylpentylsulfinyl, 4-Methylpentylsulf inyl , 1 , 1-Dimethyl - butylsulfinyl, 1, 2-Dimethylbutylsulfinyl, 1 , 3-Dimethylbutyl - sulfinyl, 2 , 2-Dimethylbutylsulfinyl, 2 , 3-Dimethylbutyl - sulfinyl, 3 , 3-Dimethylbutylsulf inyl , 1-Ethylbutylsulfinyl , 2-Ethylbutylsulfinyl, 1, 1, 2-Trimethylpropylsulfinyl, 1,2, 2-Trimethylpropylsulfinyl, 1-Ethyl-l-methylpropylsulfinyl oder l-Ethyl-2-methylpropylsulfinyl, insbesondere für SOCH3 oder SOC2H5; Cι-C-6-Alkylsulf inyl-Ci-Cβ-alkyl für: durch Cι-C6-Alkylsulf inyl wie vorstehend genannt substi uiertes Cι-C6-Alkyl, also z.B. für CH2SO-CH3, CH2SO-C2H5, CH2SO-CH2-C2H5, CH2SO-CH (CH3 ) 2 , CH2SO-CH2CH2-C2H5, ( 1-Methylpropylsulf inyl ) methyl, (2-Methyl- propylsulf inyl) methyl, CH2SO-C (CH3) 3, CH2SO- (CH2) 3-C2H5,C -Cg-alkylsulfinyl for: e.g. SOCH 3 , S0C 2 H 5 , n-propylsulfinyl, SOCH (CH 3 ) 2 , n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, SOC (CH 3 ) 3 , n-pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2, 2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, n-hexylsulfinyl, 1, 1-dimethylpropylsulfinyl, 1, 2-dimethylpropylsulfinyl, 1 -Methylpentylsulfinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1, 1-dimethylbutylsulfinyl, 1, 2-dimethylbutylsulfinyl, 1, 3-dimethylbutylsulfinyl, 2, 2-dimethylbutylsulfinyl, 2, 3-dimethylbutyl sulfinyl, 3, 3-dimethylbutylsulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1, 1, 2-trimethylpropylsulfinyl, 1,2, 2-trimethylpropylsulfinyl, 1-ethyl-l-methylpropylsulfinyl or l-ethyl-2-methylpropylsulfinyl, especially for SOCH 3 or SOC 2 H 5 ; C 1 -C 6 -alkylsulf inyl-C 1 -C 6 -alkyl for: C 1 -C 6 -alkylsulf inyl as mentioned above substituted C 1 -C 6 -alkyl, for example for CH 2 SO-CH 3 , CH2SO-C 2 H 5 , CH 2 SO-CH 2 -C 2 H 5 , CH 2 SO-CH (CH 3 ) 2 , CH 2 SO-CH 2 CH 2 -C 2 H 5 , (1-methylpropylsulfinyl) methyl, (2nd -Methyl-propylsulfinyl) methyl, CH 2 SO-C (CH 3 ) 3 , CH 2 SO- (CH 2 ) 3 -C 2 H 5 ,
CH2SO-(CH2)4-C2H5, CH(CH3)SO-CH3, CH (CH3) SO-C2H5, CH2CH2SO-CH3 , CH2CH2SO-C2H5, CH2CH2SO-CH2-C2H5, CH2CH2SO-CH (CH3) 2 , CH2CH2SO-CH2CH2-C2H5 , 2- ( 1-Methylpropylsulf inyl ) ethyl , 2- (2-Methylpropylsulfinyl) ethyl, CH2CH2SO-C (CH3) 3 , CH2CH2SO-(CH2)3-C2H5, CH2CH2SO- (CH2) -C2H5, 2- (SO-CH3) propyl ,CH 2 SO- (CH 2 ) 4-C 2 H 5 , CH (CH 3 ) SO-CH 3 , CH (CH 3 ) SO-C 2 H 5 , CH 2 CH 2 SO-CH 3 , CH 2 CH 2 SO-C 2 H 5 , CH2CH 2 SO-CH 2 -C 2 H5, CH 2 CH 2 SO-CH (CH 3 ) 2 , CH 2 CH 2 SO-CH 2 CH 2 -C 2 H 5 , 2- ( 1-methylpropylsulfinyl) ethyl, 2- (2-methylpropylsulfinyl) ethyl, CH 2 CH 2 SO-C (CH 3 ) 3 , CH 2 CH 2 SO- (CH 2 ) 3 -C 2 H 5 , CH 2 CH 2 SO- (CH 2 ) -C 2 H 5 , 2- (SO-CH 3 ) propyl,
2- (SO-C2H5) propyl, 2- (SO-CH2-C H5) propyl,2- (SO-C 2 H 5 ) propyl, 2- (SO-CH 2 -CH 5 ) propyl,
2- [SO-CH(CH3) ] propyl, 2- (SO-CH2CH2-C2H5) propyl, 2- (l-Methyl - propylsulf inyl ) propyl , 2- ( 2-Methylpropylsulf inyl ) propyl , 2- [SO-C(CH3)3] propyl, 3- (S0-CH3) ropyl, 3- (SO-C2H5) propyl, 3- (SO-CH2-C2H5) propyl, 3- [SO-CH(CH3) 2] propyl ,2- [SO-CH (CH 3 )] propyl, 2- (SO-CH 2 CH 2 -C 2 H 5 ) propyl, 2- (l-methylpropylsulfinyl) propyl, 2- (2-methylpropylsulfinyl) propyl, 2- [SO-C (CH 3 ) 3 ] propyl, 3- (S0-CH 3 ) ropyl, 3- (SO-C 2 H 5 ) propyl, 3- (SO-CH 2 -C 2 H 5 ) propyl, 3- [SO-CH (CH 3 ) 2 ] propyl,
3- (SO-CH2CH2-C2H5) propyl, 3- (1-Methylpropylsulf inyl ) propyl, 3- ( 2 -Methylpropylsulf inyl) propyl, 3- [SO-C(CH3) 3]propyl, 3- [SO- (CH2 ) 3-C2H5] propyl , 3- [SO- (CH2 ) 4-C2H5] propyl ,3- (SO-CH 2 CH 2 -C 2 H 5 ) propyl, 3- (1-methylpropylsulfinyl) propyl, 3- (2-methylpropylsulfinyl) propyl, 3- [SO-C (CH 3 ) 3 ] propyl , 3- [SO- (CH 2 ) 3 -C 2 H 5 ] propyl, 3- [SO- (CH 2 ) 4 -C 2 H 5 ] propyl,
2- (SO-CH3) butyl, 2-(SO-C2H5)butyl, 2- (SO-CH2-C2H5)butyl, 2- [SO-CH (CH3)2] butyl, 2- (SO-CH2CH2-C2H5) butyl , 2-(l-Methyl- propylsulfinyl) butyl, 2- (2-Methylpropylsulf inyDbutyl, 2- [SO-C(CH3)3]butyl, 3-(SO-CH3)butyl, 3- (SO-C2H5) butyl ,2- (SO-CH3) butyl, 2- (SO-C 2 H 5 ) butyl, 2- (SO-CH 2 -C 2 H 5 ) butyl, 2- [SO-CH (CH 3 ) 2 ] butyl, 2- (SO-CH 2 CH 2 -C 2 H 5 ) butyl, 2- (l-methylpropylsulfinyl) butyl, 2- (2-methylpropylsulfinyldbutyl, 2- [SO-C (CH 3 ) 3 ] butyl, 3- (SO-CH 3 ) butyl, 3- (SO-C 2 H 5 ) butyl,
3- (SO-CH2-C2H5)butyl, 3- [SO-CH (CH3) ] butyl ,3- (SO-CH 2 -C 2 H 5 ) butyl, 3- [SO-CH (CH 3 )] butyl,
3- (SO-CH2CH2-C2H5)butyl, 3- (1-Methylpropylsulf inyl ) butyl , 3- (2-MethylpropylsulfinyDbutyl, 3- [SO-C (CH3) 3] butyl,3- (SO-CH 2 CH 2 -C 2 H 5 ) butyl, 3- (1-methylpropylsulfinyl) butyl, 3- (2-methylpropylsulfinyDbutyl, 3- [SO-C (CH 3 ) 3 ] butyl,
4-(SO-CH3)butyl, 4- (SO-C2H5) butyl , 4- (SO-CH2-C2H5) butyl , 4-[SO-CH(CH3)2]butyl, 4- (SO-CH2CH2-C2H5)butyl , 4- (l-Methyl - propylsulfinyDbutyl, 4- (2-Methylpropylsulf inyDbutyl ,4- (SO-CH 3 ) butyl, 4- (SO-C 2 H 5 ) butyl, 4- (SO-CH 2 -C 2 H 5 ) butyl, 4- [SO-CH (CH 3 ) 2 ] butyl , 4- (SO-CH 2 CH 2 -C 2 H 5 ) butyl, 4- (l-methylpropylsulfinyDbutyl, 4- (2-methylpropylsulfinyDbutyl,
4- [SO-C (CH3) 3] butyl, 4-[SO-(CH2)3-C2H5]butyl, 4- [SO-(CH2)4-C2H5]butyl, 5- (SO-CH3) pentyl , 5- (SO-C2H5)pentyl,4- [SO-C (CH 3 ) 3 ] butyl, 4- [SO- (CH 2 ) 3 -C 2 H 5 ] butyl, 4- [SO- (CH 2 ) 4 -C 2 H 5 ] butyl, 5- (SO-CH 3 ) pentyl, 5- (SO-C 2 H 5 ) pentyl,
5- (SO-CH2-C2H5) pentyl, 5- [SO-CH (CH3) 21 pentyl ,5- (SO-CH 2 -C 2 H 5 ) pentyl, 5- [SO-CH (CH 3 ) 2 1 pentyl,
5- (SO-CH2CH2-C2H5) pentyl , 5- ( 1-Methylpropylsulf inyl ) pentyl , 5- (2-Methylpropylsulf inyl) entyl, 5- [SO-C (CH3) 3] pentyl ,5- (SO-CH 2 CH 2 -C 2 H 5 ) pentyl, 5- (1-Methylpropylsulfinyl) pentyl, 5- (2-Methylpropylsulfinyl) entyl, 5- [SO-C (CH 3 ) 3 ] pentyl ,
5- [SO- (CH2) 3-C2H5] pentyl , 5- [SO- (CH ) 4-C2H5] pentyl , 6- (SO-CH3) hexyl, 6- (SO-C2H5) hexyl, 6- (SO-CH2-C2H5) hexyl,5- [SO- (CH 2 ) 3 -C 2 H 5 ] pentyl, 5- [SO- (CH) 4 -C 2 H 5 ] pentyl, 6- (SO-CH 3 ) hexyl, 6- (SO- C 2 H 5 ) hexyl, 6- (SO-CH 2 -C 2 H 5 ) hexyl,
6- [SO-CH (CH3)2] hexyl, 6- (SO-CH2CH2-C2H5) hexyl , 6- (l-Methyl - propylsulf inyl) hexyl, 6- (2-Methylpropylsulfinyl) hexyl ,6- [SO-CH (CH 3 ) 2 ] hexyl, 6- (SO-CH 2 CH 2 -C 2 H 5 ) hexyl, 6- (l-methylpropylsulfinyl) hexyl, 6- (2-methylpropylsulfinyl) hexyl,
6- [SO-C (CH3)3] hexyl, 6- [SO- (CH2) 3-C2H5] hexyl oder 6- [SO- (CH2)4-C2H5] hexyl, insbesondere für CH2SO-CH3 oder CH2SO-C2H5;6- [SO-C (CH 3 ) 3 ] hexyl, 6- [SO- (CH 2 ) 3 -C 2 H 5 ] hexyl or 6- [SO- (CH 2 ) 4 -C 2 H 5 ] hexyl, in particular for CH 2 SO-CH 3 or CH 2 SO-C 2 H 5 ;
Ci-Ce-Alkylsulfonyl für: z.B. S02CH3, S02C2H5, n-Propyl- sulfonyl, S0CH(CH3)2, n-Butylsulfonyl, 1-Methylpropyl - sulfonyl, 2-Methylpropylsulfonyl, S02C(CH3)3, n-Pentyl - sulfonyl, 1-Methylbutylsulfonyl, 2-Methylbutylsulfonyl ,Ci-Ce-alkylsulfonyl for: e.g. S0 2 CH 3 , S0 2 C 2 H 5 , n-propylsulfonyl, S0CH (CH 3 ) 2 , n-butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, S0 2 C (CH 3 ) 3 , n-pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl,
3-Methylbutylsulfonyl, 2, 2-Dimethylpropylsulfonyl , 1-Ξthyl- propylsulfonyl, n-Hexylsulfonyl, 1, l-Dimethylpropylsulfonyl , 1, 2-Dimethylpropylsulfonyl, 1-Methylpentylsulfonyl , 2-Methyl - pentylsulfonyl, 3-Methylpentylsulfonyl, 4-Methylpentyl - sulfonyl, 1 , 1-Dimethylbutylsulfonyl, 1, 2-Dimethylbutyl - sulfonyl, 1 , 3-Dimethylbutylsulfonyl , 2, 2-Dimethylbutyl - sulfonyl, 2 , 3-Dimethylbutylsulfonyl , 3 , 3-Dimethylbutyl - sulfonyl, 1-Ethylbutylsulfonyl, 2-Ethylbutylsulfonyl , 1,1, 2-Trimethylpropylsulfonyl, 1, 2 , 2-Trimethylpropylsulfonyl , 1-Ethyl-l-methylpropylsulfonyl oder l-Ethyl-2-methylpropyl - sulfonyl, insbesondere für SO2CH3 oder S02C2H5,-3-methylbutylsulfonyl, 2, 2-dimethylpropylsulfonyl, 1-Ξthylpropylsulfonyl, n-hexylsulfonyl, 1, l-dimethylpropylsulfonyl, 1, 2-dimethylpropylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1, 1-dimethylbutylsulfonyl, 1, 2-dimethylbutylsulfonyl, 1, 3-dimethylbutylsulfonyl, 1, 3-dimethylbutylsulfonyl Dimethylbutylsulfonyl, 2, 3-dimethylbutylsulfonyl, 3, 3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1,1, 2-trimethylpropylsulfonyl, 1, 2, 2-trimethylpropylsulfonyl, 1-ethyl-ethyl l-ethyl-2-methylpropyl sulfonyl, especially for SO 2 CH 3 or S0 2 C 2 H 5
Cι-C6-Alkylsulfonyl-Cι-C6-alkyl für: durch Cx-Cg-Alkylsulf onyl wie vorstehend genannt substituiertes C!-C6-Alkyl, also z.B. für CH2S02-CH3, CH2S02-C2H5, CH2S02-CH2-C2H5, CH2S02-CH (CH3 ) 2 , CH2S02-CH2CH2-C2H5, ( 1-Methylpropylsulf onyl) methyl , (2-Methyl- propyl sulf onyl) methyl, CH S02-C (CH3) 3 , CH S02- (CH2) 3-C2H5,C 6 -C 6 -alkylsulfonyl-C 6 -C 6 -alkyl for: Cx-Cg-alkylsulfonyl substituted as C above ! -C 6 alkyl, e.g. for CH 2 S0 2 -CH 3 , CH 2 S0 2 -C 2 H 5 , CH 2 S0 2 -CH 2 -C 2 H 5 , CH 2 S0 2 -CH (CH 3 ) 2 , CH 2 S0 2 -CH 2 CH 2 -C 2 H 5 , (1-methylpropylsulfonyl) methyl, (2-methylpropylsulfonyl) methyl, CH S0 2 -C (CH 3 ) 3 , CH S0 2 - (CH 2 ) 3 -C 2 H 5 ,
CH2S02-(CH2)4-C2H5, CH(CH3)S02-CH3, CH (CH3 ) S02-C2H5 , CH2CH2S02-CH3, CH2CH2S02-C2H5, CH2CH2S02-CH2-C2H5, CH2CH2S02-CH(CH3)2, CH2CH2S02-CH2CH -C2H5, 2- ( 1-Methylpropyl - sulfonyl) ethyl, 2- (2 -Methylpropylsulf onyl) ethyl , CH2CH2S02-C(CH3)3, CH2CH2S02- (CH2) 3-C2H5, CH2CH2S02- (CH2) 4-C2H5,CH 2 S0 2 - (CH 2 ) 4 -C 2 H 5 , CH (CH 3 ) S0 2 -CH 3 , CH (CH 3 ) S0 2 -C 2 H 5 , CH 2 CH 2 S0 2 -CH 3 , CH 2 CH 2 S0 2 -C 2 H 5 , CH 2 CH 2 S0 2 -CH 2 -C 2 H 5 , CH 2 CH 2 S0 2 -CH (CH 3 ) 2 , CH 2 CH 2 S0 2 -CH 2 CH -C 2 H 5 , 2- (1-methylpropylsulfonyl) ethyl, 2- (2-methylpropylsulfonyl) ethyl, CH 2 CH 2 S0 2 -C (CH 3 ) 3 , CH 2 CH 2 S0 2 - ( CH 2 ) 3 -C 2 H 5 , CH 2 CH 2 S0 2 - (CH 2 ) 4 -C 2 H 5 ,
2- (S02-CH3) propyl, 2- (S02-C2H5) propyl, 2- (S02-CH2-C H5) propyl, 2- [S02-CH(CH3)2] propyl, 2- (S02-CH2CH2-C2H5) propyl , 2-(l-Methyl- propylsulfonyl) propyl, 2- (2-Methylpropylsulfonyl) propyl, 2- [S02-C(CH3)3] propyl, 3- (S02-CH3) propyl , 3- (S02-C2H5) propyl , 3- (S02-CH2-C2H5) propyl, 3- [S02-CH (CH3) 2] propyl,2- (S0 2 -CH 3 ) propyl, 2- (S0 2 -C 2 H 5 ) propyl, 2- (S0 2 -CH 2 -CH 5 ) propyl, 2- [S0 2 -CH (CH 3 ) 2 ] propyl, 2- (S0 2 -CH 2 CH 2 -C 2 H 5 ) propyl, 2- (l-methylpropylsulfonyl) propyl, 2- (2-methylpropylsulfonyl) propyl, 2- [S0 2 -C (CH 3 ) 3 ] propyl, 3- (S0 2 -CH 3 ) propyl, 3- (S0 2 -C 2 H 5 ) propyl, 3- (S0 2 -CH 2 -C 2 H 5 ) propyl, 3- [S0 2 -CH (CH 3 ) 2 ] propyl,
3- (S02-CH2CH2-C2H5) propyl, 3- (1-Methylpropylsulf onyl) propyl , 3- (2-Methylpropylsulfonyl) propyl, 3- [S02-C(CH3) 3] propyl, 3- [S02- (CH2) 3-C2H5] propyl, 3- [S02- (CH2) 4-C2H5] propyl ,3- (S0 2 -CH 2 CH 2 -C 2 H 5 ) propyl, 3- (1-methylpropylsulfonyl) propyl, 3- (2-methylpropylsulfonyl) propyl, 3- [S0 2 -C (CH 3 ) 3 ] propyl, 3- [S0 2 - (CH 2 ) 3 -C 2 H 5 ] propyl, 3- [S0 2 - (CH 2 ) 4 -C 2 H 5 ] propyl,
2- (S02-CH3) butyl, 2-(S02-C2H5)butyl, 2- (S02-CH2-C2H5)butyl , 2- [S02-CH(CH3)2] butyl, 2- (S02-CH2CH2-C2H5)butyl, 2- (l-Methyl - propyl sulf onyl) butyl, 2- (2 -Methylpropylsulf onyl) butyl , 2- [S02-C(CH3)3]butyl, 3- (S0 -CH3) butyl, 3- (S02-C2H5) butyl ,2- (S0 2 -CH 3 ) butyl, 2- (S0 2 -C 2 H 5 ) butyl, 2- (S0 2 -CH 2 -C 2 H 5 ) butyl, 2- [S0 2 -CH (CH 3 ) 2 ] butyl, 2- (S0 2 -CH 2 CH 2 -C 2 H 5 ) butyl, 2- (l-methylpropylsulfonyl) butyl, 2- (2-methylpropylsulfonyl) butyl, 2- [S0 2 -C (CH 3 ) 3 ] butyl, 3- (S0 -CH 3 ) butyl, 3- (S0 2 -C 2 H 5 ) butyl,
3- (S02-CH2-C2H5) butyl, 3- [S02-CH (CH3) 2] butyl,3- (S0 2 -CH 2 -C 2 H 5 ) butyl, 3- [S0 2 -CH (CH 3 ) 2 ] butyl,
3- (S02-CH2CH2-C H5) butyl, 3- (1-Methylpropylsulf onyl) butyl, 3- (2-Methylpropylsulf onyl) butyl, 3- [S02-C (CH3) 3] butyl,3- (S0 2 -CH 2 CH 2 -CH 5 ) butyl, 3- (1-methylpropylsulfonyl) butyl, 3- (2-methylpropylsulfonyl) butyl, 3- [S0 2 -C (CH 3 ) 3 ] butyl ,
4-(S0 -CH3)butyl, 4- (S02-C2H5)butyl, 4- (S02-CH2-C2H5)butyl ,4- (S0 -CH 3 ) butyl, 4- (S0 2 -C 2 H 5 ) butyl, 4- (S0 2 -CH 2 -C 2 H 5 ) butyl,
4- [S02-CH(CH3)2] butyl, 4- (S02-CH2CH2-C2H5) butyl, 4-(l-Methyl- propylsulfonyl) butyl, 4- (2-Methylpropylsulfonyl) butyl,4- [S0 2 -CH (CH 3 ) 2 ] butyl, 4- (S0 2 -CH 2 CH 2 -C 2 H 5 ) butyl, 4- (l-methylpropylsulfonyl) butyl, 4- (2-methylpropylsulfonyl ) butyl,
4- [S02-C(CH3)3]butyl, 4- [S02- (CH2) 3-C2H5]butyl , 4- [S02- (CH2) -C2H5] butyl, 5- (S02-CH3) pentyl ,4- [S0 2 -C (CH 3 ) 3 ] butyl, 4- [S0 2 - (CH 2 ) 3 -C 2 H 5 ] butyl, 4- [S0 2 - (CH 2 ) -C 2 H 5 ] butyl, 5- (S0 2 -CH 3 ) pentyl,
5- (S02-C2H5) pentyl, 5- (S02-CH2-C2H5) pentyl,5- (S0 2 -C 2 H 5 ) pentyl, 5- (S0 2 -CH 2 -C 2 H 5 ) pentyl,
5- [S02-CH(CH3)2]pentyl, 5- (S02-CH2CH2-C2H5) pentyl , 5- (l-Methyl - propylsulfonyl ) pentyl , 5- ( 2-Methylpropylsulfonyl ) pentyl ,5- [S0 2 -CH (CH 3 ) 2 ] pentyl, 5- (S0 2 -CH 2 CH 2 -C 2 H 5 ) pentyl, 5- (l-methylpropylsulfonyl) pentyl, 5- (2-methylpropylsulfonyl ) pentyl,
5- [S02-C(CH3)3] pentyl, 5- [S02- (CH2) 3-C2H5J pentyl, 5- [S02-(CH2) -C2H5] pentyl, 6- (S02-CH3) hexyl, 6- (S02-C2H5) hexyl , 6- (S02-CH2-C2H5) hexyl, 6- [S02-CH (CH3) 2] hexyl,5- [S0 2 -C (CH 3 ) 3 ] pentyl, 5- [S0 2 - (CH 2 ) 3-C2H5J pentyl, 5- [S0 2 - (CH 2 ) -C 2 H 5 ] pentyl, 6- (S0 2 -CH 3 ) hexyl, 6- (S0 2 -C 2 H 5 ) hexyl, 6- (S0 2 -CH 2 -C 2 H 5 ) hexyl, 6- [S0 2 -CH (CH 3 ) 2 ] hexyl,
6- (SO2-CH2CH2-C2H5) hexyl, 6- ( 1-Methylpropylsulfonyl) hexyl , 6- (2-Methylpropylsulfonyl) hexyl, 6- [S02-C (CH3) 3] hexyl, 6- [S02-(CH2)3-CH5] hexyl oder 6- [S02- (CH2) 4-C2H5] hexyl , insbesondere für CH2S02-CH oder CH2S02-C2H5;6- (SO 2 -CH 2 CH 2 -C 2 H5) hexyl, 6- (1-methylpropylsulfonyl) hexyl, 6- (2-methylpropylsulfonyl) hexyl, 6- [S0 2 -C (CH 3 ) 3 ] hexyl, 6- [S0 2 - (CH 2 ) 3 -CH 5 ] hexyl or 6- [S0 2 - (CH 2 ) 4 -C 2 H 5 ] hexyl, especially for CH 2 S0 2 -CH or CH 2 S0 2 -C 2 H 5 ;
Cι-C6-Alkylaminosulfonyl für: z.B. H3C-NHS02-, H5C2-NHS02-, n-Propyl-NHS02-, (CH3 ) 2CH-NHS02- , n-Butyl-NHS02- , l-Methyl - propyl-NHS02-, 2-Methylpropyl-NHS02-, (CH3) 3C-NHS0- , n-Pentyl-NHS02-, 1-Methylbutyl-NHS0- , 2-Methylbutyl-NHS02- , 3-Methylbutyl-NHS02-, 2, 2-Dimethylpropyl-NHS02- , 1-Ethyl- propyl-NHS02-, n-Hexyl-NHS02-, 1, 1-Dimethylpropyl-NHS02-, l,2-Dimethylpropyl-NHS02-, 1-Methylpentyl-NHS02- , 2-Methyl- pentyl-NHS02-, 3-Methylpentyl-NHS02-, 4-Methylpentyl-NHS02- , 1, 1-Dimethylbutyl-NHS02-, 1, 2-Dimethylbutyl-NHS0-, 1,3-Di- methylbutyl-NHS02-, 2 , 2-Dimethylbutyl-NHS02-, 2, 3-Dimethyl - butyl-NHS02-, 3, 3-Dimethylbutyl-NHS02- , 1-Ethylbutyl-NHS02-, 2-Ethylbutyl-NHS02-, 1 , 1 , 2-Trimethylpropyl-NHS02- , 1,2,2-Tri- methylpropyl-NHS02-, l-Ethyl-l-methylpropyl-NHS02- oder l-Ethyl-2-methylpropyl-NHS02-, insbesondere für H3C-NHS02- oder H5C2-NHS02-;-C-C 6 -Alkylaminosulfonyl for: for example H 3 C-NHS0 2 -, H 5 C 2 -NHS0 2 -, n-propyl-NHS0 2 -, (CH 3 ) 2 CH-NHS0 2 -, n-butyl-NHS0 2 -, l-methyl-propyl-NHS0 2 -, 2-methylpropyl-NHS0 2 -, (CH 3 ) 3 C-NHS0-, n-pentyl-NHS0 2 -, 1-methylbutyl-NHS0-, 2-methylbutyl- NHS0 2 -, 3-Methylbutyl-NHS0 2 -, 2, 2-Dimethylpropyl-NHS0 2 -, 1-Ethylpropyl-NHS0 2 -, n-Hexyl-NHS0 2 -, 1, 1-Dimethylpropyl-NHS0 2 -, l, 2-dimethylpropyl-NHS0 2 -, 1-methylpentyl-NHS0 2 -, 2-methylpentyl-NHS0 2 -, 3-methylpentyl-NHS0 2 -, 4-methylpentyl-NHS0 2 -, 1, 1-dimethylbutyl- NHS0 2 -, 1, 2-dimethylbutyl-NHS0-, 1,3-dimethylbutyl-NHS0 2 -, 2, 2-dimethylbutyl-NHS0 2 -, 2, 3-dimethyl-butyl-NHS0 2 -, 3, 3 -Dimethylbutyl-NHS0 2 -, 1-ethylbutyl-NHS0 2 -, 2-ethylbutyl-NHS0 2 -, 1, 1, 2-trimethylpropyl-NHS0 2 -, 1,2,2-trimethylpropyl-NHS0 2 -, l -Ethyl-l-methylpropyl-NHS0 2 - or l-ethyl-2-methylpropyl-NHS0 2 -, especially for H 3 C-NHS0 2 - or H 5 C 2 -NHS0 2 -;
Di- (Ci-Ce-alky aminosulfonyl für: z.B. (CH3)2N-S02-, (C2H5>2N-S02-, N,N-Dipropylamino-S02-, N,N-Di (1-methyl - ethyl) amino-S0-, N,N-Dibutylamino-S02-, N,N-Di (1-methyl - propyl) amino-S02-, N,N-Di (2-methylpropyl) amino-S02-, N,N-Di (1, l-dimethylethyl)amino-S02-, N-Ethyl-N-methyl - amino-S02-, N-Methyl-N-propylamino-S0-, N-Methyl-N- (1- methylethyl)amino-S02-, N-Butyl-N-methylamino-Sθ2-, N-Methyl-N- (1-methylpropyl) amino-S02-, N-Methyl-N- (2-methyl - propyl) amino-S02-, N- (1, 1-Dimethylethyl) -N-methylamino-S02-, N-Ethyl-N-propylamino-S02-, N-Ethyl-N- (1-methylethyl) amino- S02-, N-Butyl-N-ethylamino-S02-, N-Ethyl-N- (1-methylpropyl ) - amino-S0-, N-Ethyl-N- (2-methylpropyl) mino-S02- , N-Ethyl-N- (1,1-dimethylethyl) amino-S02-, N- (1-Methylethyl) -N-propyl - amino-S02-, N-Butyl-N-propylamino-S02-, N- (1-Methylpropyl) -N- propylamino-S02-, N- (2-Methylpropyl) -N-propylamino-S02- , N- (1, 1-Dimethylethyl) -N-propylamino-S0-, N-Butyl-N- (1- methylethyl)amino-S02-, N- (1-Methylethyl) -N- (1-methyl - propyl ) amino-S02-, N- (1-Methylethyl) -N- ( 2-methylpropyl ) - amino-S02-, N- (1, 1-Dimethylethyl) -N- (1-methylethyl) amino-S02-, N-Butyl-N- (1-methylpropyl) amino-S02-, N-Butyl-N- (2-methyl - propyl ) amino-S02- , N-Butyl-N- (1, 1-dimethylethyl) amino-S02- , N- (1-Methylpropyl) -N- (2-methylpropyl) amino-S^-, N- (1, 1-Dimethylethyl) -N- (1-methylpropy amino-SC^- oder N- (1, 1-Dimethylethyl) -N- (2-methylpropyl)amino-S02-, insbesondere für (CH3)2N-S02- oder (C2H5) N-S02- ; C2~C6-Alkenyl für: Vinyl und C3-C6-Alkenyl wie Prop-1-en-l-yl , Allyl, 1-Methylethenyl, n-Buten-1-yl , n-Buten-2-yl , n-Buten- 3-yl, 1-Methylprop-l-en-l-yl, 2-Methylprop-l-en-l-yl, l-Methylprop-2-en-l-yl , 2-Methylprop-2-en-l-yl , n-Penten- 1-yl, n-Penten-2-yl, n-Penten-3-yl, n-Penten-4-yl, l-Methyl - but-1-en-l-yl, 2-Methylbut-l-en-l-yl , 3-Methylbut-l-en-l-yl, l-Methylbut-2-en-l-yl, 2-Methylbut-2-en-l-yl, 3-Methylbut- 2-en-l-yl, l-Methylbut-3-en-l-yl, 2-Methylbut-3-en-l-yl, 3-Methylbut-3-en-l-yl, 1, l-Dimethyl-prop-2-en-l-yl , 1,2-Di- methyl-prop-1-en-l-yl, 1, 2-Dimethyl-prop-2-en-l-yl, 1-Ethyl- prop-l-en-2-yl, l-Ethylprop-2-en-l-yl, n-Hex-1-en-l-yl, n-Hex-2-en-l-yl, n-Hex-3-en-l-yl, n-Hex-4-en-l-yl , n-Hex-5- en-l-yl, 1-Methyl-pent-l-en-l-yl, 2-Methylpent-l-en-l-yl, 3-Methylpent-l-en-l-yl, 4-Methylpent-l-en-l-yl, l-Methyl - pent-2-en-l-yl, 2-Methylpent-2-en-l-yl, 3-Methylpent-2- en-l-yl, 4-Methylpent-2-en-l-yl , l-Methylpent-3-en-l-yl , 2-Methylpent-3-en-l-yl , 3-Methylpent-3-en-l-yl, 4-Methyl- pent-3-en-l-yl, l-Methylpent-4-en-l-yl, 2-Methylpent-4- en-l-yl, 3-Methylpent-4-en-l-yl , 4-Methylpent-4-en-l-yl , 1, l-Dimethyl-but-2-en-l-yl, 1, l-Dimethyl-but-3-en-l-yl , 1, 2-Dimethyl-but-l-en-l-yl, 1, 2-Dimethyl-but-2-en-l-yl , 1, 2-Dimethyl-but-3-en-l-yl, 1, 3-Dimethyl-but-l-en-l-yl, 1, 3-Dimethyl-but-2-en-l-yl, 1, 3-Dimethyl-but-3-en-l-yl, 2, 2-Dimethyl-but-3-en-l-yl, 2, 3-Dimethyl-but-l-en-l-yl, 2,3-Dimethyl-but-2-en-l-yl, 2, 3-Dimethyl-but-3-en-l-yl , 3, 3-Dimethyl-but-l-en-l-yl, 3, 3-Dimethyl-but-2-en-l-yl , 1-Ethylbut-l-en-l-yl, l-Ethylbut-2-en-l-yl, l-Ethylbut-3- en-l-yl, 2-Ethylbut-l-en-l-yl, 2-Ethylbut-2-en-l-yl , 2-Ethyl- but-3-en-l-yl, 1, 1, 2-Trimethyl-prop-2-en-l-yl , 1-Ethyl-l- methyl-prop-2-en-l-yl, l-Ethyl-2-methyl-prop-l-en-l-yl und l-Ethyl-2-methyl-prop-2-en-l-yl, insbesondere für Allyl;Di- (Ci-Ce-alkyaminosulfonyl for: e.g. (CH 3 ) 2 N-S0 2 -, (C 2 H 5 > 2 N-S0 2 -, N, N-Dipropylamino-S0 2 -, N, N- Di (1-methyl-ethyl) amino-S0-, N, N-dibutylamino-S0 2 -, N, N-Di (1-methyl-propyl) amino-S02-, N, N-Di (2-methylpropyl) amino-S02-, N, N-Di (1, l-dimethylethyl) amino-S0 2 -, N-ethyl-N-methyl - amino-S0 2 -, N-methyl-N-propylamino-S0-, N- Methyl-N- (1-methylethyl) amino-S02-, N-butyl-N-methylamino-Sθ2-, N-methyl-N- (1-methylpropyl) amino-S02-, N-methyl-N- (2- methyl-propyl) amino-S0 2 -, N- (1, 1-dimethylethyl) -N-methylamino-S0 2 -, N-ethyl-N-propylamino-S0 2 -, N-ethyl-N- (1-methylethyl ) amino-S0 2 -, N-butyl-N-ethylamino-S0 2 -, N-ethyl-N- (1-methylpropyl) - amino-S0-, N-ethyl-N- (2-methylpropyl) mino-S0 2 -, N-ethyl-N- (1,1-dimethylethyl) amino-S0 2 -, N- (1-methylethyl) -N-propyl-amino-S0 2 -, N-butyl-N-propylamino-S0 2 -, N- (1-methylpropyl) -N-propylamino-S0 2 -, N- (2-methylpropyl) -N-propylamino-S0 2 -, N- (1, 1-dimethylethyl) -N-propylamino-S0- , N-butyl-N- (1st - methylethyl) amino-S0 2 -, N- (1-methylethyl) -N- (1-methyl-propyl) amino-S0 2 -, N- (1-methylethyl) -N- (2-methylpropyl) - amino- S0 2 -, N- (1, 1-dimethylethyl) -N- (1-methylethyl) amino-S0 2 -, N-butyl-N- (1-methylpropyl) amino-S0 2 -, N-butyl-N- (2-methylpropyl) amino-S0 2 -, N-butyl-N- (1, 1-dimethylethyl) amino-S0 2 -, N- (1-methylpropyl) -N- (2-methylpropyl) amino-S ^ -, N- (1, 1-dimethylethyl) -N- (1-methylpropyamino-SC ^ - or N- (1, 1-dimethylethyl) -N- (2-methylpropyl) amino-S0 2 -, especially for (CH 3 ) 2 N-S0 2 - or (C 2 H 5 ) N-S0 2 -; C2 ~ C6 alkenyl for: vinyl and C 3 -C 6 alkenyl such as prop-1-en-l-yl, allyl, 1-methylethenyl, n-buten-1-yl, n-buten-2-yl, n -Butene-3-yl, 1-methylprop-l-en-l-yl, 2-methylprop-l-en-l-yl, l-methylprop-2-en-l-yl, 2-methylprop-2-ene -l-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, l-methyl-but-1-en-l-yl , 2-methylbut-l-en-l-yl, 3-methylbut-l-en-l-yl, l-methylbut-2-en-l-yl, 2-methylbut-2-en-l-yl, 3 -Methylbut-2-en-l-yl, l-methylbut-3-en-l-yl, 2-methylbut-3-en-l-yl, 3-methylbut-3-en-l-yl, 1, l -Dimethyl-prop-2-en-1-yl, 1,2-dimethyl-prop-1-en-1-yl, 1, 2-dimethyl-prop-2-en-1-yl, 1-ethyl prop-l-en-2-yl, l-ethylprop-2-en-l-yl, n-hex-1-en-l-yl, n-hex-2-en-l-yl, n-hex -3-en-1-yl, n-hex-4-en-1-yl, n-hex-5-en-1-yl, 1-methyl-pent-1-en-1-yl, 2-methylpent -l-en-l-yl, 3-methylpent-l-en-l-yl, 4-methylpent-l-en-l-yl, l-methyl-pent-2-en-l-yl, 2-methylpent -2-en-l-yl, 3-methylpent-2-en-l-yl, 4-methylpent-2-en-l-yl, l-methylpent-3-en-l-yl, 2-methylpent-3 -en-l-yl, 3-methylpent-3-e nl-yl, 4-methylpent-3-en-l-yl, l-methylpent-4-en-l-yl, 2-methylpent-4-en-l-yl, 3-methylpent-4-en- l-yl, 4-methylpent-4-en-l-yl, 1, l-dimethyl-but-2-en-l-yl, 1, l-dimethyl-but-3-en-l-yl, 1, 2-dimethyl-but-l-en-l-yl, 1, 2-dimethyl-but-2-en-l-yl, 1, 2-dimethyl-but-3-en-l-yl, 1, 3- Dimethyl-but-l-en-l-yl, 1, 3-dimethyl-but-2-en-l-yl, 1, 3-dimethyl-but-3-en-l-yl, 2, 2-dimethyl but-3-en-l-yl, 2,3-dimethyl-but-l-en-l-yl, 2,3-dimethyl-but-2-en-l-yl, 2,3-dimethyl-but- 3-en-l-yl, 3,3-dimethyl-but-l-en-l-yl, 3,3-dimethyl-but-2-en-l-yl, 1-ethylbut-l-en-l- yl, l-ethylbut-2-en-l-yl, l-ethylbut-3-en-l-yl, 2-ethylbut-l-en-l-yl, 2-ethylbut-2-en-l-yl, 2-ethyl-but-3-en-l-yl, 1, 1, 2-trimethyl-prop-2-en-l-yl, 1-ethyl-l-methyl-prop-2-en-l-yl, 1-ethyl-2-methyl-prop-1-en-1-yl and 1-ethyl-2-methyl-prop-2-en-1-yl, in particular for allyl;
C3 -C8-Alkenyl für: C3 -Cβ-Alkenyl wie vorstehend genannt, oder z.B. für n-Hept-2-en-l-yl, n-Hept-3 -en- 1-yl , n-Oct-2 -en- 1-yl , n-Oct-3-en-l-yl, insbesondere für Allyl;C 3 -C 8 alkenyl for: C 3 -Cβ alkenyl as mentioned above, or for example for n-hept-2-en-1-yl, n-hept-3 -en- 1-yl, n-oct- 2 -en- 1-yl, n-oct-3-en-l-yl, especially for allyl;
C3-C8-Halogenalkenyl für: C3-C8-Alkenyl wie vorstehend genannt, das partiell oder vollständig durch Fluor, Chlor, Brom und/oder lod substituiert ist, also z.B. für 2-Chlorallyl, 3-Chlorallyl, 2, 3-Dichlorallyl, 3, 3-Dichlorallyl , 2,3,3-Tri- chlorallyl, 2, 3-Dichlorbut-2-enyl, 2-Bromallyl, 3-Bromallyl, 2, 3-Dibromallyl, 3, 3-Dibromallyl, 2 , 3 , 3-Tribromallyl oder 2, 3-Dibrombut-2-enyl , insbesondere für 3 -Chlorallyl;C 3 -C 8 haloalkenyl for: C 3 -C 8 alkenyl as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example for 2-chloroallyl, 3-chloroallyl, 2, 3-dichlorallyl, 3, 3-dichlorallyl, 2,3,3-trichlorallyl, 2,3-dichlorobut-2-enyl, 2-bromoallyl, 3-bromoallyl, 2, 3-dibromoallyl, 3, 3-dibromoallyl, 2, 3, 3-tribromoallyl or 2,3-dibromobut-2-enyl, in particular for 3 -chloroallyl;
Cι-C6-Alkoxy-C3-C8-alkenyl für: durch Cι-C6-Alkoxy wie oben genannt substituiertes C3 -C8-Alkenyl , also z.B. für 3- (Methoxy) allyl; C3-C6-Alkenyloxy für : z . B . Prop-1-en- l-yloxy, Alkyloxy, 1-Methylethenyloxy, n-Buten-1-yloxy, n-Buten-2-yloxy, n-Buten-3-yloxy, 1-Methylprop-l-en-l-yloxy, 2-Methylprop- 1-en-l-yloxy, l-Methylprop-2-en-l-yloxy, 2-Methylprop-2 -en- 1-yloxy, n-Penten-1-yloxy, n-Penten-2-yloxy, n-Penten-3 -yl - oxy, n-Penten-4 -yloxy, 1-Methylbut-l-en-l-yloxy, 2-Methyl - but-1-en-l-yloxy, 3-Methylbut-l-en- l-yloxy, l-Methylbut-2 - en-1 -yloxy, 2-Methylbut-2-en- l-yloxy, 3-Methylbut-2-en-l-yl - oxy, l-Methylbut-3-en-l-yloxy, 2-Methylbut-3-en-l-yloxy, 3-Methylbut-3-en-l-yloxy, 1 , l-Dimethyl-prop-2-en-l-yloxy,C 1 -C 6 -alkoxy-C 3 -C 8 -alkenyl for: C 3 -C 8 -alkoxy substituted by -C-C 6 -alkoxy as mentioned above, for example for 3- (methoxy) allyl; C 3 -C 6 alkenyloxy for: e.g. B. Prop-1-en-l-yloxy, alkyloxy, 1-methylethenyloxy, n-buten-1-yloxy, n-buten-2-yloxy, n-buten-3-yloxy, 1-methylprop-l-en-l- yloxy, 2-methylprop-1-en-l-yloxy, l-methylprop-2-en-l-yloxy, 2-methylprop-2 -en- 1-yloxy, n-penten-1-yloxy, n-pentene 2-yloxy, n-penten-3 -yl-oxy, n-penten-4 -yloxy, 1-methylbut-l-en-l-yloxy, 2-methyl - but-1-en-l-yloxy, 3- Methylbut-l-en-l-yloxy, l-methylbut-2 - en-1-yloxy, 2-methylbut-2-en-l-yloxy, 3-methylbut-2-en-l-yl - oxy, l- Methylbut-3-en-l-yloxy, 2-methylbut-3-en-l-yloxy, 3-methylbut-3-en-l-yloxy, 1, l-dimethyl-prop-2-en-l-yloxy,
1 , 2-Dimethyl-prop- l-en-l-yloxy, 1 , 2-Dimethyl-prop-2-en- l-yl - oxy, l-Ethylprop-l-en-2-yloxy, l-Ethylprop-2-en-l-yloxy, n-Hex-1-en-l-yloxy, n-Hex-2-en-l-yloxy, n-Hex-3 -en-l-yloxy, n-Hex-4-en-l-yloxy, n-Hex-5-en-l-yloxy, 1-Methylpent- l-en- 1-yloxy, 2-Methylpent-l-en-l-yloxy, 3-Methylpent-l-en-l-yl - oxy, 4-Methylpent-l-en-l-yloxy, l-Methylpent-2-en-l-yloxy, 2-Methylpent-2-en-l-yloxy, 3-Methylpent-2-en-l-yloxy, 4-Methylpent-2-en-l-yloxy, l-Methylpent-3-en-l-yloxy, 2-Methylpent-3-en-l-yloxy, 3-Methylpent-3-en-l-yloxy, 4-Methylpent-3-en-l-yloxy, l-Methylpent-4-en-l-yloxy, 2-Methylpent-4-en-l-yloxy, 3-Methylpent-4-en-1-yloxy, 4-Methylpent-4-en-l-yloxy, 1, l-Dimethyl-but-2-en-l-yloxy, 1, l-Dimethyl-but-3-en-l-yloxy, 1, 2-Dimethyl-but-l-en-l-yloxy, 1, 2-Dimethyl-but-2-en-l-yloxy, 1 , 2-Dimethyl-but-3-en-l-yloxy, 1, 3-Dimethyl-but-l-en-l-yloxy, 1, 3-Dimethyl-but-2-en-l-yloxy,1, 2-dimethyl-prop-l-en-l-yloxy, 1, 2-dimethyl-prop-2-en-l-yloxy, l-ethylprop-l-en-2-yloxy, l-ethylprop- 2-en-l-yloxy, n-hex-1-en-l-yloxy, n-hex-2-en-l-yloxy, n-hex-3 -en-l-yloxy, n-hex-4- en-l-yloxy, n-hex-5-en-l-yloxy, 1-methylpent-l-en-1-yloxy, 2-methylpent-l-en-l-yloxy, 3-methylpent-l-en- l-yl-oxy, 4-methylpent-l-en-l-yloxy, l-methylpent-2-en-l-yloxy, 2-methylpent-2-en-l-yloxy, 3-methylpent-2-en- l-yloxy, 4-methylpent-2-en-l-yloxy, l-methylpent-3-en-l-yloxy, 2-methylpent-3-en-l-yloxy, 3-methylpent-3-en-l- yloxy, 4-methylpent-3-en-l-yloxy, l-methylpent-4-en-l-yloxy, 2-methylpent-4-en-l-yloxy, 3-methylpent-4-en-1-yloxy, 4-methylpent-4-en-l-yloxy, 1, l-dimethyl-but-2-en-l-yloxy, 1, l-dimethyl-but-3-en-l-yloxy, 1, 2-dimethyl but-l-en-l-yloxy, 1, 2-dimethyl-but-2-en-l-yloxy, 1, 2-dimethyl-but-3-en-l-yloxy, 1, 3-dimethyl-but- l-en-l-yloxy, 1, 3-dimethyl-but-2-en-l-yloxy,
1 , 3-Dimethyl-but-3-en-l-yloxy, 2 , 2-Dimethyl-but-3-en-l-yloxy,1, 3-dimethyl-but-3-en-l-yloxy, 2, 2-dimethyl-but-3-en-l-yloxy,
2 , 3-Dimethyl-but-l-en-l-yloxy, 2 , 3-Dimethyl-but-2-en-l-yloxy,2,3-dimethyl-but-l-en-l-yloxy, 2,3-dimethyl-but-2-en-l-yloxy,
2, 3-Dimethyl-but-3-en-l-yloxy, 3 , -Dimethyl-but-l-en-l-yloxy,2,3-dimethyl-but-3-en-l-yloxy, 3,3-dimethyl-but-l-en-l-yloxy,
3 , 3-Dimethyl-but-2-en-l-yloxy, 1-Ethylbut-l-en-l-yloxy, l-Ethylbut-2-en-l-yloxy, l-Ethylbut-3-en-l-yloxy, 2-Ethyl- but-1-en-l-yloxy, 2-Ethylbut-2-en-l-yloxy, 2-Ethylbut-3-en- 1-yloxy, 1, 1, 2-Trimethyl-prop-2-en-l-yloxy, 1-Ethyl-l-methyl- prop-2-en-l-yloxy, l-Ethyl-2-methyl-prop-l-en-l-yloxy oder l-Ethyl-2-methyl-prop-2-en-l-yloxy, insbesondere für Allyl - oxy;3,3-dimethyl-but-2-en-l-yloxy, 1-ethylbut-l-en-l-yloxy, l-ethylbut-2-en-l-yloxy, l-ethylbut-3-en-l- yloxy, 2-ethyl-but-1-en-l-yloxy, 2-ethylbut-2-en-l-yloxy, 2-ethylbut-3-en-1-yloxy, 1, 1, 2-trimethyl-prop- 2-en-l-yloxy, 1-ethyl-l-methyl-prop-2-en-l-yloxy, l-ethyl-2-methyl-prop-l-en-l-yloxy or l-ethyl-2- methyl-prop-2-en-l-yloxy, especially for allyl oxy;
C2-C4-Alkenyloxy-Cι-C4-alkyl für : durch C3-C4~Alkenyloxy wie Vinyloxy, Allyloxy, But-l-en-3-yloxy, But-l-en-4 -yloxy, But-2-en-l-yloxy, l-Methylprop-2-enyloxy oder 2-Methyl - prop-2-enyloxy substi tuiertes Cι~C4-Alkyl , also beispielsweise für Vinyloxymethyl , Allyloxymethyl , 2-Allyloxyethyl oder But-l-en-4-yloxymethyl , insbesondere für 2 -Al lyloxyethyl ;C 2 -C 4 -Alkenyloxy-Cι-C 4 alkyl for: by C 3 -C 4 ~ alkenyloxy such as vinyloxy, allyloxy, but-l-en-3-yloxy, but-l-en-4 -yloxy, but -2-en-l-yloxy, l-methylprop-2-enyloxy or 2-methyl-prop-2-enyloxy substituted C 1 -C 4 -alkyl, for example for vinyloxymethyl, allyloxymethyl, 2-allyloxyethyl or but-l- en-4-yloxymethyl, especially for 2-allyloxyethyl;
C3-C6-Alkinyl für : z . B . Prop-1-in-l-yl , Propargyl , 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-l-in-4-yl , n-Pent- l-in-5-yl , n-Pent-2-in-l-yl , n-Pent-2 -in-4-yl , n-Pent-2-in- 5-yl, 3-Methyl-but-l-in-3-yl, 3-Methyl-but-l-in-4-yl, n-Hex- 1-in-l-yl, n-Hex-l-in-3-yl, n-Hex-l-in-4-yl, n-Hex-l-in-5-yl , n-Hex-l-in-6-yl, n-Hex-2-in-l-yl, n-Hex-2-in-4-yl , n-Hex-2- in-5-yl, n-Hex-2-in-6-yl, n-Hex-3-in-l-yl , n-Hex-3-in-2-yl, 3-Methyl-pent-l-in-l-yl, 3-Methyl-pent-l-in-3-yl, 3-Methyl- pent-l-in-4-yl, 3-Methyl-pent-l-in-5-yl , 4-Methyl-pent-l- in-l-yl, 4-Methyl-pent-2-in-4-yl oder 4-Methyl-pent-2-in- 5-yl, insbesondere für Propargyl ;C 3 -C 6 alkynyl for: e.g. B. Prop-1-in-l-yl, propargyl, n-but-1 - in-l-yl, n-but-l-in-3-yl, n-but-l-in-4-yl, n- But-2-in-1-yl, n-pent-1-in-1-yl, n-pent-1-in-3-yl, n-pent-1-in-4-yl, n-pent l-in-5-yl, n-pent-2-in-l-yl, n-pent-2 -in-4-yl, n-pent-2-in- 5-yl, 3-methyl-but-l-in-3-yl, 3-methyl-but-l-in-4-yl, n-hex-1-in-l-yl, n-hex-l- in-3-yl, n-hex-1-in-4-yl, n-hex-1-in-5-yl, n-hex-1-in-6-yl, n-hex-2-in l-yl, n-hex-2-in-4-yl, n-hex-2-in-5-yl, n-hex-2-in-6-yl, n-hex-3-in-l- yl, n-hex-3-in-2-yl, 3-methyl-pent-l-in-l-yl, 3-methyl-pent-l-in-3-yl, 3-methyl-pent-l- in-4-yl, 3-methyl-pent-1-in-5-yl, 4-methyl-pent-1-in-1-yl, 4-methyl-pent-2-in-4-yl or 4- Methyl-pent-2-in-5-yl, especially for propargyl;
- C3-C8-Halogenalkinyl: C3-Cθ-Alkinyl wie vorstehend genannt, das partiell oder vollständig durch Fluor, Chlor, Brom und/oder lod substituiert ist, also z.B. für 1,1-Difluor- prop-2-in-l-yl, 4-Fluorbut-2-in-l-yl, 4-Chlorbut-2-in-l-yl, 1, 1-Difluorbut-2-in-l-yl, 5-Fluorpent-3-in-l-yl oder 6-Fluor- hex-4-in-l-yl;- C 3 -C 8 haloalkynyl: C 3 -C θ alkynyl as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example for 1,1-difluoroprop-2- in-l-yl, 4-fluorobut-2-in-l-yl, 4-chlorobut-2-in-l-yl, 1, 1-difluorobut-2-in-l-yl, 5-fluoropent-3- in-l-yl or 6-fluoro-hex-4-in-l-yl;
Cι-C6-Alkoxy-C3-C8-alkinyl für: durch Cι-C6-Alkoxy wie oben genannt substituiertes C3-C8-Alkinyl , also z.B. für 3-Methoxy- prop-2 - in-1-yl ;C 1 -C 6 -alkoxy-C 3 -C 8 -alkynyl for: C 3 -C 8 -alkynyl substituted by Cι-C 6 -alkoxy as mentioned above, for example for 3-methoxy-prop-2 - in-1- yl;
C3-C8-Alkinyloxy für: z.B. Propargyloxy, Prop-2-in-l-yloxy, n-But-1-in-l-yloxy, n-But-l-in-3-yloxy, n-But-l-in-4-yloxy, n-But-2-in-l-yloxy, n-Pent-1-in-l-yloxy, n-Pent-l-in-3-yloxy, n-Pent-l-in-4-yloxy, n-Pent-l-in-5-yloxy, n-Pent-2-in-l-yl - oxy, n-Pent-2-in-4-yloxy, n-Pent-2-in-5-yloxy, 3-Methyl- but-l-in-3-yloxy, 3-Methyl-but-l-in-4-yloxy, n-Hex-1-in-l-yl - oxy, n-Hex-l-in-3-yloxy, n-Hex-l-in-4-yloxy, n-Hex-l-in-5-yl - oxy, n-Hex-l-in-6-yloxy, n-Hex-2-in-l-yloxy, n-Hex-2-in-4-yl - oxy, n-Hex-2-in-5-yloxy, n-Hex-2-in-6-yloxy, n-Hex-3-in-l-yl - oxy, n-Hex-3-in-2-yloxy, 3-Methylpent-l-in-l-yloxy, 3-Methyl - pent-l-in-3-yloxy, 3-Methylpent-l-in-4-yloxy, 3-Methylpent-l- in-5-yloxy, 4-Methylpent-l-in-l-yloxy, 4-Methylpent-2-in-4-yl oder 4-Methylpent-2-in-5-yloxy, insbesondere für Propargyloxy;C 3 -C 8 alkynyloxy for: for example propargyloxy, prop-2-in-1-yloxy, n-but-1-in-1-yloxy, n-but-1-in-3-yloxy, n-but- l-in-4-yloxy, n-but-2-in-l-yloxy, n-pent-1-in-l-yloxy, n-pent-l-in-3-yloxy, n-pent-l- in-4-yloxy, n-pent-1-in-5-yloxy, n-pent-2-in-1-yl-oxy, n-pent-2-in-4-yloxy, n-pent-2- in-5-yloxy, 3-methyl-but-l-in-3-yloxy, 3-methyl-but-l-in-4-yloxy, n-hex-1-in-l-yl-oxy, n- Hex-l-in-3-yloxy, n-hex-l-in-4-yloxy, n-hex-l-in-5-yl-oxy, n-hex-l-in-6-yloxy, n- Hex-2-in-l-yloxy, n-hex-2-in-4-yl-oxy, n-hex-2-in-5-yloxy, n-hex-2-in-6-yloxy, n- Hex-3-in-l-yloxy, n-hex-3-in-2-yloxy, 3-methylpent-l-in-l-yloxy, 3-methyl-pent-l-in-3-yloxy, 3-methylpent-l-in-4-yloxy, 3-methylpent-l-in-5-yloxy, 4-methylpent-l-in-l-yloxy, 4-methylpent-2-in-4-yl or 4- Methylpent-2-in-5-yloxy, especially for propargyloxy;
C3-C4-Alkinyloxy-Cι-C -alkyl für: durch C3-C4-Alkinyloxy wie Propargyloxy, But-l-in-3-yloxy, But-l-in-4-yloxy, But-2-in-l- yloxy, l-Methylprop-2-inyloxy und 2-Methylprop-2-inyloxy, vorzugsweise Propargyloxy, substituiertes Cι-C -Alkyl, also beispielsweise für Propargyloxymethyl oder 2-Propargyioxy- ethyl, insbesondere für 2-Propargyloxyethyl;C 3 -C 4 alkynyloxy -CC -alkyl for: by C 3 -C 4 -alkynyloxy such as propargyloxy, but-l-in-3-yloxy, but-l-in-4-yloxy, but-2- in-l-yloxy, l-methylprop-2-inyloxy and 2-methylprop-2-inyloxy, preferably propargyloxy, substituted C 1 -C 4 -alkyl, for example for propargyloxymethyl or 2-propargoxyethyl, in particular for 2-propargyloxyethyl;
Die Benzylgruppe (als eine der Bedeutungen von R4) ist vorzugsweise unsubstituiert oder trägt einen Nitro-, Halogen-, Cx -C4 -Alkyl - , Ci -C4 -Alkoxy- oder (Ci -C4-Alkoxy) carbonyl - Substituenten. Im Hinblick auf die Verwendung der substituierten 2-Arylpyridine I als Herbizide und/oder als desikkant/defoliant wirksame Verbindungen haben die Variablen vorzugsweise folgende Bedeutungen, und zwar jeweils für sich allein oder in Kombination:The benzyl group (as one of the meanings of R 4 ) is preferably unsubstituted or carries a nitro, halogen, Cx -C 4 alkyl, Ci -C 4 alkoxy or (Ci -C 4 alkoxy) carbonyl substituent . With regard to the use of the substituted 2-arylpyridines I as herbicides and / or as desiccant / defoliant compounds, the variables preferably have the following meanings, individually or in combination:
n Null;n zero;
R1 Mercapto, Hydroxysulfonyl, Chlorsulfonyl, Aminosulfonyl ,R 1 mercapto, hydroxysulfonyl, chlorosulfonyl, aminosulfonyl,
Cj-Cβ -Alkylthio, Ci-Cβ -Alkylsulfinyl oder Cι-C6-Alkylsulfonyl , insbesondere Ci -C6 -Alkylsulfonyl ;Cj-Cβ-alkylthio, Ci-Cβ-alkylsulfinyl or -C-C 6 -alkylsulfonyl, in particular Ci-C 6 -alkylsulfonyl;
R2 Halogen, insbesondere Chlor;R 2 halogen, especially chlorine;
R3 Wasserstoff oder Halogen, vorzugsweise Halogen, insbesondere Fluor oder Chlor;R 3 is hydrogen or halogen, preferably halogen, especially fluorine or chlorine;
R4 Wasserstoff, Cι-C6-Alkyl, Cyano-Cι-C6 -alkyl, Cχ-C6 -Alkoxy, Ci -C6 -Alkoxy-Cι-C6- alkyl, Ci -C6 -Alkylthio-Ci -C6- alkyl, (Ci -C6 -Alkoxy) carbonyl -Cι-C6- alkyl, C3 -C8-Alkenyl, C3-C8 -Alkinyl, C3-C6-Alkenyloxy oder C3-C6 -Alkinyloxy, insbesondere Wasserstoff, Cι-C6 -Alkyl, Cyano-Cι-C6- alkyl, (Cι-C6 -Alkoxy) carbonyl -C].-C6- alkyl, C3 -C8-Alkenyl oder C3 -C8-Alkinyl;R 4 is hydrogen, C 1 -C 6 -alkyl, cyano-C 1 -C 6 -alkyl, Cχ-C 6 -alkoxy, Ci -C 6 -alkoxy-Cι-C 6 - alkyl, Ci -C 6 -alkylthio-Ci - C 6 - alkyl, (Ci -C 6 alkoxy) carbonyl -Cι-C 6 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 6 alkenyloxy or C3-C6 - Alkynyloxy, especially hydrogen, -C 6 alkyl, cyano -C 6 alkyl, (-C 6 alkoxy) carbonyl -C] . -C 6 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl;
X Sauerstoff ;X oxygen;
eine chemische Bindung oder C(R5,R6), wobei R5 und R6 unabhängig voneinander für Wasserstoff, C1-C4 -Alkyl oder (C].-C4 -Alkoxy) carbonyl stehen, insbesondere eine chemische Bindung oder Methylen.a chemical bond or C (R 5 , R 6 ), where R 5 and R 6 independently of one another are hydrogen, C 1 -C 4 alkyl or (C] .- C 4 alkoxy) carbonyl, in particular a chemical bond or Methylene.
Ganz besonders bevorzugt sind die Verbindungen der Formel Ia (= I mit n = Null; R1 = Methylsulfonyl; R2 = Chlor, R3 = Fluor und X = Sauerstoff), insbesondere die Verbindungen der Tabelle 1:The compounds of the formula Ia (= I with n = zero; R 1 = methylsulfonyl; R 2 = chlorine, R 3 = fluorine and X = oxygen) are very particularly preferred, in particular the compounds of Table 1:
Figure imgf000023_0001
Figure imgf000023_0001
Figure imgf000023_0002
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0003
Figure imgf000023_0002
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0003
Des weiteren sind die substituierten 2-Arylpyridine der Formeln Ib, Ic, Id, le, If , Ig, Ih, Ii, Ik, Im und In besonders bevorzugt, insbesondereFurthermore, the substituted 2-arylpyridines of the formulas Ib, Ic, Id, le, If, Ig, Ih, Ii, Ik, Im and In are particularly preferred, in particular
die Verbindungen Ib.l bis Ib.363, die sich von den entsprechenden Verbindungen la.l bis Ia.363 lediglich dadurch unterscheiden, daß R3 für Chlor steht:the compounds Ib.l to Ib.363, which differ from the corresponding compounds la.l to Ia.363 only in that R 3 is chlorine:
Figure imgf000033_0001
Figure imgf000033_0001
die Verbindungen Ic.l bis Ic.363, die sich von den entsprechenden Verbindungen la.l bis Ia.363 lediglich dadurch unterscheiden, daß R3 für Wasserstoff steht:the compounds Ic.l to Ic.363, which differ from the corresponding compounds la.l to Ia.363 only in that R 3 is hydrogen:
Figure imgf000033_0002
die Verbindungen Id.l bis Id.363, die sich von den entsprechenden Verbindungen la.l bis Ia.363 lediglich dadurch unterscheiden, daß R1 für Ethylsulfonyl steht:
Figure imgf000033_0002
the compounds Id.l to Id.363, which differ from the corresponding compounds la.l to Ia.363 only in that R 1 is ethylsulfonyl:
Figure imgf000034_0001
Figure imgf000034_0001
die Verbindungen Ie.l bis Ie.363, die sich von den entsprechenden Verbindungen la.l bis Ia.363 lediglich dadurch unterscheiden, daß R1 für Ethylsulfonyl und R3 für Chlor stehen:the compounds Ie.l to Ie.363, which differ from the corresponding compounds la.l to Ia.363 only in that R 1 is ethylsulfonyl and R 3 is chlorine:
Figure imgf000034_0002
die Verbindungen If.l bis If .363, die sich von den entsprechenden Verbindungen la.l bis Ia.363 lediglich dadurch unterscheiden, daß R1 für Ethylsulfonyl und R3 für Wasserstoff stehen:
Figure imgf000034_0002
the compounds If.l to If .363, which differ from the corresponding compounds la.l to Ia.363 only in that R 1 is ethylsulfonyl and R 3 is hydrogen:
Figure imgf000034_0003
Figure imgf000034_0003
die Verbindungen Ig.l bis Ig.363, die sich von den entsprechenden Verbindungen la.l bis Ia.363 lediglich dadurch unterscheiden, daß R1 für Methylsulfinyl steht:the compounds Ig.l to Ig.363, which differ from the corresponding compounds la.l to Ia.363 only in that R 1 is methylsulfinyl:
igig
Figure imgf000034_0004
die Verbindungen Ih.l bis Ih.363, die sich von den entsprechenden Verbindungen la.l bis Ia.363 lediglich dadurch unterscheiden, daß R1 für Methylsulf inyl und R3 für Chlor stehen:
Figure imgf000034_0004
the compounds Ih.l to Ih.363, which differ from the corresponding compounds la.l to Ia.363 only in that R 1 is methylsulfyl and R 3 is chlorine:
Figure imgf000035_0001
die Verbindungen Ii.l bis Ii.363, die sich von den entsprechenden Verbindungen la.l bis Ia.363 lediglich dadurch unterscheiden, daß R1 für Methylsulfinyl und R3 für Wasserstoff stehen:
Figure imgf000035_0001
the compounds Ii.l to Ii.363, which differ from the corresponding compounds la.l to Ia.363 only in that R 1 is methylsulfinyl and R 3 is hydrogen:
Figure imgf000035_0002
die Verbindungen Ik.l bis Ik.363, die sich von den entsprechenden Verbindungen la.l bis Ia.363 lediglich dadurch unterscheiden, daß R1 für Methylthio steht:
Figure imgf000035_0002
the compounds Ik.l to Ik.363, which differ from the corresponding compounds la.l to Ia.363 only in that R 1 is methylthio:
Figure imgf000035_0003
Figure imgf000035_0003
die Verbindungen Im.l bis Im.363, die sich von den entsprechenden Verbindungen la.l bis Ia.363 lediglich dadurch unterscheiden, daß R1 für Methylthio und R3 für Chlor stehen:the compounds Im.l to Im.363, which differ from the corresponding compounds la.l to Ia.363 only in that R 1 is methylthio and R 3 is chlorine:
Figure imgf000035_0004
die Verbindungen In.l bis In.363, die sich von den entsprechenden Verbindungen la.l bis Ia.363 lediglich dadurch unterscheiden, daß R1 für Methylthio und R3 für Wasserstoff stehen:
Figure imgf000035_0004
the compounds In.l to In.363, which differ from the corresponding compounds la.l to Ia.363 only in that R 1 is methylthio and R 3 is hydrogen:
Figure imgf000036_0001
Figure imgf000036_0001
Die substituierten 2 -Arylpyridine der Formel I sind auf verschiedene Weise erhältlich, beispielsweise nach einem der folgenden Verfahren:The substituted 2-arylpyridines of the formula I can be obtained in various ways, for example by one of the following processes:
Verfahren A> Oxidation von substituierten 2-Arylpyridinen der Formel I, bei denen n Null bedeutet und die Substituenten R1 und R4 sowie X und Y keinen oxidierbaren Schwefel enthalten, auf an sich bekannte Weise {vgl. z.B. A. Albini & S. Pietra, Heterocyclic N-Oxides, CRC-Press Inc., Boca Raton, USA 1991; H.S. Mosher et al . , Or . Synth. Coll. Vol. IV 1963, Seite 828; E.C. Taylor et al . , Org. Synth. Coll. Vol. IV 1963, Seite 704; T.W. Bell et. al., Org. Synth. 9_, Seite 226 (1990)}:Process A> Oxidation of substituted 2-arylpyridines of the formula I in which n is zero and the substituents R 1 and R 4 and X and Y contain no oxidizable sulfur, in a manner known per se {cf. e.g. A. Albini & S. Pietra, Heterocyclic N-Oxides, CRC-Press Inc., Boca Raton, USA 1991; HS Mosher et al. , Or. Synth. Coll. Vol. IV 1963, page 828; EC Taylor et al. , Org. Synth. Coll. Vol. IV 1963, page 704; TW Bell et. al., Org. Synth. 9_, page 226 (1990)}:
Oxidation l(n=0) ► I(n=l)Oxidation l (n = 0) ► I (n = l)
Unter den zur Oxidation des Pyridinrings üblichen Oxidations- mitteln sei beispielhaft auf Peressigsäure, Trifluorperessig- säure, Perbenzoesäure, m-Chlorperbenzoesäure, Monopermalein- säure, Magnesium onoperphthalat, Natriumperborat, OxoneExamples of the oxidizing agents customary for the oxidation of the pyridine ring are peracetic acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid, monopermaleic acid, magnesium onoperphthalate, sodium perborate and oxones
(enthält Peroxidisulfat) , Perwolframsäure und Wasserstoffperoxid verwiesen.(contains peroxydisulfate), tungsten acid and hydrogen peroxide.
Geeignete Lösungsmittel sind z.B. Wasser, Schwefelsäure, Carbonsäuren wie Essigsäure und Trifluoressigsäure sowie halogenierte Kohlenwasserstoffe wie Dichlormethan und Chloroform.Suitable solvents are e.g. Water, sulfuric acid, carboxylic acids such as acetic acid and trifluoroacetic acid and halogenated hydrocarbons such as dichloromethane and chloroform.
Normalerweise gelingt die Oxidation bei Temperaturen von 0°C bis Siedetemperatur des Reaktionsgemisches. Das Oxidationsmittel wird normalerweise in mindestens äuquimolaren Mengen, bezogen auf die Ausgangsverbindung, eingesetzt. Im allgemeinen hat sich ein Überschuß an Oxidationsmittel als besonders vorteilhaft erwiesen.The oxidation is usually successful at temperatures from 0 ° C to the boiling point of the reaction mixture. The oxidizing agent is normally used in at least equimolar amounts, based on the starting compound. In general, an excess of oxidizing agent has proven to be particularly advantageous.
Verfahren B)Procedure B)
Oxidation von substituierten 2 -Arylpyridinen der Formel I, bei denen R1 für Ci-Cδ-Alkylthio oder Cι-C6 -Alkylsulfinyl steht und die Variablen R4 , X und Y keinen oxidierbaren Schwefel enthalten, auf an sich bekannte Weise (vgl. z.B. C.S. Giam et al., Org. Prep. Proced. Int. 11(2), S. 137 (1981); S.G. Woods et al., J. Heterocycl. Chem. 21, Nl, 97-101 (1984); S.G. Woods, U.S. 4,616,087; N. Finch et al., J. Med. Chem. 21(12), 1269-1274 (1978); H. Ban-Oganowska, Pol. J. Chem. £2(9), 1609-1613 (1993); A.D. Dünn & R. Norrie, J. Prakt. Chem./Chem. -Ztg. 335. 269-272 (1993) } :Oxidation of substituted 2-arylpyridines of the formula I in which R 1 is Ci-C δ- alkylthio or -CC 6 -alkylsulfinyl and the variables R 4 , X and Y do not contain any oxidizable sulfur (cf. e.g. CS Giam et al., Org. Prep. Proced. Int. 11 (2), p. 137 (1981); SG Woods et al., J. Heterocycl. Chem. 21, Nl, 97-101 (1984) ; SG Woods, US 4,616,087; N. Finch et al., J. Med. Chem. 21 (12), 1269-1274 (1978); H. Ban-Oganowska, Pol. J. Chem. £ 2 (9), 1609-1613 (1993); AD Dünn & R. Norrie, J. Prakt. Chem./Chem. -Ztg. 335. 269-272 (1993)}:
Figure imgf000037_0001
Figure imgf000037_0001
I (n = 0; R1 = Alkylthio) I (n = 0: R1 = Alkylsulfinyl)I (n = 0; R 1 = alkylthio) I (n = 0: R 1 = alkylsulfinyl)
R = Ci- -AlkylR = Ci- alkyl
Figure imgf000037_0002
Figure imgf000037_0002
I (n = 0; R1 = Alkylsulfonyl)I (n = 0; R 1 = alkylsulfonyl)
Bezüglich geeigneter Lösungsmittel, Oxidationsmittel und Reaktionstemperaturen sei auf die Angaben bei Verfahren A> verwiesen.With regard to suitable solvents, oxidizing agents and reaction temperatures, reference is made to the information given in process A>.
Zur Herstellung von Wertprodukten I mit R1 = Alkylsulfinyl empfiehlt es sich, nicht mehr als ca. 1,1 Äquivalente des Oxidationsmittels einzusetzen. Zur Herstellung von I mit R1 = Alkylsulfonyl ist es notwendig, mindestens ein Äquivalent oder mindestens zwei Äquivalente des Oxidationsmittels einzusetzen, je nachdem, ob man von den entsprechenden Verbindungen I mit R1 = Alkylthio oder mit R1 = Alkylsulfinyl ausgeht. Verfahren C>For the production of valuable products I with R 1 = alkylsulfinyl, it is advisable not to use more than about 1.1 equivalents of the oxidizing agent. To prepare I with R 1 = alkylsulfonyl, it is necessary to use at least one equivalent or at least two equivalents of the oxidizing agent, depending on whether one starts from the corresponding compounds I with R 1 = alkylthio or with R 1 = alkylsulfinyl. Procedure C>
Übergangsmetall -katalysierte Kreuzkupplungsreaktion von 2-Halogenpyridinen II (Hai = Chlor oder Brom) mit metall- organischen Verbindungen der Formel III auf an sich bekannte Weise (vgl. z.B. WO 95/02580 und die dort auf den Seiten 21 und 22 zitierte Literatur} :Transition metal-catalyzed cross-coupling reaction of 2-halopyridines II (Hai = chlorine or bromine) with organometallic compounds of the formula III in a manner known per se (cf. e.g. WO 95/02580 and the literature cited there on pages 21 and 22}:
Figure imgf000038_0001
(Cι-C6-Alkoxy)
Figure imgf000038_0001
(-C 6 alkoxy)
I I I I I V M1 steht für B(OH)2, Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br, Zn-J, Lithium, Kupfer oder Zinntri (Ci -C4 -alkyl) , vorzugsweise für B(OH)2, Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br oder Zn-J.IIIIIVM 1 stands for B (OH) 2 , Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br, Zn-J, lithium, copper or tin tri (C 1 -C 4 alkyl), preferably for B (OH) 2 , Mg-Cl, Mg-Br, Mg-J, Zn-Cl, Zn-Br or Zn-J.
Alternativ können statt der Boronsäuren III {M1 = B(OH)2} auch die Boroxine IV eingesetzt werden.Alternatively, the boroxins IV can also be used instead of the boronic acids III {M 1 = B (OH) 2 }.
(Cι-C6-Alkoxy)(-C 6 alkoxy)
Figure imgf000038_0002
Figure imgf000038_0002
(Cι-C6-Alkoxy)(-C 6 alkoxy)
Als Katalysatoren kommen insbesondere Palladiumkatalysatoren wie Tetrakis- ( triphenylphosphin) -palladium (0) , Bis- ( triphenyl- phosphin) -palladium (II) -chlorid, 1, 4 -Bis- (diphenylphosphino) - butan-palladium(II) -chlorid, 1,2 -Bis- (diphenylphosphino) -ethan- palladium(II) -chlorid, Palladiu (II) -acetat + Triphenylphosphin, Palladium (II) -acetat + Tri - (o- tolyl) -phosphin oder Palladium auf Aktivkohle, und Nickelkatalysatoren wie Bis- (triphenylphosphin) -nickel (II) -chlorid, 1, 3 -Bis- (diphenylphosphino) -propan- nickel (II) -chlorid oder Nickel (II) -acetylacetonat in Betracht.Palladium catalysts such as tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) palladium (II) chloride, 1,4-bis (diphenylphosphino) butane-palladium (II) chloride come in particular as catalysts , 1,2-bis (diphenylphosphino) ethane-palladium (II) chloride, palladiu (II) acetate + triphenylphosphine, palladium (II) acetate + tri - (o-tolyl) -phosphine or palladium on activated carbon, and nickel catalysts such as bis (triphenylphosphine) nickel (II) chloride, 1,3-bis (diphenylphosphino) propane nickel (II) chloride or nickel (II) acetylacetonate.
Zur Herstellung von II sei auf die Ausführungen bei Verfahren Gj (xxxiva → XXXlVb → → II) verwiesen.With regard to the production of II, reference is made to the explanations given in process Gj (xxxiva → XXXlVb → → II).
Ausgehend von V sind die substituierten 2 -Arylpyridine der Forme] I (X = 0) dann gemäß Syntheseschema (1) erhältlich:
Figure imgf000039_0001
Starting from V, the substituted 2-arylpyridines of the form] I (X = 0) are then obtainable according to synthesis scheme (1):
Figure imgf000039_0001
R steht für e ne der Bedeutungen von R4 mit I {n = 0; R H; X = 0; Ausnahme von Wasserstoff. Y = C(R5,R6)} Umsetzungen dieser Art sind an sich bekannt, beispielsweise aus der folgenden Literatur:R stands for one of the meanings of R 4 with I {n = 0; RH; X = 0; Except for hydrogen. Y = C (R 5 , R 6 )} Implementations of this type are known per se, for example from the following literature:
Etherspaltung von Phenolalkylethern: 1. WO 95/02590, Seite 35, Beispiel 1, Syntheseschritt 2 ;Ether cleavage of phenol alkyl ethers: 1. WO 95/02590, page 35, example 1, synthesis step 2;
2. A.V. Blokhin et al . , Khim. Geterotsikl. Soedin , 1226-12292. A.V. Blokhin et al. , Khim. Heterotics Soedin, 1226-1229
(1990) ;(1990);
3. B. Singh et al., J. Heterocycl. Chem. 28.(4), 933-937 (1991);3. B. Singh et al., J. Heterocycl. Chem. 28. (4), 933-937 (1991);
4. CA. Howard et al . , Angew. Chem. Int. Ed. 11(8), 1028-1030 (1992);4. APPROX. Howard et al. , Appl. Chem. Int. Ed. 11 (8), 1028-1030 (1992);
5. T. Katsunori et al.. Bull. Chem. Soc. Jpn. 1, 3132-3140 (1990) ;5. T. Katsunori et al. Bull. Chem. Soc. Jpn. 1, 3132-3140 (1990);
6. M. Hamana et al . , Chem. And. Pharm. Bull. 21(6), 1256-12646. M. Hamana et al. , Chem. And. Pharm. Bull. 21 (6), 1256-1264
(1977) ;(1977);
Nitrierung von Phenolen:Nitration of phenols:
1. WO 95/02590, Seite 35, Beispiel 1, Syntheseschritt 3;1. WO 95/02590, page 35, example 1, synthesis step 3;
2. P. Keller, Bull. Soc. Chim. Fr. 111(1), 27-29 (1994);2. P. Keller, Bull. Soc. Chim. Fr. 111 (1), 27-29 (1994);
Reduktion von Nitrophenolen:Reduction of nitrophenols:
1. WO 95/02590, Seite 35, Beispiel 1, Syntheseschritt 4 ;1. WO 95/02590, page 35, example 1, synthesis step 4;
2. U.S. 4,959,492;2. U.S. 4,959,492;
3. K.J. Stutts et al., J. Org. Chem. IA, 3740 (1989);3. K.J. Stutts et al., J. Org. Chem. IA, 3740 (1989);
4. P.K. Arora et al., Ind. J. Chem. B ü, 199-200 (1979);4. P.K. Arora et al., Ind. J. Chem. B ü, 199-200 (1979);
Umsetzung von Aminophenolen mit Phosgenderivaten:Reaction of aminophenols with phosgene derivatives:
1. R.J. Nachman, J. Heterocyclic Chem. H, 1545 (1982);1. R.J. Nachman, J. Heterocyclic Chem. H, 1545 (1982);
Alkylierung von Benzoxazolonen: 1. J.J. D'Amico et al., J. Heterocyclic Chem. 21, 1487 (1988);Alkylation of benzoxazolones: 1. J.J. D'Amico et al., J. Heterocyclic Chem. 21, 1487 (1988);
2. W.J. Close et al., J. Am. Chem. Soc. 7_1, 1265 (1949);2. W.J. Close et al., J. Am. Chem. Soc. 7_1, 1265 (1949);
3. M. Yamato et al . , Chem. And. Pharm. Bull. H, 1733 (1983);3. M. Yamato et al. , Chem. And. Pharm. Bull. H, 1733 (1983);
4. U.S. 4,640,707;4. U.S. 4,640,707;
5. BG 40 729; 6. U.S. 4,790,868;5. BG 40 729; 6. U.S. 4,790,868;
7. P. Depreux et al . , Heterocycles 16., 1051 (1993);7. P. Depreux et al. , Heterocycles 16, 1051 (1993);
8. G. Pilli et al . , Arzneim. -Forschung 11, 1351 (1993);8. G. Pilli et al. , Medic. Research 11, 1351 (1993);
9. A. Benarab et al . , Tetrahedron Lett. 14, 7567 (1993);9. A. Benarab et al. , Tetrahedron Lett. 14: 7567 (1993);
Umsetzung von Aminophenolen mit α-Halogencarbonsäure (derivate)n:Reaction of aminophenols with α-halocarboxylic acid (derivatives) n:
1. X. Huang et al., Synthesis 1984, 851;1. X. Huang et al., Synthesis 1984, 851;
2. D.R. Shridhar et al . , Org. Prep. Proced. Int. H, 195 (1982);2. D.R. Shridhar et al. , Org. Prep. Proced. Int. H, 195 (1982);
3. U.S. 4,307,091;3. U.S. 4,307,091;
4. DB 3 901 461; 5. D. Kikel et al., J. Heterocyclic Chem. Q., 597 (1993);4. DB 3 901 461; 5. D. Kikel et al., J. Heterocyclic Chem. Q., 597 (1993);
6. H. Tawada et al . , Chem. Pharm. Bull. 11, 1238 (1990);6. H. Tawada et al. , Chem. Pharm. Bull. 11, 1238 (1990);
7. T. Kawakita et al . , Chem. Pharm. Bull. A0_, 624 (1992); 8. WO 95/02590, Seite 35, Beispiel 1, Syntheseschri te 5 und 6;7. T. Kawakita et al. , Chem. Pharm. Bull. A0_, 624 (1992); 8. WO 95/02590, page 35, Example 1, Syntheseschri te 5 and 6;
Alkylierung von Benzoxazinonen:Alkylation of benzoxazinones:
1. K.U.P. Rao et al., Ind. J. Chem. B 2i, 1120 (1985);1.KU.P. Rao et al., Ind. J. Chem. B 2i, 1120 (1985);
2. JP-A 61/140 572;2. JP-A 61/140 572;
3. U.S. 4,640,707;3. U.S. 4,640,707;
4. JP-A 63/107 970;4. JP-A 63/107 970;
5. U.S. 4,792,605;5. U.S. 4,792,605;
6. WO 95/02590, Seite 35, Beispiel 1, Syntheseschritt 66. WO 95/02590, page 35, example 1, synthesis step 6
Das Aminophenol VIII kann auch mit Oxalsäure (derivaten) XI wie Oxalsäurechlorid und (gewünschtenfalls substituiertem) Maleinsäureanhydrid umgesetzt werden:The aminophenol VIII can also be reacted with oxalic acid (derivatives) XI such as oxalic acid chloride and (if desired substituted) maleic anhydride:
Figure imgf000041_0001
Figure imgf000041_0001
I {n = 0;R4 = H: I {n = 0; R4 = H; X = O; Y = CO} X = 0;Y = C(R5,R6)}I {n = 0; R 4 = H: I {n = 0; R 4 = H; X = O; Y = CO} X = 0; Y = C (R 5 , R 6 )}
Syntheseschema 2Synthesis scheme 2
Auch derartige Umsetzungen sind an sich bekannt, beispielsweise aus der folgenden Literatur: 1. U.S. 4,826,833;Such reactions are also known per se, for example from the following literature: 4,826,833;
2 N. Kawahara et al., Heterocycles 21, 2803 (1986); 3 D.R. Shridhar et al . , Ind. J. Chem. B 21, 992 (1985);2 N. Kawahara et al., Heterocycles 21, 2803 (1986); 3 D.R. Shridhar et al. , Ind. J. Chem. B 21, 992 (1985);
4 CO. Okafor et al . , J. Chem. Soc, Perkin Trans. 1, 1993,4 CO. Okafor et al. , J. Chem. Soc, Perkin Trans. 1, 1993,
159.159.
Verfahren D) Die substituierten 2 -Arylpyridine I, bei denen X Sauerstoff,Process D) The substituted 2-arylpyridines I, in which X is oxygen,
Schwefel, -NH- oder -N(CH3)- bedeutet, lassen sich gemäß Syntheseschema (3) herstellen:
Figure imgf000042_0001
Sulfur, -NH- or -N (CH 3 ) - means can be prepared according to synthesis scheme (3):
Figure imgf000042_0001
X ' steht für Sauerstoff, Schwefel, -NH- oder -N(CH3)-;X 'represents oxygen, sulfur, -NH- or -N (CH 3 ) -;
R4' steht für eine der Bedeutungen von R4 mit Ausnahme von Wasserstoff. Die p-Fluorphenylpyridine der Formel XII sind beispielsweise analog Verfahren C) durch Übergangsmetall -katalysierte Kreuz - kupplungsreaktion von II mit XVIIR 4 ' represents one of the meanings of R 4 with the exception of hydrogen. The p-fluorophenylpyridines of the formula XII are, for example, analogously to process C) by transition metal-catalyzed cross-coupling reaction of II with XVII
R3 R 3
Figure imgf000043_0001
herstellbar.
Figure imgf000043_0001
producible.
Umsetzungen dieser Art sind an sich bekannt, beispielsweise aus der folgenden Literatur:Implementations of this type are known per se, for example from the following literature:
Nitrierung von Fluoraromaten:Nitration of fluoroaromatics:
1. WO 95/02590, Seite 39, Beispiel 3, Syntheseschritt 2; 2. E.A. Bliss et al., J. Chem. Soc. Perkin Trans. 1, 2217,1. WO 95/02590, page 39, example 3, synthesis step 2; 2. E.A. Bliss et al., J. Chem. Soc. Perkin Trans. 1, 2217,
(1987) ; 3. J.S. Amato et al., J. Heterocyclic Chem. H, 1153 (1979);(1987); 3. J.S. Amato et al., J. Heterocyclic Chem. H, 1153 (1979);
Umsetzung von o-Fluornitrobenzolen mit Aminen: 1. WO 95/02590, Seite 39, Beispiel 3, Syntheseschritt 3; Seite 43, Beispiel 9, Syntheseschritt 1; Seite 44, Beispiel 11, Syntheseschritt 1;Reaction of o-fluoronitrobenzenes with amines: 1. WO 95/02590, page 39, example 3, synthesis step 3; Page 43, Example 9, Synthesis Step 1; Page 44, Example 11, Synthesis Step 1;
2. T. Wagner -Jauregg et al., Chem. Ber. £9_, 253 (1956);2. T. Wagner -Jauregg et al., Chem. Ber. £ 9_, 253 (1956);
3. A.L. Levy et al., J. Am. Chem. Soc. 22, 2899 (1955); 4. G. Lang et al . , U.S. 4,910,341;3. A.L. Levy et al., J. Am. Chem. Soc. 22, 2899 (1955); 4. G. Lang et al. , U.S. 4,910,341;
Umsetzung von o-Fluornitrobenzolen mit Mercaptanen:Reaction of o-fluoronitrobenzenes with mercaptans:
1. J. Slade et al . , J. Med. Chem. 21, 1517 (1985);1. J. Slade et al. , J. Med. Chem. 21, 1517 (1985);
2. M.E. Leblanc et al., J. Fluor. Chem. 12- 233-248 (1981);2. M.E. Leblanc et al., J. Fluor. Chem. 12-233-248 (1981);
Umsetzung von o-Fluornitrobenzolen mit Alkoholen:Reaction of o-fluoronitrobenzenes with alcohols:
1. M. Enomoto et al., U.S. 4,970,322 & U.S. 4,877,444;1. M. Enomoto et al., U.S. 4,970,322 & U.S. 4,877,444;
2. E. Akimoto et al., JP-A 61/180 746;2. E. Akimoto et al., JP-A 61/180 746;
Reduktion von Nitroaromaten mit anschließender Cyclokondensation:Reduction of nitroaromatics with subsequent cyclocondensation:
1. G. Theodoridis et al . , J. Heterocyclic Chem. 1, 849 (1991);1. G. Theodoridis et al. , J. Heterocyclic Chem. 1, 849 (1991);
2. N. Kawahara et al., Heterocycles 11, 729 (1981);2. N. Kawahara et al., Heterocycles 11, 729 (1981);
3. V. Evdokimoff, Gazz. Chim. Ital. H, H33 (1960);3. V. Evdokimoff, Gazz. Chim. Ital. H, H33 (1960);
4. R.L. Wear et al., J. Am. Chem. Soc. 22, 2893 (1950); 5. U.S. 4,734,124;4. R.L. Wear et al., J. Am. Chem. Soc. 22: 2893 (1950); 5. U.S. 4,734,124;
6. Enomoto et al., U.S. 4,970,322 & U.S. 4,877,444;6. Enomoto et al., U.S. 4,970,322 & U.S. 4,877,444;
7. V.N. Lisitsyn et al . , Zh. Organ. XIMII 21, 1095 (1990);7. V.N. Lisitsyn et al. , Zh. Organ. XIMII 21, 1095 (1990);
8. M. Makosza et al . , Tetrahedron H, 7263 (1995).8. M. Makosza et al. , Tetrahedron H, 7263 (1995).
Zur Umsetzung von XlVb mit Phosgen (derivaten) und Alkylierung von Verbindung I mit R4 - H siehe die hierzu bei Verfahren C> zitierte Literatur. verfahren E>For the reaction of XlVb with phosgene (derivatives) and alkylation of compound I with R 4 - H see the literature cited for this in process C>. procedure E>
Die substituierten 2 -Arylpyridine der Formel I, bei denen X Methylen und Y eine chemische Bindung bedeuten, lassen sich gemäß Syntheseschema (4) herstellen:The substituted 2-arylpyridines of the formula I, in which X is methylene and Y is a chemical bond, can be prepared according to synthesis scheme (4):
0- Alkyl*»0- alkyl * »
o-Aikyi"
Figure imgf000044_0001
o-Aikyi "
Figure imgf000044_0001
Figure imgf000044_0002
Figure imgf000044_0002
I {n = 0; R4 = H; X = CH2; Y = Bindung}I {n = 0; R 4 = H; X = CH 2 ; Y = binding}
Figure imgf000044_0004
Figure imgf000044_0004
Syntheseschema 4
Figure imgf000044_0003
Synthesis scheme 4
Figure imgf000044_0003
I {n = 0; R H; X = CH2; Y = Bindung} *' bevorzugt Cι-C6 I {n = 0; RH; X = CH 2 ; Y = bond} * 'preferably -C 6
R4' steht für eine der Bedeutungen von R4 mit Ausnahme von Wasserstoff.R 4 'represents one of the meanings of R 4 with the exception of hydrogen.
Aus XIII {Herstellung s. Syntheseschema (3)} erhält man durch nukleophile aromatische Substitution des Fluors durch einen Malonsäureester-Rest und anschließende saure Hydrolyse mit Decarboxylierung das Phenylessigsäure -Derivat XX. Bei dessen Reduktion tritt {wie im Falle von XVI; vgl. Syntheseschema (3)} spontane Cyclokendensation zu I {n = 0; R4 = H; X = CH2; Y = Bindung} ein. Auch derartige Umsetzungen sind an sich bekannt, beispielsweis aus der folgenden Literatur:From XIII {production s. Synthesis scheme (3)} is obtained by nucleophilic aromatic substitution of the fluorine by a malonic ester residue and subsequent acid hydrolysis with decarboxylation to give the phenylacetic acid derivative XX. With its reduction occurs {as in the case of XVI; see. Synthesis scheme (3)} spontaneous cyclokendensation to I {n = 0; R 4 = H; X = CH 2 ; Y = binding}. Such implementations are also known per se, for example from the following literature:
Umsetzung von Fluornitroaromaten mit Malonestern: G.J. Quallich et al., Synthesis, 51-53 (1993);Implementation of fluoronitroaromatics with malonic esters: G.J. Quallich et al., Synthesis, 51-53 (1993);
2. J.A. Walker, U.S. 4,398,035;2. J.A. Walker, U.S. 4,398,035;
3. H. Burghard et al . , J. Pharm. Sei. £1, 933 (1980);3. H. Burghard et al. , J. Pharm. £ 1,933 (1980);
4. F.J. Goetz et al., J. Org. Chem. M, 2468 (1983);4. F.J. Goetz et al., J. Org. Chem. M, 2468 (1983);
5. N. Ogawa et al., J. Pharm. Soc. Jap. 107, 111 (1987) Hydrolyse und Decarboxylierung von Phenylmalonestern:5. N. Ogawa et al., J. Pharm. Soc. Jap. 107, 111 (1987) Hydrolysis and decarboxylation of phenylmalonic esters:
1. J.G. Atkinson et al., Tetrahedron Lett., 2857 (1979);1. J.G. Atkinson et al., Tetrahedron Lett., 2857 (1979);
2. M.M. Elshafie Sayed, Chimia M, 343 (1982);2. M.M. Elshafie Sayed, Chimia M, 343 (1982);
3. M.A.E. Bowman et al . , Org. Prep. Proced. Int. 22, 636 (1990); 4. D. Barrett et al., J. Org. Chem. 10., 3928 (1995);3. M.A.E. Bowman et al. , Org. Prep. Proced. Int. 1990, 22: 636; 4. D. Barrett et al., J. Org. Chem. 10., 3928 (1995);
Reduktion der Nitrogruppe und Cyclokondensation:Reduction of the nitro group and cyclocondensation:
1. G. Gallagher Jr. et al . , J. Med. Chem 21, 1533 (1985);1. G. Gallagher Jr. et al. , J. Med. Chem 21, 1533 (1985);
2. A.L. Davis et al., J. Med. Chem 16., 1043 (1973); 3. J.W. Cook et al . , J. Chem. Soc, 3904 (1952);2. A.L. Davis et al., J. Med. Chem 16, 1043 (1973); 3. J.W. Cook et al. , J. Chem. Soc, 3904 (1952);
4. E. Giovannini et al . , Helv. Chim. Acta 21, 1392 (1948);4. E. Giovannini et al. , Helv. Chim. Acta 21, 1392 (1948);
5. P. Lewer, J. Chem. Soc, Perkin Trans. 1, 4., 753 (1987);5. P. Lewer, J. Chem. Soc, Perkin Trans. 1, 4th, 753 (1987);
N-Alkylierung von Indolonen: 1. T.A. Blizzard et al . , J. Org. Chem. i, 2657 (1989);N-alkylation of indolones: 1. T.A. Blizzard et al. , J. Org. Chem. I, 2657 (1989);
2. T.C Crawford, U.S. 4,652,658;2. T.C Crawford, U.S. 4,652,658;
3. K. isshiki et al., J. Antibiot. ü, 1202 (1987);3. K. isshiki et al., J. Antibiot. ü, 1202 (1987);
4. D.W. Robertson et al., J. Med. Chem. 2ιl, 1476 (1989);4. D.W. Robertson et al., J. Med. Chem. 2ιl, 1476 (1989);
5. G.M. Karp et al . , J. Org. Chem. 12, 4765 (1992).5. G.M. Karp et al. , J. Org. Chem. 12, 4765 (1992).
Verfahren F)Procedure F)
Die substituierten 2 -Arylpyridine der Formel I, bei denen X und YThe substituted 2-arylpyridines of the formula I, in which X and Y
CH2 bedeuten, lassen sich gemäß Syntheseschema (5) herstellen:CH 2 , can be prepared according to synthesis scheme (5):
Figure imgf000045_0001
CHO {M3 = B(OH)2,Sn(Alkyl)3}
Figure imgf000046_0001
Figure imgf000045_0001
CHO {M 3 = B (OH) 2 , Sn (alkyl) 3 }
Figure imgf000046_0001
I {n = 0; R4 = H; X = Y = CH2} l ln = 0; R4 ≠ H; X = Y = CH?}I {n = 0; R 4 = H; X = Y = CH 2 } l ln = 0; R 4 ≠ H; X = Y = CH?}
Alkyl steht vorzugsweiseAlkyl is preferably
Syntheseschema 5 für Cι-C4-Alkyl.Synthesis scheme 5 for -CC 4 alkyl.
R4 ' steht für eine der Bedeutungen von R4 mit Ausnahme von Wasserstoff.R 4 'represents one of the meanings of R 4 with the exception of hydrogen.
Übergangsmetallkatalysierte Kreuzkupplungsreaktion des Halogen - pyridins II mit einer Boronsäure oder Trialkylzinnverbindung der Formel XXIII führt zu dem Aldehyd XXIV. XXIV erhält man aber auch durch Umsetzung von II mit dem Metallorganyl XXI und Hydrolyse des Reaktionsproduktes XXII.Transition metal-catalyzed cross-coupling reaction of the halopyridine II with a boronic acid or trialkyltin compound of the formula XXIII leads to the aldehyde XXIV. XXIV can also be obtained by reacting II with the metal organyl XXI and hydrolysis of the reaction product XXII.
XXIV selbst wird dann in einer Wittig-Horner-Emmons-Reaktion mit den Phosphonestern XXV zum Zimtester XXVI umgesetzt, dessen Hydrierung, Nitrierung und Hydrolyse zu den Carbonsäure fester) n XXVIII führt. Die Reduktion der Nitrogruppe, z.B. mit Wasserstoff, führt dann unter intramolekularer Kondensation zu I.XXIV itself is then converted in a Wittig-Horner-Emmons reaction with the phosphonic esters XXV to the cinnamon tester XXVI, the hydrogenation, nitration and hydrolysis of which leads to the carboxylic acid solid XXVIII. The reduction of the nitro group, e.g. with hydrogen, then leads to I under intramolecular condensation
Zu den aufgezeigten Umsetzungen sei beispielhaft auf die folgende Literatur verwiesen: Übergangsmetall -katlysierte Kreuzkupplungsreaktionen:The following literature is an example of the implementations shown: Transition metal-catalyzed cross-coupling reactions:
1. WO 95/02580 und die dort auf den Seiten 21 und 22 zitierte Literatur;1. WO 95/02580 and the literature cited there on pages 21 and 22;
2. A. Kasahara et al . , Bull. Chem. Soc. Jap. 11, 2434 (1982); 3. H. Jendralla et al . , Liebigs Ann. Chem., 1253-1257 (1995);2. A. Kasahara et al. , Bull. Chem. Soc. Yep 11, 2434 (1982); 3. H. Jendralla et al. , Liebigs Ann. Chem., 1253-1257 (1995);
Acetalhydrolyse :Acetal hydrolysis:
1. S. Linke in Houben-Weyl, Methoden der Organischen Chemie, Bd E3, Stuttgart-New York 1983, Seiten 362 ff. und die dort zitierte Literatur;1. S. Linke in Houben-Weyl, Methods of Organic Chemistry, Vol E3, Stuttgart-New York 1983, pages 362 ff. And the literature cited there;
Wittig -Hörner-Emmons -Reaktion:Wittig Horns Emmons Reaction:
1. M.E. Niyazybetov et al., Tetrahedron Lett. 21, 3007 (1988);1. M.E. Niyazybetov et al., Tetrahedron Lett. 1988, 21: 3007;
2. M.W. Rathke et al . , J. Org. Chem. 11, 2624 (1985); 3. G. Cainelli et al., J. Chem. Soc, Perkin Trans. 1, 2516 (1980) ;2. M.W. Rathke et al. , J. Org. Chem. 11, 2624 (1985); 3. G. Cainelli et al., J. Chem. Soc, Perkin Trans. 1, 2516 (1980);
4. A. Fuentes et al., Tetrahedron Lett. 21, 2951 (1987);4. A. Fuentes et al., Tetrahedron Lett. 21: 2951 (1987);
5. W.C. Still et al., Tetrahedron Lett. 21, 4405 (1983);5. W.C. Still et al., Tetrahedron Lett. 21: 4405 (1983);
Reduktion von Zimtestern zu Dihydrozimtestern:Reduction of cinnamon testers to dihydrocinnamon testers:
1. J.K. Youn et al., Tetrahedron Lett. 22, 2409 (1986);1. J.K. Youn et al., Tetrahedron Lett. 22: 2409 (1986);
2. A. Nose et al . , Chem. Pharm. Bull. H, 2097 (1990);2. A. Nose et al. , Chem. Pharm. Bull. H, 2097 (1990);
3. H.J. Liu et al., Synthetic Commun. H, 695 (1985);3. H.J. Liu et al., Synthetic Commun. H, 695 (1985);
4. J.W. Tillev et al . , J. Med. Chem. Ii, 1125 (1991); 5. S. Ram et al., Synth. Commun. 22, 2683 (1992);4. J.W. Tillev et al. , J. Med. Chem. II, 1125 (1991); 5. S. Ram et al., Synth. Commun. 22: 2683 (1992);
Nitrierung von Dihydrozimtsäureestern:Nitration of dihydrocinnamic acid esters:
1. C Theodoridis et al . , J. Heterocyclic Chem. 21, 849 (1991);1. C Theodoridis et al. , J. Heterocyclic Chem. 21, 849 (1991);
2. M. Tominaga et al . , Chem. Pharm. Bull. 3_i, 682 (1986);2. M. Tominaga et al. , Chem. Pharm. Bull. 3_i, 682 (1986);
Reduktion und Cyclokondensation:Reduction and cyclocondensation:
1. G. Theodoridis et al . , J. Heterocyclic Chem. 21, 849 (1991);1. G. Theodoridis et al. , J. Heterocyclic Chem. 21, 849 (1991);
2. N. Kawahara et al., Heterocycles 1£, 729 (1981);2. N. Kawahara et al., Heterocycles £ 1, 729 (1981);
3. R.C. Fuson et al . , J. Am. Chem. Soc. 21, 1169 (1954); 4. S. Niwas et al., Synthesis 12, 1027 (1983);3. R.C. Fuson et al. , J. Am. Chem. Soc. 21, 1169 (1954); 4. S. Niwas et al., Synthesis 12, 1027 (1983);
5. J.C Pelletier et al., J. Org. Chem. 12, 616 (1987);5. J.C. Pelletier et al., J. Org. Chem. 12, 616 (1987);
6. T. Kolasa et al., J. Org. Chem. H, 4246 (1990);6. T. Kolasa et al., J. Org. Chem. H, 4246 (1990);
7. M. Makosza et al . , Tetrahedron H, 7263 (1995);7. M. Makosza et al. , 1995, Tetrahedron H, 7263;
Alkylierung von Chinolinonen:Alkylation of quinolinones:
1. H. Suginome et al., J. Org. Chem. H, 4933 (1990);1. H. Suginome et al., J. Org. Chem. H, 4933 (1990);
2. D.M. Fink et al . , Tetrahedron Lett. H, 2103 (1992);2. D.M. Fink et al. , Tetrahedron Lett. H, 2103 (1992);
3. W.K. Anderson et al . , J. Med. Chem. H, 2097 (1988);3. W.K. Anderson et al. , J. Med. Chem. H, 2097 (1988);
4. M. Tominaga et al . , Chem. And Pharm. Bull. 21, 2166 (1981); 5. J.L. Mokrosz et al., Arch. Pharm. 122, 529 (1994). Auf die in Syntheseschema (5) aufgezeigte Weise lassen sich auch die Verbindungen I, bei denen Y Carbonyl oder C(R5,R6) (R5 und R6 ≠ H) bedeutet, herstellen. Entweder wird dann anstelle von XXV eine höher funktionalisierte Verbindung eingesetzt oder man alkyliert auf einer späteren Verfahrensstufe in α-Stellung zur Carbonylgruppe bzw. oxidiert erst dann.4. M. Tominaga et al. , Chem. And Pharm. Bull. 21, 2166 (1981); 5. JL Mokrosz et al., Arch. Pharm. 122, 529 (1994). The compounds I in which Y is carbonyl or C (R 5 , R 6 ) ( R 5 and R 6 ≠ H) can also be prepared in the manner shown in synthesis scheme (5). Either a more functionalized compound is then used instead of XXV, or alkylation is carried out at a later stage in the α-position to the carbonyl group or only then is oxidized.
Verfahren G)Procedure G)
Figure imgf000048_0002
Figure imgf000048_0002
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000048_0001
Figure imgf000049_0001
I {n = 0; R' = Cι-C6-Alkylthio; X = 0; Y = C(R5,R6)}I {n = 0; R '= -CC 6 alkylthio; X = 0; Y = C (R 5 , R 6 )}
Die Reduktion der Nitrogruppe am Pyridin kann sowohl vor als auch nach der Alkylierung des Benzoxazinons XXXIIa vorgenommen werden. Ausgehend von XXIX erhält man zunächst in Abhängigkeit von Reduktionsmittel, dessen Menge und den Reduktionsbedingungen XXXa oder XXXb.The nitro group on the pyridine can be reduced both before and after the alkylation of the benzoxazinone XXXIIa. Starting from XXIX, one first obtains XXXa or XXXb depending on the reducing agent, its amount and the reduction conditions.
Alle Einzelschritte sind bekannt, beispielsweise aus den folgenden Veröffentlichungen:All individual steps are known, for example from the following publications:
- Reduktion von Nitropyridinen mit Wasserstoff: F. Janssens et al . , J. Med. Chem. 21(12), S. 1943 (1985);- Reduction of nitropyridines with hydrogen: F. Janssens et al. , J. Med. Chem. 21 (12), p. 1943 (1985);
- Reduktion von Nitropyridinen mit Eisen:- Reduction of nitropyridines with iron:
B.A. Fox et al., Org. Synth. 4_i, S. 34 (1964);B.A. Fox et al., Org. Synth. 4_i, p. 34 (1964);
- Reduktion von Nitropyridinen mit Zinn (II) chlorid:- Reduction of nitropyridines with tin (II) chloride:
L.A. Perez-Medina et al . , J. Am. Chem. Soc. H, S. 2574 (1947); - Reduktion von Nitropyridinen mit Hydrazin:L.A. Perez-Medina et al. , J. Am. Chem. Soc. H, p. 2574 (1947); - Reduction of nitropyridines with hydrazine:
G. J. Clark et al . , Aust. J. Chem. 11, S. 927 (1981);G. J. Clark et al. , Aust. J. Chem. 11, p. 927 (1981);
- Reduktion von Nitropyridinen mit Zinn:- Reduction of nitropyridines with tin:
K. Wojciechowski et al . , Synthesis 1, 651-653 (1986);K. Wojciechowski et al. , Synthesis 1, 651-653 (1986);
- Reduktion von Nitropyridinen mit niedervalenten Titanverbin- düngen: M. Malinowski, B. Soc. Chim. Belg. £2(1), 51-53 (1988);- Reduction of nitropyridines with low-valent titanium compounds: M. Malinowski, B. Soc. Chim. Belg. £ 2 (1), 51-53 (1988);
- Reduktion von Nitropyridinen mit Bäckerhefe:- Reduction of nitropyridines with baker's yeast:
M. Takeshita et al., Heterocycles 11(12) , 2201-2204 (1990);Takeshita, M. et al., Heterocycles 11 (12), 2201-2204 (1990);
- Reduktion von Nitropyridinen mit Zink:- Reduction of nitropyridines with zinc:
K. Goerlitzer et al., Arch. Pharm. 324 (10) , 785-796 (1991); - Reduktion von Nitropyridinen mit Natriumdithionit: F.G. Fischer et al., Ann. Chem. Hl, S. 49 (1962);K. Goerlitzer et al., Arch. Pharm. 324 (10), 785-796 (1991); - Reduction of nitropyridines with sodium dithionite: F.G. Fischer et al., Ann. Chem. Hl, p. 49 (1962);
- Diazotierung von Aminopyridinen mit Isoamylnitrit und Umsetzung der Diazoniumsalze mit Dimethyldisulfid oder Diphenyldisulfid: CS. Giam et al . , J. Chem. Soc, Chem. Commun. H, s. 756 (1980);- Diazotization of aminopyridines with isoamyl nitrite and reaction of the diazonium salts with dimethyl disulfide or diphenyl disulfide: CS. Giam et al. , J. Chem. Soc, Chem. Commun. H, s. 756 (1980);
T. Yasumitsu et al., J. Org. Chem. ü, 3564-3567 (1981). Die Ausgangsverbindungen XXIX sind auf die in Syntheseschema (1! aufgezeigte Weise aus Verbindungen XXXIIIT. Yasumitsu et al., J. Org. Chem. Ü, 3564-3567 (1981). The starting compounds XXIX are prepared from compounds XXXIII in the manner shown in synthesis scheme (1!
XXXIIIXXXIII
Figure imgf000050_0001
O-Alkyl (vorzugsweise Ci-Cg)
Figure imgf000050_0001
O-alkyl (preferably Ci-Cg)
durch Etherspaltung und Nitrierung der hierbei erhaltenen Phenole erhältlich.obtainable by ether cleavage and nitration of the phenols obtained in this way.
Die Verbindungen XXXIII wiederum sind analog Verfahren C> durch Übergangsmetall -katalysierte Kreuzkupplungsreaktion von 2 -Halogen- 5 -nitropyridinen der Formel XXXIVa (Hai = Chlor oder Brom)The compounds XXXIII in turn are analogous to process C> by transition metal-catalyzed cross-coupling reaction of 2 -halogen-5-nitropyridines of the formula XXXIVa (Hai = chlorine or bromine)
XXXIVa
Figure imgf000050_0002
mit metallorganischen Verbindungen der Formel III oder Boroxinen IV zugänglich.XXXIVa
Figure imgf000050_0002
accessible with organometallic compounds of the formula III or boroxins IV.
Reduktion der Verbindungen XXXIVa {vgl. z.B. J. Med. Chem. H, 319-327 (1973)} führt andererseits zu den entsprechenden 5-Amino-2 -halogenpyridinen XXXIVbReduction of the compounds XXXIVa {cf. e.g. J. Med. Chem. H, 319-327 (1973)}, on the other hand, leads to the corresponding 5-amino-2-halopyridines XXXIVb
XXXIVb,
Figure imgf000050_0003
aus denen durch Diazotierung - vorzugsweise mit einem Salpetrig - säureester wie tert. -Butylnitrit und Isopentylnitrit - und anschließender Umsetzung des Diazoniumsalzes mit einem symmetrischen aliphatischen Disulfid (Cχ-C6 -Alkyl) -S- S- (Ci -C6-Alkyl) die 2-Halogenpyridine II (R1 = Cι-C6 -Alkylthio) erhältlich sind (vgl. auch oben die Überführung von XXXIId in I {n = 0; R1 = Ci-Ce-Alkylthio; X = 0; Y = C(R5,R6)}).XXXIVb,
Figure imgf000050_0003
from which by diazotization - preferably with a nitrous acid ester such as tert. -Butyl nitrite and isopentyl nitrite - and subsequent reaction of the diazonium salt with a symmetrical aliphatic disulfide (Cχ-C 6 alkyl) -S- S- (Ci -C 6 alkyl) the 2-halopyridines II (R 1 = Cι-C 6 - Alkylthio) are available (see also the conversion of XXXIId into I {n = 0; R 1 = Ci-Ce-alkylthio; X = 0; Y = C (R 5 , R 6 )}).
Die 2 -Halogenpyridine II mit R1 = Cι-C6-Alkylthio können anschließend zu den entsprechenden Verbindungen mit R1 = Cι-C6-Alkylsulfinyl oder Ci-Cβ -Alkylsulfonyl oxidiert werden, wie es unter Verfahren B) für die Verbindungen I mit R1 = Ci -C6 -Alkylthio beschrieben wurde. Verf ahren HThe 2 -Halogenpyridine II with R 1 = -C 6 -alkylthio can then be oxidized to the corresponding compounds with R 1 = -C 6 -alkylsulfinyl or Ci-Cβ-alkylsulfonyl, as described in process B) for the compounds I with R 1 = Ci -C 6 alkylthio has been described. Procedure H
kylkyl
Figure imgf000051_0002
Figure imgf000051_0001
Figure imgf000051_0002
Figure imgf000051_0001
(CrC6-Alkyl)-S(C r C 6 alkyl) -S
Syntheseschema 7Synthesis scheme 7
I {n = 0; R1 = C]-C6-Alkylthio; R4 ≠ H; X = X'; Y = C(RS,R6)}I {n = 0; R 1 = C] -C 6 alkylthio; R 4 ≠ H; X = X '; Y = C (R S , R 6 )}
X' steht für Sauerstoff, Schwefel, -NH-, -N(CH3)-;X 'represents oxygen, sulfur, -NH-, -N (CH 3 ) -;
R4 steht für eine der Bedeutungen von R4 mit Ausnahme von Wasserstoff. Zu den einzelnen Umsetzungen siehe die bei den Verfahren D) und G> zitierte Literatur.R 4 represents one of the meanings of R 4 with the exception of hydrogen. For the individual implementations, see the literature cited for methods D) and G>.
Die 2 - ( -Fluor-3-nitrophenyl) - 5-nitropyridine XXXV sind durch Nitrierung der entsprechenden 2 - (4 -Fluorphenyl) - 5-nitropyridine erhältlich {vgl. hierzu die bei Verfahren D( aufgeführte Literatur}. Die 2 - (4 -Fluorphenyl) - 5 -nitropyridine wiederum sind z.B. analog Verfahren C> durch Kreuzkupplungsreaktion der 2 -Halogen- 5-nitropyridine XXXIV mit XVII zugänglich.The 2 - (-Fluoro-3-nitrophenyl) - 5-nitropyridines XXXV can be obtained by nitrating the corresponding 2 - (4-fluorophenyl) - 5-nitropyridines {cf. refer to the literature} listed in Method D (Figure 2 -. (4-fluorophenyl) - 5 -nitropyridine in turn are, for example analogously to Process C> by cross-coupling reaction of the 2-halo-5-nitropyridine XXXIV with XVII accessible.
Normalerweise sind die substituierten 2-Arylpyridine I nach einem der vorstehend genannten Syntheseverfahren herstellbar. Aus wirtschaftlichen oder verfahrenstechnischen Gründen kann es jedoch zweckmäßiger sein, einige Verbindungen I aus ähnlichen 2-Aryl- pyridinen, die sich jedoch in der Bedeutung eines Restes unterscheiden, herzustellen.The substituted 2-arylpyridines I can normally be prepared by one of the synthesis processes mentioned above. For economic or procedural reasons, however, it may be more expedient to prepare some compounds I from similar 2-arylpyridines, but which differ in the meaning of a radical.
Sofern nicht anders angegeben, sind die für die einzelnen Verfahren angegebenen Ausgangsverbindungen entweder bekannt oder auf an sich bekannte Weise oder in Analogie zu einem der beschriebenen Verfahren erhältlich.Unless otherwise stated, the starting compounds specified for the individual processes are either known or can be obtained in a manner known per se or in analogy to one of the processes described.
Die Aufarbeitung der Reaktionsgemische erfolgt in der Regel nach an sich bekannten Methoden, beispielsweise durch Verdünnen der Reaktionslόsung mit Wasser und anschließenderThe reaction mixtures are generally worked up by methods known per se, for example by diluting the reaction solution with water and subsequent
Isolierung des Produktes mittels Filtration, Kristallisation oderIsolation of the product by filtration, crystallization or
Losungsmittelextraktion, oder durch Entfernen des Lösungsmittels, Verteilen des Rückstandes in einem Gemisch aus Wasser und einem geeigneten organischen Lösungsmittel und Aufarbeiten der organischen Phase auf dasSolvent 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 on the
Produkt hin.Product out.
Die substituierten 2-Arylpyridine I können bei der Herstellung als Isomerengemische anfallen, die jedoch gewünschtenfalls nach den hierfür üblichen Methoden wie Kristallisation oder Chromatographie, auch an einem optisch aktiven Adsorbat, in die weit¬ gehend reinen Isomeren getrennt werden können. Reine optisch aktive Isomere lassen sich vorteilhaft aus entsprechenden optisch aktiven Ausgangsprodukten herstellen.The substituted 2-arylpyridines I can be obtained as isomer mixtures which, however, can be separated, if desired, by customary methods such as crystallization or chromatography, also on an optically active adsorbate, in the far ¬ continuously pure isomers in the production. Pure optically active isomers can advantageously be prepared from corresponding optically active starting products.
Landwirtschaftlich brauchbare Salze der Verbindungen I können durch Reaktion mit einer Base des entsprechenden Kations, vorzugsweise einem Alkalimetallhydroxid oder -hydrid, gebildet werden. Salze von I, deren Metallion kein Alkalimetallion ist, können auch durch Umsalzen des entsprechenden Alkalimetallsalzes in üblicher Weise hergestellt werden, ebenso Ammonium-, Phosphonium-, Sulfonium- und Sulfoxoniumsalze mittels Ammoniak, Phosphonium-, Sulfonium- oder Sulfoxoniumhydroxiden.Agricultural salts of the compounds I can be formed by reaction with a base of the corresponding cation, preferably an alkali metal hydroxide or hydride. Salts of I, the metal ion of which is not an alkali metal ion, 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.
Die Verbindungen I und deren landwirtschaftlich brauchbaren Salze eignen sich - sowohl als Isomerengemische als auch in Form der reinen Isomeren - als Herbizide. Die I enthaltenden herbiziden Mittel bekämpfen Pflanzenwuchs auf Nichtkulturflächen sehr gut, besonders bei hohen Aufwandmengen. In Kulturen wie Weizen, Reis, Mais, Soja und Baumwolle wirken sie gegen Unkräuter und Schadgräser, ohne die Kulturpflanzen nennenswert zu schädigen. Dieser Effekt tritt vor allem bei niedrigen Aufwandmengen auf.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.
In Abhängigkeit von der jeweiligen Applikationsmethode können die Verbindungen I bzw. sie enthaltenden herbiziden Mittel noch in einer weiteren Zahl von Kulturpflanzen zur Beseitigung unerwünschter Pflanzen eingesetzt werden. In Betracht kommen beispielsweise folgende Kulturen:Depending on the particular application method, the compounds I or herbicidal compositions comprising them can also be used in a further number of crop plants for eliminating undesired plants. The following crops are considered, for example:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var . napus, Brassica napus var . napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica) , Cucu is sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine ax, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium) , Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Hu ulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimu , Lycopersicon lycopersicum, Malus spec, Manihot esculenta, Medicago sativa, Musa spec, Nicotiana tabacu (N.rustica), Olea europaea, Oryza sativa , Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec, Pisum sativum, Prunus avium, Prunus persica, Pyrus co unis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgäre), Theobroma cacao, Trifolium pratense, Triticu aestivum, Triticum durum, Vicia faba, Vitis vinifera und Zea mays .Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucu is sativus, Cynodon dactylon, Daucuses carota, Glyine ax, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Hu ulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimus, manumicicon, manumissicusculum, manumissicu Medicago sativa, Musa spec, Nicotiana tabacu (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec, Pisum sativum, Prunus avium, Prunus persica, Pyrus co unis, Ribes sylvestre, Ricinus communis , Saccharum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (see vulgar), Theobroma cacao, Trifolium pratense, Triticu aestivum, Triticum durum, Vicia faba, Vitis vinifera and zea mays.
Darüber hinaus können die Verbindungen I auch in Kulturen, die durch Züchtung einschließlich gentechnischer Methoden gegen die Wirkung von Herbiziden tolerant sind, verwandt werden. Des weiteren eignen sich die substituierten 2-Arylpyridine I auch zur Desikkation und/oder Defoliation von Pflanzen.In addition, the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods. The substituted 2-arylpyridines I are also suitable for the desiccation and / or defoliation of plants.
Als Desi antien eignen sie sich insbesondere zur Austrocknung der oberirdischen Teile von Kul urpflanzen wie Kartoffel, Raps, Sonnenblume und Sojabohne. Damit wird ein vollständig mechanisches Beernten dieser wichtigen Kulturpflanzen ermöglicht.As desitants, they are particularly suitable for drying out the above-ground parts of cultivated plants such as potatoes, rapeseed, sunflower and soybeans. This enables a fully mechanical harvesting of these important crops.
Von wirtschaftlichem Interesse ist ferner die Ernteerleichterung, die durch das zeitlich konzentrierte Abfallen oder Vermindern der Haf festigkeit am Baum bei Zitrusfruchten, Oliven oder bei anderen Arten und Sorten von Kern-, Stein- und Schalenobst ermöglicht wird. Derselbe Mechanismus, das heißt die Förderung der Ausbildung von Trenngewebe zwischen Frucht- oder Blatt- und Sproßteil der Pflanzen ist auch für ein gut kontrollierbares Entblättern von Nutzpflanzen, insbesondere Baumwolle, wesentlich.Also of economic interest is the ease of harvesting, which is made possible by the temporally concentrated decrease or decrease in the firmness of the oats on the tree in the case of citrus fruits, olives or other types and varieties of pome, stone and nuts. The same mechanism, that is to say the promotion of the formation of separating tissue between the fruit or leaf and shoot part of the plants, is also essential for a well controllable defoliation of useful plants, in particular cotton.
Außerdem führt die Verkürzung des Zeitintervalls, in dem die einzelnen Baumwollpflanzen reif werden, zu einer erhöhten Faser - qualität nach der Ernte.In addition, the shortening of the time interval in which the individual cotton plants ripen leads to increased fiber quality after the harvest.
Die Verbindungen I bzw. die sie enthaltenden Mittel können beispielsweise in Form von direkt versprühbaren wäßrigen Losungen, Pulvern, Suspensionen, auch hochprozentigen wäßrigen, öligen oder sonstigen Suspensionen oder Dispersionen, Emulsionen,The compounds I or the compositions containing them can be, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions,
Oldispersionen, Pasten, Stäubemitteln, Streumitteln oder Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gießen angewendet werden. Die Anwendungsformen richten sich nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfindungsgemäßen Wirkstoffe gewährleisten.Old dispersions, pastes, dusts, sprinkles or granules by spraying, atomizing, dusting, scattering or pouring can be used. The application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
Als inerte Hilfsstoffe kommen im Wesentlichen in Betracht: Mineralölfraktionen von mittlerem bis hohem Siedepunkt wie Kerosin und Dieselöl, ferner Kohlenteerole sowie Ole pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Paraffine, Tetrahydronaphthalin, alkylierte Naphthaline und deren Derivate, alkylierte Benzole und deren Derivate, Alkohole wie Methanol, Ethanol, Propanol, Butanol und Cyclohexanol, Ketone wie Cyclohexanon, stark polare Losungs - mittel, z.B. Amine wie N-Methylpyrrolidon und Wasser.The following are essentially considered as inert auxiliaries: mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tarols as well as 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.
Wäßrige Anwendungsformen können aus Emulsionskonzentraten, Suspensionen, Pasten, netzbaren Pulvern oder wasserdispergier- baren Granulaten durch Zusatz von Wasser bereitet werden. ZurAqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. to
Herstellung von Emulsionen, Pasten oder Oldispersionen können die Substrate als solche oder in einem 01 oder Losungsmittel gelost, mittels Netz-, Haft-, Dispergier- oder Emulgiermittel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz, Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder Öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind.Production of emulsions, pastes or old dispersions can be carried out as such or dissolved in a substrate or solvent, can be homogenized in water using wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
Als oberflächenaktive Stoffe kommen die Alkali-, Erdalkali-, Ammoniumsalze von aromatischen Sulfonsäuren, z.B. Lignin-, Phenol-, Naphthalin- und Dibutylnaphthalinsulfonsäure, sowie von Fettsäuren, Alkyl- und Alkylarylsulfonaten, Alkyl-, Laurylether- und Fettalkoholsulfaten, sowie Salze sulfatierter Hexa-, Hepta- und Octadecanolen sowie von Fettalkoholglykolether , Kondensationsprodukte von sulfonierte Naphthalin und seiner Derivate mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphthalinsulfonsäuren mit Phenol und Formaldehyd, Polyoxy- ethylenoctylphenolether, ethoxyliertes Isooctyl-, Octyl- oder Nonylphenol, Alkylphenyl-, Tributylphenylpolyglykolether , Alkyl - arylpolyetheralkohole, Isotridecylalkohol, Fettalkoholethylen- oxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylen- oder Polyoxypropylenalkylether, Laurylalkoholpolyglykoletheracetat, Sorbitester, Lignin-Sulfitablaugen oder Methylcellulose in Betracht .The alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols as well as of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives Formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ether, alkyl aryl polyether alcohols, isotridecyl ethoxylated, polyethylenethoxy alcohol, fatty alcohol alcohol, fatty alcohol Polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether acetate, sorbitol ester, lignin sulfite waste liquor or methyl cellulose.
Pulver-, Streu- und Stäubemittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden.Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
Granulate, z.B. Umhüllungs-, Imprägnierungs- und Homogengranulate können durch Bindung der Wirkstoffe an feste Trägerstoffe her- gestellt werden. Feste Trägerstoffe sind Mineralerden wie Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Produkte wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver oder andere feste Trägerstoffe.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.
Die Konzentrationen der Wirkstoffe I in den anwendungsfertigen Zubereitungen können in weiten Bereichen variiert werden. Im allgemeinen enthalten die Formulierungen etwa von 0,001 bis 98 Gew.-%, vorzugsweise 0,01 bis 95 Gew.-%, mindestens eines Wirkstoffs. Die Wirkstoffe werden dabei in einer Reinheit von 90% bis 100%, vorzugsweise 95% bis 100% (nach NMR-Spektrum) ein- gesetzt. Die folgenden Formulierungsbeispiele verdeutlichen die Herstellung solcher Zubereitungen:The concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range. In general, the formulations contain from about 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum). The following formulation examples illustrate the preparation of such preparations:
I. 20 Gewichtsteile der Verbindung Nr. Ic.4 werden in einer Mischung gelöst, die aus 80 Gewichtsteilen alkyliertemI. 20 parts by weight of compound no. Ic.4 are dissolved in a mixture which alkylated from 80 parts by weight
Benzol, 10 Gewichtsteilen des Anlagerungsproduktes von 8 bis 10 Mol Ethylenoxid an 1 Mol Ölsäure-N-monoethanolamid, 5 Gewichtsteilen Calciumsalz der Dodecylbenzolsulfonsäure und 5 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Rizinusöl besteht. Durch Ausgießen und feines Verteilen der Lösung in 100000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew.-% des Wirkstoffs enthält.Benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide in 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide in 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
II. 20 Gewichtsteile der Verbindung Nr. Ic.15 werden in einer Mischung gelöst, die aus 40 Gewichtsteilen Cyclohexanon, 30 Gewichtsteilen Isobutanol, 20 Gewichtsteilen des Anlagerungsproduktes von 7 Mol Ethylenoxid an 1 Mol Isooctyl- phenol und 10 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Rizinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew.-% des Wirkstoffs enthält.II. 20 parts by weight of compound no. Ic.15 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide of 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
III. 20 Gewichtsteile des Wirkstoffs Nr. Ic.24 werden in einer Mischung gelöst, die aus 25 Gewichtsteilen Cyclohexanon, 65 Gewichtsteilen einer Mineralölfraktion vom Siedepunkt 210 bis 280°C und 10 Gewichtsteilen des Anlagerungs- produktes von 40 Mol Ethylenoxid an 1 Mol Rizinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew.-% des Wirkstoffs enthält.III. 20 parts by weight of active ingredient no. Ic.24 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
IV. 20 Gewichtsteile des Wirkstoffs Nr. Ic.39 werden mit 3 Gewichtsteilen des Natriumsalzes der Diisobutyl- naphthalin-α-sulfonsäure, 17 Gewichtsteilen des Natriumsalzes einer Ligninsulfonsäure aus einer Sulf it-Ablauge und 60 Gewichtsteilen pulverförmigem Kieselsäuregel gut vermischt und in einer Hammermühle vermählen. Durch feines Verteilen der Mischung in 20000 Gewichtsteilen Wasser erhält man eine Spritzbrühe, die 0,1 Gew.-% des Wirkstoffs enthält. V. 3 Gewichtsteile des Wirkstoffs Nr. Ic.119 werden mitIV. 20 parts by weight of active ingredient No. Ic.39 are mixed well with 3 parts by weight of the sodium salt of diisobutyl-naphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill . By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient. V. 3 parts by weight of active ingredient no. Ic.119 are with
97 Gewichtsteilen feinteiligem Kaolin vermischt. Man erhält auf diese Weise ein Stäubemittel, das 3 Gew.-% des Wirkstoffs enthält.97 parts by weight of finely divided kaolin mixed. In this way, a dust is obtained which contains 3% by weight of the active ingredient.
VI. 20 Gewichtsteile des Wirkstoffs Nr. Ic.328 werden mitVI. 20 parts by weight of active ingredient no. Ic.328 are with
2 Gewichtsteilen Calciumsalz der Dodecylbenzolsulfonsäure, 8 Gewichtsteilen Fettalkohol-polyglykolether, 2 Gewichtsteilen Natriumsalz eines Phenol-Harnstoff-Formaldehyd- Kondensates und 68 Gewichtsteilen eines paraffinischen2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic
Mineralöls innig vermischt. Man erhält eine stabile ölige Dispersion.Mineral oil mixed intimately. A stable oily dispersion is obtained.
VII. 1 Gewichtsteil des Wirkstoffs Nr. Ic.4 wird in einer Mischung gelöst, die aus 70 Gewichtsteilen Cyclohexanon, 20 Gewichtsteilen ethoxyliertem Isooctylphenol und 10 Gewichtsteilen ethoxyliertem Rizinusöl besteht. Man erhalt ein stabiles Emulsionskonzentrat.VII. 1 part by weight of active ingredient No. Ic.4 is dissolved in a mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. A stable emulsion concentrate is obtained.
VIII. 1 Gewichtsteil des Wirkstoffs Nr. Ic.15 wird in einerVIII. 1 part by weight of active ingredient No. Ic.15 is in a
Mischung gelost, die aus 80 Gewichtsteilen Cyclohexanon und 20 Gewichtsteilen Wettol® EM 31 (= nichtionischer Emulgator auf der Basis von ethoxyliertem Rizinusöl; BASF AG) besteht. Man erhält ein stabiles Emulsionskonzentrat.Dissolved mixture, which consists of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol ® EM 31 (= nonionic emulsifier based on ethoxylated castor oil; BASF AG). A stable emulsion concentrate is obtained.
Die Applikation der Wirkstoffe I bzw. der herbiziden Mittel kann im Vorauflauf- oder im Nachauflaufverfahren erfolgen. Sind die Wirkstoffe für gewisse Kulturpflanzen weniger verträglicn, so können Ausbringungstechniken angewandt werden, bei welchen die herbiziden Mittel mit Hilfe der Spritzgeräte so gespritzt werden, daß die Blätter der empfindlichen Kulturpflanzen nach Möglichkeit nicht getroffen werden, während die Wirkstoffe auf die Blätter darunter wachsender unerwünschter Pflanzen oder die unbedeckte Bodenfläche gelangen (post-directed, lay-by) .The active ingredients I or the herbicidal compositions can be applied pre- or post-emergence. If the active ingredients are less compatible 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 as far as possible, while the active ingredients are applied to the leaves of undesirable plants growing below them or the uncovered floor area (post-directed, lay-by).
Die Aufwandmengen an Wirkstoff I betragen je nach Bekämpfungs- ziel, Jahreszeit, Zielpflanzen und Wachstumsstadium 0,001 bis 3,0, vorzugsweise 0,01 bis 1,0 kg/ha aktive Substanz (a.S.).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.
Zur Verbreiterung des Wirkungsspektrums und zur Erzielung synergistischer Effekte können die substituierten 2-Arylpyridine I mit zahlreichen Vertretern anderer herbizider oder Wachstums - regulierender Wirkstoffgruppen gemischt und gemeinsam ausgebracht werden. Beispielsweise kommen als Mischungspartner 1,2,4-Thιa- diazole, 1, 3 , 4-Thiadiazole, Amide, Aminophosphorsäure und deren Derivate, Aminotriazole, Anilide, Aryloxy-/Heteroaryloxyalkan- sauren und deren Derivate, Benzoesäure und deren Derivate, Benzo- thiadiazinone, 2 - (Hetaroyl/Aroyl) - 1, 3 -cyclohexandione, Hetero- aryl-Aryl-Ketone, Benzylisoxazolidinone, meta-CF3-Phenylderivate, Carbamate, Chinolincarbonsäure und deren Derivate, Chloracet- anilide, Cyclohexan-1, 3-dionderivate, Diazine, Dichlorpropion- säure und deren Derivate, Dihydrobenzofurane, Dihydrofuran-3-one, Dinitroaniline, Dinitrophenole, Diphenylether , Dipyridyle, Halogencarbonsäuren und deren Derivate, Harnstoffe, 3-Phenyl- uracile, Imidazole, Imidazolinone, N-Phenyl-3, 4 , 5, 6-tetrahydro- phthalimide, Oxadiazole, Oxirane, Phenole, Aryloxy- und Hetero- aryloxyphenoxypropionsäureester, Phenylessigsäure und deren Derivate, 2-Phenylpropionsäure und deren Derivate, Pyrazole, Phenylpyrazole, Pyridazine, Pyridincarbonsäure und deren Derivate, Pyri idylether, Sulfonamide, Sulfonylharnstoffe, Triazine, Triazinone, Triazolinone, Triazolcarboxamide und Uracile in Betracht.To broaden the spectrum of activity and to achieve synergistic effects, the substituted 2-arylpyridines I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups and applied together. For example, 1,2,4-thiazadiazoles, 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 thiadiazinone, 2 - (hetaroyl / aroyl) - 1, 3 -cyclohexanediones, hetero-aryl-aryl-ketones, benzylisoxazolidinones, meta-CF 3 -phenyl derivatives, carbamates, quinolinecarboxylic acid and their 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-phenyluracils, imidazoles, imidazylones 3, N 4, 5, 6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and hetero-aryloxyphenoxypropionic acid esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, sulfonides , Sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uraciles.
Außerdem kann es von Nutzen sein, die Verbindungen I allein oder in Kombination mit anderen Herbiziden auch noch mit weiteren Pflanzenschutzmitteln gemischt, gemeinsam auszubringen, bei - spielsweise mit Mitteln zur Bekämpfung von Schädlingen oder phytopathogenen Pilzen bzw. Bakterien. Von Interesse ist ferner die Mischbarkeit mit Mineralsalzlösungen, welche zur Behebung von Ernährungs- und Spurenelementmängeln eingesetzt werden. Es können auch nichtphytotoxische Öle und Ölkonzentrate zugesetzt werden.It may also be useful to apply the compounds I alone or in combination with other herbicides, mixed with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.
HerStellungsbeispieleManufacturing examples
Beispiel 1example 1
6- (3 -Chlor-5-methylsulfonylpyridin-2-yl) -7-fluor-4- (2-propin- 1-yl) -2H-l,4-benzoxazin-3-on (Tabelle 1, Nr. Ia.119)6- (3-Chloro-5-methylsulfonylpyridin-2-yl) -7-fluoro-4- (2-propyn-1-yl) -2H-l, 4-benzoxazin-3-one (Table 1, No. Ia .119)
Zu einer Suspension von 0,06 g Natriumhydrid (80 %ige Suspension in Mineralöl) in 20 ml wasserfreiem Dimethylformamid wurde eine Lösung von 0,7 g 6 - (3 -Chlor- 5 -methylsulfonylpyridin- 2 -yl) - 7 - fluor-2H- 1, 4 -benzoxazin-3 -on in 20 ml Dimethylformamid langsam zugetropft. Nach beendeter Zugabe rührte man noch 10 Minuten, bevor eine Lösung von 0,26 g Propargylbromid in 10 ml Dimethylformamid zugetropft wurde. Die erhaltene Mischung wurde 20 Stunden bei Raumtemperatur gerührt und dann in 200 ml Eiswasser gegossen. Anschließend extrahierte man dreimal mit je 50 ml tert. -Butyl - methylether. Die vereinigten organischen Phasen wurden zweimal mit wenig Wasser gewaschen, über Natriumsulfat getrocknet und schließlich eingeengt. Die Reinigung des erhaltenen Rohprodukts erfolgte mittels Chromatographie an Kieselgel (Laufmittel: Dichlormethan/tert. -Butyl -methylether = 1:1). Ausbeute: 0,2 g weißer Kristalle; Smp.: 223°C. XH-NMR (250 MHz, in CDCl3) : δ [ppm] = 2.27 (s,lH) , 3.18 (s,3H) , 4.72 (s,2H) , 4.73 (d,2H) , 6.90 (d,lH) , 7.30 <d,lH) , 8.34 (s,lH) , 9.09 (s,lH) .A solution of 0.7 g of 6 - (3-chloro-5-methylsulfonylpyridine-2-yl) - 7 - fluorine was added to a suspension of 0.06 g of sodium hydride (80% suspension in mineral oil) in 20 ml of anhydrous dimethylformamide. 2H- 1, 4 -benzoxazin-3 -one slowly added dropwise in 20 ml of dimethylformamide. After the addition had ended, the mixture was stirred for a further 10 minutes before a solution of 0.26 g of propargyl bromide in 10 ml of dimethylformamide was added dropwise. The resulting mixture was stirred at room temperature for 20 hours and then poured into 200 ml of ice water. Then extracted three times with 50 ml of tert. -Butyl - methyl ether. The combined organic phases were washed twice with a little water, dried over sodium sulfate and finally concentrated. The crude product obtained was purified by chromatography on silica gel (mobile phase: dichloromethane / tert-butyl methyl ether = 1: 1). Yield: 0.2 g of white crystals; M.p .: 223 ° C. X H-NMR (250 MHz, in CDCl 3 ): δ [ppm] = 2.27 (s, 1H), 3.18 (s, 3H), 4.72 (s, 2H), 4.73 (d, 2H), 6.90 (d, lH), 7.30 <d, lH), 8.34 (s, lH), 9.09 (s, lH).
Vorstufe 1.1Preliminary stage 1.1
3-Chlor-2- (2 -fluor -4 -methoxyphenyl) - 5-methylsulfonylpyridin3-chloro-2- (2-fluoro -4-methoxyphenyl) - 5-methylsulfonylpyridine
5,1 g 2 , 3 -Dichlor- 5-methylsulfonylpyridin, 5,6 g 2-Fluor-4- methoxybenzolboronsäure, 5,6 g Natriumhydrogencarbonat und 0,5 g Tetrakistriphenylphosphinpalladium(O) wurden in einer Mischung aus 80 ml Tetrahydrofuran und 80 ml Wasser 24 Stunden auf Rückflußtemperatur erhitzt. Nach dem Abkühlen extrahierte man dreimal mit je 100 ml tert . -Butyl -methylether. Die vereinigten organischen Phasen wurden noch über Natriumsulfat getrocknet und dann eingeengt. Die Reinigung des Rohprodukts erfolgte mittels Chromatographie (Laufmittel: Cyclohexan/tert . - Butyl -methylether = 3:1, danach reiner tert . -Butyl -methylether) . Ausbeute: 3,75 g eines farblosen Öls. 1H-NMR (270 MHz, in CDC13): δ [ppm] = 3.18 (s,3H), 3.85 (s,3H), 6.74 (dd,lH), 6.85 (dd,lH), 7.42 (t,lH), 8.30 (s,lH), 9.07 (S,1H) .5.1 g of 2,3-dichloro-5-methylsulfonylpyridine, 5.6 g of 2-fluoro-4-methoxybenzeneboronic acid, 5.6 g of sodium hydrogen carbonate and 0.5 g of tetrakistriphenylphosphine palladium (O) were mixed in a mixture of 80 ml of tetrahydrofuran and 80 ml of water heated to reflux temperature for 24 hours. After cooling, extracted three times with 100 ml of tert. Butyl methyl ether. The combined organic phases were dried over sodium sulfate and then concentrated. The crude product was purified by chromatography (mobile phase: cyclohexane / tert-butyl methyl ether = 3: 1, then pure tert-butyl methyl ether). Yield: 3.75 g of a colorless oil. 1 H-NMR (270 MHz, in CDC1 3 ): δ [ppm] = 3.18 (s, 3H), 3.85 (s, 3H), 6.74 (dd, lH), 6.85 (dd, lH), 7.42 (t, lH), 8.30 (s, lH), 9.07 (S, 1H).
Vorstufe 1.2Preliminary stage 1.2
3-Chlor-2- (2 -fluor -4 -hydroxyphenyl) -5-methylsulfonylpyridin3-chloro-2- (2-fluoro -4-hydroxyphenyl) -5-methylsulfonylpyridine
3,75 g 3-Chlor-2- (2-f luor -4 -methoxyphenyl) - 5-methylsulfonyl - pyridin wurden in 50 ml 47 %iger wäßriger HBr-Lösung vier Stunden auf Rückflußte peratur erhitzt. Die erkaltete Reaktionsmischung verdünnte man mit 150 ml Wasser. Anschließend wurde dreimal mit je 50 ml Essigsäureethylester extrahiert. Die vereinigten organischen Phasen trocknete man noch über Natriumsulfat und engte danach ein. Ausbeute: 4,0 g eines farblosen Öls. !H-NMR (250 MHz, in d6 -Di ethylsulfoxid) : δ [ppm] = 3.44 (s,3H), 6.70-6.84 (m,2H), 7.36 (t,lH), 7.5-8.5 (br.,lH), 8.55 (s,lH), 9.08 (S,1H) .3.75 g of 3-chloro-2- (2-fluorine -4-methoxyphenyl) -5-methylsulfonyl-pyridine were heated in 50 ml of 47% aqueous HBr solution for four hours at reflux temperature. The cooled reaction mixture was diluted with 150 ml of water. The mixture was then extracted three times with 50 ml of ethyl acetate each time. The combined organic phases were dried over sodium sulfate and then concentrated. Yield: 4.0 g of a colorless oil. ! H-NMR (250 MHz, in d 6 -diethylsulfoxide): δ [ppm] = 3.44 (s, 3H), 6.70-6.84 (m, 2H), 7.36 (t, lH), 7.5-8.5 (br. , lH), 8.55 (s, lH), 9.08 (S, 1H).
Vorstufe 1.3Preliminary stage 1.3
3-Chlor-2- (2 -fluor-4 -hydroxy-5-nitrophenyl) - 5-methylsulfonylpyridin3-chloro-2- (2-fluoro-4-hydroxy-5-nitrophenyl) -5-methylsulfonylpyridine
4, 0 g 3 -Chlor -2 - (2 -fluor- 4 -hydroxyphenyl) -5 -methylsulfonylpyridin und 1,4 g Kaliumnitrat in 100 ml Eisessig wurden 1,5 Stunden bei 50°C gerührt, wonach man die Mischung kalt stellte. Das auskristallisierte Produkt wurde abfiltriert, mit Wasser gewaschen, getrocknet und aus Toluol umkristallisiert. Ausbeute: 1,3 g weißer Kristalle. ^-NMR (270 MHz, in d6 -Dimethylsulfoxid) : δ [ppm] = 3.47 (s,3H), 7 . 11 ( d , lH ) , 8 . 22 ( d , lH) , 8 . 63 ( s , lH ) , 9 . 12 ( s , l H) , 12 . 1 (br . , 1H) .4.0 g of 3 -chlorine -2 - (2-fluoro-4-hydroxyphenyl) -5-methylsulfonylpyridine and 1.4 g of potassium nitrate in 100 ml of glacial acetic acid were stirred at 50 ° C. for 1.5 hours, after which the mixture was cooled . The crystallized product was filtered off, washed with water, dried and recrystallized from toluene. Yield: 1.3 g of white crystals. ^ -NMR (270 MHz, in d 6 -dimethyl sulfoxide): δ [ppm] = 3.47 (s, 3H), 7. 11 (d, lH), 8. 22 (d, lH), 8. 63 (s, lH), 9. 12 (s, l H), 12. 1 (br., 1H).
Vorstufe 1.4 5 2 - (5-Amino-2 -fluor - -hydroxyphenyl) -3 -chlor- 5-methylsulfonylpyridinPrecursor 1.4 5 2 - (5-amino-2-fluoro - -hydroxyphenyl) -3-chloro-5-methylsulfonylpyridine
0,63 g Eisenpulver in 20 ml Eisessig wurden bei Rückflußtemperatur portionsweise mit 1,3 g 3 -Chlor-2 - (2 - fluor-4 -hydroxy-0.63 g of iron powder in 20 ml of glacial acetic acid were added in portions at the reflux temperature with 1.3 g of 3-chloro-2 - (2-fluoro-4-hydroxy-
10 5 -nitrophenyl) -5-methylsulfonylpyridin versetzt. Nach beendeter Zugabe erhitzte man noch zwei Stunden auf Rückflußtemperatur. Nach dem Abkühlen auf Raumtemperatur wurde die Reaktionsmischung mit 200 ml Wasser verdünnt. Anschließend extrahierte man dreimal mit jeweils 70 ml Essigsäureethylester . Die vereinigten organi -10 5 -nitrophenyl) -5-methylsulfonylpyridine were added. After the addition had ended, the mixture was heated to the reflux temperature for a further two hours. After cooling to room temperature, the reaction mixture was diluted with 200 ml of water. The mixture was then extracted three times with 70 ml of ethyl acetate each time. The united organi
15 sehen Phasen wurden mit wenig Wasser gewaschen und dann über Natriumsulfat getrocknet.15 phases were washed with a little water and then dried over sodium sulfate.
Ausbeute: 1,1 g eines Öls, das ohne Reinigung weiter umgesetzt wurde.Yield: 1.1 g of an oil which was reacted further without purification.
20 Vorstufe 1.520 Prepress 1.5
6- (3-Chlor-5-methylsulfonylpyridin-2-yl) -7 -fluor -2H- 1, 4 -benz- oxazin-3 -on6- (3-chloro-5-methylsulfonylpyridin-2-yl) -7-fluoro -2H- 1,4 -benz-oxazin-3 -one
1,1 g 2 - (5-Amino- 2 - fluor-4 -hydroxyphenyl) -3 -Chlor- 5 -methyl- 25 sulfonylpyridin, 1,0 g Kaliumcarbonat und 0,5 g Chloracetyl- chlorid wurden in 50 ml wasserfreiem Dimethylformamid zunächst zwei Stunden bei Raumtemperatur und dann vier Stunden bei 90°C gerührt. Nach dem Abkühlen goß man die Reaktionsmischung in 200 ml Eiswasser. Anschließend extrahierte man dreimal mit je 30 50 ml Essigsäureethylester. Die vereinigten organischen Phasen wurden zweimal mit wenig Wasser gewaschen, dann über Natriumsulfat getrocknet und schließlich eingeengt. Die Reinigung des erhaltenen Rohprodukts erfolgte mittels Chromatographie an Kieselgel (Laufmittel: zunächst tert. -Butyl -methylether, dann 35 Essigsäureethylester). Ausbeute: 0,7 g eines farblosen Öls. ϊ-H-NMR (270 MHz, in d6 -Dimethylsulfoxid) : δ [ppm] = 3.43 (s,3H), 4.69 (d,2H), 7.00 (d,lH), 7.10 (d,lH), 8.57 (S,1H), 9.07 (s,lH), 11.0 (br. ,1H) .1.1 g of 2 - (5-amino-2-fluoro-4-hydroxyphenyl) -3-chloro-5-methyl-25 sulfonylpyridine, 1.0 g of potassium carbonate and 0.5 g of chloroacetyl chloride were dissolved in 50 ml of anhydrous dimethylformamide first stirred at room temperature for two hours and then at 90 ° C. for four hours. After cooling, the reaction mixture was poured into 200 ml of ice water. The mixture was then extracted three times with 30 50 ml portions of ethyl acetate. The combined organic phases were washed twice with a little water, then dried over sodium sulfate and finally concentrated. The crude product obtained was purified by chromatography on silica gel (mobile phase: first tert-butyl methyl ether, then 35 ethyl acetate). Yield: 0.7 g of a colorless oil. ϊ-H NMR (270 MHz, in d 6 -dimethylsulfoxide): δ [ppm] = 3.43 (s, 3H), 4.69 (d, 2H), 7.00 (d, lH), 7.10 (d, lH), 8.57 (S, 1H), 9.07 (s, 1H), 11.0 (br., 1H).
40 Zu einer Suspension von 0,06 g Natriumhydrid (80 %ige Suspension in Mineralöl) in 20 ml wasserfreiem Dimethylformamid wurde eine Lösung von 0,7 g 6 - (3 -Chlor- 5-methylsulfonylpyridin-2 -yl) - 7 - fluor-2H- 1, 4 -benzoxazin-3 -on in 20 ml Dimethylformamid langsam zugetropft. Nach beendeter Zugabe rührte man noch 10 Minuten, be-40 A solution of 0.7 g of 6 - (3-chloro-5-methylsulfonylpyridin-2-yl) - 7 - fluorine was added to a suspension of 0.06 g of sodium hydride (80% suspension in mineral oil) in 20 ml of anhydrous dimethylformamide -2H- 1, 4 -benzoxazin-3 -one slowly added dropwise in 20 ml of dimethylformamide. After the addition was complete, stirring was continued for 10 minutes,
45 vor eine Lösung von 0,26 g Propargylbromid in 10 ml Dimethylformamid zugetropft wurde. Die erhaltene Mischung wurde 20 Stunden bei Raumtemperatur gerührt und dann in 200 ml Eiswasser gegossen. Anschließend extrahierte man dreimal mit je 50 ml tert. -Butyl - methylether. Die vereinigten organischen Phasen wurden zweimal mit wenig Wasser gewaschen, über Natriumsulfat getrocknet und schließlich eingeengt. Die Reinigung des erhaltenen Rohprodukts erfolgte mittels Chromatographie an Kieselgel (Laufmittel: Dichlor ethan/tert . -Butyl -methylether = 1:1). Ausbeute: 0,2 g weißer Kristalle; Smp . : 223°C.45 before a solution of 0.26 g of propargyl bromide in 10 ml of dimethylformamide was added dropwise. The resulting mixture was stirred at room temperature for 20 hours and then poured into 200 ml of ice water. Then extracted three times with 50 ml of tert. -Butyl - methyl ether. The combined organic phases were washed twice with a little water, dried over sodium sulfate and finally concentrated. The crude product obtained was purified by chromatography on silica gel (mobile phase: dichloroethane / tert-butyl methyl ether = 1: 1). Yield: 0.2 g of white crystals; M.p. : 223 ° C.
*H-NMR (250 MHz, in CDC13): δ [ppm] = 2.27 (S,1H), 3.18 (s,3H), 4.72 (s,2H), 4.73 (d,2H), 6.90 (d,lH), 7.30 (d,lH), 8.34 (s,lH), 9.09 (s,lH) .* H-NMR (250 MHz, in CDC1 3 ): δ [ppm] = 2.27 (S, 1H), 3.18 (s, 3H), 4.72 (s, 2H), 4.73 (d, 2H), 6.90 (d, lH), 7.30 (d, lH), 8.34 (s, lH), 9.09 (s, lH).
Beispiel 2Example 2
5- (3 -Chlor -5 -methylsulfonylpyridin-2 -yl) -1 - (2 -propenyl) -benz- oxazol-2-on (Tabelle 1, Verbindung Nr. Ic.328)5- (3-Chloro-5-methylsulfonylpyridin-2-yl) -1 - (2-propenyl) -benz-oxazol-2-one (Table 1, compound no. Ic.328)
Die Herstellung erfolgte nach folgendem ReaktionsschemaThe preparation was carried out according to the following reaction scheme
Figure imgf000061_0001
Figure imgf000061_0001
N02 N0 2
Figure imgf000061_0002
Figure imgf000062_0001
Figure imgf000061_0002
Figure imgf000062_0001
1. Reaktionsschritt:1st reaction step:
3-Chlor-2- (4 -methoxyphenyl) - 5 -methylthiopyridin3-chloro-2- (4-methoxyphenyl) -5-methylthiopyridine
30,5 g 2, 3 -Dichlor- 5 -methylthiopyridin, 23,9 g 4 -Methoxybenzol - boronsäure, 3,6 g Tetrakistriphenylphosphinpalladium(O) und 39,6 g Natriu hydrogencarbonat wurden in einer Mischung aus30.5 g of 2,3-dichloro-5-methylthiopyridine, 23.9 g of 4-methoxybenzene-boronic acid, 3.6 g of tetrakistriphenylphosphine palladium (O) and 39.6 g of sodium bicarbonate were mixed in a mixture
300 ml Tetrahydrofuran und 300 ml Wasser 72 Stunden auf Rückfluß - temperatur erhitzt. Nach dem Abkühlen trennte man die wäßrige Phase ab. Anschließend wurde zweimal mit je 150 ml Methyl -tert - butylether extrahiert. Die vereinigten organischen Phasen trock- nete man noch über Natriumsulfat, bevor eingeengt wurde. Durch Rühren mit wenig Methanol brachte man das Rohprodukt zur Kristallisation. Die abfiltrierten Kristalle wurden schließlich noch mit wenig Methanol gewaschen und bei reduziertem Druck getrocknet. Ausbeute: 30,2 g farbloser Kristalle; Smp.: 90°C. iH-NMR (250 MHz, in CDC13): δ [ppm] = 2.54 (s,3H), 3.87 (s,3H), 6.99 (d,2H), 7.62 (s,lH), 7.72 (d,2H), 8.44 (s,lH).300 ml of tetrahydrofuran and 300 ml of water are heated to reflux temperature for 72 hours. After cooling, the aqueous phase was separated off. The mixture was then extracted twice with 150 ml each of methyl tert-butyl ether. The combined organic phases were dried over sodium sulfate before being concentrated. The crude product was crystallized by stirring with a little methanol. The crystals filtered off were finally washed with a little methanol and dried under reduced pressure. Yield: 30.2 g of colorless crystals; M.p .: 90 ° C. iH-NMR (250 MHz, in CDC1 3 ): δ [ppm] = 2.54 (s, 3H), 3.87 (s, 3H), 6.99 (d, 2H), 7.62 (s, lH), 7.72 (d, 2H) ), 8.44 (s, lH).
2. Reaktionsschritt:2nd reaction step:
3-Chlor-2- (4 -methoxyphenyl ) - 5-methylsulfonylpyridin3-chloro-2- (4-methoxyphenyl) -5-methylsulfonylpyridine
Zu einer Lösung von 24,3 g 3 -Chlor -2 - (4 -methoxyphenyl) - 5 -methyl - thiopyridin (aus Stufe 1) in 150 ml Trichlormethan wurde bei 15 bis 20°C portionsweise eine Suspension von 55,4 g 3-Chlorper- benzoesäure (von Aldrich; Gehalt 56 bis 87 gew.-%ig) in 250 ml Trichlormethan gegeben. Nach beendeter Zugabe rührte man zunächst noch 45 Minuten. Dann wurde die entstandene 3 -Chlorbenzoesäure abfiltriert und mit Trichlormethan gewaschen. Die vereinigten Trichlormethan-Phasen wurden nacheinander mit zweimal 100 ml einer 40 %igen NaHS03 -Lösung und zweimal 100 ml einer 10 %igen Natriumhydrogencarbonat -Lösung gewaschen, über Natriumsulfat getrocknet und schließlich eingeengt. Ausbeute: 25,7 g eines farblosen Öls.A suspension of 55.4 g 3 was added in portions at 15 to 20 ° C. to a solution of 24.3 g of 3-chlorine -2 - (4-methoxyphenyl) -5-methyl-thiopyridine (from stage 1) in 150 ml of trichloromethane -Chlorper- benzoic acid (from Aldrich; content 56 to 87 wt .-%) in 250 ml trichloromethane. After the addition was complete, stirring was continued for 45 minutes. The resulting 3-chlorobenzoic acid was then filtered off and washed with trichloromethane. The combined trichloromethane phases were washed successively with twice 100 ml of a 40% NaHS0 3 solution and twice 100 ml of a 10% sodium hydrogen carbonate solution, dried over sodium sulfate and finally concentrated. Yield: 25.7 g of a colorless oil.
XH-NMR (250 MHz, in CDC13): δ [ppm] = 3.18 (s,3H), 3,89 (s,3H), 7.02 (d,2H), 7.82 (d,2H), 8.29 (s,lH), 9.05 (s,lH). 3. Reaktionsschritt: X H-NMR (250 MHz, in CDC1 3 ): δ [ppm] = 3.18 (s, 3H), 3.89 (s, 3H), 7.02 (d, 2H), 7.82 (d, 2H), 8.29 ( s, lH), 9.05 (s, lH). 3rd reaction step:
3-Chlor-2- (4 -hydroxyphenyl ) - 5-methylsulfonylpyridin3-chloro-2- (4-hydroxyphenyl) -5-methylsulfonylpyridine
25,7 g 3 -Chlor-2 - ( -methoxyphenyl) -5 -methylsulfonylpyridin (aus Stufe 2) wurden in 350 ml 47 %iger wäßriger HBr-Lösung 4 Stunden auf Rückflußtemperatur erhitzt. Nach dem Abkühlen goß man die Mischung auf 1 Liter Eiswasser. Das entstandene feste Wertprodukt wurde abgetrennt, mit Wasser gewaschen und bei reduziertem Druck getrocknet. Ausbeute: 21,2 g weißer Kristalle; Smp.: 226°C. iH-NMR (250 MHz, in d6 -Dimethylsulfoxid) : δ [ppm] = 3.42 (s,3H), 6.92 (d,2H), 7.70 (d,2H), 8.50 (s,lH), 9.04 (s,lH), 10.0 (s,br., IH) .25.7 g of 3-chloro-2 - (-methoxyphenyl) -5-methylsulfonylpyridine (from stage 2) were heated in 350 ml of 47% strength aqueous HBr solution for 4 hours at reflux temperature. After cooling, the mixture was poured onto 1 liter of ice water. The resulting solid product of value was separated off, washed with water and dried under reduced pressure. Yield: 21.2 g of white crystals; M.p .: 226 ° C. i H-NMR (250 MHz, in d 6 -dimethylsulfoxide): δ [ppm] = 3.42 (s, 3H), 6.92 (d, 2H), 7.70 (d, 2H), 8.50 (s, lH), 9.04 ( s, lH), 10.0 (s, br., IH).
4. Reaktionsschritt: 3-Chlor-2- (4 -hydroxy- 3 -nitrophenyl) - 5-methylsulfonylpyridin4th reaction step: 3-chloro-2- (4-hydroxy-3-nitrophenyl) - 5-methylsulfonylpyridine
Zu einer Lösung von 3,0 g 3 -Chlor-2 - (4 -hydroxyphenyl) - 5 -methyl - sulfonylpyridin (aus Stufe 3) in 20 ml 96 %iger Schwefelsäure und 20 ml Eisessig wurden bei 0 bis 5°C 0,67 g 100 %ige Salpetersäure getropft. Nach beendeter Zugabe rührte man noch eine Stunde bei 0 bis 5°C . Anschließend goß man die Reaktionsmischung in 200 ml Eiswasser. Das entstandene feste Wertprodukt wurde abfiltriert, mit Wasser gewaschen und bei reduziertem Druck getrocknet. Ausbeute: 3,1 g weißer Kristalle; Smp.: 182°C. XH-NMR (250 MHz, in d6 -Dimethylsulfoxid) : δ [ppm] = 3.43 (s,3H), 7.30 (d,lH), 8.02 (dd,lH), 8.35 (d,lH), 8.58 (s,lH), 9.09 (s,lH), 11.65 (s, br.,lH) .A solution of 3.0 g of 3-chloro-2 - (4-hydroxyphenyl) -5-methyl-sulfonylpyridine (from stage 3) in 20 ml of 96% sulfuric acid and 20 ml of glacial acetic acid was added at 0 to 5 ° C. Dropped 67 g of 100% nitric acid. After the addition had ended, the mixture was stirred at 0 to 5 ° C. for one hour. The reaction mixture was then poured into 200 ml of ice water. The resulting solid product of value was filtered off, washed with water and dried under reduced pressure. Yield: 3.1 g of white crystals; M.p .: 182 ° C. X H-NMR (250 MHz, in d 6 -dimethylsulfoxide): δ [ppm] = 3.43 (s, 3H), 7.30 (d, lH), 8.02 (dd, lH), 8.35 (d, lH), 8.58 ( s, lH), 9.09 (s, lH), 11.65 (s, br., lH).
5. Reaktionsschritt: 2- (3 -Amino-4 -hydroxyphenyl) -3 -chlor- 5-methylsulfonylpyridin5th reaction step: 2- (3-amino-4-hydroxyphenyl) -3-chloro-5-methylsulfonylpyridine
Zu einer gut gerührten Suspension von 8,2 g Eisenpulver in einer siedenden Mischung aus 180 ml Eisessig und 45 ml Methanol wurden portionsweise 16,1 g 3-Chlor- 2- (4 -hydroxy-3 -nitrophenyl) - 5- methylsulfonylpyridin (aus Stufe 4) gegeben. Nach beendeterTo a well-stirred suspension of 8.2 g of iron powder in a boiling mixture of 180 ml of glacial acetic acid and 45 ml of methanol, 16.1 g of 3-chloro-2- (4-hydroxy-3-nitrophenyl) -5-methylsulfonylpyridine (from Level 4) given. After finished
Zugabe rührte man noch zwei Stunden bei Rückflußtemperatur. Die abgekühlte Reaktionsmischung wurde filtriert. Das Filtrat verdünnte man mit 1 Liter Wasser. Dabei bildeten sich dunkel gefärbte Kristalle, die abfiltriert, mit Wasser gewaschen und bei reduziertem Druck getrocknet wurden. Das erhaltene Rohprodukt (15,0 g) war ohne Reinigung für die weitere Umsetzung geeignet. 6. Reaktionsschritt:The addition was stirred for two hours at the reflux temperature. The cooled reaction mixture was filtered. The filtrate was diluted with 1 liter of water. Dark-colored crystals formed, which were filtered off, washed with water and dried under reduced pressure. The crude product obtained (15.0 g) was suitable for further reaction without purification. 6th reaction step:
5- (3 -Chlor-5 -methylsulfonylpyridin-2 -yl) -benzoxazol-2 -on5- (3-Chloro-5-methylsulfonylpyridin-2-yl) -benzoxazol-2 -one
Eine Lösung von 4,0 g 2 - (3 -Amino-4 -hydroxyphenyl) - 3 -chlor- 5- methylsulfonylpyridin und 3,3 g Carbonyldiimidazol in einer Mischung aus 100 ml wasserfreiem Tetrahydrofuran und 80 ml Dimethylformamid wurde vier Stunden bei 80 bis 90°C gerührt. Danach destillierte man das Tetrahydrofuran ab. Der Rückstand wurde in 400 ml Wasser eingerührt, wobei sich dunkel gefärbte Kristalle (0,4 g) ausbildeten. Die abfiltrierten Kristalle waren ohne Reinigung für die weitere Umsetzung geeignet.A solution of 4.0 g of 2 - (3-amino-4-hydroxyphenyl) -3-chloro-5-methylsulfonylpyridine and 3.3 g of carbonyldiimidazole in a mixture of 100 ml of anhydrous tetrahydrofuran and 80 ml of dimethylformamide was at 80 to 90 ° C stirred. The tetrahydrofuran was then distilled off. The residue was stirred into 400 ml of water, whereby dark-colored crystals (0.4 g) formed. The crystals filtered off were suitable for further reaction without purification.
7. Reaktionsschritt:7th reaction step:
5- (3 -chlor-5 -methylsulfonylpyridin-2 -yl) -1- (2-propenyl) -benz- oxazol-2-on5- (3-chloro-5-methylsulfonylpyridin-2-yl) -1- (2-propenyl) -benz-oxazol-2-one
0,4 g einer 80 %igen Suspension von Natriumhydrid in Mineralöl wurden in 10 ml wasserfreiem Dimethylformamid suspendiert und unter Rühren tropfenweise mit einer Lösung von 4,0 g 5-(3-Chlor- 5-methylsulfonylpyridin-2-yl) -benzoxazol -2 -on (aus Stufe sechs) in 120 ml wasserfreiem Dimethylformamid versetzt. Nach beendeter Zugabe rührte man noch 30 Minuten. Dann wurden 1,64 g Allylbromid zugetropft. Anschließend rührte man noch 16 Stunden bei 23°C. Zur Aufarbeitung wurde die Reaktionsmischung in 400 ml Eiswasser gegossen. Danach extrahierte man mit dreimal 100 ml Essigsäureethylester. Die vereinigten organischen Phasen wurden noch mit 50 ml Wasser gewaschen, über Natriumsulfat getrocknet und schließlich eingeengt. Die Reinigung des Rohproduktes erfolgte mittels Chromatographie an Kieselgel, wobei nacheinander die folgenden Elutionsmittel verwendet wurden: Cyclohexan/Methyl - tert . -butylether (4:1), Methyl - tert . -butylether und Essigsäureethylester. Ausbeute: 2,57 g weißer Kristalle; Smp.: 175°C. l-H-NMR (250 MHz, in CDC13): δ [ppm] = 3.19 (S,3H), 4.51 (d,2H), 5.30 (S,1H), 5.38 (d,lH), 5.83-6.03 (m, IH) , 7.33 (d, IH) , 7.41 (d,lH), 7.61 (dd,lH), 8.35 (s,lH), 9.04 (S,1H).0.4 g of an 80% suspension of sodium hydride in mineral oil was suspended in 10 ml of anhydrous dimethylformamide and added dropwise with stirring with a solution of 4.0 g of 5- (3-chloro-5-methylsulfonylpyridin-2-yl) benzoxazole - 2 -one (from stage six) in 120 ml of anhydrous dimethylformamide. After the addition had ended, the mixture was stirred for a further 30 minutes. Then 1.64 g of allyl bromide were added dropwise. The mixture was then stirred at 23 ° C. for a further 16 hours. For working up, the reaction mixture was poured into 400 ml of ice water. The mixture was then extracted with three times 100 ml of ethyl acetate. The combined organic phases were washed with 50 ml of water, dried over sodium sulfate and finally concentrated. The crude product was purified by means of chromatography on silica gel, the following eluents being used in succession: cyclohexane / methyl-tert. -butyl ether (4: 1), methyl - tert. -butyl ether and ethyl acetate. Yield: 2.57 g of white crystals; M.p .: 175 ° C. 1 H-NMR (250 MHz, in CDC1 3 ): δ [ppm] = 3.19 (S, 3H), 4.51 (d, 2H), 5.30 (S, 1H), 5.38 (d, 1H), 5.83-6.03 (m , IH), 7.33 (d, IH), 7.41 (d, lH), 7.61 (dd, lH), 8.35 (s, lH), 9.04 (S, 1H).
In der folgenden Tabelle 2 sind neben den vorstehend beschriebenen substituierten 2 -Arylpyridinen I noch weitere erfindungsgemäße Verbindungen aufgeführt, die nach einem der beschriebenen Verfahren hergestellt wurden oder herstellbar sind: Tabelle 2In addition to the substituted 2-arylpyridines I described above, Table 2 below lists further compounds according to the invention which were prepared or can be prepared by one of the processes described: Table 2
H3CH 3 C
Figure imgf000065_0001
Figure imgf000065_0001
Figure imgf000065_0002
Anwendungsbeispiele (herbizide Wirksamkeit)
Figure imgf000065_0002
Examples of use (herbicidal activity)
Die herbizide Wirkung der substituierten 2 -Arylpyridine I ließ sich durch die folgenden Gewächshausversuche zeigen:The herbicidal activity of the substituted 2-arylpyridines I was demonstrated by the following greenhouse tests:
Als Kulturgefäße dienten Plastikblumentöpfe mit lehmigem Sand mit etwa 3,0 % Humus als Substrat. Die Samen der Testpflanzen wurden nach Arten getrennt eingesät.Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels. The seeds of the test plants were sown separately according to species.
Bei Vorauflaufbehandlung wurden die in Wasser suspendierten oder emulgierten Wirkstoffe direkt nach Einsaat mittels fein verteilender Düsen aufgebracht. Die Gefäße wurden leicht beregnet, um Keimung und Wachstum zu fördern, und anschließend mit durchsichtigen Plastikhauben abgedeckt, bis die Pflanzen angewachsen waren. Diese Abdeckung bewirkt ein gleichmäßiges Keimen der Test- pflanzen, sofern dies nicht durch die Wirkstoffe beeinträchtigt wurde.In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles. The tubes were lightly sprinkled to promote germination and growth, and then covered with clear plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, provided that this has not been impaired by the active ingredients.
Zum Zweck der Nachauflaufbehandlung wurden die Testpflanzen je nach Wuchsform erst bis zu einer Wuchshöhe von 3 bis 15 cm angezogen und erst dann mit den in Wasser suspendierten oder emulgierten Wirkstoffen behandelt. Die Testpflanzen wurden dafür entweder direkt gesät und in den gleichen Gefäßen aufgezogen oder sie wurden erst als Keimpflanzen getrennt angezogen und einige Tage vor der Behandlung in die Versuchsgefäße verpflanzt. Die Aufwandmenge für die Nachauflaufbehandlung betrug 15,6 oder 7,8 g/ha a.S. (aktive Substanz).For the purpose of post-emergence 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. 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 vessels a few days before the treatment. The application rate for the post-emergence treatment was 15.6 or 7.8 g / ha aS (active substance).
Die Pflanzen wurden artenspezifisch bei Temperaturen von 10 bis 25°C bzw. 20 bis 35°C gehalten. Die Versuchsperiode erstreckte sich über 2 bis 4 Wochen. Während dieser Zeit wurden die Pflanzen gepflegt, und ihre Reaktion auf die einzelnen Behandlungen wurde ausgewertet.The plants were kept in a species-specific manner at temperatures of 10 to 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.
Bewertet wurde nach einer Skala von 0 bis 100. Dabei bedeutet 100 kein Aufgang der Pflanzen bzw. völlige Zerstörung zumindest der oberirdischen Teile und 0 keine Schädigung oder normaler Wachstumsverlauf.Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
Die in den Gewächshausversuchen verwendeten Pflanzen setzten sich aus folgenden Arten zusammen:The plants used in the greenhouse experiments are composed of the following types:
Figure imgf000066_0001
Figure imgf000066_0001
Bei Aufwandmengen von 15,6 und 7,8 g/ha zeigte die Verbindung Nr. Ic.4 im Nachauflaufverfahren eine sehr gute herbizide Wirkung gegen die obengenannten unerwünschten Pflanzen.At application rates of 15.6 and 7.8 g / ha, compound no. Ic.4 showed a very good herbicidal action against the above-mentioned undesirable plants in the post-emergence process.
Anwendungsbeispiele (desikkative/defoliante Wirksamkeit)Examples of use (desiccative / defolian effectiveness)
Als Testpflanzen dienten junge, 4blättrige (ohne Keimblätter) Baumwollpflanzen, die unter Gewächshausbedingungen angezogen wurden (rel. Luftfeuchtigkeit 50 bis 70 %; Tag-/Nachttemperatur 27/20°C) .Young, 4-leaf (without cotyledons) cotton plants served as test plants, which were grown under greenhouse conditions (relative humidity 50 to 70%; day / night temperature 27/20 ° C.).
Die jungen Baumwollpflanzen wurden tropfnaß mit wäßrigen Aufbereitungen der Wirkstoffe (unter Zusatz von 0,15 Gew. -% des Fettalkoholalkoxylats Plurafac® LF 700 1) , bezogen auf dieThe young cotton plants were dripping wet with aqueous preparations of the active ingredients (with an addition of 0.15 wt -.% Of the fatty alcohol alkoxylate Plurafac LF ® 700 1), based on the
Spritzbrühe) blattbehandelt. Die ausgebrachte Wassermenge betrug umgerechnet 1000 1/ha. Nach 13 Tagen wurde die Anzahl der abgeworfenen Blätter und der Grad der Entblätterung in % bestimmt.Spray broth) treated with leaves. 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.
Bei den unbehandelten Kontrollpflanzen trat kein Blattfall auf.No leaf fall occurred in the untreated control plants.
1 J ein schaumarmes, nichtionisches Tensid der BASF AG 1 J a low-foaming, nonionic surfactant from BASF AG

Claims

Patentansprüche claims
1. Substituierte 2 -Arylpyridine der allgemeinen Formel I1. Substituted 2-arylpyridines of the general formula I
Figure imgf000067_0001
Figure imgf000067_0001
in der die Variablen folgende Bedeutungen haben:in which the variables have the following meanings:
n Null oder 1;n zero or 1;
R1 Mercapto, Hydroxysulfonyl, Chlorsulfonyl, Amino- sulfonyl, Ci-Cö-Alkylthio, Cι-C6 -Alkylsulfinyl, Cι-C6 -Alkylsulfonyl, Cι-C6 -Alkyla inosulfonyl oder Di- (Cι-C6 -alkyl) a inosulfonyl;R 1 mercapto, hydroxysulfonyl, chlorosulfonyl, aminosulfonyl, Ci-Cö-alkylthio, -C-C 6 -alkylsulfinyl, Cι-C 6 -alkylsulfonyl, Cι-C 6 -alkyla inosulfonyl or di- (Cι-C 6 -alkyl) a inosulfonyl;
R2,R3 unabhängig voneinander Wasserstoff oder Halogen;R 2 , R 3 independently of one another are hydrogen or halogen;
R4 Wasserstoff, Cι-C6 -Alkyl, Cχ-C6 -Halogenalkyl , Cyano- Cι-C6-alkyl, Cι-C6-Alkoxy, Cι-C6 -Alkoxy-Cι-C6-alkyl, Ci - C4 -Halogenalkoxy-Cι-C - alkyl, Cι-C6 -Alkylthio - Ci -C6 - alkyl , Ci - C6 -Alkylsulf inyl -Ci - C6 -alkyl , Ci-Cβ -Alkylsulfonyl- Cι-C6- alkyl, Cχ-C4 -Alkoxy-Cι-C4 - alkoxy-Cι-C4-alkyl, (Cι-C6 -Alkoxy) carbonyl -Cx -C6-alkyl ,R 4 are hydrogen, C 6 alkyl, Cχ-C 6 haloalkyl, cyano, Cι-C 6 -alkyl, C 6 -alkoxy, C 6 -alkoxy-Cι-C 6 alkyl, Ci - C 4 -haloalkoxy -CC-alkyl, -CC 6 -alkylthio - C 1 -C 6 -alkyl, C 1 -C 6 -alkylsulfonyl-Ci - C 6 -alkyl, C 1 -C 6 -alkylsulfonyl -CC 6 - alkyl, Cχ-C 4 -alkoxy-Cι-C 4 - alkoxy-Cι-C 4 alkyl, (-C-C 6 alkoxy) carbonyl -C x -C 6 alkyl,
C1-C3 -Alkoxy- (Cχ-C3 -alkoxy) carbonyl -Cι-C6 -alkyl, C -C -Alkenyloxy- Cχ-C4-alkyl, C3 -C -Alkinyloxy-Ci -C4 - alkyl, C3-C7 -Cycloalkyl, C3 -C -Cycloalkyl -Cι-C6 -alkyl, C3 -C7 -Cycloalkyloxy-Ci - C6 -alkyl , C3 - C7 -Cycloalkyl - thio-Cι-C6-alkyl, C3-C8-Alkenyl, C3 -C8 -Alkinyl,C 1 -C 3 alkoxy- (Cχ-C 3 -alkoxy) carbonyl -Cι-C 6 -alkyl, C -C -alkenoxy-Cχ-C 4 -alkyl, C 3 -C -alkynyloxy-Ci -C 4 - alkyl, C 3 -C 7 cycloalkyl, C 3 -C cycloalkyl -Cι-C 6 alkyl, C 3 -C 7 cycloalkyloxy-Ci - C 6 alkyl, C 3 - C 7 cycloalkyl - thio-Cι -C 6 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl,
C3 - C8 -Halogenalkenyl , C3 -C8 -Halogenalkinyl , Ci -CÖ -Alkoxy-C3 - C8 - alkenyl , Ci -C6 -Alkoxy-C3 -C8 - alkinyl , (Cι-C6 -Alkoxy) carbonyl, Cι-C6 -Alkylsulfonyl, C3-C6-Alkenyloxy, C3-C6"Alkinyloxy oder Benzyl, das unsubstituiert sein oder am Phenylring ein bis dreiC 3 - C 8 haloalkenyl, C 3 -C 8 haloalkynyl, Ci -C Ö alkoxy-C 3 - C 8 - alkenyl, Ci -C 6 alkoxy-C 3 -C 8 - alkynyl, (-C-C 6 -alkoxy) carbonyl, -CC 6 -alkylsulfonyl, C 3 -C 6 -alkenyloxy, C 3 -C 6 "alkynyloxy or benzyl, which may be unsubstituted or on the phenyl ring one to three
Substituenten tragen kann, jeweils ausgewählt aus der Gruppe bestehend aus Nitro, Halogen, Cι-C6 -Alkyl, CI-CÖ -Alkoxy und (Ci -C6 -Alkoxy) carbonyl ;May bear substituents, each selected from the group consisting of nitro, halogen, Cι-C6 alkyl, CI-C Ö alkoxy and (Ci-C6 alkoxy) carbonyl;
X Sauerstoff, Schwefel, -NH-, -N(CH3)- oder Methylen; Y eine chemische Bindung, Carbonyl oder C(R5,R6), wobeiX is oxygen, sulfur, -NH-, -N (CH 3 ) - or methylene; Y is a chemical bond, carbonyl or C (R 5 , R 6 ), where
R5,R6 unabhängig voneinander für Wasserstoff, Nitro,R 5 , R 6 independently of one another for hydrogen, nitro,
Cyano, Methoxy, Methylthio, Halogen, C1-C4 -Alkyl, Cι-C4-Halogenalkyl, (Ci -C4-Alkoxy) carbonyl,Cyano, methoxy, methylthio, halo, C 1 -C 4 -alkyl, C 4 haloalkyl, (Ci -C 4 alkoxy) carbonyl,
C2-C6-Alkenyl, C3-C6 -Alkinyl oder (C1-C4 -Alkoxy) carbonyl -Cι-C4 -alkyl stehen,C 2 -C 6 alkenyl, C 3 -C 6 alkynyl or (C 1 -C 4 alkoxy) carbonyl -C-C 4 alkyl,
sowie die landwirtschaftlich brauchbaren Salze der Ver- bindungen I mit R1 = Hydroxysulfonyl .and the agriculturally useful salts of the compounds I with R 1 = hydroxysulfonyl.
2. Substituierte 2 -Arylpyridine der Formel I nach Anspruch 1, wobei die Variablen die folgenden Bedeutungen haben:2. Substituted 2-arylpyridines of formula I according to claim 1, wherein the variables have the following meanings:
n Null;n zero;
Rl Mercapto, Hydroxysulfonyl , Chlorsulfonyl, Amino- sulfonyl, Ci-Cβ -Alkylthio, Ci-Cß -Alkylsulfinyl oder Ci -C6-Alkylsulfonyl;R l mercapto, hydroxysulfonyl, chlorosulfonyl, aminosulfonyl, Ci-Cβ-alkylthio, Ci-Cß-alkylsulfinyl or Ci -C 6 -alkylsulfonyl;
R2,R3 unabhängig voneinander Halogen;R 2 , R 3 independently of one another halogen;
R4 Wasserstoff, Cχ-C6-Alkyl, Cyano-Cι-C6 -alkyl ,R 4 is hydrogen, Cχ-C 6 alkyl, cyano-Cι-C 6 alkyl,
Ci-Ce-Alkoxy, Cι-C6-Alkoxy-Cι-C6 -alkyl, Cι-C6-Alkyl- thio-Cι-C6-alkyl, (Ci -C6 -Alkoxy) carbonyl -C^CÖ -alkyl,Ci-Ce-alkoxy, -C-C6-alkoxy-Cι-C 6 -alkyl, Cι-C 6 -alkyl-thio-Cι-C 6 -alkyl, (Ci -C 6 -alkoxy) carbonyl -C ^ C Ö - alkyl,
C3-C8-Alkenyl, C3-C8-Alkinyl, C3-C6-Alkenyloxy oder C3-Ce-Alkinyloxy;C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 6 alkenyloxy or C 3 -Ce alkynyloxy;
Sauerstoff;Oxygen;
eine chemische Bindung oder C(R5,R5), wobeia chemical bond or C (R 5 , R 5 ), where
R5,R6 unabhängig voneinander für Wasserstoff,R 5 , R 6 independently of one another for hydrogen,
Cι-C -Alkyl oder (Ci -C4 -Alkoxy) carbonyl stehen.-C -C alkyl or (Ci -C 4 alkoxy) carbonyl.
3. Substituierte 2 -Arylpyridine der Formel I nach Anspruch 1, wobei n für Null, R1 für Cι-C6 -Alkylsulfonyl, R2 für Chlor, R3 für Fluor oder Chlor, X für Sauerstoff, Y für eine chemische Bindung oder für Methylen und R4 für Wasserstoff, Cχ-C6-Alkyl, Cyano -Cι-C6-alkyl, (Cι-C6 -Alkoxy) carbonyl - Ci-Cδ-alkyl, C3 -C8-Alkenyl oder C3-C8 -Alkinyl stehen.3. Substituted 2-arylpyridines of the formula I according to claim 1, wherein n for zero, R 1 for C 1 -C 6 alkylsulfonyl, R 2 for chlorine, R 3 for fluorine or chlorine, X for oxygen, Y for a chemical bond or for methylene and R 4 for hydrogen, Cχ-C 6 alkyl, cyano -Cι-C 6 alkyl, (Cι-C 6 alkoxy) carbonyl - Ci-C δ alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl.
4. Verwendung der substituierten 2-Arylpyridine der Formel I und der landwirtschaftlich brauchbaren Salze von I, gemäß Anspruch 1, als Herbizide oder zur Desikkation und/oder Defoliation von Pflanzen. 4. Use of the substituted 2-arylpyridines of the formula I and the agriculturally useful salts of I, according to claim 1, as herbicides or for desiccation and / or defoliation of plants.
5. Herbizides Mittel, enthaltend eine herbizid wirksame Menge mindestens eines substituierten 2-Arylpyridins der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I, gemäß Anspruch 1, und mindestens einen inerten flüssigen und/oder5. Herbicidal composition comprising a herbicidally effective amount of at least one substituted 2-arylpyridine of the formula I or an agriculturally useful salt of I, according to claim 1, and at least one inert liquid and / or
5 festen Trägerstoff sowie gewünschtenfalls mindestens einen oberflächenaktiven Stoff.5 solid carrier and, if desired, at least one surface-active substance.
6. Mittel zur Desikkation und/oder Defoliation von Pflanzen, enthaltend eine desikkant und/oder defoliant wirksame Menge6. Agent for the desiccation and / or defoliation of plants, containing a desiccant and / or defoliantly effective amount
10 mindestens eines substituierten 2-Arylpyridins der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I, gemäß Anspruch 1, und mindestens einen inerten flüssigen und/oder festen Trägerstoff sowie gewünschtenfalls mindestens einen oberflächenaktiven Stoff.10 at least one substituted 2-arylpyridine of the formula I or an agriculturally useful salt of I, according to claim 1, and at least one inert liquid and / or solid carrier and, if desired, at least one surfactant.
1515
7. Verfahren zur Herstellung von herbizid wirksamen Mitteln, dadurch gekennzeichnet, daß man eine herbizid wirksame Menge mindestens eines substituierten 2-Arylpyridins der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I, gemäß7. A process for the preparation of herbicidally active agents, characterized in that a herbicidally effective amount of at least one substituted 2-arylpyridine of the formula I or an agriculturally useful salt of I, according to
20 Anspruch 1, und mindestens einen inerten flüssigen und/oder festen Trägerstoff sowie gewünschtenfalls mindestens einen oberflächenaktiven Stoff mischt.20 claim 1, and mixes at least one inert liquid and / or solid carrier and, if desired, at least one surfactant.
8. Verfahren zur Herstellung von desikkant und/oder defoliant 25 wirksamen Mitteln, dadurch gekennzeichnet, daß man eine desikkant und/oder defoliant wirksame Menge mindestens eines substituierten 2-Arylpyridins der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I, gemäß Anspruch 1, und mindestens einen inerten flüssigen und/oder festen 30 Trägerstoff sowie gewünschtenfalls mindestens einen oberflächenaktiven Stoff mischt.8. A process for the preparation of desiccant and / or defoliant agents, characterized in that a desiccant and / or defoliant amount of at least one substituted 2-arylpyridine of the formula I or an agriculturally useful salt of I, according to claim 1, and mixes at least one inert liquid and / or solid carrier and, if desired, at least one surfactant.
9. Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs, dadurch gekennzeichnet, daß man eine herbizid wirksame Menge9. A method for controlling unwanted vegetation, characterized in that a herbicidally effective amount
35 mindestens eines substituierten 2-Arylpyridins der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I, gemäß Anspruch 1, auf Pflanzen, deren Lebensraum oder auf Saatgut einwirken läßt.35 at least one substituted 2-arylpyridine of the formula I or an agriculturally useful salt of I, according to claim 1, on plants, their habitat or on seeds.
40 10. Verfahren zur Desikkation und/oder Defoliation von Pflanzen, dadurch gekennzeichnet, daß man eine desikkant und/oder defoliant wirksame Menge mindestens eines substituierten 2-Arylpyridins der Formel I oder eines landwirtschaf lich brauchbaren Salzes von I, gemäß Anspruch 1, auf Pflanzen40 10. A process for the desiccation and / or defoliation of plants, characterized in that a desiccant and / or defoliantly effective amount of at least one substituted 2-arylpyridine of the formula I or an agriculturally useful salt of I, according to claim 1, on plants
45 einwirken läßt. 45 can act.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß man Baumwolle behandelt.11. The method according to claim 10, characterized in that cotton is treated.
12. Verfahren zur Herstellung von substituierten 2-Arylpyridinen der Formel I gemäß Anspruch 1, bei denen n für 1 und R1 für12. A process for the preparation of substituted 2-arylpyridines of the formula I according to claim 1, in which n is 1 and R 1 is
Cι-C6-Alkylsulfonyl stehen und die Variablen R4, X und Y keinen oxidierbaren Schwefel enthalten, dadurch gekennzeichnet, daß man entsprechend substituierte 2-Arylpyridine, bei denen aber n Null bedeutet, in einem inerten Losungs-/ Verdünnungsmittel oxidiert.-CC 6 alkylsulfonyl and the variables R 4 , X and Y contain no oxidizable sulfur, characterized in that appropriately substituted 2-arylpyridines, but in which n is zero, are oxidized in an inert solvent / diluent.
13. Verfahren zur Herstellung von substituierten 2-Arylpyridinen der Formel I gemäß Anspruch 1, bei denen R1 für Cι-C6-Alkyl- sulfinyl oder Ci-Cβ-Alkylsulfonyl steht und die Variablen R4, X und Y keinen oxidierbaren Schwefel enthalten, dadurch gekennzeichnet, daß man entsprechend substituierte 2-Aryl- pyridine, bei denen aber R1 Cx-Ce-Al ylthio oder Cι-C6-Alkyl - sulfinyl bedeutet, in einem inerten Losungs-/ Verdünnungsmittel oxidiert.13. A process for the preparation of substituted 2-arylpyridines of the formula I according to claim 1, in which R 1 is C 1 -C 6 alkylsulfinyl or C 1 -C 6 -alkylsulfonyl and the variables R 4 , X and Y do not contain any oxidizable sulfur , characterized in that appropriately substituted 2-arylpyridines, but in which R 1 is Cx-Ce-Al ylthio or -CC 6 -alkyl-sulfinyl, are oxidized in an inert solvent / diluent.
14. Verfahren zur Herstellung von substituierten 2-Arylpyridinen der Formel I gemäß Anspruch 1, bei denen R1 für C;L-C6-Alkyl- thio und X für Sauerstoff, Schwefel, -NH- oder -N (anstehen, dadurch gekennzeichnet, daß man entsprechend substi- tuierte 5-Amino-2-arylpyridine XXXVIIa14. A process for the preparation of substituted 2-arylpyridines of the formula I according to claim 1, in which R 1 is C; L -C 6 alkyl thio and X for oxygen, sulfur, -NH- or -N (are present, characterized in that appropriately substituted 5-amino-2-arylpyridines XXXVIIa
XXXVIIa,XXXVIIa,
Figure imgf000070_0001
wobei R2, R3, R5 und R6 die in Anspruch 1 angegebenen Bedeu- tungen haben und X' für Sauerstoff, Schwefel, -NH- oder
Figure imgf000070_0001
wherein R 2 , R 3 , R 5 and R 6 have the meanings given in claim 1 and X 'for oxygen, sulfur, -NH- or
-N(CH3)- steht, in Gegenwart einer Base mit R4'-Cl, R '-Br oder R4'-J, wobei R4' für eine der in Anspruch 1 bezüglich R4 angegebenen Bedeutungen mit Ausnahme von Wasserstoff steht, umsetzt, das Verfahrensprodukt XXXVIIb XXXVI Ib-N (CH 3 ) - in the presence of a base with R 4 '-Cl, R' -Br or R 4 '-J, where R 4 ' has one of the meanings given in Claim 1 with respect to R 4 , with the exception of hydrogen stands, implements, the process product XXXVIIb XXXVI Ib
Figure imgf000071_0001
in einem inerten Losungs- /Verdünnungsmittel diazotiert und das so hergestellte Diazoniu salz mit einem aliphatischen Disulfid (Cι-C6-Alkyl)-S-S- (Cι-C4-Alkyl) umsetzt.
Figure imgf000071_0001
diazotized in an inert solvent / diluent and the diazoniu salt thus prepared is reacted with an aliphatic disulfide (-CC 6 -alkyl) -SS- (-C-C 4 -alkyl).
15. 2- (p-Hydroxyphenyl)pyridine der Formeln X, XXXIa und XXXIb15. 2- (p-hydroxyphenyl) pyridines of the formulas X, XXXIa and XXXIb
Figure imgf000071_0002
wobei die Substituenten R1, R2, R3 , R5 und R6 die in Anspruch 1 angegebenen Bedeutungen haben.
Figure imgf000071_0002
wherein the substituents R 1 , R 2 , R 3 , R 5 and R 6 have the meanings given in claim 1.
16. 2-Aryl-5-nitropyridine der Formeln XXXIIa und XXXIIc16. 2-aryl-5-nitropyridines of the formulas XXXIIa and XXXIIc
Figure imgf000071_0003
wobei die Substituenten R2, R3 , R5 und R6 die in Anspruch 1 angegebenen Bedeutungen haben und R4' für eine der in Anspruch 1 bezüglich R4 angegebenen Bedeutungen mit Ausnahme von Wasserstoff steht.
Figure imgf000071_0003
wherein the substituents R 2 , R 3 , R 5 and R 6 have the meanings given in claim 1 and R 4 'represents one of the meanings given in claim 1 with respect to R 4 with the exception of hydrogen.
17 . 5-Amino- 2 -arylpyridine der Formel XXXVI I17th 5-amino-2-arylpyridines of the formula XXXVI I.
XXXVI I ,XXXVI I,
Figure imgf000072_0001
wobei die Substituenten R2 bis R6 die in Anspruch 1 angegebenen Bedeutungen haben und X' für Sauerstoff, Schwefel, -NH- oder -N(CH3)- steht.
Figure imgf000072_0001
wherein the substituents R 2 to R 6 have the meanings given in claim 1 and X 'represents oxygen, sulfur, -NH- or -N (CH 3 ) -.
18. 2- (m-Nitrophenyl)pyridine der Formeln XVI, XXXVIa und XXXVIb18. 2- (m-nitrophenyl) pyridines of formulas XVI, XXXVIa and XXXVIb
Figure imgf000072_0002
lkoxy
Figure imgf000072_0002
lkoxy
Figure imgf000072_0003
xy wobei die Substituenten R1, R2, R3, R5 und R6 die in Anspruch 1 angegebenen Bedeutungen haben und X' für Sauerstoff, Schwefel, -NH- oder -N(CH3)- steht.
Figure imgf000072_0003
xy wherein the substituents R 1 , R 2 , R 3 , R 5 and R 6 have the meanings given in claim 1 and X 'represents oxygen, sulfur, -NH- or -N (CH 3 ) -.
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US6225313B1 (en) 1997-09-17 2001-05-01 Basf Aktiengesellschaft Substituted 2-phenyl-3(2H)-pyridazinones
WO2012041789A1 (en) 2010-10-01 2012-04-05 Basf Se Herbicidal benzoxazinones
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