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EP1401827A2 - Herbicidal substituted pyridines, method for producing the same and their use as herbicidal agents and plant growth regulators - Google Patents

Herbicidal substituted pyridines, method for producing the same and their use as herbicidal agents and plant growth regulators

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Publication number
EP1401827A2
EP1401827A2 EP02748802A EP02748802A EP1401827A2 EP 1401827 A2 EP1401827 A2 EP 1401827A2 EP 02748802 A EP02748802 A EP 02748802A EP 02748802 A EP02748802 A EP 02748802A EP 1401827 A2 EP1401827 A2 EP 1401827A2
Authority
EP
European Patent Office
Prior art keywords
radicals
substituted
alkyl
formula
unsubstituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02748802A
Other languages
German (de)
French (fr)
Inventor
Klaus Haaf
Lothar Willms
Thomas Auler
Hubert Menne
Hermann Bieringer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
Original Assignee
Bayer CropScience AG
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Filing date
Publication date
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Publication of EP1401827A2 publication Critical patent/EP1401827A2/en
Withdrawn legal-status Critical Current

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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
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C07D213/643—2-Phenoxypyridines; Derivatives thereof
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • 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
    • C07D213/69—Two or more oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • Herbicide-substituted pyridines processes for their preparation and their use as herbicides and plant growth regulators
  • substituted pyridines can have herbicidal and plant growth-regulating properties (cf., for example, EP-A-0955300, WO 98/04550, EP-A-0955292, WO 00/75112, WO 01/00580 and WO 99/28301 ). However, some of these have disadvantages when used, such as high persistence or insufficient selectivity in important crops. Substituted pyridines are also described in EP-A-0196184.
  • the present invention thus relates to compounds of the formula (I) and / or their salts,
  • R 1 the same or different, H, halogen, CN, nitro, SF 5 , (C r C 8 ) alkyl which is unsubstituted or substituted, for example by one or more radicals from the group halogen, (C, -C 8 ) alkoxy, (C alkylthio, (CC 8 ) alkysulfinyl, (C, - C 8 ) alkylsulfonyl, [(CC 8 ) alkoxy] carbonyl and CN is substituted,
  • R 7 means (CyC ⁇ ) alkyl, (C r C 8 ) haloalkyl or NR 8 R 9
  • R 8 , R 9, independently of one another, are identical or different H, (C, - C 8 ) alkyl, (C 2 -C 8 ) alkenyl, (C 7 -C 10 ) arylalkyl, (C 7 -C 10 ) alkylaryl or (C 6 - C 10 ) aryl, where each of the last five radicals is unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, (CC 8 ) alkoxy and (C r C 8 ) alkylthio, or one Group of the formula
  • A is optionally substituted aryl, for example an optionally substituted phenyl radical, or an optionally substituted heterocyclic radical, for example an optionally substituted heteroaromatic radical, such as optionally substituted pyridyl, pyrazolyl or thie ⁇ yl
  • XO or S means R 2 , R 3 , R, R 5 mean the same or different H, halogen, CN, (C., - C 8 ) alkoxy or (C r C 8 ) alkyl, each of the latter two radicals being unsubstituted or substituted, for example are substituted by one or more radicals from the group halogen, CN, (
  • Radicals is unsubstituted or substituted, for example by one or more radicals from the group halogen, (C, -C 8 ) alkoxy, (C r C 8 ) alkylthio, (C, -C 8 ) alkylsulfinyl, (C r C 8 ) alkylsulfonyl [(CC 8) alkoxy] carbonyl and CN is substituted, (C 2 - C 8) alkenyl or (C 2 -C 8) alkynyl, which are unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, (C, -C 8 ) alkoxy and (CC 8 ) alkylthio are substituted,
  • acyl group such as formyl, [(C 1 -C 8) alkyl] -carbonyi, [(C 2 - C 8) alkenyl] -carbonyl, [(C 2 -C 8) alkynyl] carbonyl, (C 1 -C 8 ) alkylsulfonyl, (C 2 - C 8 ) alkenylsulfonyl or (C 2 -C 8 ) alkynylsulfonyl, each of the latter six radicals being unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, (C , -C 8 ) alkoxy and (C 1 -C 8 ) alkylthio is substituted, phenylcarbonyl or phenylsulfonyl, the phenyl radical in each of the latter two radicals being unsubstituted or substituted, for example by one or more radicals from the group
  • B is an acyl radical, e.g. such as linear or branched [(C, -C 8 ) alkyl] carbonyl or [(C 3 -C 6 ) cycloalkyl] carbonyl, where each of the radicals is unsubstituted or substituted, for example by one or more radicals from the group halogen .
  • (C r C 8 ) alkylsulfonyl such as linear or branched CC 8 alkylsulfonyl or
  • W is an oxygen or sulfur atom (i.e. O or S),
  • R 11 (C 1 -C 8 ) alkyl, (C 2 -C 8 ) alkenyl or, (C 2 -C 8 ) alkynyl, where each of the last three radicals' is unsubstituted or substituted, for example by one or more radicals from the Group halogen, CN, (C, - C 8 ) alkoxy, (C r C 8 ) alkylthio, and [(C r C 8 ) alkoxy] - ⁇ carbonyl is substituted,
  • R 12 , R 13 are identical or different H, (CrC alkyl, (C 2 -C 8 ) alkenyl or (C 2 -C 8 ) alkynyl, each of the last three radicals being unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, (C, -C 8 ) alkoxy, (C r C 8 ) alkylthio, and [(C r C 8 ) alkoxy] carbonyl is substituted, and the radicals R 12 and R 13 together with the N atom can form a heterocyclic radical with 5 or 6 ring members, which further heteroatoms from the group N, O and S can contain and is unsubstituted or substituted, for example by (C 1 -C 8 ) alkyl or an oxo group, or
  • the carbon-containing radicals such as alkyl, alkoxy, haloalkyl, alkylamino and alkylthio radicals and the corresponding unsaturated and / or substituted radicals in the carbon skeleton can each be straight-chain or branched or, for carbon numbers from 3, also cyclic , Unless specifically stated, the lower carbon skeletons, for example having 1 to 6 carbon atoms or, in the case of unsaturated groups, having 2 to 6 carbon atoms, are preferred for these radicals.
  • Alkyl radicals also in the composite meanings such as alkoxy, haloalkyl, etc., mean, for example, methyl, ethyl, n-, i- or cyclopropyl, n-, i-, t-, 2- or cyclo-butyl, pentyls, hexyls, such as ⁇ ⁇ hexyl, i-hexyl and 1, 3-dimethylbutyl, heptyls such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl;
  • Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals;
  • Alkenyl means, for example, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1 ⁇ yl , 1-methyl-but-3-
  • Halogen means, for example, fluorine, chlorine, bromine or iodine.
  • Haloalkyl, -alkenyl and -alkynyl are partly or completely substituted alkyl, alkenyl or alkynyl, for example CF 3 , CHF 2 , CH 2 F, CF, by halogen, preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine 3 CF 2 , CH 2 FCHCI, CCI 3 , CHCI 2 , CH 2 CH 2 CI;
  • Haloalkoxy is, for example, OCF 3 , OCHF 2 , OCH 2 F, CF 3 CF 2 0, OCH 2 CF 3 and OCH 2 CH 2 CI; The same applies to haloalkenyl and other halogen-substituted radicals.
  • a hydrocarbon containing residue is a straight chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic residue which contains hydrocarbon units e.g. Alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl;
  • Aryl here means a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl;
  • a hydrocarbon radical is preferably alkyl, alkenyl or alkynyl having up to 12 carbon atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl.
  • Aryl is preferably phenyl which is substituted by one or more, preferably 1, 2 or 3, radicals from the group halogen, such as F, CI, Br, I, preferably F, CI and Br, furthermore alkyl, haloalkyl, alkoxy, haloalkoxy, hydroxy, Amino, nitro, cyano, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyi, mono- and dialkylaminocarbonyl, mono- and dialkylamino, alkylsulfinyl and alkylsulfonyl, and in the radicals with C atoms, those with 1 to 4 C atoms, in particular 1 or 2, are preferred.
  • halogen such as F, CI, Br, I, preferably F, CI and Br
  • Preferred in this context are generally substituents from the group halogen, for example fluorine and chlorine, C 1 -C 4 -A [kyl, preferably methyl or ethyl, C, -C 4 - haloalkyl, preferably trifluoromethyl, C 1 -C 4 alkoxy , preferably methoxy or ethoxy, C, -C 4 haloalkoxy, nitro and cyano.
  • halogen for example fluorine and chlorine
  • C 1 -C 4 -A alkoxy
  • C, -C 4 -haloalkyl preferably trifluoromethyl
  • C 1 -C 4 alkoxy preferably methoxy or ethoxy
  • C, -C 4 haloalkoxy nitro and cyano.
  • a heterocyclic radical or ring can be saturated, unsaturated or heteroaromatic and unsubstituted or substituted, it can also be fused on; it preferably contains one or more heteroatoms in the ring, preferably from the group N, O and S; it is preferably an aliphatic heterocyclyl radical with 3 to 7 ring atoms or a heteroaromatic radical with 5 or 6 ring atoms and contains 1, 2 or 3 heteroatoms.
  • the heterocyclic radical can be, for example, a heteroaromatic radical or ring (heteroaryl), such as a mono-, bi- or polycyclic aromatic system in which at least 1 ring contains one or more heteroatoms, or is a partially or fully hydrogenated radical, for example pyrrolidyl , Piperidyl, pyrazolyl, morpholinyl, indolyl, quinolinyl, pyrimidinyl, triazolyl, oxazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, thiazolyl, thienyl, pyrrolyl.oxazolinyl, isoxazolinyl, isoxazolyi, imidazolyl and benzoxazolyl.
  • heteroaryl such as a mono-, bi- or polycyclic aromatic system in which at least 1 ring contains one or more heteroatoms, or is a partially or
  • Possible substituents for a substituted heterocyclic radical are the substituents mentioned below, and additionally oxo.
  • the oxo group can also occur on the hetero ring atoms, which can exist in different oxidation states, for example in the case of N and S.
  • Substituted radicals such as substituted hydrocarbon-containing radicals, for example substituted alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or substituted heterocyclyl or heteroaryl, mean, for example, a substituted radical derived from the unsubstituted basic body, the substituents being, for example, one or more, preferably 1, 2 or 3 radicals from the group halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro, carboxy, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyi, mono- and dialkylaminocarbonyl, substituted amino, such as acylamino, mono- and dialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyi, haloalkylsulfonyl and
  • radicals with carbon atoms those with 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred.
  • substituents from the group halogen for example fluorine and chlorine, (C r C4) alkyl, preferably methyl or Eth l, (C ⁇ : C 4) haloalkyl, preferably Trifluoromethyl, (C r C 4 ) alkoxy, preferably methoxy or ethoxy, (C, -C 4 ) haloalkoxy, nitro and cyano.
  • halogen for example fluorine and chlorine
  • alkyl preferably methyl or Eth l
  • C ⁇ : C 4 haloalkyl, preferably Trifluoromethyl, (C r C 4 ) alkoxy, preferably methoxy or ethoxy, (C, -C 4 ) haloalkoxy, nitro and cyano.
  • substituents methyl, methoxy, cyano and chlorine are particularly preferred.
  • Optionally substituted phenyl is preferably phenyl which is unsubstituted or one or more times, preferably up to three times, by identical or different radicals from the group halogen, (CC 4 ) alkyl, (C., - C 4 ) alkoxy, (C, -C 4 ) haloalkyl, (C, -C 4 ) haloalkoxy, cyano and nitro, for example o-, m- and p-tolyl, dimethylphenyl, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4- Trifluoro- and trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-cyanophenyl.
  • An acyl residue means the residue of an organic acid which is formally formed by splitting off an OH group from the organic acid, e.g. the rest of a carboxylic acid and residues derived therefrom, such as thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the residues of carbonic acid monoesters, optionally N-substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.
  • An acyl radical is preferably formyl or aliphatic acyl from the group CO-R x , CS-R X , CO-OR x , CO-CO-R *, CS-OR x , CS-SR X , SOR ⁇ or SO 2 R ⁇ , where R x and R ⁇ each represents a C, -C 10 hydrocarbon radical which is unsubstituted or substituted, or aminocarbonyl or aminosulfonyl, the latter two radicals being unsubstituted, N-monosubstituted or N, N-disubstituted.
  • Acyl means, for example, formyl, haloalkylcarbonyl, alkylcarbonyl such as (C 1 -C 4 ) alkylcarbonyl, phenylcarbonyl, where the phenyl ring can be substituted, for example as indicated above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N ⁇ -alkyl- 1-iminoalkyl and other residues of organic acids.
  • the invention also relates to all stereoisomers which are encompassed by formula (I) and mixtures thereof.
  • the possible stereoisomers defined by their specific spatial shape, such as enantiomers, diastereomers, Z and E isomers, are all encompassed by the formula (I) and can be obtained from mixtures of the stereoisomers by customary methods or else by stereoselective reactions in combination with the use of stereochemically pure starting materials can be produced.
  • the compounds of formula (I) can form salts, e.g. those in which the nitrogen atom of pyridine or optionally a further heteroatom is protonated.
  • These salts are, for example, salts of mineral acids such as hydrochloric acid, hydrobromic acid and sulfuric acid or salts of organic acids such as formic acid, acetic acid, oxalic acid, citric acid or aromatic carboxylic acids such as benzoic acids.
  • R are identical or different H, halogen, CN, (-C-C 8 ) alkyl or (d-Cs) alkoxy, each of the latter two radicals being unsubstituted or by one or more radicals from the group halogen, CN, (-C-C 8 ) alkoxy and (Ci-C 8 ) alkylthio is substituted,
  • A is a phenyl radical or a 5- or 6-membered heterocyclic radical such as a 5- or 6-membered N- or S-containing heteroaromatic radical, where the radicals are unsubstituted or with one or more radicals from the group halogen, CN, (C ⁇ -C 8 ) alkyl, (-C-C 8 ) alkoxy, halo (-C-C 8 ) alkyl, halo (C ⁇ - C 8 ) alkyloxy, halo (C ⁇ -C 8 ) alkylthio, and (C ⁇ -C 8 ) alkoxy- (-CC 8 ) alkoxy are substituted,
  • X is O or S
  • R 6 H formyl, (C 1 -C 8 ) alkyl, (C 3 -C 8 ) alkenyl, (C 3 -C 8 ) alkynyl, (C 1 -C 8 ) alkoxy or [(C 1 -C 8 ) alkyl] is carbonyl, each of the latter five residues unsubstituted or substituted by one or more radicals from the group halogen, CN, (C, -.
  • B is an acyl radical such as [(C, -CG) alkyl] carbonyl such as linear or branched [(CC 8 ) alkyl] carbonyl or [(C 3 -C 6 ) cycloalkyl] carbonyl, where each of the radicals is unsubstituted or substituted, for example by one or more radicals from the group halogen, (CC 8 ) alkoxy, (C 1 -C 8 ) alkylthio, (C r C 8 ) alkylsulfinyl, (C., - C 8 ) alkylsulfonyl, [(CC 8 ) alkyl] carbonyl, [(C 1 -C 8 ) Alkoxy] carbonyl and CN is substituted, or [(C 2 -C 8 ) alkenyl] carbonyl or [(C 2 -C 8 ) alkynyl]
  • (C, -C 8 ) alkylsulfonyl such as linear or branched C, -C 8 alkylsulfonyl or (C 3 -C 8 ) cycloalkylsulfonyl, or (C 2 -C 8 ) alkenylsulfonyl or (C 2 - C 8 ) alkynylsulfonyl, where each of the radicals is unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, (C r C 8 ) alkoxy and (C, -C 8 ) alkylthio is substituted.
  • R 1 in the 3-position and in the 5-position of the pyridine ring are identical or different H or halogen, preferably fluorine or chlorine, and R 1 in the 4-position the pyridine ring H, halogen, preferably fluorine or chlorine, CN,
  • R 4 is the same or different halogen, CN, (C, -C 8 ) alkyl, (C, -C 8 ) alkoxy or (C, - (C- ⁇ -Cs) are alkylthio, where each of the latter three radicals is unsubstituted or substituted by one or more radicals from the group halogen, CN, (C ⁇ -C 8 ) alkoxy and (Ci-C 8 ) alkylthio, for example ( C 1 -C 8 ) haloalkyl, (C 1 -C 8 ) haloalkyloxy, (C 1 -C 8 ) haloalkylthio or (C 1 -C 8 ) alkoxy (C 1 -C 8 ) alkyloxy, I is 1 or 2,
  • R 6 is H or (-C-C 4 ) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, CN, (C- ⁇ -Cs) alkoxy and (C ⁇ -Cs) alkylthio
  • B is an acyl radical is like [(C 1 -C 8 ) alkyl] carbonyl such as linear or branched [(C 1 -C 8 ) alkyl] carbonyl or [(C3-C6) cycloalkyl] carbonyl, each of the radicals being unsubstituted or substituted, for example by one or more radicals from the group halogen, (CrC 8 ) alkoxy, (C ⁇ -C 8 ) alkylthio, (C ⁇ -Cs) alkylsulfinyl, (C ⁇ -Cs) alkylsulfonyl, [(C ⁇ -C 8 ) alkyl] carbonyl , [(-C-C 8
  • (-C-C 8 ) alkylsulfonyl such as linear or branched C ⁇ -C 8 alkylsulfonyl or (C3-C 8 ) cycloalkylsulfonyl, or (C2-C 8 ) alkenylsulfonyl or (C 2 - C 8 ) alkynylsulfonyl, each of the radicals being unsubstituted or substituted, for example (8 Ci- C) alkoxy and (C ⁇ -Cs) alkylthio substituted by one or more radicals from the group halogen, CN, means.
  • A is a phenyl, pyridyl, pyrazolyl or thienyl radical which has a Carbon atom is bound to X and is unsubstituted or by one or more radicals from the group halogen, CN, (C 1 -C 8 ) alkyl, (C, -C 8 ) alkoxy, (CC 8 ) haloalkyl, (C r C 8 ) Haloalkylthio, (C r C 8 ) haloalkyloxy and (C r C 8 ) alkoxyalkyloxy is substituted.
  • Preferred radicals A are those in which a substituent R 14 is in the 3-position of the radical A, based on the carbon atom which is bonded to the group X in the formula (I).
  • R 14 identical or different, halogen, cyano or an optionally substituted (C, -
  • C 8 alkyl group such as (C 1 -C 8 ) haloalkyl, preferably CF 3 or cyano
  • R 15 is a (C 1 -C 8 ) alkyl group, preferably methyl, and I 'is an integer from 0 to 4, preferably 0 or 1; preferably A is
  • R 2 , R 3 , R 6 , R 14 and X have the meaning given in formula (I), including the preferred ranges given above,
  • L are identical or different to H or halogen such as fluorine or chlorine
  • WV together are N-CH-CH, S-CH, CH-CH-CH or NN (CH 3 )
  • B is an acyl radical such as [(C., - C 8 ) alkyl] carbonyl such as linear or branched [(C, -C 8 ) alkyl] carbonyl or [(C 3 -C 6 ) cycloalkyl] carbonyl, or (C.
  • alkylsulfonyl such as linear or branched or (C 3 - C 8 ) cycloaikylsulfonyl, where each of the radicals is unsubstituted or by one or more radicals from the group halogen, in particular fluorine or chlorine, CN, (C r C 8 ) alkoxy and (C., - C ⁇ ) Alkylthio is substituted.
  • the compounds of formula (I) according to the invention can be prepared by known methods. Of particular interest are e.g. following syntheses:
  • radicals R 1 have the meaning given in formula (I) and L 'is a leaving group such as halogen or pseudohalogen or a group of the formula A-X-, where A and X are as defined in formula (I), can be known from the literature First, the oxygen of the N-oxide is alkylated and then reacted with cyanides to nitrites of the general formula (III) (see, for example, WR Fife and EFV Seriven, Heterocycles 22, 2375 (1984) and the literature cited therein),
  • Pyridine-N-oxides of the general formula (II) can be prepared from suitably substituted pyridines by various processes.
  • General synthetic methods are e.g. described in A. Albini et al. S. Pietra, Heterocyclic N-Oxides, CRS-Press, Inc., Boca Raton, USA, 1991.
  • Alkyl halogens or alkyl pseudohalogens such as dimethyl sulfate or methyl iodide can preferably be used as alkylating agents for compounds of the formula (II).
  • Alkali or alkaline earth metal cyanides or cyanides of organic bases such as quaternary ammonium salts are used (see e.g. Ellman, Tetrahedron 41 (1985) pp. 4941-4948).
  • a and X are as defined in formula (I), are converted into compounds of the formula (III) (see, for example, US 6,080,861, US 6,130,188 and WO 94/22833 and the literature cited therein), in which L 'is a group of the formula A - X - means.
  • the compounds of the general formula (III) in which L 1 denotes a group A - X -, in which A, X and R 1 are as defined in formula (I), can be converted into the amino compounds of the general formula (V) by suitable reduction processes be transferred.
  • Compounds of the formula (VI) can also be obtained by reducing the corresponding amides (see, for example, embodiment 3a) (see, for example, Gaylord, Reduction with Complex Metal Hydrides, Wiley, New York 1956, pp; 322-373). Suitable Examples include borane complexes such as borane-tetrahydrofuran complexes or borane dimethyl sulfide complexes (see, for example, Brown G. R, AJ Foubister, J. Chem SOC Per T 1 (8), 1401-1403 (1989)). The compounds of formula (VI) can then be acylated by known methods.
  • Nitriles of the general formula (III) can be reductively converted into aldehydes of the general formula (XII) (see, for example, Miller, Biss, Schwartzmann; J. Org. Chem. 1970, 35, 858; or Jerry March, Advanced Organic Chemistry ( Reaction Mechanisms and Structure) 4 th Edition, John Wiley & Sons, New York, 1992, pp 919, 920.) the aldehydes of general formula (XII) may be reduced by known methods to the corresponding alcohols of the general formula (XIII) (see e.g. Hudlicky, Reductions in Organic Chemistry; Ellis Horwood; Chichester 1984 pp. 96-129.
  • Die Hydroxyl groups of the alcohols of the formula (XIII) can then be converted into leaving groups L '.
  • Halogens such as chlorine or bromine (see, for example, Wiley, Hershkowitz, Rein Chung, J. Am. Chem. Soc 1964, 86, 964; Schaefer, Weinberg J. Org. Chem. 1965, 30, 2635) or sulfonic acid ester groups such as Tosylates or mesylates (see eg Crossland, Wells, Shiner; J. Am. Chem. Soc. 1971, 93, 4217) are introduced.
  • the ester groups of the compounds of formula (IX) can then be converted into the free carboxylic acids. This can be done, for example, by basic saponification of the alkyl esters or can also be carried out under acidic saponification conditions, the carboxylic acid group then decarboxylating under, for example, acidic conditions to give compounds of the general formula (X) (Lit .: N. Desideri; F. Manna, J. Heterocycl. Chem., 25 (1), 333-335, 1988).
  • A, X, R 1 and R 2 have the meaning given in formula (I).
  • the cyano compounds of the general formula (X) which are accessible in this way can be converted into the corresponding amino compounds of the general formula (XI) by suitable reduction processes, as has already been described in the preparation of the amines of the formula (V) from the nitriles of the general formula (III) be implemented.
  • the amines of the general formula (XI) which are accessible in this way can be reacted analogously to the amines of the general formula (V) to give compounds of the formula (I) in which A, X, R 2 , R 6 and B correspond to those in formula (I ) have the meaning given.
  • Collections of compounds of formula (I) and their salts, which can be synthesized according to the above-mentioned schemes, can also be produced in a parallelized manner, which can be done ip manually, partially automated or fully automated. It is possible, for example, to automate the reaction, the work-up or the cleaning of the products or intermediate stages. Overall, this is understood to mean a procedure such as that described by SH DeWitt in "Annual Reports in Combinatorial Chemistry and Molecular Diversity: Automated Synthesis ", Volume 1, Publisher Escom 1997, pages 69 to 77.
  • a number of commercially available devices can be used for the parallel reaction and processing, for example from the companies Stern Corporation, Woodrolfe road, Tollesbury, Essex, England, H + P Labortechnik GmbH, Bruckmannring 28, 85764 Oberschleissheim, Germany or the company Radleys, Shirehill, Saffron Waiden, Essex, CB-ll: 3AZ, England.
  • the parallelized purification of compounds of the general formula (I) and their salts or of intermediates obtained in the preparation are, inter alia
  • Chromatography apparatuses are available, for example from ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.
  • Automation systems of this type can be obtained, for example, from Zymark Corporation, Zymark Center, Hopkinton, MA 01748, USA.
  • the compounds of the formula (I) according to the invention and their salts, hereinafter referred to collectively as (compounds) of the formula (I) according to the invention have excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants.
  • Perennial weeds which are difficult to control and which sprout from rhizomes, rhizomes or other permanent organs are also well covered by the compounds according to the invention.
  • the compounds of the invention can e.g. are applied in the pre-sowing, pre-emergence or post-emergence process.
  • Some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned in detail, which can be controlled by the compounds according to the invention without the name being intended to restrict them to certain species.
  • the compounds according to the invention are applied to the surface of the earth before germination, either the weed seedlings emerge completely or the weeds grow to the cotyledon stage, but then stop growing and finally die completely after three to four weeks.
  • the compounds of the invention have excellent herbicidal activity against mono- and dicotyledon weeds, crops of economically important crops e.g. dicotyledonous crops such as soybeans, cotton, rapeseed, sugar beet, especially soybeans, or Gramineae crops such as wheat, barley, rye, rice or maize, only slightly or not at all damaged.
  • crops of economically important crops e.g. dicotyledonous crops such as soybeans, cotton, rapeseed, sugar beet, especially soybeans, or Gramineae crops such as wheat, barley, rye, rice or maize, only slightly or not at all damaged.
  • the present compounds are very suitable for the selective control of undesired plant growth in agricultural crops or in ornamental crops.
  • the compounds of the invention have excellent growth regulatory properties in cultivated plants. You grab regulate the plant's own metabolism and can thus be used to specifically influence plant constituents and to facilitate harvesting, such as by triggering desiccation and stunted growth. Furthermore, they are also suitable for general control and inhibition of undesired vegetative growth without killing the plants. Inhibiting vegetative growth plays a major role in many monocotyledonous and dicotyledonous crops, as this can reduce or completely prevent storage. Because of their herbicidal and plant growth regulatory properties, the active compounds can also be used to control harmful plants in crops of known or still to be developed genetically modified plants.
  • the transgenic plants are generally distinguished by special advantageous properties, for example resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
  • Other special properties concern e.g. B. the crop in terms of quantity, quality, storability, composition and special ingredients.
  • Transgenic plants with an increased starch content or altered starch quality or with a different fatty acid composition of the crop are known.
  • B. of cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn or also crops of sugar beet, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetables.
  • the compounds of the formula (I) can preferably be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made resistant to genetic engineering.
  • new plants with modified properties can be produced using genetic engineering methods (see, for example, EP-A-0221044, EP-A-0131624).
  • genetic engineering changes in crop plants have been described in order to modify the starch synthesized in the plants (e.g. WO 92/11376, WO 92/14827,
  • Glufosinate see e.g. EP-A-0242236, EP-A-242246) or glyphosate
  • Bacillus thuringiensis toxins (Bt toxins) which the
  • nucleic acid molecules can be introduced into plasmids which allow mutageresis or a sequence change by recombination of DNA sequences. With the help of the above standard procedures such. B. base exchanges, partial sequences removed or natural or synthetic sequences added. To connect the DNA fragments to one another, adapters or linkers can be attached to the fragments.
  • the production of plant cells with a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to achieve a cosuppression effect or the expression of at least one appropriately constructed ribozyme which specifically cleaves transcripts of the gene product mentioned above.
  • DNA molecules can be used that comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules that only comprise parts of the coding sequence, these parts having to be long enough to be in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but which are not completely identical.
  • the synthesized protein When nucleic acid molecules are expressed in plants, the synthesized protein can be located in any compartment of the plant cell. However, in order to achieve localization in a particular compartment, z. B. the coding region can be linked to DNA sequences that ensure localization in a particular compartment. Such sequences are known to the person skilled in the art (see, for example, Braun et al., EMBO J. 11_ (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1: 95-106 (1991).
  • the transgenic plant cells can be regenerated into whole plants using known techniques.
  • the transgenic plants can in principle be plants of any plant species, i.e. both monocot and dicot plants.
  • the compounds (I) according to the invention can preferably be used in transgenic crops which are resistant to herbicides from the group of the sulfonylureas, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active compounds.
  • the active compounds according to the invention are used in transgenic crops, in addition to the effects on harmful plants which can be observed in other crops, there are often effects which are specific to the application in the respective transgenic culture, for example a changed or specially expanded weed spectrum which can be controlled changed Application rates which can be used for the application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and influencing the growth and yield of the transgenic crop plants.
  • the invention therefore also relates to the use of the compounds (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
  • the compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations.
  • the invention therefore also relates to herbicidal and plant growth-regulating compositions which comprise compounds of the formula (I).
  • the compounds of formula (I) can be formulated in different ways, depending on which biological and / or chemical-physical parameters are specified. Possible formulation options are, for example: wettable powder (WP), water-soluble powder (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), dispersions based on oil or water, oil-miscible solutions, capsule suspensions (CS), Dusts (DP), mordants, granules for spreading and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
  • WP wettable powder
  • SP water-soluble powder
  • EC emulsifiable concentrates
  • EW e
  • combinations with other pesticidally active substances e.g. Manufacture insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers and / or growth regulators, e.g. in the form of a finished formulation or as a tank mix.
  • pesticidally active substances e.g. Manufacture insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers and / or growth regulators, e.g. in the form of a finished formulation or as a tank mix.
  • Spray powders are preparations which are uniformly dispersible in water and, in addition to the active substance, are not only a diluent or inert substance, but also ionic surfactants and / or non-ionic (wetting agents, dispersing agents), for example polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, ligninsulfonic acid sodium, 2,2'-dinaphthylmethane-6,6'-sodium-disulfonylsulfonic acid also contain sodium oleoylmethyl tauric acid.
  • the herbicidal active ingredients are finely ground, for example in conventional apparatus such as hammer mills, fan mills and air jet mills, and mixed at the same time or subsequently with
  • Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers).
  • organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents.
  • emulsifiers which can be used are: alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as e.g. Sorbitan fatty acid esters or polyoxethylene sorbitan esters such as e.g. Polyoxyethylene.
  • alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate
  • nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as e.g. Sor
  • Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • finely divided solid substances e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • Suspension concentrates can be water or oil based. They can be prepared, for example, by wet milling, using commercially available bead mills and, if appropriate, adding surfactants, such as those already listed above for the other types of formulation.
  • Emulsions for example oil-in-water (EW) emissions, can be produced, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as those already listed above for the other types of formulation.
  • Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. Polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.
  • adhesives e.g. Polyvinyl alcohol, sodium polyacrylic acid or mineral oils
  • Water-dispersible granules are generally produced using the customary methods, such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
  • the agrochemical preparations generally contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of active ingredient, of the formula (I) and / or salts thereof.
  • the active ingredient concentration in wettable powders is, for example, about 10 to 90% by weight, the remainder to 100% by weight consists of customary formulation constituents.
  • the active substance concentration can be about 1 to 90, preferably 5 to 80,% by weight.
  • Dusty formulations included 1 to 30% by weight of active ingredient, preferably mostly 5 to 20% by weight of active ingredient
  • sprayable solutions contain about 0.05 to 80, preferably 2 to 50% by weight of active ingredient.
  • the active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulating aids, fillers, etc. are used.
  • the active ingredient content of the water-dispersible granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the active ingredient formulations mentioned may contain the usual adhesives, wetting agents, dispersing agents, emulsifying agents, penetration agents, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and the pH and Agents influencing viscosity.
  • Mixture formulations or in the tank mix can be used, for example, known active ingredients such as herbicides, insecticides, fungicides or safeners, such as those e.g. out
  • Methyl ester, NC-319); haloxyfop and its esters; haloxyfop-P ( R-haloxyfop) and its esters; hexazinone; imazamethabenz-methyl; imazamox; imazapyr; imazaquin and salts such as the ammonium salt; imazethamethapyr; imazethapyr; imazosulfuron; indanofan (MK-243), iodosulfuron and its salts and esters such as iodosulfuron-methyl-sodium; ioxynil; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxaflutole; isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop; mefenaeet; mefluidide; meso
  • the active compounds according to the invention can also be used in combination with one or more compounds which act as safeners.
  • the formulations present in the commercial form are optionally diluted in the customary manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules using water. Preparations in the form of dust, ground granules or scattering granules and sprayable solutions are usually no longer diluted with other inert substances before use.
  • the required application rate of the compounds of formula (I) varies with the external conditions, such as temperature, humidity, the type of herbicide used, and others. It can vary within wide limits, for example between 0.001 and 10.0 kg / ha or more of active substance, but is preferably between 0.005 and 5 kg / ha.
  • external conditions such as temperature, humidity, the type of herbicide used, and others. It can vary within wide limits, for example between 0.001 and 10.0 kg / ha or more of active substance, but is preferably between 0.005 and 5 kg / ha.
  • Structure 1 Structure 2:
  • a dusting agent is obtained by mixing 10 parts by weight of a compound of the formula (I) and 90 parts by weight of talc as an inert substance and comminuting in a hammer mill.
  • a slightly dispersible, wettable powder in water is obtained by adding 25 parts by weight of a compound of the formula (I), 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of olepylmethyl tauric acid sodium as a and dispersant mixes and grinds in a pin mill.
  • a dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of a compound of the formula (I) with 6 parts by weight of alkylphenol polyglycol ether ( ⁇ Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to above 277 C) are mixed and ground in a attritor to a fineness of less than 5 microns.
  • An emulsifiable concentrate is obtained from 15 parts by weight of a compound of formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol as emulsifier.
  • Seeds or rhizome pieces of monocotyledonous and dicotyledonous weed plants were placed in cardboard pots in sandy loam and covered with soil.
  • the compounds according to the invention formulated in the form of wettable powders or emulsion concentrates were then applied as aqueous suspensions or emulsions with a water application rate of the equivalent of 600 to 800 l / ha in different dosages to the surface of the covering earth. After the treatment, the pots were placed in the greenhouse and kept under good growth conditions for the weeds. After the test plants had emerged, the optical damage to the plants or the emergence damage was assessed after a test period of 3 to 4 weeks in comparison to untreated controls.
  • compounds according to the invention have good herbicidal pre-emergence activity against a broad spectrum of grasses and weeds.
  • Examples 4, 5, 10, 18, 19, 20, 21, 22, 24, 25, 26, 27, 28, 29, 30, 31, 34, 66, 78, 79, 134, 147, 148, 149, 150, 153, 155, 157, 159, 261, 275, 276, 279, 281, 283, 284, 285, 286, 287, 533, 539, 541, 542, 543, 544, 545, 546, 549 and other compounds from Table 1 very good herbicidal activity against harmful plants such as Sinapis alba, Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus and Panicum miliaceum in advance Application rate of 1 kg and less active substance per hectare.
  • Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds were placed in plastic pots in sandy loam soil ( covered with earth and in the Greenhouse grown under good growing conditions.
  • the test plants were treated at the three-leaf stage three weeks after sowing.
  • the compounds according to the invention formulated as wettable powder or as emulsion concentrates were sprayed onto the green parts of the plant in various dosages with an amount of water converted from 600 to 800 l / ha. After the test plants had stood in the greenhouse for about 3 to 4 weeks under optimal growth conditions, the effect of the preparations was assessed visually in comparison with untreated controls.
  • the agents according to the invention also have good herbicidal activity against a broad spectrum of economically important grasses and weeds, even after emergence.
  • Examples Nos. 4, 5, 10, 18, 19, 20, 21, 22, 24, 25, 26, 27, 28, 29, 30, 31, 34, 66, 78, 79, 134, 147, 148, 149, 150, 153, 155, 157, 159, 261, 275, 276, 279, 281, 283, 284, 285, 286, 287, 533, 539, 541, 542, 543, 544, 545, 546, 549 and other compounds from Table 1 very good herbicidal activity against harmful plants such as Sinapis alba, Echinochloa crus-galli, Lolium multiflorum, Chrysanthemum segetum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus, Panicum miliaceum and Avena sativa in the post-emergence process with a post-emergence procedure kg and less of active ingredient per

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Abstract

The invention relates to a compound of formula (I) and/or the salts thereof, wherein A represents an optionally substituted aryl or an optionally substituted heterocyclic group, X represents O or S, R?1, R2, R3, R4, R5¿ have the same or different definition mentioned in the description, m is 0 or 1, R6 represents H, (C¿1?-C8)alkyl, (C1-C8)alkoxy, (C2-C8)alkenyl or (C2-C8)alkinyl, and any of the last-mentioned four groups is unsubstituted or substituted, represents hydroxy or an acyl group, and B is an acyl group, or B and R?6¿ together form a 4- or 5-membered chain, with the exception of N-hydroxy-N-[(6-phenoxy-2-pyridyl)methyl]-acetamide and the salts thereof. The inventive compounds are suitable for use as herbicidal agents or growth regulators.

Description

BESCHREIBUNGDESCRIPTION
Herbizide substituierte Pyridine, Verfahren zu ihrer Herstellung und ihre Verwendung als Herbizide und PflanzenwachstumsregulatorenHerbicide-substituted pyridines, processes for their preparation and their use as herbicides and plant growth regulators
Es ist bekannt, daß substituierte Pyridine herbizide und pflanzenwachstums- regulierende Eigenschaften besitzen können (vgl. z.B. EP-A-0955300, WO 98/04550, EP-A-0955292, WO 00/75112, WO 01/00580 und WO 99/28301). Diese weisen jedoch bei ihrer Anwendung zum Teil Nachteile auf, wie beispielsweise eine hohe Persistenz oder unzureichende Selektivität in wichtigen Nutzpflanzenkulturen. Femer sind in der EP-A-0196184 substituierte Pyridine beschrieben.It is known that substituted pyridines can have herbicidal and plant growth-regulating properties (cf., for example, EP-A-0955300, WO 98/04550, EP-A-0955292, WO 00/75112, WO 01/00580 and WO 99/28301 ). However, some of these have disadvantages when used, such as high persistence or insufficient selectivity in important crops. Substituted pyridines are also described in EP-A-0196184.
Es wurden nun spezielle 2,6-substituierte Pyridine gefunden, die mit Vorteilen als Herbizide und Pflanzenwachstumsregulatoren eingesetzt werden können.Special 2,6-substituted pyridines have now been found which can be used with advantages as herbicides and plant growth regulators.
Gegenstand der vorliegenden Erfindung sind somit Verbindungen der Formel (I) und/oder deren Salze,The present invention thus relates to compounds of the formula (I) and / or their salts,
Formel (I)Formula (I)
worinwherein
R1 gleich oder verschieden H, Halogen, CN, Nitro, SF5, (CrC8)Alkyl, das unsubstituiert oder substituiert ist, z.B. durch einen oder mehrere Reste aus der Gruppe Halogen, (C,-C8)Alkoxy, (C Alkylthio, (C C8)AlkyJsulfinyl, (C,- C8)Alkylsulfonyl, [(C C8)Alkoxy]-carbonyl und CN substituiert ist,R 1, the same or different, H, halogen, CN, nitro, SF 5 , (C r C 8 ) alkyl which is unsubstituted or substituted, for example by one or more radicals from the group halogen, (C, -C 8 ) alkoxy, (C alkylthio, (CC 8 ) alkysulfinyl, (C, - C 8 ) alkylsulfonyl, [(CC 8 ) alkoxy] carbonyl and CN is substituted,
(C2-C8)Alkenyl oder (C2-C8)Alkinyl, die unsubstituiert oder substituiert sind, z.B. durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (Cr (C 2 -C 8 ) alkenyl or (C 2 -C 8 ) alkynyl which are unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, (C r
C8)Alkoxy und (CrC^Alkylthio substituiert sind,C 8 ) alkoxy and (CrC ^ alkylthio are substituted,
(CrC8)Alkoxy, [(CrC8)Alkyl]-carbonyl oder (C1-C8)Alkylsulfonyl, wobei jeder der Reste unsubstituiert oder substituiert ist, z.B. durch ein oder mehrere(C r C 8 ) alkoxy, [(C r C 8 ) alkyl] carbonyl or (C 1 -C 8 ) alkylsulfonyl, each of the radicals being unsubstituted or substituted, for example by one or more
Reste aus der Gruppe Halogen, CN, (C,-C8)Alkoxy und (CrC8)Alkylthio substituiert ist,Radicals from the group halogen, CN, (C, -C 8 ) alkoxy and (C r C 8 ) alkylthio is substituted,
S(O)p-R7, wobei p = 0, 1 oder 2 undS (O) p -R 7 , where p = 0, 1 or 2 and
R7 (CyCβ)Alkyl, (CrC8)Haloalkyl oder NR8R9 bedeutet.wobeiR 7 means (CyC β ) alkyl, (C r C 8 ) haloalkyl or NR 8 R 9
R8,R9 unabhängig voneinander gleich oder verschieden H, (C,- C8)Alkyl, (C2-C8)Alkenyl, (C7-C10)Arylalkyl, (C7-C10)Alkylaryl oder (C6- C10)Aryl sind, wobei jeder der letztgenannten fünf Reste unsubstituiert oder substituiert ist, z.B. durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C C8)Alkoxy und (CrC8)Alkylthio substituiert ist, oder eine Gruppe der FormelR 8 , R 9, independently of one another, are identical or different H, (C, - C 8 ) alkyl, (C 2 -C 8 ) alkenyl, (C 7 -C 10 ) arylalkyl, (C 7 -C 10 ) alkylaryl or (C 6 - C 10 ) aryl, where each of the last five radicals is unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, (CC 8 ) alkoxy and (C r C 8 ) alkylthio, or one Group of the formula
WW
bedeutet, wobei R10 (C1-C8)Alkyl, welches unsubstituiert oder substituiert ist.z.B. durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C,-C8)Alkoxy und (C,-C8)Alkyϊthio substituiert ist, bedeutet und W = O oder S bedeutet, A optional substituiertes Aryl, z.B. einen optional substituierten Phenylrest, oder einen optional substituierten heterocyclischen Rest, z.B. einen optional substituierten heteroaromatischen Rest, wie optional substituiertes Pyridyl, Pyrazolyl oder Thieηyl, bedeutet, X O oder S bedeutet, R2,R3,R ,R5 gleich oder verschieden H, Halogen, CN, (C.,-C8)Alkoxy oder (CrC8)Alkyl bedeuten, wobei jeder der beiden letztgenannten Reste unsubstituiert oder substituiert ist, z.B. durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C1-C8)Alkoxy und (C.,-C8)Alkylthio substituiert sind, m 0 oder 1 bedeutet,means, where R 10 is (C 1 -C 8 ) alkyl which is unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, (C, -C 8 ) alkoxy and (C, -C 8 ) alkythio is substituted and W = O or S, A is optionally substituted aryl, for example an optionally substituted phenyl radical, or an optionally substituted heterocyclic radical, for example an optionally substituted heteroaromatic radical, such as optionally substituted pyridyl, pyrazolyl or thieηyl, XO or S means R 2 , R 3 , R, R 5 mean the same or different H, halogen, CN, (C., - C 8 ) alkoxy or (C r C 8 ) alkyl, each of the latter two radicals being unsubstituted or substituted, for example are substituted by one or more radicals from the group halogen, CN, (C 1 -C 8 ) alkoxy and (C., - C 8 ) alkylthio, m denotes 0 or 1,
R6 H, (C C8)Alkyl oder (C,-C8)Alkoxy, wobei jeder der beiden letztgenanntenR 6 H, (CC 8 ) alkyl or (C, -C 8 ) alkoxy, each of the latter two
Reste unsubstituiert oder substituiert ist, z.B. durch einen oder mehrere Reste aus der Gruppe Halogen, (C,-C8)Alkoxy, (CrC8)Alkylthio, (C,-C8)Alkylsulfinyl, (CrC8)Alkylsulfonyl, [(C C8)Alkoxy]-carbonyl und CN substituiert ist, (C2- C8)Alkenyl oder (C2-C8)Alkinyl, die unsubstituiert oder substituiert sind, z.B. durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C,-C8)Alkoxy und (C C8)Alkylthio substituiert sind,Radicals is unsubstituted or substituted, for example by one or more radicals from the group halogen, (C, -C 8 ) alkoxy, (C r C 8 ) alkylthio, (C, -C 8 ) alkylsulfinyl, (C r C 8 ) alkylsulfonyl [(CC 8) alkoxy] carbonyl and CN is substituted, (C 2 - C 8) alkenyl or (C 2 -C 8) alkynyl, which are unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, (C, -C 8 ) alkoxy and (CC 8 ) alkylthio are substituted,
Hydroxy oder ein Acylrest ist wie Formyl, [(C1-C8)Alkyl]-carbonyi, [(C2- C8)Alkenyl]-carbonyl, [(C2-C8)Alkinyl]-carbonyl, (C1-C8)Alkylsulfonyl, (C2- C8)Alkenylsulfonyl oder (C2-C8)Alkinylsulfonyl, wobei jeder der letztgenannten sechs Reste unsubstituiert oder substituiert ist, z.B. durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C,-C8)Alkoxy und (C1-C8)Alkylthio substituiert ist, Phenylcarbonyl oder Phenylsulfonyl, wobei der Phenylrest in jedem der beiden letztgenannten Reste unsubstituiert oder substituiert ist, z.B. durch einen oder mehrere Reste aus der Gruppe Halogen, CN, NO2, (C,-C8)Alkyl, und (CrC8)Alkoxy substituiert ist, wobei R6 bevorzugt verschieden von Hydroxy ist, undHydroxy or an acyl group such as formyl, [(C 1 -C 8) alkyl] -carbonyi, [(C 2 - C 8) alkenyl] -carbonyl, [(C 2 -C 8) alkynyl] carbonyl, (C 1 -C 8 ) alkylsulfonyl, (C 2 - C 8 ) alkenylsulfonyl or (C 2 -C 8 ) alkynylsulfonyl, each of the latter six radicals being unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, (C , -C 8 ) alkoxy and (C 1 -C 8 ) alkylthio is substituted, phenylcarbonyl or phenylsulfonyl, the phenyl radical in each of the latter two radicals being unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, NO 2 , (C, -C 8 ) alkyl, and (C r C 8 ) alkoxy is substituted, wherein R 6 is preferably different from hydroxy, and
B ein Acylrest ist, z.B. wie lineares oder verzweigtes [(C,- C8)-Alkyl]-carbonyl oder [(C3-C6)Cycloalkyl]-carbonyl, wobei jeder der Reste unsubstituiert oder substituiert ist, z.B. durch einen oder mehrere Reste aus der Gruppe Halogen,. (C,-C8)Alkoxy, (CrC8«)Alkylthio, (C^C^Alkylsulfinyl, (C.,-C8)Alkyisulfonyl, [(C.,-C8)Alkyl]-carbonyl( [(C1-C8)Alkoxy]-carbonyl und CN substituiert ist, oder [(C2-C8)Alkenyl]-carbonyl oder [(C2-C8)Alkinyl]-carbonyl, wobei jeder der letztgenannten zwei Reste unsubstituiert oder substituiert ist, z.B. durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C,-C8)Alkoxy und (C,- C8)Alkylthio substituiert ist,B is an acyl radical, e.g. such as linear or branched [(C, -C 8 ) alkyl] carbonyl or [(C 3 -C 6 ) cycloalkyl] carbonyl, where each of the radicals is unsubstituted or substituted, for example by one or more radicals from the group halogen . (C, -C 8 ) alkoxy, (C r C 8 ") alkylthio, (C ^ C ^ alkylsulfinyl, (C., - C 8 ) alkysulfonyl, [(C., - C 8 ) alkyl] -carbonyl ( [ (C 1 -C 8 ) alkoxy] carbonyl and CN is substituted, or [(C 2 -C 8 ) alkenyl] carbonyl or [(C 2 -C 8 ) alkynyl] carbonyl, each of the latter two radicals being unsubstituted or is substituted, for example by one or more radicals from the group halogen, CN, (C, -C 8 ) alkoxy and (C, - C 8 ) alkylthio is substituted,
(CrC8)Alkylsulfonyl, wie lineares oder verzweigtes C C8-Alkylsulfonyl oder(C r C 8 ) alkylsulfonyl, such as linear or branched CC 8 alkylsulfonyl or
(C3-C8)Cycloalkylsulfonyl, oder (C2-C8)Alkenylsulfonyl oder (C2-(C 3 -C 8 ) cycloalkylsulfonyl, or (C 2 -C 8 ) alkenylsulfonyl or (C 2 -
C8)Alkinylsulfonyl, wobei jeder der Reste unsubstituiert oder substituiert ist, z.B. durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C,-C 8 ) alkynylsulfonyl, where each of the radicals is unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, (C, -
C8)Alkoxy und (CTC Alkylthio substituiert ist, oder Phenylcarbonyl oder Phenylsulfonyl, wobei der Phenylrest in jedem der beiden letztgenannten Reste unsubstituiert oder substituiert ist, z.B. durch einen oder mehrere Reste aus der Gruppe Halogen, CN, NO2, (C^C^Alkyl,C 8 ) alkoxy and (C T C alkylthio is substituted, or phenylcarbonyl or phenylsulfonyl, where the phenyl radical in each of the latter two radicals is unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, NO 2 , (C ^ C ^ alkyl,
(C C8)Haloalkyl und (C.,-C8)Alkoxy substituiert ist, oder Mono- oder Di-[(C1-C8)Alkyl]-aminosulfonyl, Formyl oder eine Gruppe der Formel -CO-CO-R', worin R'=H, OH, (C,-C8)-Alkoxy oder (C1-C8)Alkyl ist, wobei jeder der letztgenannten beiden Reste unsubstituiert oder substituiert ist, z.B. durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C,-(CC 8 ) haloalkyl and (C., - C 8 ) alkoxy is substituted, or mono- or di - [(C 1 -C 8 ) alkyl] -aminosulfonyl, formyl or a group of the formula -CO-CO-R ' , wherein R '= H, OH, (C, -C 8 ) alkoxy or (C 1 -C 8 ) alkyl, each of the latter two radicals being unsubstituted or substituted, for example by one or more radicals from the group halogen , CN, (C, -
C8)Alkoxy und (C1-C8)Alkylthio substituiert ist, oder eine Gruppe der FormelC 8 ) alkoxy and (C 1 -C 8 ) alkylthio is substituted, or a group of the formula
bedeutet, worinmeans what
W ein Sauerstoff- oder Schwefelatom (d.h. O oder S),W is an oxygen or sulfur atom (i.e. O or S),
T O oder S,T O or S,
R11 (C1-C8)Alkyl, (C2-C8)Alkenyl oder, (C2-C8)Alkinyl, wobei jeder der drei letztgenannten Reste' unsubstituiert oder substituiert ist, z.B. durch einen oder mehrere Reste aus der Gruppe Halogen, CN, (C,- C8)Alkoxy, (CrC8)Alkylthio, und [(Cr C8)Alkoxy]-<carbonyl substituiert ist,R 11 (C 1 -C 8 ) alkyl, (C 2 -C 8 ) alkenyl or, (C 2 -C 8 ) alkynyl, where each of the last three radicals' is unsubstituted or substituted, for example by one or more radicals from the Group halogen, CN, (C, - C 8 ) alkoxy, (C r C 8 ) alkylthio, and [(C r C 8 ) alkoxy] - < carbonyl is substituted,
R12, R13 gleich oder verschieden H, (CrC Alkyl, (C2-C8)Alkenyl oder (C2-C8)Alkinyl, wobei jeder der drei letztgenannten Reste unsubstituiert oder substituiert ist, z.B. durch einen oder mehrere Reste aus der Gruppe Halogen, CN, (C,-C8)Alkoxy, (CrC8)Alkylthio, und [(CrC8)Alkoxy]-carbonyl substituiert ist, und die Reste R12 und R13 gemeinsam mit dem N-Atom einen heterocyclischen Rest mit 5 oder 6 Ringgliedern bilden können, der weitere Heteroatome aus der Gruppe N, O und S enthalten kann und unsubstituiert oder substituiert ist, z.B. durch (C.,-C8)Alkyl oder eine Oxogruppe substituiert ist, oderR 12 , R 13 are identical or different H, (CrC alkyl, (C 2 -C 8 ) alkenyl or (C 2 -C 8 ) alkynyl, each of the last three radicals being unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, (C, -C 8 ) alkoxy, (C r C 8 ) alkylthio, and [(C r C 8 ) alkoxy] carbonyl is substituted, and the radicals R 12 and R 13 together with the N atom can form a heterocyclic radical with 5 or 6 ring members, which further heteroatoms from the group N, O and S can contain and is unsubstituted or substituted, for example by (C 1 -C 8 ) alkyl or an oxo group, or
B und R6 bilden gemeinsam eine 4- oder 5-gliedrige Kette, z.B. der Formel (-CH2)m-D- oder -D1-(CH2)m1-D-, wobei die Kette unsubstituiert oder substituiert ist, z.B. durch einen oder mehrere, vorzugsweise ein bis vier (C,- C4)Alkylreste substituiert ist, D, D1 unabhängig voneinander SO2 oder CO sind, und m=3 oder 4 und m1=2 oder 3 sind, ausgenommen N-Hydroxy-N-[(6-phenoxy-2-pyridyl)methyl]-acetamid und dessen Salze.B and R 6 together form a 4- or 5-membered chain, for example of the formula (-CH 2 ) m -D- or -D 1 - (CH 2 ) m1 -D-, the chain being unsubstituted or substituted, for example is substituted by one or more, preferably one to four (C, - C 4 ) alkyl radicals, D, D 1 are independently SO 2 or CO, and m = 3 or 4 and m 1 = 2 or 3, except N- Hydroxy-N - [(6-phenoxy-2-pyridyl) methyl] acetamide and its salts.
In der Formel (I) und im folgenden können die kohlenstoffhaltigen Reste wie Alkyl-, Alkoxy-, Haloalkyl-, Alkylamino- und Alkylthioreste sowie die entsprechenden ungesättigten und/oder substituierten Reste im Kohlenstoffgerüst jeweils geradkettig oder verzweigt oder für Kohlenstoffanzahlen ab 3 auch cyclisch sein. Wenn nicht speziell angegeben, sind bei diesen Resten die niederen Kohlenstoffgerüste, z.B. mit 1 bis 6 C-Atomen bzw. bei ungesättigten Gruppen mit 2 bis 6 C-Atomen, bevorzugt. Alkylreste, auch in den zusammengesetzten Bedeutungen wie Alkoxy, Haloalkyl usw., bedeuten z.B. Methyl, Ethyl, n-, i- oder Cyclo-Propyl, n-, i-, t-, 2- oder Cyclo-Butyl, Pentyle, Hexyle, wie ατHexyl, i-Hexyl und 1 ,3-Dimethylbutyl, Heptyle, wie n-Heptyl, 1-Methylhexyl und 1,4-Dimethylpentyl; Alkenyl- und Alkinylreste haben die Bedeutung der den Alkylresten entsprechenden möglichen ungesättigten Reste; Alkenyl bedeutet z.B. Allyl, 1-Methylprop-2-en-1-yl, 2-Methyl-prop-2-en-1-yl, But-2-en-1-yl, But-3-en-1~yl, 1-Methyl-but-3-en-1-yl und 1-Methyl-but-2-en-1-yl; Alkinyl bedeutet z.B. Propargyl, But-2-in-1-yl, But-3-in-1-yl, 1-Methyl-but-3-in-1-yl.In the formula (I) and in the following, the carbon-containing radicals such as alkyl, alkoxy, haloalkyl, alkylamino and alkylthio radicals and the corresponding unsaturated and / or substituted radicals in the carbon skeleton can each be straight-chain or branched or, for carbon numbers from 3, also cyclic , Unless specifically stated, the lower carbon skeletons, for example having 1 to 6 carbon atoms or, in the case of unsaturated groups, having 2 to 6 carbon atoms, are preferred for these radicals. Alkyl radicals, also in the composite meanings such as alkoxy, haloalkyl, etc., mean, for example, methyl, ethyl, n-, i- or cyclopropyl, n-, i-, t-, 2- or cyclo-butyl, pentyls, hexyls, such as α τ hexyl, i-hexyl and 1, 3-dimethylbutyl, heptyls such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl; Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; Alkenyl means, for example, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1 ~ yl , 1-methyl-but-3-en-1-yl and 1-methyl-but-2-en-1-yl; Alkynyl means, for example, propargyl, but-2-in-1-yl, but-3-in-1-yl, 1-methyl-but-3-in-1-yl.
Halogen bedeutet beispielsweise Fluor, Chlor, Brom oder lod. Haloalkyl, -alkenyl und -alkinyl bedeuten durch Halogen, vorzugsweise durch Fluor, Chlor und/oder Brom, insbesondere durch Fluor oder Chlor, teilweise oder vollständig substituiertes Alkyl, Alkenyl bzw. Alkinyl, z.B. CF3, CHF2, CH2F, CF3CF2, CH2FCHCI, CCI3, CHCI2, CH2CH2CI; Haloalkoxy ist z.B. OCF3, OCHF2, OCH2F, CF3CF20, OCH2CF3 und OCH2CH2CI; entsprechendes gilt für Haloalkenyl und andere durch Halogen substituierte Reste.Halogen means, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, -alkenyl and -alkynyl are partly or completely substituted alkyl, alkenyl or alkynyl, for example CF 3 , CHF 2 , CH 2 F, CF, by halogen, preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine 3 CF 2 , CH 2 FCHCI, CCI 3 , CHCI 2 , CH 2 CH 2 CI; Haloalkoxy is, for example, OCF 3 , OCHF 2 , OCH 2 F, CF 3 CF 2 0, OCH 2 CF 3 and OCH 2 CH 2 CI; The same applies to haloalkenyl and other halogen-substituted radicals.
Ein kohlenwasserstoffhaltiger Rest ist ein geradkettiger, verzweigter oder cyclischer und gesättigter oder ungesättigter aliphatischer oder aromatischer Rest, der Kohlenwasserstoffeinheiten aufweist, z.B. Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl oder Aryl; Aryl bedeutet dabei ein mono-, bi- oder polycyclisches aromatisches System, beispielsweise Phenyl, Naphthyl, Tetrahydronaphthyl, Indenyl, Indanyl, Pentalenyl, Fluorenyl und ähnliches, vorzugsweise Phenyl; vorzugsweise bedeutet ein Kohlenwasserstoffrest Alkyl, Alkenyl oder Alkinyl mit bis zu 12 C-Atomen oder Cycloalkyl mit 3, 4, 5, 6 oder 7 Ringatomen oder Phenyl.A hydrocarbon containing residue is a straight chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic residue which contains hydrocarbon units e.g. Alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl; Aryl here means a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl; A hydrocarbon radical is preferably alkyl, alkenyl or alkynyl having up to 12 carbon atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl.
Aryl bedeutet vorzugsweise Phenyl, das durch einen oder mehrere, vorzugsweise 1 , 2 oder 3 Reste aus der Gruppe Halogen, wie F, CI, Br, I, vorzugsweise F, CI und Br, femer Alkyl, Haloalkyl, Alkoxy, Haloalkoxy, Hydroxy, Amino, Nitro, Cyano, Alkoxycarbonyl, Alkylcarbonyl, Formyl, Carbamoyi, Mono- und Dialkylaminocarbonyl, Mono- und Dialkylamino, Alkylsulfinyl und Alkylsulfonyl substituiert ist, und bei den Resten mit C-Atomen, solche mit 1 bis 4 C-Atomen, insbesondere 1 oder 2, bevorzugt sind. Bevorzugt sind dabei in der Regel Substituenten aus der Gruppe Halogen, z.B. Fluor und Chlor, C1-C4-A[kyl, vorzugsweise Methyl oder Ethyl, C,-C4- Haloalkyl, vorzugsweise Trifluormethyl, C1-C4-Alkoxy, vorzugsweise Methoxy oder Ethoxy, C,-C4-Haloalkoxy, Nitro und Cyano. Ein heterocyclischer Rest oder Ring (Heterocyclyl) kann gesättigt, ungesättigt oder heteroaromatisch und unsubstituiert oder substituiert sein, er kann auch ankondensiert sein; er enthält vorzugsweise ein oder mehrere Heteroatome im Ring, vorzugsweise aus der Gruppe N, O und S; vorzugsweise ist er ein aliphatischer Heterocyclylrest mit 3 bis 7 Ringatomen oder ein heteroaromatischer Rest mit 5 oder 6 Ringatomen und enthält 1 , 2 oder 3 Heteroatome. Der heterocyclische Rest kann z.B. ein heteroaromatischer Rest oder Ring (Heteroaryl) sein, wie z.B. ein mono-, bi- oder polycyclisches aromatisches System, in dem mindestens 1 Ring ein oder mehrere Heteroatome enthält, oder ist ein partiell oder vollständig hydrierter Rest, z.B. Pyrrolidyl, Piperidyl, Pyrazolyl, Morpholinyl, Indolyl, Chinolinyl, Pyrimidinyl, Triazolyl, Oxazolyl, Pyridyl, Pyrimidinyl, Pyridazinyl, Pyrazinyl, Thiazolyl, Thienyl, Pyrrolyl.Oxazolinyl, Isoxazolinyl, Isoxazolyi, Imidazolyl und Benzoxazolyl. Als Substituenten für einen substituierten heterocyclischen Rest kommen die weiter unten genannten Substituenten in Frage, zusätzlich auch Oxo. Die Oxogruppe kann auch an den Heteroringatomen, die in verschiedenen Oxidationsstufen existieren können, z.B. bei N und S, auftreten.Aryl is preferably phenyl which is substituted by one or more, preferably 1, 2 or 3, radicals from the group halogen, such as F, CI, Br, I, preferably F, CI and Br, furthermore alkyl, haloalkyl, alkoxy, haloalkoxy, hydroxy, Amino, nitro, cyano, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyi, mono- and dialkylaminocarbonyl, mono- and dialkylamino, alkylsulfinyl and alkylsulfonyl, and in the radicals with C atoms, those with 1 to 4 C atoms, in particular 1 or 2, are preferred. Preferred in this context are generally substituents from the group halogen, for example fluorine and chlorine, C 1 -C 4 -A [kyl, preferably methyl or ethyl, C, -C 4 - haloalkyl, preferably trifluoromethyl, C 1 -C 4 alkoxy , preferably methoxy or ethoxy, C, -C 4 haloalkoxy, nitro and cyano. A heterocyclic radical or ring (heterocyclyl) can be saturated, unsaturated or heteroaromatic and unsubstituted or substituted, it can also be fused on; it preferably contains one or more heteroatoms in the ring, preferably from the group N, O and S; it is preferably an aliphatic heterocyclyl radical with 3 to 7 ring atoms or a heteroaromatic radical with 5 or 6 ring atoms and contains 1, 2 or 3 heteroatoms. The heterocyclic radical can be, for example, a heteroaromatic radical or ring (heteroaryl), such as a mono-, bi- or polycyclic aromatic system in which at least 1 ring contains one or more heteroatoms, or is a partially or fully hydrogenated radical, for example pyrrolidyl , Piperidyl, pyrazolyl, morpholinyl, indolyl, quinolinyl, pyrimidinyl, triazolyl, oxazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, thiazolyl, thienyl, pyrrolyl.oxazolinyl, isoxazolinyl, isoxazolyi, imidazolyl and benzoxazolyl. Possible substituents for a substituted heterocyclic radical are the substituents mentioned below, and additionally oxo. The oxo group can also occur on the hetero ring atoms, which can exist in different oxidation states, for example in the case of N and S.
Substituierte Reste, wie substituierte kohlenwasserstoffhaltige Reste, z.B. substituiertes Alkyl, Alkenyl, Alkinyl, Aryl, Phenyl und Benzyl, oder substituiertes Heterocyclyl oder Heteroaryl, bedeuten beispielsweise einen vom unsubstituierten Grundkörper abgeleiteten substituierten Rest, wobei die Substituenten beispielsweise einen oder mehrere, vorzugsweise 1 , 2 oder 3 Reste aus der Gruppe Halogen, Alkoxy, Haloalkoxy, Alkylthio, Hydroxy, Amino, Nitro, Carboxy, Cyano, Azido, Alkoxycarbonyl, Alkylcarbonyl, Formyl, Carbamoyi, Mono- und Dialkylaminocarbonyl, substituiertes Amino, wie Acylamino, Mono- und Dialkylamino, und Alkylsulfinyl, Haloalkyisulfinyl, Alkylsulfonyi, Haloalkylsulfonyl und, im Falle cyclischer Reste, auch Alkyl. und Haioajkyl sowie den genannten gesättigten kohlenwasserstoffhaltigen Resten entsprechende ungesättigte aliphatische Reste, wie Alkenyl, Alkinyl, Alkenyloxy, Alkinyloxy etc. bedeuten. Bei Resten mit C-Atomen sind solche mit 1 bis 4 C-Atomen, insbesondere 1 oder 2 C-Atomen, bevorzugt. Bevorzugt sind in der Regel Substituenten aus der Gruppe Halogen, z.B. Fluor und Chlor, (CrC4)Alkyl, vorzugsweise Methyl oder Eth l, (Cι:C4)Haloalkyl, vorzugsweise Trifluormethyl, (CrC4)Alkoxy, vorzugsweise Methoxy oder Ethoxy, (C,-C4)Haloalkoxy, Nitro und Cyano. Besonders bevorzugt sind dabei die Substituenten Methyl, Methoxy, Cyano und Chlor.Substituted radicals, such as substituted hydrocarbon-containing radicals, for example substituted alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or substituted heterocyclyl or heteroaryl, mean, for example, a substituted radical derived from the unsubstituted basic body, the substituents being, for example, one or more, preferably 1, 2 or 3 radicals from the group halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro, carboxy, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyi, mono- and dialkylaminocarbonyl, substituted amino, such as acylamino, mono- and dialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyi, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl . and Haioajkyl and the saturated hydrocarbon-containing radicals corresponding to unsaturated aliphatic radicals, such as alkenyl, alkynyl, alkenyloxy, alkynyloxy, etc. In the case of radicals with carbon atoms, those with 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred. Are generally preferred substituents from the group halogen, for example fluorine and chlorine, (C r C4) alkyl, preferably methyl or Eth l, (C ι: C 4) haloalkyl, preferably Trifluoromethyl, (C r C 4 ) alkoxy, preferably methoxy or ethoxy, (C, -C 4 ) haloalkoxy, nitro and cyano. The substituents methyl, methoxy, cyano and chlorine are particularly preferred.
Gegebenenfalls substituiertes Phenyl ist vorzugsweise Phenyl, das unsubstituiert oder ein- oder mehrfach, vorzugsweise bis zu dreifach durch gleiche oder verschiedene Reste aus der Gruppe Halogen, (C C4)Alkyl, (C.,-C4)Alkoxy, (C,-C4)Halogenalkyl, (C,-C4)Halogenalkoxy, Cyano und Nitro substituiert ist, z.B. o-, m- und p-Tolyl, Dimethylphenyle, 2-, 3- und 4-Chlorphenyl, 2-, 3- und 4-Trifluor- und -Trichlorphenyl, 2,4-, 3,5-, 2,5- und 2,3-Dichlorphenyl, o-, m- und p-Cyanophenyl.Optionally substituted phenyl is preferably phenyl which is unsubstituted or one or more times, preferably up to three times, by identical or different radicals from the group halogen, (CC 4 ) alkyl, (C., - C 4 ) alkoxy, (C, -C 4 ) haloalkyl, (C, -C 4 ) haloalkoxy, cyano and nitro, for example o-, m- and p-tolyl, dimethylphenyl, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4- Trifluoro- and trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-cyanophenyl.
Ein Acylrest bedeutet den Rest einer organischen Säure, der formal durch Abspaltung einer OH-Gruppe aus der organischen Säure entsteht, z.B. der Rest einer Carbonsäure und Reste davon abgeleiteter Säuren wie der Thiocarbonsäure, gegebenenfalls N-substituierten Iminocarbonsäuren oder die Reste von Kohlensäuremonoestern, gegebenenfalls N-substituierter Carbaminsäuren, Sulfonsäuren, Sulfinsäuren, Phosphonsäuren, Phosphinsäuren.An acyl residue means the residue of an organic acid which is formally formed by splitting off an OH group from the organic acid, e.g. the rest of a carboxylic acid and residues derived therefrom, such as thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the residues of carbonic acid monoesters, optionally N-substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.
Ein Acylrest ist bevorzugt Formyl oder aliphatisches Acyl aus der Gruppe CO-Rx, CS-RX, CO-ORx, CO-CO-R*, CS-ORx, CS-SRX, SORγ oder SO2Rγ, wobei Rxund Rγ jeweils einen C,-C10-Kohlenwasserstoffrest bedeutet, der unsubstituiert oder substituiert ist, oder Aminocarbonyl oder Aminosulfonyl, wobei die beiden letztgenannten Reste unsubstituiert, N-monosubstituiert oder N,N-disubstituiert sind. Acyl bedeutet beispielsweise Formyl, Halogenalkylcarbonyl, Alkylcarbonyl wie (C1-C4)Alkylcarbonyl, Phenylcarbonyl, wobei der Phenylring substituiert sein kann, z.B. wie oben für Phenyl angegeben, oder Alkyloxycarbonyl, Phenyloxycarbonyl, Benzyloxycarbonyl, Alkylsulfonyl, Alkylsulfinyl, N<-Alkyl-1-iminoalkyl und andere Reste von organischen Säuren.An acyl radical is preferably formyl or aliphatic acyl from the group CO-R x , CS-R X , CO-OR x , CO-CO-R *, CS-OR x , CS-SR X , SOR γ or SO 2 R γ , where R x and R γ each represents a C, -C 10 hydrocarbon radical which is unsubstituted or substituted, or aminocarbonyl or aminosulfonyl, the latter two radicals being unsubstituted, N-monosubstituted or N, N-disubstituted. Acyl means, for example, formyl, haloalkylcarbonyl, alkylcarbonyl such as (C 1 -C 4 ) alkylcarbonyl, phenylcarbonyl, where the phenyl ring can be substituted, for example as indicated above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N <-alkyl- 1-iminoalkyl and other residues of organic acids.
Gegenstand der Erfindung sind auch alle Stereoisomeren, die von Formel (I) umfaßt sind, und deren Gemische. Solche Verbindungen der Formel (!) enthalten ein oder mehrere asymmetrische C-Atome oder auch Doppelbindungen, die in den allgemeinen Formeln (I) nicht gesondert angegeben sind. Die durch ihre spezifische Raumform definierten möglichen Stereoisomeren, wie Enantiomere, Diastereomere, Z- und E-Isomere sind alle von der Formel (I) umfaßt und können nach üblichen Methoden aus Gemischen der Stereoisomeren erhalten oder auch durch stereoselektive Reaktionen in Kombination mit dem Einsatz von stereochemisch reinen Ausgangsstoffen hergestellt werden.The invention also relates to all stereoisomers which are encompassed by formula (I) and mixtures thereof. Such compounds of the formula (!) Contain one or more asymmetric carbon atoms or double bonds, which in the general formulas (I) are not specified separately. The possible stereoisomers defined by their specific spatial shape, such as enantiomers, diastereomers, Z and E isomers, are all encompassed by the formula (I) and can be obtained from mixtures of the stereoisomers by customary methods or else by stereoselective reactions in combination with the use of stereochemically pure starting materials can be produced.
Die Verbindungen der Formel (I) können Salze bilden, z.B. solche bei denen das Stickstoffatom des Pyridins oder gegebenenfalls ein weiteres Heteroatom protoniert vorliegt. Diese Salze sind beispielsweise Salze von Mineralsäuren wie Salzsäure, Bromwasserstoff säure und Schwefelsäure oder auch Salze von organischen Säuren wie Ameisensäure, Essigsäure, Oxalsäure, Zitronensäure oder aromatischen Carbonsäuren wie Benzoesäuren.The compounds of formula (I) can form salts, e.g. those in which the nitrogen atom of pyridine or optionally a further heteroatom is protonated. These salts are, for example, salts of mineral acids such as hydrochloric acid, hydrobromic acid and sulfuric acid or salts of organic acids such as formic acid, acetic acid, oxalic acid, citric acid or aromatic carboxylic acids such as benzoic acids.
Bevorzugt sind Verbindungen der Formel (I) und/oder deren Salze, worinCompounds of formula (I) and / or their salts are preferred, wherein
R gleich oder verschieden H, Halogen, CN, (Cι-C8)Alkyl oder (d-Cs)Alkoxy sind, wobei jeder der letztgenannten beiden Reste unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (Cι-C8)Alkoxy und (Ci- C8)Alkylthio substituiert ist,R are identical or different H, halogen, CN, (-C-C 8 ) alkyl or (d-Cs) alkoxy, each of the latter two radicals being unsubstituted or by one or more radicals from the group halogen, CN, (-C-C 8 ) alkoxy and (Ci-C 8 ) alkylthio is substituted,
A ein Phenylrest oder ein 5- oder 6-gliedriger heterocyclischer Rest wie ein 5- oder 6-gliedriger N- oder S-enthaltender heteroaromatischer Rest ist, wobei die Reste unsubstituiert oder mit einem oder mehreren Resten aus der Gruppe Halogen, CN, (Cι-C8)Alkyl, (Cι-C8)Alkoxy, Halo(Cι-C8)Alkyl, Halo(Cι- C8)Alkyloxy, Halo(Cι-C8)Alkylthio, und (Cι-C8)Alkoxy-(Cι-C8)Alkoxy substituiert sind,A is a phenyl radical or a 5- or 6-membered heterocyclic radical such as a 5- or 6-membered N- or S-containing heteroaromatic radical, where the radicals are unsubstituted or with one or more radicals from the group halogen, CN, (Cι -C 8 ) alkyl, (-C-C 8 ) alkoxy, halo (-C-C 8 ) alkyl, halo (Cι- C 8 ) alkyloxy, halo (Cι-C 8 ) alkylthio, and (Cι-C 8 ) alkoxy- (-CC 8 ) alkoxy are substituted,
X O oder S ist,X is O or S,
R2, R3 gleich oder verschieden H oder (Cι-C8)Alkyl sind, wobei der Alkylrest unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C-ι-C8)Alkoxy und (Cι-Cs)Alkylthio substituiert ist, m = 0 ist,R 2 , R 3 are identical or different H or (-C-C 8 ) alkyl, the alkyl radical being unsubstituted or by one or more radicals from the group halogen, CN, (C-ι-C 8 ) alkoxy and (Cι-Cs ) Alkylthio is substituted, m = 0,
R6 H, Formyl, (Cι-C8)Alkyl, (C3-C8)Alkenyl, (C3-C8)Alkinyl, (Cι-C8)-Alkoxy oder [(Cι-C8)Alkyl]-carbonyl ist, wobei jeder der letztgenannten fünf Reste unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C.,-C8)Alkoxy und (C,-C8)Alkylthio substituiert ist, und B ein Acylrest ist wie [(C,-Cg)Alkyl]-carbonyl wie lineares oder verzweigtes [(C C8)-Alkyl]-carbonyl oder [(C3-C6)Cycloalkyl]-carbonyl, wobei jeder der Reste unsubstituiert oder substituiert ist, z.B. durch einen oder mehrere Reste aus der Gruppe Halogen, (C C8)Alkoxy, (C1-C8)Alkylthio, (CrC8)Alkylsulfinyl, (C.,-C8)Alkylsulfonyl, [(C C8)Alkyl]-carbonyl, [(C1-C8)Alkoxy]-carbonyl und CN substituiert ist, oder [(C2-C8)Alkenyl]-carbonyl oder [(C2-C8)Alkinyl]-carbonyl, wobei jeder der Reste unsubstituiert oder substituiert ist, z.B. durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C,-C8)Alkoxy und (C,- C8)Alkylthio substituiert ist,R 6 H, formyl, (C 1 -C 8 ) alkyl, (C 3 -C 8 ) alkenyl, (C 3 -C 8 ) alkynyl, (C 1 -C 8 ) alkoxy or [(C 1 -C 8 ) alkyl] is carbonyl, each of the latter five residues unsubstituted or substituted by one or more radicals from the group halogen, CN, (C, -. C 8) alkoxy and (C, -C8) alkylthio, and B is an acyl radical such as [(C, -CG) alkyl] carbonyl such as linear or branched [(CC 8 ) alkyl] carbonyl or [(C 3 -C 6 ) cycloalkyl] carbonyl, where each of the radicals is unsubstituted or substituted, for example by one or more radicals from the group halogen, (CC 8 ) alkoxy, (C 1 -C 8 ) alkylthio, (C r C 8 ) alkylsulfinyl, (C., - C 8 ) alkylsulfonyl, [(CC 8 ) alkyl] carbonyl, [(C 1 -C 8 ) Alkoxy] carbonyl and CN is substituted, or [(C 2 -C 8 ) alkenyl] carbonyl or [(C 2 -C 8 ) alkynyl] carbonyl, where each of the radicals is unsubstituted or substituted, for example by a or several residues from the group halogen, CN, (C, -C 8 ) alkoxy and (C, - C 8 ) alkylthio are substituted,
(C,-C8)Alkylsuifonyl, wie lineares oder verzweigtes C,-C8-Alkylsulfonyl oder (C3-C8)Cycloalkylsulfonyl, oder (C2-C8)Alkenylsulfonyl oder (C2- C8)Alkinylsulfonyl, wobei jeder der Reste unsubstituiert oder substituiert ist, z.B. durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (Cr C8)Alkoxy und (C,-C8)Alkyϊthio substituiert ist, bedeutet.(C, -C 8 ) alkylsulfonyl, such as linear or branched C, -C 8 alkylsulfonyl or (C 3 -C 8 ) cycloalkylsulfonyl, or (C 2 -C 8 ) alkenylsulfonyl or (C 2 - C 8 ) alkynylsulfonyl, where each of the radicals is unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, (C r C 8 ) alkoxy and (C, -C 8 ) alkylthio is substituted.
Besonders bevorzugt sind Verbindungen der Formel (I) und/oder deren Salze, worin R1 in 3-Position und in 5-Position des Pyridinrings gleich oder verschieden H oder Halogen, bevorzugt Fluor oder Chlor, sind, und R1 in 4-Position des Pyridinrings H, Halogen, bevorzugt Fluor oder Chlor, CN,Particularly preferred are compounds of formula (I) and / or their salts, wherein R 1 in the 3-position and in the 5-position of the pyridine ring are identical or different H or halogen, preferably fluorine or chlorine, and R 1 in the 4-position the pyridine ring H, halogen, preferably fluorine or chlorine, CN,
(C,-C8)Alkyl oder (C,-C8)Alkoxy ist, wobei jeder der letztgenannten zwei Reste unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen,Is (C, -C 8 ) alkyl or (C, -C 8 ) alkoxy, each of the latter two radicals being unsubstituted or by one or more radicals from the group halogen,
CN, (C,-C8)Alkoxy und (CrC8)Alkylthio substituiert ist, A eine Gruppe der Formel (A') ist,CN, (C, -C 8 ) alkoxy and (C r C 8 ) alkylthio is substituted, A is a group of the formula (A '),
worin R 4 gleich oder verschieden Halogen, CN, (C,-C8)Alkyi, (C,-C8)Alkoxy oder (C,- (C-ι-Cs)Alkylthio sind, wobei jeder der letztgenannten drei Reste unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (Cι-C8)Alkoxy und (C-i- C8)Alkylthio substituiert ist, z.B. (Cι-C8)Haloalkyl, (Cι-Cs)Haloalkyloxy, (Ci- C8)Haloalkylthio oder (Cι-C8)Alkoxy(Cι-C8)alkyloxy, I 1 oder 2 ist,wherein R 4 is the same or different halogen, CN, (C, -C 8 ) alkyl, (C, -C 8 ) alkoxy or (C, - (C-ι-Cs) are alkylthio, where each of the latter three radicals is unsubstituted or substituted by one or more radicals from the group halogen, CN, (Cι-C 8 ) alkoxy and (Ci-C 8 ) alkylthio, for example ( C 1 -C 8 ) haloalkyl, (C 1 -C 8 ) haloalkyloxy, (C 1 -C 8 ) haloalkylthio or (C 1 -C 8 ) alkoxy (C 1 -C 8 ) alkyloxy, I is 1 or 2,
V CH, C(R14) oder N(Cι-Cβ-Alkyl) wie N(CH3) ist, W N, S, N-CH, N-C(R14), CH-CH, CH-C(R14) oder C(R14)-C(R14) ist, R2, R3 gleich oder verschieden H oder (Cι-C8)Alkyl sind, welches unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (Cι-Cβ)Alkoxy und (Cι-Cβ)Alkylthio substituiert ist, m = 0 ist,V is CH, C (R 14 ) or N (-CC-alkyl) such as N (CH 3 ), WN, S, N-CH, NC (R 14 ), CH-CH, CH-C (R 14 ) or C (R 14 ) -C (R 14 ), R 2 , R 3 are identical or different H or (-C-C 8 ) alkyl, which is unsubstituted or by one or more radicals from the group halogen, CN, (Cι -Cβ) alkoxy and (-C-Cβ) alkylthio is substituted, m = 0,
R6 H oder (Cι-C4)Alkyl ist, welches unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C-ι-Cs)Alkoxy und (Cι-Cs)Alkylthio substituiert ist, und B ein Acylrest ist wie [(Cι-C8)Alkyl]-carbonyl wie lineares oder verzweigtes [(Cι- C8)-Alkyl]-carbonyl oder [(C3-C6)Cycloalkyl]-carbonyl, wobei jeder der Reste unsubstituiert oder substituiert ist, z.B. durch einen oder mehrere Reste aus der Gruppe Halogen, (CrC8)Alkoxy, (Cι-C8)Alkylthio, (Cι-Cs)Alkylsulfinyl, (Cι-Cs)Alkylsulfonyl, [(Cι-C8)Alkyl]-carbonyl, [(Cι-C8)Alkoxy]-carbonyl und CN substituiert ist, oder [(C2-C8)Alkenyl]-carbonyl oder [(C2-C8)Alkinyl]-carbonyl, wobei jeder der Reste unsubstituiert oder substituiert ist, z.B. durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (Cι-C8)Alkoxy und (C-i- C8)Alkylthio substituiert ist,R 6 is H or (-C-C 4 ) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, CN, (C-ι-Cs) alkoxy and (Cι-Cs) alkylthio, and B is an acyl radical is like [(C 1 -C 8 ) alkyl] carbonyl such as linear or branched [(C 1 -C 8 ) alkyl] carbonyl or [(C3-C6) cycloalkyl] carbonyl, each of the radicals being unsubstituted or substituted, for example by one or more radicals from the group halogen, (CrC 8 ) alkoxy, (Cι-C 8 ) alkylthio, (Cι-Cs) alkylsulfinyl, (Cι-Cs) alkylsulfonyl, [(Cι-C 8 ) alkyl] carbonyl , [(-C-C 8 ) alkoxy] carbonyl and CN is substituted, or [(C 2 -C 8 ) alkenyl] carbonyl or [(C2-C 8 ) alkynyl] carbonyl, each of the radicals being unsubstituted or substituted is, for example, substituted by one or more radicals from the group halogen, CN, (C 1 -C 8 ) alkoxy and (C 1 -C 8 ) alkylthio,
(Cι-C8)Alkylsulfonyl, wie lineares oder verzweigtes Cι-C8-Alkylsulfonyl oder (C3-C8)Cycloalkylsulfonyl, oder (C2-C8)Alkenylsulfonyl oder (C2- C8)Alkinylsulfonyl, wobei jeder der Reste unsubstituiert oder substituiert ist, z.B. durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (Ci- C8)Alkoxy und (Cι-Cs)Alkylthio substituiert ist, bedeutet.(-C-C 8 ) alkylsulfonyl, such as linear or branched Cι-C 8 alkylsulfonyl or (C3-C 8 ) cycloalkylsulfonyl, or (C2-C 8 ) alkenylsulfonyl or (C 2 - C 8 ) alkynylsulfonyl, each of the radicals being unsubstituted or substituted, for example (8 Ci- C) alkoxy and (Cι-Cs) alkylthio substituted by one or more radicals from the group halogen, CN, means.
Von besonderem Interesse sind erfindungsgemäße Verbindungen der Formel (I) und/oder deren Salze, worinOf particular interest are compounds of formula (I) according to the invention and / or their salts, in which
A ein Phenyl-, Pyridyl-, Pyrazolyl- oder Thienylrest bedeutet, der über ein Kohlenstoffatom an X gebunden ist und unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, CN, (C1-C8)Alkyl, (C,-C8)Alkoxy, (C C8)Haloalkyl, (CrC8)Haloalkylthio, (CrC8)Haloalkyloxy und (Cr C8)Alkoxyalkyloxy substituiert ist. Bevorzugt sind solche Reste A, bei denen sich ein Substituent R14 in 3-Position des Restes A, bezogen auf das Kohlenstoffatom, welches an die Gruppe X in der Formel (I) gebunden ist, befindet.A is a phenyl, pyridyl, pyrazolyl or thienyl radical which has a Carbon atom is bound to X and is unsubstituted or by one or more radicals from the group halogen, CN, (C 1 -C 8 ) alkyl, (C, -C 8 ) alkoxy, (CC 8 ) haloalkyl, (C r C 8 ) Haloalkylthio, (C r C 8 ) haloalkyloxy and (C r C 8 ) alkoxyalkyloxy is substituted. Preferred radicals A are those in which a substituent R 14 is in the 3-position of the radical A, based on the carbon atom which is bonded to the group X in the formula (I).
Besonders bevorzugt sind Verbindungen der Formel (I) und/oder deren Salze, worin A einen substituierten Phenyl-, Pyridyl-, Thienyl- oder Pyrazolylrest der folgenden Formel darstellt,Compounds of the formula (I) and / or their salts are particularly preferred, in which A represents a substituted phenyl, pyridyl, thienyl or pyrazolyl radical of the following formula,
worin wherein
R14 gleich oder verschieden Halogen, Cyano oder eine optional substituierte (C,-R 14, identical or different, halogen, cyano or an optionally substituted (C, -
C8)Alkylgruppe, wie (C1-C8)Haloalkyl, vorzugsweise CF3 oder Cyano sind, R15 eine (C1-C8)Alkylgruppe, vorzugsweise Methyl ist, und I' eine ganze Zahl von 0 bis 4 ist, bevorzugt 0 oder 1 ; vorzugsweise ist AC 8 ) alkyl group, such as (C 1 -C 8 ) haloalkyl, preferably CF 3 or cyano, R 15 is a (C 1 -C 8 ) alkyl group, preferably methyl, and I 'is an integer from 0 to 4, preferably 0 or 1; preferably A is
Ganz besonders bevorzugt sind Verbindungen der Formel (I') und/oder deren Salze, Compounds of the formula (I ') and / or their salts are very particularly preferred,
worin R\ R2, R3, R6, R14 und X die in Formel (I) angegebene Bedeutung, inklusive der oben angegebenen Vorzugsbereiche, haben, wherein R 2 , R 3 , R 6 , R 14 and X have the meaning given in formula (I), including the preferred ranges given above,
L gleich oder verschieden H oder Halogen wie Fluor oder Chlor bedeuten, W-V zusammen N-CH-CH, S-CH, CH-CH-CH oder N-N(CH3) bedeuten, und B einen Acylrest wie [(C.,-C8)Alkyl]-carbonyl wie lineares oder verzweigtes [(C,- C8)-Alkyl]-carbonyl oder [(C3-C6)Cycloalkyl]-carbonyl, oder (C . C8)Alkylsulfonyl, wie lineares oder verzweigtes oder (C3- C8)Cycloaikylsulfonyl, bedeutet, wobei jeder der Reste unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, insbesondere Fluor oder Chlor, CN, (CrC8)-Alkoxy und (C.,-Cβ)Alkylthio substituiert ist.L are identical or different to H or halogen such as fluorine or chlorine, WV together are N-CH-CH, S-CH, CH-CH-CH or NN (CH 3 ), and B is an acyl radical such as [(C., - C 8 ) alkyl] carbonyl such as linear or branched [(C, -C 8 ) alkyl] carbonyl or [(C 3 -C 6 ) cycloalkyl] carbonyl, or (C. C 8 ) alkylsulfonyl, such as linear or branched or (C 3 - C 8 ) cycloaikylsulfonyl, where each of the radicals is unsubstituted or by one or more radicals from the group halogen, in particular fluorine or chlorine, CN, (C r C 8 ) alkoxy and (C., - Cβ ) Alkylthio is substituted.
Die erfindungsgemäßen Verbindungen der Formel (I) können über bekannte Methoden dargestellt werden. Von besonderem Interesse sind z.B. folgende Synthesen:The compounds of formula (I) according to the invention can be prepared by known methods. Of particular interest are e.g. following syntheses:
Ausgehend von Verbindungen der Formel (II),Starting from compounds of the formula (II),
worin die Reste R1 die in Formel (I) angegebene Bedeutung haben und L' eine Abgangsgruppe wie Halogen oder Pseudohalogen oder eine Gruppe der Formel A- X- ist, wobei A und X wie in Formel (I) definiert sind, kann auf literaturbekanntem Weg zunächst der Sauerstoff des N-Oxids alkyliert und anschließend mit Cyaniden, zu Nitriten der allgemeinen Formel (III) umgesetzt werden (siehe z.B. W.R. Fife und E.F.V. Seriven, Heterocycles 22, 2375 (1984) und dort zitierte Literatur),wherein the radicals R 1 have the meaning given in formula (I) and L 'is a leaving group such as halogen or pseudohalogen or a group of the formula A-X-, where A and X are as defined in formula (I), can be known from the literature First, the oxygen of the N-oxide is alkylated and then reacted with cyanides to nitrites of the general formula (III) (see, for example, WR Fife and EFV Seriven, Heterocycles 22, 2375 (1984) and the literature cited therein),
worin R1 und L' wie in Formel (II) definiert sind. wherein R 1 and L 'are as defined in formula (II).
Pyridin-N-oxide der allgemeinen Formel (II) können nach verschiedenen Verfahren aus geeignet substituierten Pyridinen hergestellt werden. Generelle Syntheseverfahren sind z.B. beschrieben in A. Albini u. S. Pietra, Heterocyclic N- Oxides, CRS-Press, Inc., Boca Raton, USA, 1991.Pyridine-N-oxides of the general formula (II) can be prepared from suitably substituted pyridines by various processes. General synthetic methods are e.g. described in A. Albini et al. S. Pietra, Heterocyclic N-Oxides, CRS-Press, Inc., Boca Raton, USA, 1991.
Als Alkylierungsmittel für Verbindungen der Formel (II) können vorzugsweise Alkylhalogene oder Alkylpseudohalogene wie Dimethylsulfat oder Methyliodid verwendet werden, als Cyanide werden z.B. Alkali- oder Erdalkalicyanide oder Cyanide von organischen Basen wie quartemären Ammoniumsalzen eingesetzt (siehe z.B. Ellman, Tetrahedron 41 (1985) S. 4941 - 4948).Alkyl halogens or alkyl pseudohalogens such as dimethyl sulfate or methyl iodide can preferably be used as alkylating agents for compounds of the formula (II). Alkali or alkaline earth metal cyanides or cyanides of organic bases such as quaternary ammonium salts are used (see e.g. Ellman, Tetrahedron 41 (1985) pp. 4941-4948).
Verbindungen der Formel (III), worin U eine Abgangsgruppe wie Halogen oder Pseudohalogen bedeutet, können mit Verbindungen der Formel (IV) oder deren SalzenCompounds of the formula (III), in which U denotes a leaving group such as halogen or pseudohalogen, can be reacted with compounds of the formula (IV) or their salts
A-X-H (IV)A-X-H (IV)
wobei A und X wie in Formel (I) definiert sind, zu Verbindungen der Formel (III) umgesetzt werden (siehe z.B. US 6,080,861 , US 6,130,188 und WO 94/22833 und darin zitierte Literatur), worin L' eine Gruppe der Formel A - X - bedeutet. Die Verbindungen der allgemeinen Formel (III), bei denen L1 eine Gruppe A - X - bedeutet, worin A, X und R1 wie in Formel (I) definiert sind, können durch geeignete Reduktionsverfahren in die Aminoverbindungen der allgemeinen Formel (V) überführt werden.where A and X are as defined in formula (I), are converted into compounds of the formula (III) (see, for example, US 6,080,861, US 6,130,188 and WO 94/22833 and the literature cited therein), in which L 'is a group of the formula A - X - means. The compounds of the general formula (III) in which L 1 denotes a group A - X -, in which A, X and R 1 are as defined in formula (I), can be converted into the amino compounds of the general formula (V) by suitable reduction processes be transferred.
Die Reduktion von Nitrilen zu Aminen ist in der Literatur vielfältig beschrieben (siehe z.B. Eugen Müller, Methoden der organischen Chemie (Houben-Weyl) Band XI/1 , Stickstoffverbindungen II, S. 343 ff., Georg Thieme Verlag, Stuttgart 1957). Unter anderem kommen edelmetallkatalysierte Hydrierungen in Betracht, wobei Palladium und Platin katalysierte Reaktionen von besonderem Interesse sind aber auch Reduktionen mit Raney-Nickel möglich sind. The reduction of nitriles to amines has been widely described in the literature (see, for example, Eugen Müller, Methods of Organic Chemistry (Houben-Weyl) Volume XI / 1, Nitrogen Compounds II, p. 343 ff., Georg Thieme Verlag, Stuttgart 1957). Among other things, noble metal-catalyzed hydrogenations are possible, palladium and platinum-catalyzed reactions being of particular interest, but reductions with Raney nickel are also possible.
Verbindungen der allgemeinen Formel (V) können durch Umsetzung mit Acylierungsreagentien wie Säurehalogenide, Isocyanate, Carbamoylchloride, Chlorameisensäureestern, Sulfonylchloride, Sulfamoylchloride, Sulfenylchloriden, Isothiocyanaten zu Verbindungen der allgemeinen Formel (I) umgesetzt werden, worin R6 = H, m = 0 und A, X, R1, R2, R3, B die in Formel (I) angegebene Bedeutung haben. Ein Zugang zu allgemeinen und speziellen chemischen Methoden der Acylierungen findet sich z.B. in: Jerry March, Advanced Organic Chemistry (Reaction, Mechanisms and Structure 4th Edition, John Wiley & Sons, New York, 1992).Compounds of the general formula (V) can be converted into compounds of the general formula (I) by reaction with acylating reagents such as acid halides, isocyanates, carbamoyl chlorides, chloroformic acid esters, sulfonyl chlorides, sulfamoyl chlorides, sulfenyl chlorides, isothiocyanates, in which R 6 = H, m = 0 and A , X, R 1 , R 2 , R 3 , B have the meaning given in formula (I). Access to general and special chemical methods of acylation found for example in Jerry March, Advanced Organic Chemistry (Reaction, Mechanisms and Structure 4 th Edition, John Wiley & Sons, New York, 1992).
Die Verbindungen der allgemeinen Formel (I), bei denen R6 z.B. eine gegebenenfalls substituierte Alkylgruppe bedeutet, sind ausgehend von Verbindungen der allgemeinen Formel (V) zugänglich, die mit entsprechenden Aldehyden durch reduktive Alkylierung zu Verbindungen der allgemeinen Formel (VI) alkyliert werden (Lit: Rylander Hydrogenation Methode, Academic Press, New York, 1985 pp. 92 - 93).The compounds of the general formula (I) in which R 6 is, for example, an optionally substituted alkyl group are accessible starting from compounds of the general formula (V) which are alkylated with corresponding aldehydes by reductive alkylation to give compounds of the general formula (VI) ( Lit: Rylander Hydrogenation Method, Academic Press, New York, 1985 pp. 92-93).
Verbindungen der Formel (VI) sind auch durch Reduktion der entsprechenden Amide (siehe z.B. Ausführungsbeispiel 3a) erhältlich (siehe z.B. Gaylord, Reduction with Complex Metal Hydrides, Wiley, New York 1956, pp; 322 - 373). Geeignet hierzu sind z.B. Boran-Komplexe wie Boran-Tetrahydrofuran-Komplexe oder Borandimethylsulfid-Komplexe (siehe z.B. Brown G. R, A. J. Foubister, J. Chem SOC Per T 1 (8), 1401 - 1403 (1989)). Die Verbindungen der Formel (VI) können anschließend nach bekannten Methoden acyliert werden. Verbindungen der Formel (VI) mit R6 = optional substituiertes Alkenyl oder Alkinyl sind durch reduktive Aminierung aus Verbindungen der Formel (III) erhältlich. Die Verbindungen der Formel (VI) können anschließend nach bekannten Methoden zu Verbindungen der Formel (I) acyliert werden. Verbindungen der Formel (I) mit R6 = Acyl sind z.B. nach bekannten Methoden erhältlich durch geeignete N-Acylierung von Verbindungen der Formel (VI), bei denen R6 = H bedeutet.Compounds of the formula (VI) can also be obtained by reducing the corresponding amides (see, for example, embodiment 3a) (see, for example, Gaylord, Reduction with Complex Metal Hydrides, Wiley, New York 1956, pp; 322-373). Suitable Examples include borane complexes such as borane-tetrahydrofuran complexes or borane dimethyl sulfide complexes (see, for example, Brown G. R, AJ Foubister, J. Chem SOC Per T 1 (8), 1401-1403 (1989)). The compounds of formula (VI) can then be acylated by known methods. Compounds of the formula (VI) with R 6 = optionally substituted alkenyl or alkynyl can be obtained from compounds of the formula (III) by reductive amination. The compounds of the formula (VI) can then be acylated by known methods to give compounds of the formula (I). Compounds of the formula (I) with R 6 = acyl can be obtained, for example, by known methods by suitable N-acylation of compounds of the formula (VI) in which R 6 = H.
Verbindungen der Formel (I) mit R6 = Hydroxy und Alkoxy sind beispielsweise nach folgendem Reaktionsschema erhältlich:Compounds of the formula (I) with R 6 = hydroxy and alkoxy can be obtained, for example, according to the following reaction scheme:
Reduktionreduction
Nitrile der allgemeinen Formel (III) können dabei reduktiv in Aldehyde der allgemeinen Formel (XII) überführt werden, (siehe z.B. Miller, Biss, Schwartzmann; J. Org. Chem. 1970, 35, 858; oder Jerry March, Advanced Organic Chemistry (Reaction, Mechanisms and Structure) 4th Edition, John Wiley & Sons, New York, 1992, S. 919, 920.) Die Aldehyde der allgemeinen Formel (XII) können nach bekannten Verfahren zu den entsprechenden Alkoholen der allgemeinen Formel (XIII) reduziert werden (siehe z.B. Hudlicky, Reductions in Organic Chemistry; Ellis Horwood; Chichester 1984 S. 96-129. Liste möglicher Reagentien siehe Larock ; Comprehensive Organic Transformations VCH: New York, 1989, S. 993.) Die Hydroxylgruppen der Alkohole der Formel (XIII) können dann in Abgangsgruppen L' überführt werden. Als Abgangsgruppe können z.B. Halogene wie Chlor oder Brom (siehe z.B. Wiley, Hershkowitz, Rein Chung, J. Am. Chem.Soc 1964, 86, 964 ; Schaefer, Weinberg J.Org. Chem. 1965, 30, 2635) oder Sulfonsäureestergruppen wie Tosylate oder Mesylate (siehe z.B. Crossland, Wells, Shiner; J. Am. Chem. Soc. 1971 ,93, 4217) eingeführt werden. Die Verbindungen der allgemeinen Formel (XIV) können dann mit Hydroxylaminen oder mit O-alkylierten Hydroxylaminen zu Verbindungen der allgemeinen Formel (VI) bei denen R6 = Hydroxy oder Alkoxy bedeutet, umgesetzt werden. Diese Reaktionen werden bevorzugt in Anwesenheit von organischen oder anorganischen Basen in einem inerten Lösemittel durchgeführt. Die Verbindungen der allgemeinen Formel (VI), bei denen R6 verschieden von H ist, und m = 0 bedeuten, können dann, wie oben für Verbindungen der Formel (V) angegeben nach bekannten Methoden zu Verbindungen der Formel (I) acyliert werden.Nitriles of the general formula (III) can be reductively converted into aldehydes of the general formula (XII) (see, for example, Miller, Biss, Schwartzmann; J. Org. Chem. 1970, 35, 858; or Jerry March, Advanced Organic Chemistry ( Reaction Mechanisms and Structure) 4 th Edition, John Wiley & Sons, New York, 1992, pp 919, 920.) the aldehydes of general formula (XII) may be reduced by known methods to the corresponding alcohols of the general formula (XIII) (see e.g. Hudlicky, Reductions in Organic Chemistry; Ellis Horwood; Chichester 1984 pp. 96-129. For a list of possible reagents see Larock; Comprehensive Organic Transformations VCH: New York, 1989, p. 993.) Die Hydroxyl groups of the alcohols of the formula (XIII) can then be converted into leaving groups L '. Halogens such as chlorine or bromine (see, for example, Wiley, Hershkowitz, Rein Chung, J. Am. Chem. Soc 1964, 86, 964; Schaefer, Weinberg J. Org. Chem. 1965, 30, 2635) or sulfonic acid ester groups such as Tosylates or mesylates (see eg Crossland, Wells, Shiner; J. Am. Chem. Soc. 1971, 93, 4217) are introduced. The compounds of the general formula (XIV) can then be reacted with hydroxylamines or with O-alkylated hydroxylamines to give compounds of the general formula (VI) in which R 6 = hydroxy or alkoxy. These reactions are preferably carried out in the presence of organic or inorganic bases in an inert solvent. The compounds of the general formula (VI) in which R 6 is different from H and m = 0 can then, as indicated above for compounds of the formula (V), be acylated by known methods to give compounds of the formula (I).
Verbindungen der allgemeinen Formel (I), bei denen m = 1 bedeutet, können z.B. wie nachfolgend beschrieben hergestellt werden:Compounds of the general formula (I) in which m = 1 can e.g. as described below:
Verseifungsaponification
Decarboxylierung decarboxylation
Acylierungacylation
Verbindungen der Formel (VII), bei denen A, X und R1 wie in Formel (I) definiert sind und L' eine Abgangsgruppe wie Halogen oder Pseudohalogen ist, oder eine substituierbare Heteroaryloxygruppe A - X ist, können mit gegebenenfalls substituierten Cyanessigsäurealkylestern der allgemeinen Formel (VIII) umgesetzt werden, wobei R2 wie in Formel (I) definiert ist und vorzugsweise (CrC6) Alkyl-Ester eingesetzt werden (Lit: N. Desideri; F. Manna, J. Heterocycl. Chem., 25 (1), 333 - 335, 1988). Compounds of formula (VII) in which A, X and R 1 are as defined in formula (I) and L 'is a leaving group such as halogen or pseudohalogen or is a substitutable heteroaryloxy group A - X can be substituted with optionally substituted alkyl cyanoacetates of the general Formula (VIII) are implemented, wherein R 2 is as defined in formula (I) and preferably (C r C 6 ) alkyl esters are used (Lit: N. Desideri; F. Manna, J. Heterocycl. Chem., 25 (1), 333-335, 1988).
Die Estergruppen der Verbindungen der Formel (IX) können anschließend in die freien Carbonsäuren überführt werden. Dies kann z.B. durch basische Verseifung der Alkylester geschehen oder auch unter sauren Verseifungsbedingungen durchgeführt werden, wobei die Carbonsäuregruppe anschließend unter z.B. sauren Bedingungen zu Verbindungen der allgemeinen Formel (X) decarboxyliert (Lit.: N. Desideri; F. Manna, J. Heterocycl. Chem., 25 (1), 333 - 335, 1988). In Formel (X) haben A, X, R1 und R2 die in Formel (I) angegebene Bedeutung.The ester groups of the compounds of formula (IX) can then be converted into the free carboxylic acids. This can be done, for example, by basic saponification of the alkyl esters or can also be carried out under acidic saponification conditions, the carboxylic acid group then decarboxylating under, for example, acidic conditions to give compounds of the general formula (X) (Lit .: N. Desideri; F. Manna, J. Heterocycl. Chem., 25 (1), 333-335, 1988). In formula (X), A, X, R 1 and R 2 have the meaning given in formula (I).
Die so zugänglichen Cyanoverbindungen der allgemeinen Formel (X) können durch geeignete Reduktionsverfahren, wie sie bereits bei der Darstellung der Amine der Formel (V) aus den Nitrilen der allgemeinen Formel (III) beschrieben wurde, in die entsprechenden Aminoverbindungen der allgemeinen Formel (XI) umgesetzt werden. Die so zugänglichen Amine der allgemeinen Formel (XI) können analog zu den Aminen der allgemeinen Formel (V) zu Verbindungen der Formel (I) umgesetzt werden, worin A, X, R\ R2, R6 und B die in Formel (I) angegebene Bedeutung haben.The cyano compounds of the general formula (X) which are accessible in this way can be converted into the corresponding amino compounds of the general formula (XI) by suitable reduction processes, as has already been described in the preparation of the amines of the formula (V) from the nitriles of the general formula (III) be implemented. The amines of the general formula (XI) which are accessible in this way can be reacted analogously to the amines of the general formula (V) to give compounds of the formula (I) in which A, X, R 2 , R 6 and B correspond to those in formula (I ) have the meaning given.
Kollektionen aus Verbindungen der Formel (I) und deren Salzen, die nach oben genannten Schemata synthetisiert werden können, können auch in parallelisierter Weise hergestellt werden, wobei dies ip manueller, teilweise automatisierter oder vollständig automatisierter Weise geschehen kann. Dabei ist es beispielsweise möglich, die Reaktionsdurchführung, die Aufarbeitung oder die Reinigung der Produkte bzw. Zwischenstufen zu automatisieren. Insgesamt wird hierunter eine Vorgehensweise verstanden, wie sie beispielsweise durch S.H. DeWitt in "Annual Reports in Combinatorial Chemistry and Molecular Diversity: Automated Synthesis", Band 1 , Verlag Escom 1997, Seite 69 bis 77 beschrieben ist.Collections of compounds of formula (I) and their salts, which can be synthesized according to the above-mentioned schemes, can also be produced in a parallelized manner, which can be done ip manually, partially automated or fully automated. It is possible, for example, to automate the reaction, the work-up or the cleaning of the products or intermediate stages. Overall, this is understood to mean a procedure such as that described by SH DeWitt in "Annual Reports in Combinatorial Chemistry and Molecular Diversity: Automated Synthesis ", Volume 1, Publisher Escom 1997, pages 69 to 77.
Zur parallelisierten Reaktionsdurchführung und Aufarbeitung können eine Reihe von im Handel erhältlichen Geräten verwendet werden, wie sie beispielsweise von den Firmen Stern Corporation, Woodrolfe road, Tollesbury, Essex, England, H+P Labortechnik GmbH, Bruckmannring 28, 85764 Oberschleißheim, Deutschland oder der Firma Radleys, Shirehill, Saffron Waiden, Essex, CB - ll:3AZ, England angeboten werden. Für die parallelisierte Aufreinigung von Verbindungen der allgemeinen Formel (l) und deren Salze beziehungsweise von bei der Herstellung anfallenden Zwischenprodukten stehen unter anderemA number of commercially available devices can be used for the parallel reaction and processing, for example from the companies Stern Corporation, Woodrolfe road, Tollesbury, Essex, England, H + P Labortechnik GmbH, Bruckmannring 28, 85764 Oberschleissheim, Germany or the company Radleys, Shirehill, Saffron Waiden, Essex, CB-ll: 3AZ, England. The parallelized purification of compounds of the general formula (I) and their salts or of intermediates obtained in the preparation are, inter alia
Chromatographieapparaturen zur Verfügung, beispielsweise der Firma ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.Chromatography apparatuses are available, for example from ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.
Die aufgeführten Apparaturen führen zu einer modularen Vorgehensweise, bei der die einzelnen Arbeitsschritte automatisiert sind, zwischen den Arbeitsschritten jedoch manuelle Operationen durchgeführt werden müssen. Dies kann durch den Einsatz von teilweise oder vollständige integrierten Automationssystemen umgangen werden, bei denen die jeweiligen Automationsmodule beispielsweise durch Roboter bedient werden. Derartige Automationssysteme können zum Beispiel von der Firma Zymark Corporation, Zymark Center, Hopkinton, MA 01748, USA bezogen werden.The equipment listed leads to a modular procedure in which the individual work steps are automated, but manual operations must be carried out between the work steps. This can be avoided by using partially or completely integrated automation systems in which the respective automation modules are operated, for example, by robots. Automation systems of this type can be obtained, for example, from Zymark Corporation, Zymark Center, Hopkinton, MA 01748, USA.
Neben den hier beschriebenen kann die Herstellung von Verbindungen der allgemeinen Formel (!) und deren Salze vollständig oder partiell durch Festphasen unterstützte Methoden erfolgen. Zu diesem Zweck werden einzelne Zwischenstufen oder alle Zwischenstufen der Synthese. oder einer für die entsprechende Vorgehensweise angepaßten Synthese an,ein Syntheseharz gebunden. Festphasen- unterstützte -Synthesemethoden sind in der Fachliteratur hinreichend beschrieben, z.B. Barry A. Bunin in "The Combinatorial Index", Verlag Academic Press, 1998. Die Verwendung von Festphasen- unterstützten -Synthesemethoden erlaubt eine Reihe von literaturbekannten Protokollen, die wiederum manuell oder automatisiert ausgeführt werden können. Zum Beispiel kann die "Teebeutelmethode" (Houghten, US 4,631 ,211; Houghten et al., Proc. Natl. Acad. Sei, 1985, 82, 5131-5135) mit Produkten der Firma IRORI, 11149 North Torrey Pines Road, La Jolla, CA 92037, USA teilweise automatisiert werden. Die Automatisierung von Festphasen unterstützten Parallelsynthesen gelingt beispielsweise durch Apparaturen der Firmen Argonaut Technologies, Inc., 887 Industrial Road, San Carlos, CA 94070, USA oder MultiSynTech GmbH, Wullener Feld 4, 58454 Witten, Deutschland. Die Herstellung gemäß der hier beschriebenen Verfahren liefert Verbindungen der Formel (I) und deren Salze in Form von Substanzkollektionen, die Bibliotheken genannt werden. Gegenstand der vorliegenden Erfindung sind auch Bibliotheken, die mindestens zwei Verbindungen der Formel (I) und deren Salze enthalten.In addition to those described here, compounds of the general formula (!) And their salts can be prepared completely or partially by methods supported by solid phases. For this purpose, individual intermediates or all intermediates of the synthesis. or a synthesis adapted for the corresponding procedure, bound to a synthetic resin. Solid-phase-assisted synthesis methods are adequately described in the specialist literature, for example Barry A. Bunin in "The Combinatorial Index", published by Academic Press, 1998. The use of solid-phase-assisted synthesis methods allows a number of protocols known from the literature, which in turn can be carried out manually or automatically. For example, the "teabag method" (Houghten, US 4,631,211; Houghten et al., Proc. Natl. Acad. Sei, 1985, 82, 5131-5135) can be used with products from IRORI, 11149 North Torrey Pines Road, La Jolla , CA 92037, USA are partially automated. The automation of solid-phase-supported parallel syntheses is possible, for example, using apparatus from Argonaut Technologies, Inc., 887 Industrial Road, San Carlos, CA 94070, USA or MultiSynTech GmbH, Wullener Feld 4, 58454 Witten, Germany. The preparation according to the processes described here provides compounds of the formula (I) and their salts in the form of substance collections which are called libraries. The present invention also relates to libraries which contain at least two compounds of the formula (I) and their salts.
Die erfindungsgemäßen Verbindungen der Formel (I) und deren Salze, im folgenden zusammen als (erfindungsgemäße) Verbindungen der Formel (I) bezeichnet, weisen eine ausgezeichnete herbizide Wirksamkeit gegen ein breites Spektrum wirtschaftlich wichtiger mono- und dikotyler Schadpflanzen auf. Auch schwer bekämpfbare perennierende Unkräuter, die aus Rhizomen, Wurzelstöcken oder anderen Dauerorganen austreiben, werden durch die erfindungsgemäßen Verbindungen gut erfaßt. Dabei können die erfindungsgemäßen Verbindungen z.B. im Vorsaat-, Vorauflauf- oder Nachauflaufverfahren ausgebracht werden. Im einzelnen seien beispielhaft einige Vertreter der mono- und dikotylen Unkrautflora genannt, die durch die erfindungsgemäßen Verbindungen kontrolliert werden können, ohne daß durch die Nennung eine Beschränkung auf bestimmte Arten erfolgen soll.The compounds of the formula (I) according to the invention and their salts, hereinafter referred to collectively as (compounds) of the formula (I) according to the invention, have excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants. Perennial weeds which are difficult to control and which sprout from rhizomes, rhizomes or other permanent organs are also well covered by the compounds according to the invention. The compounds of the invention can e.g. are applied in the pre-sowing, pre-emergence or post-emergence process. Some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned in detail, which can be controlled by the compounds according to the invention without the name being intended to restrict them to certain species.
Auf der Seite der monokotylen Unkrautarten werden z.B. Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria sowie Bromusarten und Cyperusarten aus der annuellen Gruppe und auf Seiten der perennierenden Spezies Agropyron, Cynodoη, Imperata sowie Sorghum und auch ausdauernde Cyperusarten gut erfaßt. Bei dikotylen Unkrautarten erstreckt sich das Wirkungsspektrum auf Arten wie z.B. Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon und Sida auf der annuellen Seite sowie Convolvulus, Cirsium, Rumex und Artemisia bei den perennierenden Unkräutern. Unter den spezifischen Kulturbedingungen im Reis vorkommende Schadpflanzen wie z.B. Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus und Cyperus werden von den erfindungsgemäßen Verbindungen ebenfalls hervorragend bekämpft.On the monocotyledon weed species, for example, Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria as well as Bromus and Cyperus species from the annual group and on the part of the perennial species Agropyron, Cynodoη, Imperata and Sorghum as well as perennial Cyperus species are well recorded. In the case of dicotyledon weed species, the spectrum of action extends to species such as Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida on the annual side as well as Convolvulus, Cirsium, Rumex and Artemisia for the perennial weeds. Harmful plants occurring in the rice under the specific culture conditions, such as, for example, Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus, are also superbly controlled by the compounds according to the invention.
Werden die erfindungsgemäßen Verbindungen vor dem Keimen auf die Erdoberfläche appliziert, so wird entweder das Auflaufen der Unkrautkeimlinge vollständig verhindert oder die Unkräuterwachsen bis zum Keimblattstadium heran, stellen jedoch dann ihr Wachstum ein und sterben schließlich nach Ablauf von drei bis vier Wochen vollkommen ab.If the compounds according to the invention are applied to the surface of the earth before germination, either the weed seedlings emerge completely or the weeds grow to the cotyledon stage, but then stop growing and finally die completely after three to four weeks.
Bei Applikation der erfindungsgemäßen Verbindungen auf die grünen Pflanzenteile im Nachauflaufverfahren tritt ebenfalls sehr rasch nach der Behandlung ein drastischer Wachstumsstop ein und die Unkrautpflanzen bleiben in dem zum Applikationszeitpunkt vorhandenen Wachstumsstadium stehen oder sterben nach einer gewissen Zeit ganz ab, so daß auf diese Weise eine für die Kulturpflanzen schädliche Unkrautkonkurrenz sehr früh und nachhaltig beseitigt wird.When the compounds according to the invention are applied to the green parts of the plants in the post-emergence process, there is also a drastic growth stop very quickly after the treatment and the weed plants remain in the growth stage present at the time of application or die completely after a certain time, so that one for them Crops harmful weed competition is eliminated very early and sustainably.
Obgleich die erfindungsgemäßen Verbindungen eine ausgezeichnete herbizide Aktivität gegenüber mono- und dikotylen Unkräutern aufweisen, werden Kulturpflanzen wirtschaftlich bedeutender Kulturen z.B. zweikeimblättriger Kulturen wie Soja, Baumwolle, Raps, Zuckerrüben, insbesondere Soja, oder Gramineen- Kulturen wie Weizen, Gerste, Roggen, Reis oder Mais, nur unwesentlich oder gar nicht geschädigt. Die vorliegenden Verbindungen- eignen sich aus diesen Gründen sehr gut zur selektiven Bekämpfung von unerwünschtem Pflanzenwuchs in landwirtschaftlichen Nutzpflanzungen oder in Zierpflanzungen.Although the compounds of the invention have excellent herbicidal activity against mono- and dicotyledon weeds, crops of economically important crops e.g. dicotyledonous crops such as soybeans, cotton, rapeseed, sugar beet, especially soybeans, or Gramineae crops such as wheat, barley, rye, rice or maize, only slightly or not at all damaged. For these reasons, the present compounds are very suitable for the selective control of undesired plant growth in agricultural crops or in ornamental crops.
Darüberhinaus weisen die erfindungsgemäßen Verbindungen hervorragende wachstumsregulatorische Eigenschaften bei Kultu pflanzen auf. Sie greifen regulierend in den pflanzeneigenen Stoffwechsel ein und können damit zur gezielten Beeinflussung von Pflanzeninhaltsstoffen und zur Ernteerleichterung wie z.B. durch Auslösen von Desikkation und Wuchsstauchung eingesetzt werden. Desweiteren eignen sie sich auch zur generellen Steuerung und Hemmung von unerwünschtem vegetativen Wachstum, ohne dabei die Pflanzen abzutöten. Eine Hemmung des vegetativen Wachstums spielt bei vielen mono- und dikotylen Kulturen eine große Rolle, da die Lagerbarkeit hierdurch verringert oder völlig verhindert werden kann. Aufgrund ihrer herbiziden und pflanzenwachstumsregulatorischen Eigenschaften können die Wirkstoffe auch zur Bekämpfung von Schadpflanzen in Kulturen von bekannten oder noch zu entwickelnden gentechnisch veränderten Pflanzen eingesetzt werden. Die transgenen Pflanzen zeichnen sich in der Regel durch besondere vorteilhafte Eigenschaften aus, beispielsweise durch Resistenzen gegenüber bestimmten Pestiziden, vor allem bestimmten Herbiziden, Resistenzen gegenüber Pflanzenkrankheiten oder Erregern von Pflanzenkrankheiten wie bestimmten Insekten oder Mikroorganismen wie Pilzen, Bakterien oder Viren. Andere besondere Eigenschaften betreffen z. B. das Erntegut hinsichtlich Menge, Qualität, Lagerfähigkeit, Zusammensetzung und spezieller Inhaltsstoffe. So sind transgene Pflanzen mit erhöhtem Stärkegehalt oder veränderter Qualität der Stärke oder solche mit anderer Fettsäurezusammensetzung des Ernteguts bekannt.In addition, the compounds of the invention have excellent growth regulatory properties in cultivated plants. You grab regulate the plant's own metabolism and can thus be used to specifically influence plant constituents and to facilitate harvesting, such as by triggering desiccation and stunted growth. Furthermore, they are also suitable for general control and inhibition of undesired vegetative growth without killing the plants. Inhibiting vegetative growth plays a major role in many monocotyledonous and dicotyledonous crops, as this can reduce or completely prevent storage. Because of their herbicidal and plant growth regulatory properties, the active compounds can also be used to control harmful plants in crops of known or still to be developed genetically modified plants. The transgenic plants are generally distinguished by special advantageous properties, for example resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties concern e.g. B. the crop in terms of quantity, quality, storability, composition and special ingredients. Transgenic plants with an increased starch content or altered starch quality or with a different fatty acid composition of the crop are known.
Bevorzugt ist die Anwendung der erfindungsgemäßen Verbindungen der Formel (I) oder deren Salze in wirtschaftlich bedeutenden transgenen Kulturen von Nutz- und Zierpflanzen, z. B. von Getreide wie Weizen, Gerste, Roggen, Hafer, Hirse, Reis, Maniok und Mais oder auch Kulturen von Zuckerrübe, Baumwolle, Soja, Raps, Kartoffel, Tomate, Erbse und anderen Gemüsesorten. Vorzugsweise können die Verbindungen der Formel (I) als Herbizide in Nutzpflanzenkulturen eingesetzt werden.-, welche gegenüber den phytotoxischen Wirkungen der Herbizide resistent sind zw. gentechnisch resistent gemacht worden sind.Preference is given to using the compounds of the formula (I) according to the invention or their salts in economically important transgenic crops of useful and ornamental plants, for. B. of cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn or also crops of sugar beet, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetables. The compounds of the formula (I) can preferably be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made resistant to genetic engineering.
Herkömmliche Wege zur Herstellung neuer Pflanzen, die im Vergleich zu bisher vorkommenden Pflanzen modifizierte Eigenschaften aufweisen, bestehen beispielsweise in klassischen Züchtungsverfahren und der Erzeugung von Mutanten. Alternativ können neue Pflanzen mit veränderten Eigenschaften mit Hilfe gentechnischer Verfahren erzeugt werden (siehe z. B. EP-A-0221044, EP-A-0131624). Beschrieben wurden beispielsweise in mehreren Fällen gentechnische Veränderungen von Kulturpflanzen zwecks Modifikation der in den Pflanzen synthetisierten Stärke (z. B. WO 92/11376, WO 92/14827,There are conventional ways of producing new plants which have modified properties in comparison to previously occurring plants for example in classic breeding methods and the generation of mutants. Alternatively, new plants with modified properties can be produced using genetic engineering methods (see, for example, EP-A-0221044, EP-A-0131624). In several cases, for example, genetic engineering changes in crop plants have been described in order to modify the starch synthesized in the plants (e.g. WO 92/11376, WO 92/14827,
WO 91/19806), transgene Kulturpflanzen, welche gegen bestimmte Herbizide vom TypWO 91/19806), transgenic crop plants which are active against certain herbicides of the type
Glufosinate (vgl. z. B. EP-A-0242236, EP-A-242246) oder GlyphosateGlufosinate (see e.g. EP-A-0242236, EP-A-242246) or glyphosate
(WO 92/00377) oder der Sulfonylharnstoffe (EP-A-0257993, US-A-5013659) resistent sind, transgene Kulturpflanzen, beispielsweise Baumwolle, mit der Fähigkeit(WO 92/00377) or the sulfonylureas (EP-A-0257993, US-A-5013659) are resistant to transgenic crop plants, for example cotton, with the ability
Bacillus thuringiensis-Toxine (Bt-Toxine) zu produzieren, welche dieBacillus thuringiensis toxins (Bt toxins) which the
Pflanzen gegen bestimmte Schädlinge resistent machen (EP-A-0142924,Making plants resistant to certain pests (EP-A-0142924,
EP-A-0193259). transgene Kulturpflanzen mit modifizierter FettsäurezusammensetzungEP-A-0193259). transgenic crops with modified fatty acid composition
(WO 91/13972).(WO 91/13972).
Zahlreiche molekularbiologische Techniken, mit denen neue transgene Pflanzen mit veränderten Eigenschaften hergestellt werden können, sind im Prinzip bekannt; siehe z.B. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2. Aufl. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; oder Winnacker "Gene und Klone", VCH Weinheim 2. Auflage 1996 oder Christou, "Trends in Plant Science" 1 (1996) 423-431).In principle, numerous molecular biological techniques with which new transgenic plants with modified properties can be produced are known; see e.g. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Gene and Clones", VCH Weinheim 2nd edition 1996 or Christou, "Trends in Plant Science" 1 (1996) 423-431).
Für derartige gentechnische Manipulationen können Nucleinsäuremoleküle in Plasmide eingebracht werden, die eine,Mutagercese oder eine Sequenzveränderung durch Rekombination von DNA-Sequenzen, erlauben. Mit Hilfe der obengenannten Standardverfahren können z. B. Basenaustausche vorgenommen, Teilsequenzen entfernt oder natürliche oder synthetische Sequenzen hinzugefügt werden. Für die Verbindung der DNA-Fragmente untereinander können an die Fragmente Adaptoren oder Linker angesetzt werden. Die Herstellung von Pflanzenzellen mit einer verringerten Aktivität eines Genprodukts kann beispielsweise erzielt werden durch die Expression mindestens einer entsprechenden antisense-RNA, einer sense-RNA zur Erzielung eines Cosuppressionseffektes oder die Expression mindestens eines entsprechend konstruierten Ribozyms, das spezifisch Transkripte des obengenannten Genprodukts spaltet.For such genetic engineering manipulations, nucleic acid molecules can be introduced into plasmids which allow mutageresis or a sequence change by recombination of DNA sequences. With the help of the above standard procedures such. B. base exchanges, partial sequences removed or natural or synthetic sequences added. To connect the DNA fragments to one another, adapters or linkers can be attached to the fragments. The production of plant cells with a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to achieve a cosuppression effect or the expression of at least one appropriately constructed ribozyme which specifically cleaves transcripts of the gene product mentioned above.
Hierzu können zum einen DNA-Moleküle verwendet werden, die die gesamte codierende Sequenz eines Genprodukts einschließlich eventuell vorhandener flankierender Sequenzen umfassen, als auch DNA-Moleküle, die nur Teile der codierenden Sequenz umfassen, wobei diese Teile lang genug sein müssen, um in den Zellen einen antisense-Effekt zu bewirken. Möglich ist auch die Verwendung von DNA-Sequenzen, die einen hohen Grad an Homologie zu den codiereden Sequenzen eines Genprodukts aufweisen, aber nicht vollkommen identisch sind.For this purpose, DNA molecules can be used that comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules that only comprise parts of the coding sequence, these parts having to be long enough to be in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but which are not completely identical.
Bei der Expression von Nucleinsäuremolekülen in Pflanzen kann das synthetisierte Protein in jedem beliebigen Kompartiment der pflanzlichen Zelle lokalisiert sein. Um aber die Lokalisation in einem bestimmten Kompartiment zu erreichen, kann z. B. die codierende Region mit DNA-Sequenzen verknüpft werden, die die Lokalisierung in einem bestimmten Kompartiment gewährleisten. Derartige Sequenzen sind dem Fachmann bekannt (siehe beispielsweise Braun et al., EMBO J. 11_ (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sei. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106).When nucleic acid molecules are expressed in plants, the synthesized protein can be located in any compartment of the plant cell. However, in order to achieve localization in a particular compartment, z. B. the coding region can be linked to DNA sequences that ensure localization in a particular compartment. Such sequences are known to the person skilled in the art (see, for example, Braun et al., EMBO J. 11_ (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1: 95-106 (1991).
Die transgenen Pflanzenzellen können nach bekannten Techniken zu ganzen Pflanzen regeneriert werden. Bei den transgenen' Pflanzen kann es sich prinzipiell um Pflanzen jeder beliebigen Pflanzenspezies handeln, d.h. sowohl monokotyle als auch dikotyle Pflanzen.The transgenic plant cells can be regenerated into whole plants using known techniques. The transgenic plants can in principle be plants of any plant species, i.e. both monocot and dicot plants.
So sind transgene Pflanzen erhältlich, die veränderte Eigenschaften durch Überexpression, Suppression oder Inhibierung hqmologer (= natürlicher) Gene oder Gensequenzen oder Expression heterologer (= fremder) Gene oder Gensequenzen aufweisen.Thus, transgenic plants are available which have changed properties through overexpression, suppression or inhibition of hqmologic (= natural) genes or Show gene sequences or expression of heterologous (= foreign) genes or gene sequences.
Vorzugsweise können die erfindungsgemäßen Verbindungen (I) in transgenen Kulturen eingesetzt werden, welche gegen Herbizide aus der Gruppe der Sulfonylhamstoffe, Glufosinate-ammonium oder Glyphosate-isopropylammonium und analoge Wirkstoffe resistent sind.The compounds (I) according to the invention can preferably be used in transgenic crops which are resistant to herbicides from the group of the sulfonylureas, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active compounds.
Bei der Anwendung der erfindungsgemäßen Wirkstoffe in transgenen Kulturen treten neben den in anderen Kulturen zu beobachtenden Wirkungen gegenüber Schadpflanzen oftmals Wirkungen auf, die für die Applikation in der jeweiligen transgenen Kultur spezifisch sind, beispielsweise ein verändertes oder speziell erweitertes Unkrautspektrum, das bekämpft werden kann, veränderte Aufwandmengen, die für die Applikation eingesetzt werden können, vorzugsweise gute Kombinierbarkeit mit den Herbiziden, gegenüber denen die transgene Kultur resistent ist, sowie Beeinflussung von Wuchs und Ertrag der transgenen Kulturpflanzen.When the active compounds according to the invention are used in transgenic crops, in addition to the effects on harmful plants which can be observed in other crops, there are often effects which are specific to the application in the respective transgenic culture, for example a changed or specially expanded weed spectrum which can be controlled changed Application rates which can be used for the application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and influencing the growth and yield of the transgenic crop plants.
Gegenstand der Erfindung ist deshalb auch die Verwendung der erfindungsgemäßen Verbindungen (I) als Herbizide zur Bekämpfung von Schadpflanzen in transgenen Kulturpflanzen.The invention therefore also relates to the use of the compounds (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
Die erfindungsgemäßen Verbindungen können in Form von Spritzpulvern, emulgierbaren Konzentraten, versprühbaren Lösungen, Stäubemitteln oder Granulaten in den üblichen Zubereitungen angewendet werden. Gegenstand der Erfindung sind deshalb auch herbizide und pflanzenwachstumsregulierende Mittel, die Verbindungen der Formel (I) enthalten.The compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations. The invention therefore also relates to herbicidal and plant growth-regulating compositions which comprise compounds of the formula (I).
Die Verbindungen der Formel (I) können auf verschiedene Art formuliert werden, je nachdem welche biologischen und/oder chemisch-physikalischen Parameter vorgegeben sind. Als Formulierungsmöglichkeiten kommen beispielsweise in Frage: Spritzpulver (WP), wasserlösliche Pulver (SP), wasserlösliche Konzentrate, emulgierbare Konzentrate (EC), Emulsionen (EW), wie Öl-in-Wasser- und Wasser-in-ÖI-Emulsionen, versprühbare Lösungen, Suspensionskonzentrate (SC), Dispersionen auf Öl- oder Wasserbasis, ölmischbare Lösungen, Kapselsuspensionen (CS), Stäubemittel (DP), Beizmittel, Granulate für die Streu- und Bodenapplikation, Granulate (GR) in Form von Mikro-, Sprüh-, Aufzugs- und Adsorptionsgranulaten, wasserdispergierbare Granulate (WG), wasserlösliche Granulate (SG), ULV-Formulierungen, Mikrokapseln und Wachse. Diese einzelnen Formulierungstypen sind im Prinzip bekannt und werden beispielsweise beschrieben in: Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hauser Verlag München, 4. Aufl. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.The compounds of formula (I) can be formulated in different ways, depending on which biological and / or chemical-physical parameters are specified. Possible formulation options are, for example: wettable powder (WP), water-soluble powder (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), dispersions based on oil or water, oil-miscible solutions, capsule suspensions (CS), Dusts (DP), mordants, granules for spreading and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes. These individual formulation types are known in principle and are described, for example, in: Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th Edition 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY , 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.
Die notwendigen Formulierungshilfsmittel wie Inertmaterialien, Tenside, Lösungsmittel und weitere Zusatzstoffe sind ebenfalls bekannt und werden beispielsweise beschrieben in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caidwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Grenzflächenaktive Äthylenoxidaddukte", Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hauser Verlag München, 4. Aufl. 1986.The necessary formulation aids such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caidwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y .; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J .; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Interface-active ethylene oxide adducts", Wiss. Publishing company, Stuttgart 1976; Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.
Auf der Basis dieser Formulierungen lassen sich auch Kombinationen mit anderen pestizid wirksamen Stoffen, wie z.B. lnsektiziden,.Akariziden, Herbiziden, Fungiziden, sowie mit Safenern, Düngemitteln und/oder Wachstumsregulatoren herstellen, z.B. in Form einer Fertigformulierung oder als Tankmix.Based on these formulations, combinations with other pesticidally active substances, e.g. Manufacture insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers and / or growth regulators, e.g. in the form of a finished formulation or as a tank mix.
Spritzpulver sind in Wasser gleichmäßig dispergierbare Präparate, die neben dem Wirkstoff außer einem Verdünnungs- oder inertstoff noch Tenside ionischer und/oder nichtionischer Art (Netzmittel, Dispergiermittel), z.B. polyoxyethylierte Alkylphenole, polyoxethylierte Fettalkohole, polyoxethylierte Fettamine, Fettalkoholpolyglykolethersulfate, Alkansulfonate, Alkylbenzolsulfonate, ligninsulfonsaures Natrium, 2,2'-dinaphthylmethan-6,6'-disulfonsaures Natrium, dibutylnaphthalin-sulfonsaures Natrium oder auch oleoylmethyltaurinsaures Natrium enthalten. Zur Herstellung der Spritzpulver werden die herbiziden Wirkstoffe beispielsweise in üblichen Apparaturen wie Hammermühlen, Gebläsemühlen und Luftstrahlmühlen feingemahlen und gleichzeitig oder anschließend mit den Formulierungshilfsmitteln vermischt.Spray powders are preparations which are uniformly dispersible in water and, in addition to the active substance, are not only a diluent or inert substance, but also ionic surfactants and / or non-ionic (wetting agents, dispersing agents), for example polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, ligninsulfonic acid sodium, 2,2'-dinaphthylmethane-6,6'-sodium-disulfonylsulfonic acid also contain sodium oleoylmethyl tauric acid. To produce the wettable powders, the herbicidal active ingredients are finely ground, for example in conventional apparatus such as hammer mills, fan mills and air jet mills, and mixed at the same time or subsequently with the formulation auxiliaries.
Emulgierbare Konzentrate werden durch Auflösen des Wirkstoffes in einem organischen Lösungsmittel z.B. Butanol, Cyclohexanon, Dimethylformamid, Xylol oder auch höhersiedenden Aromaten oder Kohlenwasserstoffen oder Mischungen der organischen Lösungsmittel unter Zusatz von einem oder mehreren Tensiden ionischer und/oder nichtionischer Art (Emulgatoren) hergestellt. Als Emulgatoren können beispielsweise verwendet werden: Alkylarylsulfonsaure Calzium-Salze wie Ca-Dodecylbenzolsulfonat oder nichtionische Emulgatoren wie Fettsäurepolyglykolester, Alkylarylpolyglykolether, Fettalkoholpolyglykolether, Propylenoxid-Ethylenoxid-Kondensationsprodukte, Alkylpolyether, Sorbitanester wie z.B. Sorbitanfettsäureester oder Polyoxethylensorbitanester wie z.B. Polyoxyethylensorbitanfettsäureester.Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers). Examples of emulsifiers which can be used are: alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as e.g. Sorbitan fatty acid esters or polyoxethylene sorbitan esters such as e.g. Polyoxyethylene.
Stäubemittel erhält man durch Vermählen des Wirkstoffes mit fein verteilten festen Stoffen, z.B. Talkum, natürlichen Tonen, wie Kaolin, Bentonit und Pyrophyllit, oder Diatomeenerde.Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
Suspensionskonzentrate können auf Wasser- oder Ölbasis sein. Sie können beispielsweise durch Naß-Vermahlung, mittels handelsüblicher Perlmühlen und gegebenenfalls Zusatz von Tensiden, wie sie z.B. oben bei den anderen Formulierungstypen bereits aufgeführt sind, hergestellt werden. Emulsionen, z.B. ÖI-in-Wasser-Emuisionen (EW), lassen sich beispielsweise mittels Rührern, Kolloidmühlen und/oder statischen Mischern unter Verwendung von wäßrigen organischen Lösungsmitteln und gegebenenfalls Tensiden, wie sie z.B. oben bei den anderen Formulierungstypen bereits aufgeführt sind, herstellen.Suspension concentrates can be water or oil based. They can be prepared, for example, by wet milling, using commercially available bead mills and, if appropriate, adding surfactants, such as those already listed above for the other types of formulation. Emulsions, for example oil-in-water (EW) emissions, can be produced, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as those already listed above for the other types of formulation.
Granulate können entweder durch Verdüsen des Wirkstoffes auf adsorptionsfähiges, granuliertes Inertmaterial hergestellt werden oder durch Aufbringen von Wirkstoffkonzentraten mittels Klebemitteln, z.B. Polyvinylalkohol, polyacrylsaurem Natrium oder auch Mineralölen, auf die Oberfläche von Trägerstoffen wie Sand, Kaolinite oder von granuliertem Inertmaterial. Auch können geeignete Wirkstoffe in der für die Herstellung von Düngemittelgranulaten üblichen Weise - gewünschtenfalls in Mischung mit Düngemitteln - granuliert werden.Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. Polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.
Wasserdispergierbare Granulate werden in der Regel nach den üblichen Verfahren wie Sprühtrocknung, Wirbelbett-Granulierung, Teller-Granulierung, Mischung mit Hochgeschwindigkeitsmischern und Extrusion ohne festes Inertmaterial hergestellt.Water-dispersible granules are generally produced using the customary methods, such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
Zur Herstellung von Teller-, Fließbett-, Extruder- und Sprühgranulate siehe z.B. Verfahren in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, Seiten 147 ff; "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, S. 8-57.For the production of plate, fluidized bed, extruder and spray granules, see e.g. Procedure in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff; "Perry's Chemical Engineer's Handbook," 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.
Für weitere Einzelheiten zur Formulierung von Pflanzenschutzmitteln siehe z.B. G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961 , Seiten 81-96 und J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, Seiten 101-103. Die agrochemischen Zubereitungen enthalten in der Regel 0,1 bis 99 Gew.-%, insbesondere 0.1 bis 95 Gew.-%, Wirkstoff,der Formel (I) und/oder deren Salze. In Spritzpulvern beträgt die Wirkstoffkonzentration z.B. etwa 10 bis 90 Gew.-%, der Rest zu 100 Gew.-% besteht aus üblichen Formulierungsbestandteiien. Bei emulgierbaren Konzentraten kann die Wirkstoffkonzentration etwa 1 bis 90, vorzugsweise 5 bis 80 Gew.-% betragen. Staubförrnige .Formulierungen enthalten 1 bis 30 Gew.-% Wirkstoff, vorzugsweise meistens 5 bis 20 Gew.-% an Wirkstoff, versprühbare Lösungen enthalten etwa 0,05 bis 80, vorzugsweise 2 bis 50 Gew.-% Wirkstoff. Bei wasserdispergierbaren Granulaten hängt der Wirkstoffgehalt zum Teil davon ab, ob die wirksame Verbindung flüssig oder fest vorliegt und welche Granulierhilfsmittel, Füllstoffe usw. verwendet werden. Bei den in Wasser dispergierbaren Granulaten liegt der Gehalt an Wirkstoff beispielsweise zwischen 1 und 95 Gew.-%, vorzugsweise zwischen 10 und 80 Gew.-%. Daneben enthalten die genannten Wirkstofformulierungen gegebenenfalls die jeweils üblichen Haft-, Netz-, Dispergier-, Emulgier-, Penetrations-, Konservierungs-, Frostschutz- und Lösungsmittel, Füll-, Träger- und Farbstoffe, Entschäumer, Verdunstungshemmer und den pH-Wert und die Viskosität beeinflussende Mittel.For further details on the formulation of crop protection agents, see, for example, GC Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and JD Freyer, SA Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103. The agrochemical preparations generally contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of active ingredient, of the formula (I) and / or salts thereof. The active ingredient concentration in wettable powders is, for example, about 10 to 90% by weight, the remainder to 100% by weight consists of customary formulation constituents. In the case of emulsifiable concentrates, the active substance concentration can be about 1 to 90, preferably 5 to 80,% by weight. Dusty formulations included 1 to 30% by weight of active ingredient, preferably mostly 5 to 20% by weight of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50% by weight of active ingredient. In the case of water-dispersible granules, the active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulating aids, fillers, etc. are used. The active ingredient content of the water-dispersible granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight. In addition, the active ingredient formulations mentioned may contain the usual adhesives, wetting agents, dispersing agents, emulsifying agents, penetration agents, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and the pH and Agents influencing viscosity.
Als Kombinationspartner für die erfindungsgemäßen Wirkstoffe inAs a combination partner for the active substances according to the invention in
Mischungsformulierungen oder im Tank-Mix sind beispielsweise bekannte Wirkstoffe wie Herbizide, Insektizide, Fungizide oder Safener einsetzbar, wie sie z.B. ausMixture formulations or in the tank mix can be used, for example, known active ingredients such as herbicides, insecticides, fungicides or safeners, such as those e.g. out
Weed Research 26 (1986) 441-445 oder "The Pesticide Manual", 11th edition, TheWeed Research 26 (1986) 441-445 or "The Pesticide Manual", 11th edition, The
British Crop Protection Council and the Royal Soc. of Chemistry, 1997 und dort zitierter Literatur beschrieben sind. Als bekannte Herbizide, die mit denBritish Crop Protection Council and the Royal Soc. of Chemistry, 1997 and the literature cited therein. As known herbicides that with the
Verbindungen der Formel (I) kombiniert werden können, sind z.B. folgendeCompounds of formula (I) can be combined are e.g. the following
Wirkstoffe zu nennen (Anmerkung: Die Verbindungen sind entweder mit demActive substances (note: The compounds are either with the
"common name" nach der International Organization for Standardization (ISO) oder mit dem chemischen Namen, ggf. zusammen mit einer üblichen Codenummer bezeichnet): acetochlor; acifluorfen; aclonifen; AKH 7088, d.h. [[[1-[5-[2-Chloro-4-(trifluoromethyl)- phenoxy]-2-nitrophenyl]-2-methoxyethylidene]-amino]-oxy]-essigsäure und"common name" according to the International Organization for Standardization (ISO) or with the chemical name, if necessary together with a usual code number): acetochlor; acifluorfen; aclonifen; AKH 7088, i.e. [[[1- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidenes] amino] oxy] acetic acid and
-essigsäuremethylester; alachlor; alloxydim; ametryn; amidosulfuron; amitrol; AMS, d.h. Ammoniumsulfamat; anilofos; asulam; atrazin; azafenidin; azimsulfuronacetate; alachlor; alloxydim; ametryn; amidosulfuron; amitrol; AMS, i.e. ammonium sulfamate; anilofos; asulam; atrazine; azafenidin; azimsulfuron
(DPX-A8947); aziprotryn; barban; BAS,516 H, d.h.(DPX-A8947); aziprotryn; barban; BAS , 516 H, i.e.
5-Fluor-2-phenyl-4H-3,1-benzoxazin-4-on; BAS 620 H; BAS 65400H; BAY FOE5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; BAS 620 H; BAS 65400H; BAY FOE
5043; benazolin; benfluralin; benfuresate; bensulfuron-methyl; bensulide; r bentazone; benzofenap; benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox; bispyribac-Na; bromacil; bromobutide; brpmofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butamifos; butenachlor; buthidazole; butralin; butroxydim; butylate; cafenstrole (CH-900); caloxydim; carbetamide; carfentrazone-ethyl; CDAA, d.h. 2-Chlor-N,N-di-2-propenylacetamid; CDEC, d.h. Diethyldithiocarbaminsäure-2-chlorallylester; chlomethoxyfen; chloramben; chlorazifop-butyl, chlorbromuron; chlorbufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron ethyl; chlornitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlorthal-dimethyl; chlorthiamid; cinmethylin; cinosulfuron; clethodim; clodinafop und dessen Esterderivate (z.B. clodinafop-propargyl); clomazone; clomeprop; cloproxydim; clopyralid; cloransulam-methyl; cumyluron (JC 940); cyanazine; cycloate; cyclosulfamuron (AC 104); cycloxydim; cycluron; cyhalofop und dessen Esterderivate (z.B. Butylester, DEH-112); cyperquat; cyprazine; cyprazole; daimuron; 2,4-DB; dalapon; desmedipham; desmetryn; di-allate; dicamba; dichlobenil; dichlorprop; diclofop und dessen Ester wie diclofop-methyl; diclosulam, d.h. N-(2,6-Dichlorphenyl)-5-ethoxy- 7-fluor-[1 ,2,4itriazolo[1 ,5-c]pyrimidin-2-sulfonamid; diethatyl; difenoxuron; difenzoquat; diflufenican; diflufenzopyr (BAS 654 00H), dimefuron; dimethachlor; dimethametryn; dimethenamid (SAN-582H); dimethazone, clomazon; dimethipin; dimetrasulfuron, dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 77, d.h. 5-Cyano-1-(1 ,1-dimethylethyl)- N-methyl-1H-pyrazole-4-carboxamid; endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl; ethidimuron; ethiozin; ethofumesate; F5231 , d.h. N-[2-Chlor-4-fluor-5-[4-(3-fluorpropyl)-4,5-dihydro-5-oxo-1 H-tetrazol-1-yl]-phenyl]- ethansulfonamid; ethoxyfen und dessen Ester (z.B. Ethylester, HN-252); etobenzanid (HW 52); fenoprop; fenoxan, fenoxaprop und fenoxaprop-P sowie deren Ester, z.B. fenoxaprop-P-ethyl und fenoxaprop-ethyl; fenoxydim; fenuron; flamprop-methyl; flazasulfuron; fluazifop und fluazifop-P und deren Ester, z.B. fluazifop-butyl und fluazifop-P-butyl; fluchloralin;'flumetsulam; flumeturon; flumiclorac und dessen Ester (z.B. Pentylester, S-23031); flumioxazin (S-482); flumipropyn; flupoxam (KNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil (UBIC-4243); flupyrsulfuron-methyl-sodium; fluridone; flurochloridone; fluroxypyr; flurtamone; fluthiacet-methyl; fomesafen; foramsulfuron und dessen Salze; fosamine; furyloxyfen; glufosinate; glyphosate; halosafen; halosulfuron und dessen Ester (z.B. Methylester, NC-319); haloxyfop und dessen Ester; haloxyfop-P (= R-haloxyfop) und dessen Ester; hexazinone; imazamethabenz-methyl; imazamox; imazapyr; imazaquin und Salze wie das Ammoniumsalz; imazethamethapyr; imazethapyr; imazosulfuron; indanofan (MK-243), iodosulfuron und dessen Salze und Ester wie iodosulfuron-methyl-natrium; ioxynil; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxaflutole; isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop; mefenaeet; mefluidid; mesosulfuron und dessen Salze und Ester wie mesosulfuron-methyl; metamitron; metazachlor; methabenzthiazuron; metham; methazole; methoxyphenone; methyldymron; metobenzuron; metobromuron; metolachlor; metosulam (XRD 511); metoxuron; metribuzin; metsulfuron-methyl; MH; molinate; monalide; monocarbamide dihydrogensulfate; monolinuron; monuron; MT 128, d.h. 6-Chlor-N-(3-chlor-2-propenyl)-5-methyl-N-phenyl-3-pyridazinamin; MT 5950, d.h. N-[3-Chlor-4-(1-methylethyl)-phenyl]-2-methyipentanamid; naproanilide; napropamide; naptalam; NC 310, d.h. 4-(2,4-dichlorbenzoyl)-1- methyl-5-benzyloxypyrazol; neburon; nicosulfuron; nipyraclophen; nitralin; nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxasulfuron; oxaziclomefone (MY-100); oxyfluorfen; paraquat; pebulate; pendimethalin; pentoxazone (KPP-314); perfluidone; phenisopham; phenmedipham; picloram; piperophos; piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl; proeyazine; prodiamine; profluralin; proglinazine-ethyl; prometon; prometryn; propachlor; propanil; propaquizafop und dessen Ester; propazine; propham; propisochlor; propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA-152005); prynachlor; pyroflufen-ethyl; pyrazolinate; pyrazon; pyrazosulfuron-ethyl; pyrazoxyfen; pyribenzoxim (LGC-40836); pyributicarb; pyridate; pyriminobac-methyl; pyrithiobac (KIH-2031); pyroxofop und dessen Ester (z.B. Propargylester); quinclorac; quinmerac; quinofop und dessen Esterderivate, quizalofop und quizalofop-P und deren Esterderivate z,B. quizalofop-ethyl; quizalofop-P-tefuryl und -ethyl; renriduron; rimsulfuron (DPX-E 9636); S 275, d.h. 2-[4-Chlor-2-fluor-5- (2-propynyloxy)-phenyl]-4,5,6,7-tetrahydro-2H-indazol; seebumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, d.h.5043; benazolin; benfluralin; benfuresate; bensulfuron-methyl; bensulide; r bentazone; benzofenap; benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox; bispyribac-Na; bromacil; bromobutide; brpmofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butamifos; butenachlor; buthidazole; butraline; butroxydim; butylate; cafenstrole (CH-900); caloxydim; carbetamide; carfentrazone-ethyl; CDAA, ie 2-chloro-N, N-di-2-propenylacetamide; CDEC, ie 2-chloroallyl ester of diethyldithiocarbamic acid; chlomethoxyfen; chloramben; chlorazifop-butyl, chlorbromuron; chlorbufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron ethyl; chlornitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlorthal-dimethyl; chlorthiamid; cinmethylin; cinosulfuron; clethodim; clodinafop and its ester derivatives (eg clodinafop-propargyl); clomazone; clomeprop; cloproxydim; clopyralid; cloransulam-methyl; cumyluron (JC 940); cyanazine; cycloate; cyclosulfamuron (AC 104); cycloxydim; cycluron; cyhalofop and its ester derivatives (eg butyl ester, DEH-112); cyperquat; cyprazine; cyprazole; daimuron; 2,4-DB; dalapon; desmedipham; Desmetryn; di-allate; dicamba; dichlobenil; dichloroprop; diclofop and its esters such as diclofop-methyl; diclosulam, ie N- (2,6-dichlorophenyl) -5-ethoxy-7-fluoro- [1,2,4itriazolo [1,5-c] pyrimidine-2-sulfonamide; diethatyl; difenoxuron; difenzoquat; diflufenican; diflufenzopyr (BAS 654 00H), dimefuron; dimethachlor; dimethametryn; dimethenamid (SAN-582H); dimethazone, clomazone; dimethipin; dimetrasulfuron, dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 77, ie 5-cyano-1- (1, 1-dimethylethyl) - N-methyl-1H-pyrazole-4-carboxamide; endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl; Ethidimuron; ethiozin; ethofumesate; F5231, ie N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo-1H-tetrazol-1-yl] phenyl] ethanesulfonamide; ethoxyfen and its esters (eg ethyl ester, HN-252); etobenzanide (HW 52); fenoprop; fenoxan, fenoxaprop and fenoxaprop-P and their esters, for example fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim; fenuron; flamprop-methyl; flazasulfuron; fluazifop and fluazifop-P and their esters, for example fluazifop-butyl and fluazifop-P-butyl; fluchloralin; 'flumetsulam;flumeturon; flumiclorac and its esters (eg pentyl ester, S-23031); flumioxazin (S-482); flumipropyn; flupoxam (KNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil (UBIC-4243); flupyrsulfuron-methyl-sodium; fluridone; flurochloridone; fluroxypyr; flurtamone; fluthiacet-methyl; fomesafen; foramsulfuron and its salts; fosamine; furyloxyfen; glufosinate; glyphosate; halo safen; halosulfuron and its esters (e.g. Methyl ester, NC-319); haloxyfop and its esters; haloxyfop-P (= R-haloxyfop) and its esters; hexazinone; imazamethabenz-methyl; imazamox; imazapyr; imazaquin and salts such as the ammonium salt; imazethamethapyr; imazethapyr; imazosulfuron; indanofan (MK-243), iodosulfuron and its salts and esters such as iodosulfuron-methyl-sodium; ioxynil; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxaflutole; isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop; mefenaeet; mefluidide; mesosulfuron and its salts and esters such as mesosulfuron-methyl; metamitron; metazachlor; methabenzthiazuron; metham; methazole; methoxyphenone; methyldymron; metobenzuron; metobromuron; metolachlor; metosulam (XRD 511); metoxuron; metribuzin; metsulfuron-methyl; MH; molinate; monalide; monocarbamide dihydrogen sulfates; monolinuron; monuron; MT 128, ie 6-chloro-N- (3-chloro-2-propenyl) -5-methyl-N-phenyl-3-pyridazinamine; MT 5950, ie N- [3-chloro-4- (1-methylethyl) phenyl] -2-methyipentanamide; naproanilide; napropamide; naptalam; NC 310, ie 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitralin; nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxasulfuron; oxaziclomefone (MY-100); oxyfluorfen; paraquat; pebulate; pendimethalin; pentoxazone (KPP-314); perfluidone; phenisopham; phenmedipham; picloram; piperophos; piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl; proeyazine; prodi amines; profluralin; proglinazine-ethyl; prometon; prometryne; propachlor; propanil; propaquizafop and its esters; propazine; propham; propisochlor; Propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA-152005); prynachlor; pyroflufen-ethyl; pyrazolinate; pyrazon; pyrazosulfuron-ethyl; pyrazoxyfen; pyribenzoxim (LGC-40836); pyributicarb; pyridate; pyriminobac-methyl; pyrithiobac (KIH-2031); pyroxofop and its esters (eg propargyl esters); quinclorac; quinmerac; quinofop and its ester derivatives, quizalofop and quizalofop-P and their ester derivatives e.g. quizalofop-ethyl; quizalofop-P-tefuryl and ethyl; renriduron; rimsulfuron (DPX-E 9636); S 275, ie 2- [4-chloro-2-fluoro-5- (2-propynyloxy) phenyl] -4,5,6,7-tetrahydro-2H-indazole; seebumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, that is
2-[[7-[2-Chlor-4-(trifluor-methyl)-phenoxy]-2-naphthalenyl]-oxy]-propansäure und -methylester; sulcotrione; sulfentrazon (FMC-9728/5, F-6285); sulfazuron; sulfometuron-methyl; sulfosate (ICI-A0224); sulfosulfuron; TCA; tebutam (GCP-5544); tebuthiuron; terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryn; TFH 450, d.h. N,N-Diethyl-3-2 - [[7- [2-chloro-4- (trifluoromethyl) phenoxy] -2-naphthalenyl] oxy] propanoic acid and methyl ester; sulcotrione; sulfentrazone (FMC-9728/5, F-6285); sulfazuron; sulfometuron-methyl; sulfosate (ICI-A0224); sulfosulfuron; TCA; tebutam (GCP-5544); tebuthiuron; terbacil; terbucarb; terbuchlor; terbumeton; Terbuthylazine; terbutryn; TFH 450, ie N, N-diethyl-3-
[(2-ethyl-6-methylphenyl)-sulfonyl]-1 H-1 ,2,4-triazol-1-carboxamid; thenylchlor (NSK-850); thiazafluron; thiazopyr (Mon-13200); thidiazimin (SN-24085); thifensulfuron-methyl; thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triaziflam, triazofenamide; tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin; triflusulfuron und Ester (z.B. Methylester, DPX-66037); trimeturon; tsitodef; vernolate; WL 110547, d.h. 5-Phenoxy-1-[3-(trifluormethyl)-phenyl]-1H-tetrazol; JTC-101; UBH-509; D-489; LS 82-556; KPP-300; NC-324; NC-330; KH-218; DPX-N8189; SC-0774; DOWCO-535; DK-8910; V-53482; PP-600; MBH-001; KIH-9201; ET-751; KIH-6127 und KIH-2023.[(2-ethyl-6-methylphenyl) sulfonyl] -1 H-1, 2,4-triazole-1-carboxamide; thenylchlor (NSK-850); thiazafluron; thiazopyr (Mon-13200); thidiazimin (SN-24085); thifensulfuron-methyl; thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triaziflam, triazofenamide; tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin; triflusulfuron and esters (e.g. methyl ester, DPX-66037); trimeturon; tsitodef; vernolate; WL 110547, i.e. 5-phenoxy-1- [3- (trifluoromethyl) phenyl] -1H-tetrazole; JTC-101; UBH-509; D-489; LS 82-556; KPP-300; NC-324; NC-330; KH-218; DPX-N8189; SC-0774; Dowco-535; DK-8910; V-53482; PP-600; MBH-001; KIH-9201; ET-751; KIH-6127 and KIH-2023.
Die erfindungsgemäßen Wirkstoffe können auch in Kombination mit einem oder mehreren als Safener wirkenden Verbindungen eingesetzt werden. Zur Anwendung werden die in handelsüblicher Form voriiegenden Formulierungen gegebenenfalls in üblicherweise verdünnt z.B. bei Spritzpulvern, emulgierbaren Konzentraten, Dispersionen und wasserdispergierbaren Granulaten mittels Wasser. Staubförmige Zubereitungen, Boden- bzw. Streugranulate sowie versprühbare Lösungen werden vor der Anwendung üblicherweise nicht mehr mit weiteren inerten Stoffen verdünnt.The active compounds according to the invention can also be used in combination with one or more compounds which act as safeners. For use, the formulations present in the commercial form are optionally diluted in the customary manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules using water. Preparations in the form of dust, ground granules or scattering granules and sprayable solutions are usually no longer diluted with other inert substances before use.
Mit den äußeren Bedingungen wie Temperatur, Feuchtigkeit, der Art des verwendeten Herbizids, u.a. variiert die erforderliche Aufwandmenge der Verbindungen der Formel (I). Sie kann innerhalb weiter Grenzen schwanken, z.B. zwischen 0,001 und 10,0 kg/ha oder mehr Aktivsubstanz, vorzugsweise liegt sie jedoch zwischen 0,005 und 5 kg/ha. A. Chemische BeispieleThe required application rate of the compounds of formula (I) varies with the external conditions, such as temperature, humidity, the type of herbicide used, and others. It can vary within wide limits, for example between 0.001 and 10.0 kg / ha or more of active substance, but is preferably between 0.005 and 5 kg / ha. A. Chemical examples
Abkürzungen: Die %-Angaben und Mengenverhältnisse beziehen sich auf dasAbbreviations: The percentages and proportions refer to the
Gewicht, wenn nicht näher spezifiziert, i. Vak. = unter reduziertem Druck h = Stunde(n)Weight, if not specified, i. Vak. = under reduced pressure h = hour (s)
Beispiel 1example 1
2-(1-Methyl-3-trifluormethylpyrazol-5-yloxy)-6-(but-2-enoyl-aminomethyl)-pyridin.2- (1-methyl-3-trifluoromethylpyrazol-5-yloxy) -6- (but-2-enoyl-aminomethyl) -pyridine.
1 a) 2-(1 -Methyl-3-trifluoromethylpyrazol-5-yloxy)-6-cyanopyridin.1a) 2- (1-Methyl-3-trifluoromethylpyrazol-5-yloxy) -6-cyanopyridine.
4,00 g (240 mmol) 1-Methyl-3-(trifluormethyl)-2-pyrazol-2-on wurden unter Stickstoffatmosphäre in 40 ml Sulfolan vorgelegt und bei Raumtemperatur portionsweise mit 2,70 g (24,0 mmol) Kaliumtert. butylat versetzt. Anschließend gab man 2,56 g (18,5 mmol) 2-Chlor-6-cyanopyridin zu und erwärmte für 3 h auf 130°C, kühlte auf Raumtemperatur ab und gab die Lösung auf Eiswasser. Der ausgefallene Niederschlag wurde abfiltriert und mehrfach mit Wasser gewaschen und anschießend getrocknet. Ausbeute 4,26 g (86 %); Schmelzpunkt 87°C.4.00 g (240 mmol) of 1-methyl-3- (trifluoromethyl) -2-pyrazol-2-one were placed in 40 ml of sulfolane under a nitrogen atmosphere and were portioned at room temperature with 2.70 g (24.0 mmol) of potassium. added butylate. Then 2.56 g (18.5 mmol) of 2-chloro-6-cyanopyridine were added and the mixture was heated at 130 ° C. for 3 h, cooled to room temperature and the solution was poured onto ice water. The precipitate was filtered off and washed several times with water and then dried. Yield 4.26 g (86%); Melting point 87 ° C.
1 b) 2-(1 -Methyl-3-trifluoromethylpyrazol-5-yloxy)-6-(aminomethyl)-pyridin. 7,00 g (26,1 mmol) 2-(1-Methyl-3-trifluoromethylpyrazol-5-yloxy)-6- cyanopyridin wurden in 150 ml Eisessig gelöst und mit 1 ,40 g Pd(OH)220 %ig auf Kohle versetzt und bei 17 bar Wasserstoffüberdruck hydriert. Nach 2 h wurde vom Katalysator abfiltriert und eingedampft. Der Rückstand wurde in Wasser aufgenommen, mit 20 ml 2nHCI versetzt und mehrfach mit Essigsäureethylester extrahiert. Die wässrige Phase wurde darauf mit 2 n NaOH auf pH 10 eingestellt und mehrfach mit Essigsäureethylester extrahiert. Die vereinigten organischen Extrakte wurden dann mit Mg SO getrocknet, filtriert und eingeengt. Ausbeute 2,58 g (34 %); Schmelzpunkt: 44°C. 1 c) 2-(1 -Methyl-3-trifluormethylpyrazol-5-yloxy)-6-(but-2-enoyl-aminomethyl)- pyridin.1 b) 2- (1-Methyl-3-trifluoromethylpyrazol-5-yloxy) -6- (aminomethyl) pyridine. 7.00 g (26.1 mmol) of 2- (1-methyl-3-trifluoromethylpyrazol-5-yloxy) -6-cyanopyridine were dissolved in 150 ml of glacial acetic acid and 20.4% with 1.40 g of Pd (OH) 2 Coal added and hydrogenated at 17 bar hydrogen pressure. After 2 hours, the catalyst was filtered off and evaporated. The residue was taken up in water, 20 ml of 2NHCl were added and the mixture was extracted several times with ethyl acetate. The aqueous phase was then adjusted to pH 10 with 2N NaOH and extracted several times with ethyl acetate. The combined organic extracts were then dried with MgSO4, filtered and concentrated. Yield 2.58 g (34%); Melting point: 44 ° C. 1 c) 2- (1-methyl-3-trifluoromethylpyrazol-5-yloxy) -6- (but-2-enoylaminomethyl) pyridine.
0,100 g (0,368 mmol) 2-(1-Methyl-3-trifluoromethylpyrazol-5-yloxy)-6- (aminomethyl)-pyridin wurden in 5 ml Methylenchlorid zusammen mit 71.1 mg (0,55 mmol) Diisopropyiethylamin vorgelegt und bei Raumtemperatur mit 46,1 mg (0,44 mmol) But-2-enoylchlorid versetzt und für 3 h bei Raumtemperatur gerührt. Das Rohprodukt wurde eingeengt, mit 1 n HCI und Essigsäureethylester extrahiert und anschließend über ein Kieselgelbett filtriert. Das Filtrat wurde eingeengt. Der Rückstand wurde kristallin. Ausbeute 0,059 g (47 %); Schmelzpunkt 75°C.0.100 g (0.368 mmol) of 2- (1-methyl-3-trifluoromethylpyrazol-5-yloxy) -6- (aminomethyl) pyridine were placed in 5 ml of methylene chloride together with 71.1 mg (0.55 mmol) of diisopropyiethylamine and at room temperature with 46.1 mg (0.44 mmol) of but-2-enoyl chloride were added and the mixture was stirred at room temperature for 3 h. The crude product was concentrated, extracted with 1N HCl and ethyl acetate and then filtered through a bed of silica gel. The filtrate was concentrated. The residue became crystalline. Yield 0.059 g (47%); Melting point 75 ° C.
Beispiel 2Example 2
2-(1-Methyl-3-trifluormethylpyrazol-5-yloxy)-6-(formylaminomethyl)-pyridin.2- (1-methyl-3-trifluoromethylpyrazol-5-yloxy) -6- (formylaminomethyl) -pyridine.
0,100 g (0,368 mmol) 2-(1-Methyl-3-trifluormethyl-pyrazol-5-yloxy)-6-(aminomethyl)- pyridin wurden in 5 ml Ameisensäureethylester 3 h auf Rückfluß erhitzt.0.100 g (0.368 mmol) of 2- (1-methyl-3-trifluoromethyl-pyrazol-5-yloxy) -6- (aminomethyl) pyridine were refluxed in 5 ml of ethyl formate for 3 hours.
Anschließend wurde die Lösung über eine Kartusche mit 3 g Kieselgel gefüllt, filtriert und diese Kartusche mit Essigsäureethylester nachgewaschen. Das Filtrat wurde eingeengtThe solution was then filled with 3 g of silica gel through a cartridge, filtered and this cartridge was washed with ethyl acetate. The filtrate was concentrated
Ausbeute 0,101 g (91 %); Schmelzpunkt 84°C. NMR zeigt die erwarteten Signale:Yield 0.101 g (91%); Melting point 84 ° C. NMR shows the expected signals:
1H NMR (CDCI3/TMS): δ (ppm) = 3,80 (s, 3H, N-CH3), 4,57 (d, 2H, J = 7 Hz, N-CH2-1H NMR (CDCI 3 / TMS): δ (ppm) = 3.80 (s, 3H, N-CH 3 ), 4.57 (d, 2H, J = 7 Hz, N-CH 2 -
), 6,26 (s, 1H, C-Hpyrazol), 6,30 (s, br, 1H, N-H), 6,95 (d, 1H, J = 8 Hz, pyridin C-H),), 6.26 (s, 1H, C-Hpyrazole), 6.30 (s, br, 1H, N-H), 6.95 (d, 1H, J = 8 Hz, pyridine C-H),
7,15 (d, 1H, J = 8 Hz, pyridin C-H), 7,78 (t, 1H, J = 8 Hz, pyridin C-H), 8,27 (s, 1H, H-7.15 (d, 1H, J = 8 Hz, pyridine C-H), 7.78 (t, 1H, J = 8 Hz, pyridine C-H), 8.27 (s, 1H, H-
CO).CO).
Beispiel 3Example 3
3a) 2-(1-Methyl-3-trifluormethylpyrazol-5-yloxy)-6-(methylaminomethyl)-pyridin. 4,40 g (14,7 mmol) 2-(1-Methyl-3-trifluormethylpyrazol-5-yloxy)-6- (formylaminomethyl)-pyridin wurden unter Schutzgasatmosphäre in 45 ml wasserfreiem THF gelöst und bei 0°C mit 4,17 ml (44,0 mmol) Borandimethylsulfid-komplex versetzt. Das Gemisch wurde für 2,5 h auf 50°C erwärmt. Nach Abkühlen auf Raumtemperatur wurde die Reaktionslösung mit 100 ml 2 n HCI versetzt und 1 h gerührt und anschließend mit Essigsäureethylester extrahiert. Die wässrige Phase wurde mit 2 n NaOH alkalisch gestellt und mehrfach mit Essigsäureethylester extrahiert. Die Extrakte trocknete man über MgSO4 und engte bis zur Trockene ein. Ausbeute 2.22 g Öl; NMR zeigte die erwarteten Signale: 1H NMR (DMSO-d6/TMS): δ (ppm) = 2,25 (s, 3H, N-CH3 pyrazol 3,3 (s br., 1H, N-H (zusammen mit H2O)), 3,63 (s, 2H, CH2-N) 3,75 (s, 3H, CH3-N), 6,60 (s, 1 H, C-H Pyrazol), 7,08 (d, 1H, J = 8 Hz, C-H Pyridin), 7,30 (d, 1H, J = 8 Hz, C-H Pyridin), 7,93 (t, 1H, J = 8 Hz, C-H Pyridin).3a) 2- (1-methyl-3-trifluoromethylpyrazol-5-yloxy) -6- (methylaminomethyl) pyridine. 4.40 g (14.7 mmol) of 2- (1-methyl-3-trifluoromethylpyrazol-5-yloxy) -6- (formylaminomethyl) pyridine were added in 45 ml under a protective gas atmosphere dissolved anhydrous THF and added 4.17 ml (44.0 mmol) of borane dimethyl sulfide complex at 0 ° C. The mixture was heated to 50 ° C for 2.5 h. After cooling to room temperature, 100 ml of 2N HCl were added to the reaction solution and the mixture was stirred for 1 h and then extracted with ethyl acetate. The aqueous phase was made alkaline with 2N NaOH and extracted several times with ethyl acetate. The extracts were dried over MgSO 4 and concentrated to dryness. Yield 2.22 g of oil; NMR showed the expected signals: 1H NMR (DMSO-d6 / TMS): δ (ppm) = 2.25 (s, 3H, N-CH 3 pyrazole 3.3 (s br., 1H, NH (together with H 2 O)), 3.63 (s, 2H, CH 2 -N) 3.75 (s, 3H, CH 3 -N), 6.60 (s, 1 H, CH pyrazole), 7.08 (d, 1H, J = 8 Hz, CH pyridine), 7.30 (d, 1H, J = 8 Hz, CH pyridine), 7.93 (t, 1H, J = 8 Hz, CH pyridine).
2-(1-Methyl-3-trifluormethylpyrazol-5-yloxy)-6-[(N-isopropylcarbonyl-N- methyl)-aminomethyl]-pyridin.2- (1-Methyl-3-trifluoromethylpyrazol-5-yloxy) -6 - [(N-isopropylcarbonyl-N-methyl) aminomethyl] pyridine.
0,100 g (0,349 mmol) 2-(1-Methyl-3-trifluormethyl-pyrazol-5-yloxy)-6-(methyl aminomethyl)-pyridin wurden in 4,0 ml Methylenchlorid zusammen mit 68 mg (0,53 mmol) Diisopropylethylamin vorgelegt und mit 45 mg (0,42 mmol) Isobuttersäurechlorid versetzt. Nach 45 min rühren bei Raumtemperatur wurde die Reaktionslösung auf 1 n HCI gegeben und mit Methylenchlorid extrahiert. Die organische Phase wurde eingeengt und man erhielt ein Öl. Ausbeute 0,096 g (77 %); NMR zeigte die erwarteten Signale: Das Spektrum zeigt zwei Konformere, die als A (75 %) und B (25 %) beschrieben werden:0.100 g (0.349 mmol) of 2- (1-methyl-3-trifluoromethyl-pyrazol-5-yloxy) -6- (methyl aminomethyl) pyridine were dissolved in 4.0 ml of methylene chloride together with 68 mg (0.53 mmol) of diisopropylethylamine submitted and treated with 45 mg (0.42 mmol) of isobutyric acid chloride. After stirring for 45 min at room temperature, the reaction solution was added to 1N HCl and extracted with methylene chloride. The organic phase was concentrated and an oil was obtained. Yield 0.096 g (77%); NMR showed the expected signals: The spectrum shows two conformers, which are described as A (75%) and B (25%):
Konformer A: 1 H NMR (CDCI3/TMS) δ (ppm) = 1 ,11 (d, 6H, J = 8 Hz, (CH3)2- CH), 2,82 (sept, 1H, J = 8 Hz, (CH3)2-CH), 3,06 (s, 3H, CO-N-CH3), 3,75 (s, 3H, N-CH3 Pyrazol), 4,53 (s, 2H, CH2-N), 6*,28 (s, 1H, C-H Pyrazol), 6,90 (d, 1H, J = 8 Hz, C-H Pyridin), 7,07 ,(d, 1H, J = 8 Hz, C-H Pyridin), 7,73 (t, 1H, J = 8 Hz, C-H Pyridin).Conformer A: 1 H NMR (CDCI 3 / TMS) δ (ppm) = 1, 11 (d, 6H, J = 8 Hz, (CH 3 ) 2 - CH), 2.82 (sept, 1H, J = 8 Hz, (CH 3 ) 2 -CH), 3.06 (s, 3H, CO-N-CH 3 ), 3.75 (s, 3H, N-CH 3 pyrazole), 4.53 (s, 2H, CH 2 -N), 6 * , 28 (s, 1H, CH pyrazole), 6.90 (d, 1H, J = 8 Hz, CH pyridine), 7.07, (d, 1H, J = 8 Hz, CH pyridine), 7.73 (t, 1H, J = 8 Hz, CH pyridine).
Konformer B: 1 H NMR (CDCI3/TMS) δ (ppm) = 1 ,07 (d, 6H, J = 8 Hz, (CH3)2CH), 2,75 (sept. 1H, J = 8 Hz, (CH3)2-CH), 2,96 (s, 3H, CO-N-CH3), 3,81 (s, 3H, N-CH3 Pyrazol), 4,53 (s, 2H, qH2-N),-6,33 (s, 1H, C-H Pyrazol), 6,97 (d, 1 H, J = 8 Hz, C-H Pyridin), 6,99 (d, 1 H, J = 8 Hz, C-H Pyridin), 7,80 (t, 1 H, J = 8 Hz, C-H Pyridin).Conforming B: 1 H NMR (CDCI 3 / TMS) δ (ppm) = 1.07 (d, 6H, J = 8 Hz, (CH 3 ) 2 CH), 2.75 (sept. 1H, J = 8 Hz , (CH 3 ) 2 -CH), 2.96 (s, 3H, CO-N-CH 3 ), 3.81 (s, 3H, N-CH 3 pyrazole), 4.53 (s, 2H, qH 2 -N), - 6.33 (s, 1H, CH pyrazole), 6.97 (d, 1 H, J = 8 Hz, CH pyridine), 6.99 (d, 1 H, J = 8 Hz, CH pyridine), 7.80 (t, 1 H, J = 8 Hz, CH pyridine).
Beispiel 4Example 4
2-(1-Methyl-3-trifluormethylpyrazol-5-yloxy)-6-[(N-methylsulfonyl-N-methyl)- aminomethylj-pyridin.2- (1-Methyl-3-trifluoromethylpyrazol-5-yloxy) -6 - [(N-methylsulfonyl-N-methyl) - aminomethylj-pyridine.
0,080 g (0,28 mmol) 2-(1-Methyl-3-trifluormethylpyrazol-5-yloxy)-6-0.080 g (0.28 mmol) 2- (1-methyl-3-trifluoromethylpyrazol-5-yloxy) -6-
(methylaminomethyl)-pyridin wurden in 5 ml Methylenchlorid zusammen mit 0,108 g(methylaminomethyl) pyridine was dissolved in 5 ml of methylene chloride together with 0.108 g
(0,837 mmol) Diisopropylethylamin vorgelegt und mit 0,096 g (0,837 mmol)(0.837 mmol) of diisopropylethylamine and 0.096 g (0.837 mmol)
Methansulfonsäurechlorid versetzt. Nach 4 h rühren bei Raumtemperatur wurde mitMethanesulfonic acid chloride added. After stirring for 4 h at room temperature
2 n NaOH extrahiert und die organische Phase neutral gewaschen und anschließend über Na2SO4 getrocknet und eingedampft. Nach chromatographischer2N NaOH extracted and the organic phase washed neutral and then dried over Na 2 SO 4 and evaporated. According to chromatographic
Reinigung (Kieselgel /Essigsäureethylester) erhielt man ein Öl.Purification (silica gel / ethyl acetate) gave an oil.
Ausbeute 0,088 g (82 %); Das NMR zeigte die erwarteten Signale:Yield 0.088 g (82%); The NMR showed the expected signals:
1 H NMR (CDC /TMS) δ (ppm) = 2,74 (s, 3H, CH3-N-SO2), 2,83 (s, 3H, SO2-CH3),1 H NMR (CDC / TMS) δ (ppm) = 2.74 (s, 3H, CH3-N-SO2), 2.83 (s, 3H, SO 2 -CH 3 ),
3,78 (s, 3H, N-CH3 Pyrazol), 4,39 (s, 2H, CH2-N), 6,30 (s, 1 H, C-H Pyrazol), 7,00 (d,3.78 (s, 3H, N-CH3 pyrazole), 4.39 (s, 2H, CH 2 -N), 6.30 (s, 1 H, CH pyrazole), 7.00 (d,
1 H, J = 8 Hz, CH Pyridin), 7,26 (d, 1 H, J = 8 Hz, CH Pyridin), 7,80 (t, 1H, CH1 H, J = 8 Hz, CH pyridine), 7.26 (d, 1 H, J = 8 Hz, CH pyridine), 7.80 (t, 1H, CH
Pyridin).Pyridine).
Beispiel 5Example 5
5a) 2-(3-Trifluormethylphenyloxy)-6-cyanopyridin5a) 2- (3-trifluoromethylphenyloxy) -6-cyanopyridine
4,00 g (28,9 mmol) 2-Chlor-6-cyanopyridin wurden zusammen mit 9,57 g (69,3 mmol) Kaliumcarbonat in 20 ml wasserfreiem DMF vorgelegt und mit 5,62 g (34,6 mmol) 3-Hydroxybenzotrifluorid versetzt. Nach 10 h rühren bei 90°C wurde mit H2O versetzt und mit Essigsäureethylester mehrfach extrahiert. Die organische Phase wurde dann zweifach mit Wasser gewaschen, über MgSθ4 getrocknet und eingeengt. Ausbeute (Öl): 6,24 g (82 %); NMR zeigte die erwarteten Signale: 1 H NMR (CDCI3/TMS) δ (ppm) = 7,20 (d, 1 H, J = 8 Hz, aromatische H), 7,38 (mc, 1 H, aromatische H), 7,4 - 7,6 (m, 4H, aromatiche H), 7,83 (t, 1 H, J = 8 Hz, CH Pyridin).4.00 g (28.9 mmol) of 2-chloro-6-cyanopyridine were introduced together with 9.57 g (69.3 mmol) of potassium carbonate in 20 ml of anhydrous DMF and with 5.62 g (34.6 mmol) of 3 -Hydroxybenzotrifluorid added. After stirring for 10 h at 90 ° C., H 2 O was added and the mixture was extracted several times with ethyl acetate. The organic phase was then washed twice with water, dried over MgSO4 and concentrated. Yield (oil): 6.24 g (82%); NMR showed the expected signals: 1 H NMR (CDCI3 / TMS) δ (ppm) = 7.20 (d, 1 H, J = 8 Hz, aromatic H), 7.38 (mc, 1 H, aromatic H), 7.4 - 7, 6 (m, 4H, aromatic H), 7.83 (t, 1 H, J = 8 Hz, CH pyridine).
5b) 2-(3-Trifluormethylphenyloxy)-6-(aminomethyl)-pyridin5b) 2- (3-trifluoromethylphenyloxy) -6- (aminomethyl) pyridine
3,00 g (11 ,4 mmol) 2-(3-Trifluormethylphenyloxy)-6-cyanopyridin wurden in 120 ml Essigsäure gelöst und nach Zugabe von 300 mg Pd (OH)2 20%ig auf Kohle für 3 h bei Raumtemperatur bei 17 bar Wasserstoffdruck hydriert. Anschließend filtrierte man vom Katalysator ab, eigte die organische Phase ein und nahm den Rückstand in Wasser auf. Diese Lösung wurde zweimal mit Essigsäureethylester gewaschen, anschließend mit 2 n NaOH auf PH 10 eingestellt und mehrfach mit Essigsäureethylester extrahiert. Die vereinigten organischen Extrakte wurden über MgSO4 getrocknet und anschließend bis zur Trockne eingedampft.3.00 g (11.4 mmol) of 2- (3-trifluoromethylphenyloxy) -6-cyanopyridine were dissolved in 120 ml of acetic acid and after addition of 300 mg of Pd (OH) 2 20% on carbon for 3 h at room temperature at 17 bar hydrogen pressure hydrogenated. The catalyst was then filtered off, the organic phase was evaporated and the residue was taken up in water. This solution was washed twice with ethyl acetate, then adjusted to pH 10 with 2N NaOH and extracted several times with ethyl acetate. The combined organic extracts were dried over MgSO 4 and then evaporated to dryness.
Ausbeute 1 ,02 g (67 %); NMR zeigte die erwarteten Signale: 1H NMR (CDCI3/TMS) δ (ppm) = 1.7 (s, br, 2H, NH2), 3,83 (s, 2H, CH2-N), 6,78 (d, 1H, J = 8 Hz, CH Pyridin), 7,02 (d, 1 H, J = 8 Hz, CH Pyridin), 7,35 (m, 1 H, C-H-Phenyl), 7,4 - 7,55 (m, 3H, Phenyl-H), 7,67 (t, 1 H, J = 8 Hz, CH Pyridin).Yield 1.02 g (67%); NMR showed the expected signals: 1H NMR (CDCI 3 / TMS) δ (ppm) = 1.7 (s, br, 2H, NH 2 ), 3.83 (s, 2H, CH2-N), 6.78 (d, 1H, J = 8 Hz, CH pyridine), 7.02 (d, 1 H, J = 8 Hz, CH pyridine), 7.35 (m, 1 H, CH-phenyl), 7.4 - 7.55 (m, 3H, phenyl-H), 7.67 (t, 1H, J = 8 Hz, CH pyridine).
5c) 2-(3-Trifluorphenyloxy)-6-(dichloracetyl-aminomethyl-pyridin5c) 2- (3-trifluorophenyloxy) -6- (dichloroacetylaminomethylpyridine
0,100 g (0,373 mmol) 2-(3-Trifluorphenyloxy)-6-(aminomethyl)-pyridin wurden in 4,0 ml Methylenchlorid zusammen mit 0,072 g (0,56 mmol) Diisopropylethylamin vorgelegt und mit 0,066 g (0,450 mmol) Dichloracetylchlorid versetzt. Nach 3 h rühren bei Raumtemperatur wurde mit 1 n HCI extrahiert, die organische Phase getrocknet und eingedampft. Der Rückstand war kristallin. Ausbeute 0,070 g (50 %); Schmelzpunkt 70,8°C.0.100 g (0.373 mmol) of 2- (3-trifluorophenyloxy) -6- (aminomethyl) pyridine were placed in 4.0 ml of methylene chloride together with 0.072 g (0.56 mmol) of diisopropylethylamine, and 0.066 g (0.450 mmol) of dichloroacetyl chloride was added , After stirring for 3 h at room temperature, the mixture was extracted with 1 N HCl, the organic phase was dried and evaporated. The residue was crystalline. Yield 0.070 g (50%); Melting point 70.8 ° C.
Die in den nachfolgenden Tabellen 1 und 2 aufgeführten Verbindungen der Formel (I") und (H) können analog zu den Beispielen 1 - 5 erhalten werden. Tabelle 1The compounds of the formula (I ") and (H) listed in Tables 1 and 2 below can be obtained analogously to Examples 1-5. Table 1
Tabelle 2: Table 2:
Erläuterungen zu Tabellen 1 und 2:Explanations to Tables 1 and 2:
Struktur 1 : Struktur 2:Structure 1: Structure 2:
B. FormulierungsbeispieleB. Examples of formulation
a) Ein Stäubemittel wird erhalten, indem man 10 Gew.-Teile einer Verbindung der Formel (I) und 90 Gew.-Teile Talkum als Inertstoff mischt und in einer Schlagmühle zerkleinert.a) A dusting agent is obtained by mixing 10 parts by weight of a compound of the formula (I) and 90 parts by weight of talc as an inert substance and comminuting in a hammer mill.
b) Ein in Wasser leicht dispergieφares, benetzbares Pulver wird erhalten, indem man 25 Gewichtsteile einer Verbindung der Formel (I), 64 Gew.-Teile kaolinhaltigen Quarz als Inertstoff, 10 Gewichtsteile ligninsulfonsaures Kalium und 1 Gew.-Teil olepylmethyltaurinsaures Natrium als Netz- und Dispergiermittel mischt und in einer Stiftmühle mahlt. c) Ein in Wasser leicht dispergierbares Dispersionskonzentrat wird erhalten, indem man 20 Gew.-Teile einer Verbindung der Formel (I) mit 6 Gew.-Teilen Alkylphenolpolyglykolether (©Triton X 207), 3 Gew.-Teilen Isotridecanolpolyglykolether (8 EO) und 71 Gew.-Teilen paraffinischem Mineralöl (Siedebereich z.B. ca. 255 bis über 277 C) mischt und in einer Reibkugelmühle auf eine Feinheit von unter 5 Mikron vermahlt.b) A slightly dispersible, wettable powder in water is obtained by adding 25 parts by weight of a compound of the formula (I), 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of olepylmethyl tauric acid sodium as a and dispersant mixes and grinds in a pin mill. c) A dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of a compound of the formula (I) with 6 parts by weight of alkylphenol polyglycol ether (© Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to above 277 C) are mixed and ground in a attritor to a fineness of less than 5 microns.
d) Ein emulgierbares Konzentrat wird erhalten aus 15 Gew.-Teilen einer Verbindung der Formel (I), 75 Gew.-Teilen Cyclohexanon als Lösungsmittel und 10 Gew.-Teilen oxethyliertes Nonylphenol als Emulgator.d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol as emulsifier.
e) Ein in Wasser dispergierbares Granulat wird erhalten indem man 75 Gew.-Teile einer Verbindung der Formel (I),e) Water-dispersible granules are obtained by adding 75 parts by weight of a compound of the formula (I),
10 Gew.-Teile ligninsulfonsaures Calcium,10 parts by weight of calcium lignosulfonate,
5 Gew.-Teile Natriumlaurylsulfat,5 parts by weight of sodium lauryl sulfate,
3 Gew.-Teile Polyvinylalkohol und3 parts by weight of polyvinyl alcohol and
7 Gew.-Teile Kaolin mischt, auf einer Stiftmühle mahlt und das Pulver in einem Wirbelbett durchMix 7 parts by weight of kaolin, grind on a pin mill and mix the powder in a fluidized bed
Aufsprühen von Wasser als Granulierflüssigkeit granuliert.Spraying water granulated as granulating liquid.
f) Ein in Wasser dispergierbares Granulat wird auch erhalten, indem man 25 Gew.-Teile einer Verbindung der Formel (I),f) Water-dispersible granules are also obtained by adding 25 parts by weight of a compound of the formula (I),
5 Gew.-Teile 2,2'-dinaphthylmethan-6,6'-disulfonsaures Natrium5 parts by weight of 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium
2 Gew.-Teile oleoylmethyltaurinsaures Natrium,2 parts by weight of sodium oleoylmethyl taurine,
1 Gew.-Teil Polyvinylalkohol,1 part by weight of polyvinyl alcohol,
17 Gew.-Teile Calciumcarbona und17 parts by weight of calcium carbonate and
50 Gew.-Teile Wasser auf einer Kolloidmühle homogenisiert und vorzerkleinert, anschließend auf einer Perlmühle mahlt und die so erhaltene Suspension in einem Sprühturm r mittels einer Einstoffdüse zerstäubt und trocknet. C. Biologische Beispiele50 parts by weight of water are homogenized and pre-comminuted on a colloid mill, then ground on a bead mill and the suspension thus obtained is atomized and dried in a spray tower r by means of a single-component nozzle. C. Biological examples
1. Unkrautwirkung im Vorauflauf1. Pre-emergence weed action
Samen bzw. Rhizomstücke von mono- und dikotylen Unkrautpflanzen wurden in Papptöpfen in sandiger Lehmerde ausgelegt und mit Erde abgedeckt. Die in Form von benetzbaren Pulvern oder Emulsionskonzentraten formulierten erfindungsgemäßen Verbindungen wurden dann als wäßrige Suspensionen bzw. Emulsionen mit einer Wasseraufwandmenge von umgerechnet 600 bis 800 l/ha in unterschiedlichen Dosierungen auf die Oberfläche der Abdeckerde appliziert. Nach der Behandlung wurden die Töpfe im Gewächshaus aufgestellt und unter guten Wachstumsbedingungen für die Unkräuter gehalten. Die optische Bonitur der Pflanzen- bzw. Auflaufschäden erfolgte nach dem Auflaufen der Versuchspflanzen nach einer Versuchszeit von 3 bis 4 Wochen im Vergleich zu unbehandelten Kontrollen. Wie die Ergebnisse zeigen, weisen erfindungsgemäße Verbindungen eine gute herbizide Vorauflaufwirksamkeit gegen ein breites Spektrum von Ungräsern und Unkräutern auf. Beispielsweise haben die Beispiele Nr.4, 5, 10, 18, 19, 20, 21, 22, 24, 25, 26, 27, 28, 29, 30, 31 , 34, 66, 78, 79, 134, 147, 148, 149, 150, 153, 155, 157, 159, 261 , 275, 276, 279, 281 , 283, 284, 285, 286, 287, 533, 539, 541 , 542, 543, 544, 545, 546, 549 und andere Verbindungen aus Tabelle 1 sehr gute herbizide Wirkung gegen Schadpflanzen wie Sinapis alba, Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus und Panicum miliaceum im Vorauflaufverfahren bei einer Aufwandmenge von 1 kg und weniger Aktivsubstanz pro Hektar.Seeds or rhizome pieces of monocotyledonous and dicotyledonous weed plants were placed in cardboard pots in sandy loam and covered with soil. The compounds according to the invention formulated in the form of wettable powders or emulsion concentrates were then applied as aqueous suspensions or emulsions with a water application rate of the equivalent of 600 to 800 l / ha in different dosages to the surface of the covering earth. After the treatment, the pots were placed in the greenhouse and kept under good growth conditions for the weeds. After the test plants had emerged, the optical damage to the plants or the emergence damage was assessed after a test period of 3 to 4 weeks in comparison to untreated controls. As the results show, compounds according to the invention have good herbicidal pre-emergence activity against a broad spectrum of grasses and weeds. For example, Examples 4, 5, 10, 18, 19, 20, 21, 22, 24, 25, 26, 27, 28, 29, 30, 31, 34, 66, 78, 79, 134, 147, 148, 149, 150, 153, 155, 157, 159, 261, 275, 276, 279, 281, 283, 284, 285, 286, 287, 533, 539, 541, 542, 543, 544, 545, 546, 549 and other compounds from Table 1 very good herbicidal activity against harmful plants such as Sinapis alba, Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus and Panicum miliaceum in advance Application rate of 1 kg and less active substance per hectare.
2. Unkrautwirkung im Nachauflauf2. Post-emergence weed action
Samen bzw. Rhizomstücke von mono- und dikotylen Unkräutern wurden in Plastiktöpfen in sandigem Lehmboden ausgelegt( mit Erde abgedeckt und im Gewächshaus unter guten Wachstumsbedingungen angezogen. Drei Wochen nach der Aussaat wurden die Versuchspflanzen im Dreiblattstadium behandelt. Die als Spritzpulver bzw. als Emulsionskonzentrate formulierten erfindungsgemäßen Verbindungen wurden in verschiedenen Dosierungen mit einer Wasseraufwand menge von umgerechnet 600 bis 800 l/ha auf die grünen Pflanzenteile gesprüht. Nach ca. 3 bis 4 Wochen Standzeit der Versuchspflanzen im Gewächshaus unter optimalen Wachstumsbedingungen wurde die Wirkung der Präparate optisch im Vergleich zu unbehandelten Kontrollen bonitiert. Die erfindungsgemäßen Mittel weisen auch im Nachauflauf eine gute herbizide Wirksamkeit gegen ein breites Spektrum wirtschaftlich wichtiger Ungräser und Unkräuter auf. Beispielsweise haben die Beispiele Nr. 4, 5, 10, 18, 19, 20, 21 , 22, 24, 25, 26, 27, 28, 29, 30, 31 , 34, 66, 78, 79, 134, 147, 148, 149, 150, 153, 155, 157, 159, 261 , 275, 276, 279, 281 , 283, 284, 285, 286, 287, 533, 539, 541 , 542, 543, 544, 545, 546, 549 und andere Verbindungen aus Tabelle 1 sehr gute herbizide Wirkung gegen Schadpflanzen wie Sinapis alba, Echinochloa crus-galli, Lolium multiflorum, Chrysanthemum segetum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus, Panicum miliaceum und Avena sativa im Nachauflaufverfahren bei einer Aufwandmenge von 1 kg und weniger Aktivsubstanz pro Hektar.Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds were placed in plastic pots in sandy loam soil ( covered with earth and in the Greenhouse grown under good growing conditions. The test plants were treated at the three-leaf stage three weeks after sowing. The compounds according to the invention formulated as wettable powder or as emulsion concentrates were sprayed onto the green parts of the plant in various dosages with an amount of water converted from 600 to 800 l / ha. After the test plants had stood in the greenhouse for about 3 to 4 weeks under optimal growth conditions, the effect of the preparations was assessed visually in comparison with untreated controls. The agents according to the invention also have good herbicidal activity against a broad spectrum of economically important grasses and weeds, even after emergence. For example, Examples Nos. 4, 5, 10, 18, 19, 20, 21, 22, 24, 25, 26, 27, 28, 29, 30, 31, 34, 66, 78, 79, 134, 147, 148, 149, 150, 153, 155, 157, 159, 261, 275, 276, 279, 281, 283, 284, 285, 286, 287, 533, 539, 541, 542, 543, 544, 545, 546, 549 and other compounds from Table 1 very good herbicidal activity against harmful plants such as Sinapis alba, Echinochloa crus-galli, Lolium multiflorum, Chrysanthemum segetum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus, Panicum miliaceum and Avena sativa in the post-emergence process with a post-emergence procedure kg and less of active ingredient per hectare.
3. Kulturpflanzenverträglichkeit3. Crop tolerance
In weiteren Versuchen im Gewächshaus wurden Samen einer größeren Anzahl von Kulturpflanzen und Unkräutern in sandigem Lehmboden ausgelegt und mit Erde abgedeckt. Ein Teil der Töpfe wurde sofort wie unter Abschnitt 1 beschrieben behandelt, die übrigen im Gewächshaus aufgestellt, bis die Pflanzen zwei bis drei echte Blätter entwickelt haben und dann wie unter Abschnitt 2 beschrieben mit den erfindungsgemäßen Substanzen der Formel (I) in unterschiedlichen Dosierungen besprüht. Vier bis fünf Wochen nach der Applikation und Standzeit im Gewächshaus wurde mittels optischer Bonitur festgestellt, daß erfindungsgemäße Verbindungen zweikeimblättrige Kulturen wie Soja', Baumwolle, Raps, Zuckerrüben oder Kartoffeln im Vor- und Nachauflaufverfahren selbst bei hohen Wirkstoffdosierungen ungeschädigt ließen. Einige Substanzen schonten darüber hinaus auch Gramineen-Kulturen wie Gerste, Weizen, Roggen, Hirsen, Mais oder Reis. Die Verbindungen der Formel (I) zeigen teilweise eine hohe Selektivität und eignen sich deshalb zur Bekämpfung von unerwünschten Pflanzenwuchs in landwirtschaftlichen Kulturen. In further experiments in the greenhouse, seeds of a large number of crop plants and weeds were laid out in sandy loam soil and covered with soil. Some of the pots were immediately treated as described in Section 1, the rest were placed in the greenhouse until the plants had developed two to three true leaves and then sprayed as described in Section 2 with the substances of the formula (I) according to the invention in different dosages. Four to five weeks after application and standing in the greenhouse, it was found by means of optical scoring that compounds according to the invention dicotyledonous crops such as soybean, cotton, rape, sugar beet or pre- and post-emergence potatoes, even with high doses of active ingredient, undamaged. Some substances also protect Gramineae crops such as barley, wheat, rye, millet, corn or rice. Some of the compounds of the formula (I) are highly selective and are therefore suitable for combating undesirable plant growth in agricultural crops.

Claims

Patentansprüche claims
Verbindung der Formel (I) und/oder deren Salze,Compound of the formula (I) and / or salts thereof,
Formel (I)Formula (I)
worin R1 gleich oder verschieden H, Halogen, CN, Nitro, SF5, (CrC8)Alkyl, (C2-wherein R 1 is the same or different H, halogen, CN, nitro, SF 5 , (C r C 8 ) alkyl, (C 2 -
C8)Alkenyl, (C2-C8)Alkinyi, (C C8)Alkoxy, [(CrC8)Alkyl]-carbonyl oderC 8 ) alkenyl, (C 2 -C 8 ) alkinyi, (CC 8 ) alkoxy, [(C r C 8 ) alkyl] carbonyl or
(C,-C8)Alkylsulfonyl, wobei jeder der letztgenannten sechs Reste unsubstituiert oder substituiert ist,(C, -C 8 ) alkylsulfonyl, each of the latter six radicals being unsubstituted or substituted,
S(O)p-R7, wobei p = 0, 1 oder 2 undS (O) p -R 7 , where p = 0, 1 or 2 and
R7 (d-CβJAlkyl, (CrC8)Haloalkyl oder NR8R9 bedeutet.wobeiR 7 represents (d-CβJ alkyl, (C r C 8 ) haloalkyl or NR 8 R 9
R8,R9 unabhängig voneinander gleich oder verschieden H, (C,- C8)Alkyl, (C2-C8)Alkenyl, (C7-C10)Arylalkyl, (C7-C10)Alkylaryl oder (C6- C10)Aryl sind, wobei jeder der letztgenannten fünf Reste unsubstituiert oder substituiert ist, oder eine Gruppe der FormelR 8 , R 9, independently of one another, are identical or different H, (C, - C 8 ) alkyl, (C 2 -C 8 ) alkenyl, (C 7 -C 10 ) arylalkyl, (C 7 -C 10 ) alkylaryl or (C 6 - C 10 ) are aryl, each of the latter five radicals being unsubstituted or substituted, or a group of the formula
WW
bedeutet, wobei R10,(C1-C8)Alkyl bedeutet, welches unsubstituiert oder substituiert ist, und W = O oder S bedeutet, A optional substituiertes Aryl oder einen optional substituierten heterocyciischenmeans where R 10 is (C 1 -C 8 ) alkyl which is unsubstituted or substituted, and W = O or S means A optionally substituted aryl or an optionally substituted heterocyclic
Rest bedeutet, X O oder S bedeutet, R2,R3,R4,R5 gleich oder verschieden H, Halogen, CN, (CrC8)Alkoxy oder (C1-C8)Alkyl bedeuten, wobei jeder der beiden letztgenannten Reste unsubstituiert oder substituiert ist, m 0 oder 1 bedeutet, R6 H, (CrC8)Alkyl, (CrC8)Alkoxy, (C2-C8)Alkenyl oder (C2-C8)Alkinyl, wobei jeder der vier letztgenannten Reste unsubstituiert oder substituiert ist, oder Hydroxy oder einen Acylrest bedeutet, und B ein Acylrest ist, oderRadical means XO or S, R 2 , R 3 , R 4 , R 5 are identical or different and are H, halogen, CN, (C r C 8 ) alkoxy or (C 1 -C 8 ) alkyl, each of the two the latter radicals is unsubstituted or substituted, m is 0 or 1, R 6 is H, (C r C 8 ) alkyl, (C r C 8 ) alkoxy, (C 2 -C 8 ) alkenyl or (C 2 -C 8 ) alkynyl , wherein each of the last four radicals is unsubstituted or substituted, or is hydroxyl or an acyl radical, and B is an acyl radical, or
B und R6 bilden gemeinsam eine 4- oder 5-gliedrige Kette, ausgenommen N-Hydroxy-N-[(6-phenoxy-2-pyridyl)methyl]-acetamid und dessenB and R 6 together form a 4- or 5-membered chain, with the exception of N-hydroxy-N - [(6-phenoxy-2-pyridyl) methyl] -acetamide and its
Salze.Salts.
2. Verbindung der Formel (I) und/oder deren Salze, gemäß Anspruch 1 , worin2. A compound of formula (I) and / or salts thereof, according to claim 1, wherein
R1 gleich oder verschieden H, Halogen, CN, Nitro, SF5, (C CgJAlkyl, das unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen,R 1, the same or different, H, halogen, CN, nitro, SF 5 , (C CgJ alkyl, which is unsubstituted or by one or more radicals from the group halogen,
(CrC8)Alkoxy, (CrC^Alkylthio, (CrC8)Alkylsulfinyl, (C^C Alkylsulfonyl, [(G,-(C r C 8 ) alkoxy, (CrC ^ alkylthio, (C r C 8 ) alkylsulfinyl, (C ^ C alkylsulfonyl, [(G, -
C8)Alkoxy]-carbonyl und CN substituiert ist,C 8 ) alkoxy] carbonyl and CN is substituted,
(C2-C8)Alkenyl oder (C2-C8)Alkinyl, das unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C,-C8)Alkoxy und (C,-(C 2 -C 8 ) alkenyl or (C 2 -C 8 ) alkynyl which is unsubstituted or by one or more radicals from the group halogen, CN, (C, -C 8 ) alkoxy and (C, -
C8)Alkylthio substituiert ist,C 8 ) alkylthio is substituted,
(C.,-C8)Alkoxy, [(C,-C8)Alkyl]-carbonyl oder,(CrC8)Alkylsulfonyl, wobei jeder der Reste unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe(C., - C 8 ) alkoxy, [(C, -C 8 ) alkyl] carbonyl or, (C r C 8 ) alkylsulfonyl, each of the radicals being unsubstituted or by one or more radicals from the group
Halogen, CN, substituiert ist,Halogen, CN, is substituted,
S(O)p-R7, wobei S (O) p -R 7 , where
R7 (C1-C8)Alkyl, oder NR8R9 bedeutet.wobei R8,R9 unabhängig voneinander gleich oder verschieden H, (Cr C8)Alkyl, (C2-C8)Alkenyl, (C7-C10)Arylalkyl, (C7-C10)Alkylaryl oder (C6- C10)Aryl sind, wobei jeder der letztgenannten fünf Reste unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (G,- C8)Alkoxy und (C.,-C8)Alkylthio substituiert ist, oder eine Gruppe der FormelR 7 (C 1 -C 8 ) alkyl, or NR 8 R 9 means R 8 , R 9, independently of one another, are identical or different H, (C r C 8 ) alkyl, (C 2 -C 8 ) alkenyl, (C 7 -C 10 ) arylalkyl, (C 7 -C 10 ) alkylaryl or (C 6 - C 10 ) aryl, where each of the latter five radicals is unsubstituted or substituted by one or more radicals from the group halogen, CN, (G, - C 8 ) alkoxy and (C., - C 8 ) alkylthio, or one Group of the formula
WW
wobei R10 (C,-C8)Alkyl bedeutet, welches unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C C8)Alkoxy und (C C8)Alkylthio substituiert ist, und W = O oder S bedeutet,where R 10 is (C, -C 8 ) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, CN, (CC 8 ) alkoxy and (CC 8 ) alkylthio, and W = O or S,
A ein optional substituierter Phenylrest oder ein optional substituierter heteroaromatischer Rest bedeutet,A represents an optionally substituted phenyl radical or an optionally substituted heteroaromatic radical,
X O oder S bedeutet,X means O or S,
R2,R3,R ,R5 gleich oder verschieden H, Halogen, CN, (C.,-C8)Alkoxy oder (C,-C8)Alkyl bedeuten, wobei jeder der beiden letztgenannten Reste unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (CrC8)Alkoxy und (C C8)Alkylthio substituiert ist, m 0 oder 1 bedeutet,R 2 , R 3 , R, R 5, identical or different, denote H, halogen, CN, (C., - C 8 ) alkoxy or (C, -C 8 ) alkyl, each of the latter two radicals being unsubstituted or by one or several radicals from the group halogen, CN, (C r C 8 ) alkoxy and (CC 8 ) alkylthio are substituted, m denotes 0 or 1,
R6 H, (C-rCgJAlkyl, das unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, (CrC8)Alkoxy, (CrC8)Alkylthio, (CyCgJAlkylsulfinyl, (Cr C8)Alkylsulfonyl, [(C,-C8)Alkoxyj-carbonyl und CN substituiert ist, (C2- C8)Alkenyl oder (C2-G8)Alkinyl, die unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen,yCNr (CrC8)Alkoxy und (CrC8)Alkylthio substituiert sind,R 6 H, (C-rCgJ alkyl which is unsubstituted or by one or more radicals from the group halogen, (C r C 8 ) alkoxy, (C r C 8 ) alkylthio, (CyCgJ alkyl sulfinyl, (C r C 8 ) alkyl sulfonyl, [ (C, -C 8 ) alkoxyj-carbonyl and CN is substituted, (C 2 - C 8 ) alkenyl or (C 2 -G 8 ) alkynyl which is unsubstituted or by one or more radicals from the group halogen, y CN r ( C r C 8 ) alkoxy and (C r C 8 ) alkylthio are substituted,
Hydroxy, (C|-C8)Alkoχy oder Acyl wie Formyl, [(C1-C8)Alkyl]-carbonyl, [(C2- C8)Alkenyl]-carbonyl, [(C2-C8)Alkinyl]-carbonyl, (CrC8)Alk Jsulfbnyl, (C2- C8)Alkenylsulfonyl oder (C2-C8)AlkinyIsulfonyl, wobei jeder der letztgenannten sechs Reste unsubstituiert oder substituiert ist, Phenylcarbonyl oder Phenylsulfonyl, wobei der Phenylrest in jedem der beiden letztgenannten Reste unsubstituiert oder substituiert ist, und [(C,-C8)Alkyl]-carbonyl wie lineares oder verzweigtes [(CrC8)-Alkyl]-carbonyl oder [(C3-C6)Cycloalkyl]-carbonyl, wobei jeder der Reste unsubstituiert oder substituiert ist, oderHydroxy, (C | -C 8 ) Alkoχy or acyl such as formyl, [(C 1 -C 8 ) alkyl] carbonyl, [(C 2 - C 8 ) alkenyl] carbonyl, [(C 2 -C 8 ) alkynyl ] -carbonyl, (C r C 8 ) Alk Jsulfbnyl, (C 2 - C 8 ) alkenylsulfonyl or (C 2 -C 8 ) alkynyl isulfonyl, each of the latter six radicals being unsubstituted or substituted, phenylcarbonyl or phenylsulfonyl, the phenyl radical in each of the latter two radicals being unsubstituted or substituted, and [(C, -C 8 ) alkyl] carbonyl such as linear or branched [(C r C 8 ) alkyl] carbonyl or [(C 3 -C 6 ) cycloalkyl] carbonyl, each of the radicals being unsubstituted or substituted, or
[(C2-C8)Alkenyl]-carbonyl oder [(C2-C8)AIkinyl]-carbonyl, wobei jeder der letztgenannten zwei Reste unsubstituiert oder substituiert ist, (C1-C8)Alkylsulfonyl, wie lineares oder verzweigtes Cj-Cs-Alkylsulfonyl oder (C3-C8)Cycloalkylsulfonyl, oder (C2-C8)Alkenylsulfonyl oder (C2- C8)Alkinylsulfonyl, wobei jeder der Reste unsubstituiert oder substituiert ist, oder Phenylcarbonyl oder Phenylsulfonyl, wobei der Phenylrest in jedem der beiden letztgenannten Reste unsubstituiert oder substituiert ist, oder Mono- oder Di-[(G,-C8)Alkyl]-aminosulfonyl, Formyl oder eine Gruppe der Formel -CO-CO-R', worin R'=H, OH, (C1-C8)-Alkoxy oder (CrC8)Alkyl ist, wobei jeder der letztgenannten beiden Reste unsubstituiert oder substituiert ist, oder eine Gruppe der Formel[(C 2 -C 8 ) alkenyl] carbonyl or [(C 2 -C 8 ) alkynyl] carbonyl, each of the latter two radicals being unsubstituted or substituted, (C 1 -C 8 ) alkylsulfonyl, such as linear or branched Cj-Cs-alkylsulfonyl or (C 3 -C 8 ) cycloalkylsulfonyl, or (C 2 -C 8 ) alkenylsulfonyl or (C 2 - C 8 ) alkynylsulfonyl, where each of the radicals is unsubstituted or substituted, or phenylcarbonyl or phenylsulfonyl, where the Phenyl radical in each of the latter two radicals is unsubstituted or substituted, or mono- or di - [(G, -C 8 ) alkyl] -aminosulfonyl, formyl or a group of the formula -CO-CO-R ', where R' = H , OH, (C 1 -C 8 ) alkoxy or (C r C 8 ) alkyl, each of the latter two radicals being unsubstituted or substituted, or a group of the formula
R13 R 13
bedeutet, worinmeans what
W ein Sauerstoff- oder Schwefelatom (d.h. O oder S),W is an oxygen or sulfur atom (i.e. O or S),
T O oder S,T O or S,
R11 (C,-C8)AIkyl, (C2-C8)Alkenyl oder (C2-C8)Alkinyl, wobei jeder der drei letztgenannten Reste unsubstituiert oder substituiert ist, R12, R13 gleich oder verschieden H, (CrC8)Alkyl, (C2-C8)Alkenyl oder (C2-C8)Alkinyl, wobei jeder der drei letztgenannten Reste unsubstituiert oder substituiert ist, und die Reste R12 und R13 gemeinsam mit dem N-Atom einen heterocyciischen Rest mit 5 oder 6 Ringgliedern bilden können, der weitere Heteroatome aus der Gruppe N, O und S enthalten kann und unsubstituiert oder substituiert ist, oderR 11 (C, -C 8 ) alkyl, (C 2 -C 8 ) alkenyl or (C 2 -C 8 ) alkynyl, where each of the last three radicals is unsubstituted or substituted, R 12 , R 13 are identical or different H, (C r C 8 ) alkyl, (C 2 -C 8 ) alkenyl or (C 2 -C 8 ) alkynyl, where each of the last three radicals is unsubstituted or substituted, and the radicals R 12 and R 13 together with the N atom can form a heterocyclic radical with 5 or 6 ring members, which further heteroatoms from the May contain group N, O and S and is unsubstituted or substituted, or
B und R6 bilden gemeinsam eine 4- oder 5-gliedrige Kette, z.B. der Formel ("CH2)m-D- oder -D1-(CH2)m1-D-, wobei die Kette unsubstituiert oder substituiert ist, D, D1 unabhängig voneinander SO2 oder CO sind, und m=3 oder 4 und m1=2 oder 3 sind.B and R 6 together form a 4- or 5-membered chain, for example of the formula ("CH 2 ) m -D- or -D 1 - (CH 2 ) m1 -D-, the chain being unsubstituted or substituted, D , D 1 are independently SO 2 or CO, and m = 3 or 4 and m 1 = 2 or 3.
3. Verbindung der Formel (I) und/oder deren Salze gemäß Anspruch 1 oder 2, worin3. A compound of formula (I) and / or salts thereof according to claim 1 or 2, wherein
R1 gleich oder verschieden H, Halogen, CN, (C,-C8)Alkyl oder (C C8)Alkoxy sind, wobei jeder der letztgenannten beiden Reste unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C C8)Alkoxy und (Cr C8)Alkylthio substituiert ist,R 1 are the same or different H, halogen, CN, (C, -C 8 ) alkyl or (CC 8 ) alkoxy, each of the latter two radicals being unsubstituted or by one or more radicals from the group halogen, CN, (CC 8 ) Alkoxy and (C r C 8 ) alkylthio is substituted,
A ein Phenylrest oder ein 5- oder 6-gliedriger heterocyclischer Rest wie ein 5- oder 6-gliedriger N- oder S-enthaltender heteroaromatischer Rest ist, wobei die Reste unsubstituiert oder mit einem oder mehreren Resten aus der Gruppe Halogen, CN, (C,-CB)Alkyl, (C,-Cβ)Alkoxy, Halo(CrC8)Alkyl, Halo(Cr C8)Alkyloxy, Halo(CrC8)Alkylthio, und (C1-C8)Alkoxy-(C1-C8)Alkoxy substituiert sind,A is a phenyl radical or a 5- or 6-membered heterocyclic radical such as a 5- or 6-membered N- or S-containing heteroaromatic radical, where the radicals are unsubstituted or with one or more radicals from the group halogen, CN, (C , -C B ) alkyl, (C, -C β ) alkoxy, halo (C r C 8 ) alkyl, halo (C r C 8 ) alkyloxy, halo (C r C 8 ) alkylthio, and (C 1 -C 8 ) Alkoxy- (C 1 -C 8 ) alkoxy are substituted,
X O oder S ist,X is O or S,
R2, R3 gleich oder verschieden H oder (C,-C8)Alkyl sind, wobei der Alkylrest unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (CrC8)Alkoxy und (C1-C8)Alkylthio substituiert ist, m = 0 ist,R 2 , R 3 are identical or different H or (C, -C 8 ) alkyl, the alkyl radical being unsubstituted or by one or more radicals from the group halogen, CN, (C r C 8 ) alkoxy and (C 1 -C 8 ) alkylthio is substituted, m = 0,
R6 H, Formyl, (CyC8)Alkyl, (C3-C8)Alkenyl, (C3-C8)Alkinyl, (C.,-C8)-Alkoxy oder [(CrC8)Alkyl]-carbonyl ist, wobei jeder der letztgenannten fünf Reste unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C.,-C8)Alkoxy und (C.,-C8)Alkylthio substituiert ist, und B [(C,-C8)Alkyl]-carbonyl wie lineares oder verzweigtes [(C,-C8)-Alkyl]-carbonyl oder [(C3-C6)Cycloalkyl]-carbonyl, wobei jeder der Reste unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, (C1-C8)Alkoxy, (C,- C8)Alkylthio, (C1-C8)Alkylsulfinyl, [(C1-C8)Alkyl]-carbonyl, [(C,-C8)Alkoxy]-carbonyl und CN substituiert ist, oder [(C2-C8)Alkenyl]-carbonyl oder [(C2-C8)Alkinyl]-carbonyl, wobei jeder der Reste unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, und (CrC8)Alkylthio substituiert ist, (C1-C8)Alkylsulfonyl, wie lineares oder verzweigtes CyCg-Alkylsulfonyl oder (C3-C8)Cycloalkylsulfonyl, oder (C2-C8)Alkenylsulfonyl oder (C2- C8)Alkinylsulfonyl, wobei jeder der Reste unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C C8)Alkoxy und (G,- C8)Alkylthio substituiert ist, bedeutet.R 6 H, formyl, (CyC 8 ) alkyl, (C 3 -C 8 ) alkenyl, (C 3 -C 8 ) alkynyl, (C., - C 8 ) alkoxy or [(C r C 8 ) alkyl] is carbonyl, each of the last five radicals being unsubstituted or by one or more radicals from the group halogen, CN, (C., - C 8 ) alkoxy and (C., - C 8 ) alkylthio is substituted, and B [(C, -C 8 ) alkyl] carbonyl such as linear or branched [(C, -C 8 ) -Alkyl] -carbonyl or [(C 3 -C 6 ) cycloalkyl] -carbonyl, where each of the radicals is unsubstituted or by one or more radicals from the group halogen, (C 1 -C 8 ) alkoxy, (C, - C 8 ) Alkylthio, (C 1 -C 8 ) alkylsulfinyl, [(C 1 -C 8 ) alkyl] carbonyl, [(C, -C 8 ) alkoxy] carbonyl and CN is substituted, or [(C 2 -C 8 ) alkenyl] carbonyl or [(C 2 -C 8 ) alkynyl] carbonyl, where each of the radicals is unsubstituted or by one or more radicals from the group halogen, CN, and (C r C 8 ) alkylthio is substituted, (C 1 -C 8 ) alkylsulfonyl, such as linear or branched CyCg-alkylsulfonyl or (C 3 -C 8 ) cycloalkylsulfonyl, or (C 2 -C 8 ) alkenylsulfonyl or (C 2 - C 8 ) alkynylsulfonyl, where each of the radicals is unsubstituted or substituted by one or more radicals from the group halogen, CN, (CC 8 ) alkoxy and (G, - C 8 ) alkylthio.
4. Verbindung der Formel (I) und/oder deren Salze gemäß einen oder mehreren der Ansprüche 1 bis 3, worin4. A compound of formula (I) and / or salts thereof according to one or more of claims 1 to 3, wherein
R in 3 und in 5-Position des Pyridinrings gleich oder verschieden H oderR in the 3 and in the 5-position of the pyridine ring are identical or different H or
Halogen sind, und R1 in 4-Position des Pyridinrings H, Halogen, CN, (C|-C8)Alkyl oder (CrC8)Alkoxy ist, wobei jeder der letztgenannten zwei Reste unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C,-C8)Alkoxy und (C,-Are halogen, and R 1 in the 4-position of the pyridine ring is H, halogen, CN, (C 1 -C 8 ) alkyl or (C r C 8 ) alkoxy, each of the latter two residues being unsubstituted or by one or more residues from the group halogen, CN, (C, -C 8 ) alkoxy and (C, -
C8)Alkylthio substituiert ist, A eine Gruppe der Formel (A') ist,C 8 ) alkylthio is substituted, A is a group of the formula (A '),
worin R14 gleich oder verschieden Halogen, CN, (CyCgJAlkyl, (CrC8)Alkoxy oder (C.,-C8)Alkylthio sind, wobei jeder der letztgenannten drei Reste unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C1-C8)Alkoxy und (C,-C8)Alkylthio substituiert ist, I 1 oder 2 ist, wherein R 14 are identical or different halogen, CN, (CyCgJalkyl, (C r C 8 ) alkoxy or (C., - C 8 ) alkylthio), each of the latter three radicals unsubstituted or by one or more radicals from the group halogen, CN, (C 1 -C 8 ) alkoxy and (C, -C 8 ) alkylthio is substituted, I is 1 or 2,
V CH, C(R14) oder N(C1-C8-Alkyl) wie N(CH3) ist,V is CH, C (R 14 ) or N (C 1 -C 8 alkyl) such as N (CH 3 ),
W N, S, N-CH, N-C(R14), CH-CH, CH-C(R14) oder C(R14)-C(R14) ist,WN, S, N-CH, NC (R 14 ), CH-CH, CH-C (R 14 ) or C (R 14 ) -C (R 14 ),
R2, R3 gleich oder verschieden H oder (C C8)Alkyl sind, welches unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, und (C C8)Alkyrthio substituiert ist, m = 0 ist,R 2 , R 3 are identical or different H or (CC 8 ) alkyl which is unsubstituted or by one or more radicals from the group halogen, CN, and (CC 8 ) alkyrthio is substituted, m = 0,
R6 H oder (CrC4)Alkyl ist, welches substituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (CrC8)Alkoxy und (CyCaJAlkylthio substituiert ist, undR 6 is H or (C r C 4 ) alkyl which is substituted or substituted by one or more radicals from the group halogen, CN, (C r C 8 ) alkoxy and (CyCaJalkyl thio), and
B [(C^CaJAlkylj-carbonyl wie lineares oder verzweigtes [(C,-C8)-Alkyl]-carbonyl oder [(C3-C6)Cycloalkyl]-carbonyl, wobei jeder der Reste unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, (C C8)Alkoxy, (G,- C8)Alkylthio, (C,-C8)Alkylsulfonyl, [(C,-Cg)Alkyl]-carbonyl, [(C C8)Alkoxy]-carbonyl und CN substituiert ist, oderB [(C ^ C a JAlkylj-carbonyl such as linear or branched [(C, -C 8 ) alkyl] carbonyl or [(C 3 -C 6 ) cycloalkyl] carbonyl, each of the radicals unsubstituted or by one or several residues from the group halogen, (CC 8 ) alkoxy, (G, - C 8 ) alkylthio, (C, -C 8 ) alkylsulfonyl, [(C, -Cg) alkyl] carbonyl, [(CC 8 ) alkoxy] carbonyl and CN is substituted, or
[(C2-C8)Alkenyl]-carbonyl oder [(C2-C8)Alkinyl]-carbonyl, wobei jeder der Reste unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, (C C8)Alkoxy und (C.,-C8)Alkylthio substituiert ist, wie lineares oder verzweigtes oder (C3-C8)Cycloalkylsulfonyl, oder (C2-C8)Alkenylsulfonyl oder (C2- C8)Alkinylsulfonyl, wobei jeder der Reste unsubstituiert oder durch ein oder mehrere Reste aus der Gruppe Halogen, CN, und (C,- C8)Alkylthio substituiert ist, bedeutet.[(C 2 -C 8 ) alkenyl] carbonyl or [(C 2 -C 8 ) alkynyl] carbonyl, where each of the radicals is unsubstituted or by one or more radicals from the group halogen, CN, (CC 8 ) alkoxy and (C., - C 8 ) alkylthio is substituted, like linear or branched or (C 3 -C 8) cycloalkylsulfonyl, or (C2-C8) alkenylsulfonyl or (C 2 - C 8) alkynylsulfonyl, each of said radicals unsubstituted or substituted by one or more radicals from the group halogen, CN and (C, - C 8 ) alkylthio is substituted.
5. Verbindung der Formel (I) und/oder deren Salze gemäß einem oder mehreren der Ansprüche 1 bis 4, worin5. A compound of formula (I) and / or salts thereof according to one or more of claims 1 to 4, wherein
A ein Phenyl-, Pyridyl-,. Pyrazolyl- oder Thienylrest bedeutet, der unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, CN, (C,- C8)Alkyl, (C1-C8)Alkoxy, (C C8)Haloalkyl, (CrCa)Haloalkylthio, (C C8)Haloalkyloxy, und (C C8)Alkoxyalkyloxy substituiert ist. A is phenyl, pyridyl ,. Pyrazolyl or thienyl radical which is unsubstituted or by one or more radicals from the group halogen, CN, (C, - C 8 ) alkyl, (C 1 -C 8 ) alkoxy, (CC 8 ) haloalkyl, (C r C a ) Haloalkylthio, (CC 8 ) haloalkyloxy, and (CC 8 ) alkoxyalkyloxy.
6. Verbindung der Formel (I') und/oder deren Salze,6. Compound of the formula (I ') and / or salts thereof,
worin R1, R2, R3, R6, R14 und X wie in Formel (I) gemäß einem oder mehreren der Ansprüche 1 bis 5 definiert sind,wherein R 1 , R 2 , R 3 , R 6 , R 14 and X are as defined in formula (I) according to one or more of claims 1 to 5,
L gleich oder verschieden H oder Halogen bedeuten, W-V zusammen N-CH-CH, S-CH, CH-CH-CH oder N-N(CH3) bedeuten, und B [(C,-Cg)Alkyl]-carbonyl oder bedeutet, wobei jeder der Reste unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, CN, (C1-C8)-Alkoxy und (C,-C8)Alkylthio substituiert ist.L are identical or different H or halogen, WV together are N-CH-CH, S-CH, CH-CH-CH or NN (CH 3 ), and B [(C, -Cg) alkyl] carbonyl or means, wherein each of the radicals is unsubstituted or substituted by one or more radicals from the group halogen, CN, (C 1 -C 8 ) alkoxy and (C, -C 8 ) alkylthio.
7. Herbizides oder pflanzenwachstumsregulierendes Mittel, enthaltend a) mindestens eine Verbindung der Formel (I) und/oder deren Salze, gemäß einem oder mehreren der Ansprüche 1 bis 6 und b) im Pflanzenschutz übliche Formulierungshilfsmittel.7. Herbicidal or plant growth regulating agent, comprising a) at least one compound of the formula (I) and / or salts thereof, according to one or more of claims 1 to 6 and b) formulation auxiliaries customary in crop protection.
8. Verfahren zur Bekämpfung von Schadpflanzen oder zur Wachstumsregulierung von Kulturpflanzen, wobei eine wirksame Menge von mindestens einer Verbindung der Formel (I) und/oder deren Salze, gemäß einem oder mehreren Ansprüche 1 bis 6 auf die Pflanzen, Pflanzensamen oder die Fläche, auf der sie wachsen, appliziert wird.8. A method for controlling harmful plants or for regulating the growth of crop plants, an effective amount of at least one compound of the formula (I) and / or salts thereof, according to one or more of claims 1 to 6, on the plants, plant seeds or the area of which they grow, is applied.
9. Verwendung der Verbindungen der Formel- (I) und/oder deren Salze gemäß einem der Ansprüche 1 bis 6 als Herbizide oder Pflanzenwachstumsregulatoren.9. Use of the compounds of formula (I) and / or their salts according to one of claims 1 to 6 as herbicides or plant growth regulators.
10. Verwendung nach Anspruch 9, wobei die Verbindungen der Formel (I) und/oder deren Salze zur Bekämpfung von Schadpflanzen oder zur Wachstumsregulierung von Kulturpflanzen eingesetzt werden. 10. Use according to claim 9, wherein the compounds of formula (I) and / or their salts are used to control harmful plants or to regulate the growth of crop plants.
11. Verwendung nach Anspruch 10, wobei die Kulturpflanzen transgene Kulturpflanzen sind.11. Use according to claim 10, wherein the crop plants are transgenic crop plants.
12. Verfahren zur Herstellung einer Verbindung der Formel (I) und/oder deren Salze gemäß einem oder mehreren der Ansprüche 1 bis 6, worin12. A process for the preparation of a compound of formula (I) and / or its salts according to one or more of claims 1 to 6, wherein
a) eine Verbindung der Formel (II),a) a compound of the formula (II),
worin die Reste R1 wie in Formel (I) gemäß einem oder mehreren der Ansprüche 1 bis 6 definiert sind und L eine Abgangsgruppe oder eine Gruppe der Formel A-X- ist, wobei A und X wie in Formel (I) gemäß einem oder mehreren der Ansprüche 1 bis 6 definiert sind, alkyliert und anschließend mit Cyanid, zu einem Nitril der allgemeinen Formel (III) umgesetzt wird, wherein the radicals R 1 are as defined in formula (I) according to one or more of claims 1 to 6 and L is a leaving group or a group of the formula AX-, wherein A and X as in formula (I) according to one or more of the Claims 1 to 6 are defined, alkylated and then reacted with cyanide to give a nitrile of the general formula (III),
worin R1 und L wie in Formel (II) definiert sind; wherein R 1 and L are as defined in formula (II);
b) die Verbindung der Formel (III), worin L eine Abgangsgruppe bedeutet, mit einer Verbindung der Formel (IV) und/oder deren Salzenb) the compound of the formula (III), in which L represents a leaving group, with a compound of the formula (IV) and / or salts thereof
A-X-H (IV)A-X-H (IV)
worin A und X wie in Formel (I) gemäß einem oder mehreren der Ansprüche 1 1 bbiiss 66 ddeeffiinniieertrt ssiinndd,, zzuu eeiinneerr VVeerrbbiinndduunngg ddeerr FFoorrmel (III) umgesetzt wird, worin L eine Gruppe der Formel A - X - bedeutet; c) die in Schritt a) oder b) erhaltene Verbindung der allgemeinen Formel (III), worin L eine Gruppe A -X - bedeutet und worin A, X und R1 wie in Formel (I) gemäß einem oder mehreren der Ansprüche 1 bis 6 definiert sind, durch Reduktion in die Aminoverbindung der allgemeinen Formel (V) überführt wird,in which A and X are reacted as in formula (I) according to one or more of claims 1 to 66 ddeeffiinniieertt ssiinndd ,, zu zu eeiinneerr VVererrbbiinndduunngg ddeerr FFoorrmel (III), wherein L is a group of the formula A - X -; c) the compound of the general formula (III) obtained in step a) or b), in which L denotes a group A -X - and in which A, X and R 1 as in formula (I) according to one or more of claims 1 to 6 are converted into the amino compound of the general formula (V) by reduction,
worin R1 , R2, R3, A und X wie in Formel (I) gemäß einem oder mehreren der Ansprüche 1 bis 6 definiert sind; und anschließendwherein R 1 , R 2 , R 3 , A and X are as defined in formula (I) according to one or more of claims 1 to 6; and subsequently
d1) die Verbindung der Formel (V) durch Umsetzung mit Acylierungsreagentien zu einer Verbindung der Formel (I) umgesetzt wird, worin R6 = H, m = 0, und A, X, R1, R2, R3 und B wie in Formel (I) gemäß einem oder mehreren der Ansprüche 1 bis 6 definiert sind; und optional Verbindungen der Formel (I), worin R6 = H ist, anschließend acyliert werden; oderd1) the compound of the formula (V) is reacted with acylating reagents to give a compound of the formula (I) in which R 6 = H, m = 0, and A, X, R 1 , R 2 , R 3 and B as are defined in formula (I) according to one or more of claims 1 to 6; and optionally compounds of formula (I) wherein R 6 = H are then acylated; or
d2) die Verbindung der Formel (V) mit Aldehyden reduktiv alkyliert wird und anschließend acyliert wird. d2) the compound of formula (V) is reductively alkylated with aldehydes and then acylated.
EP02748802A 2001-06-23 2002-06-20 Herbicidal substituted pyridines, method for producing the same and their use as herbicidal agents and plant growth regulators Withdrawn EP1401827A2 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2508731A1 (en) 2003-02-19 2004-09-02 Neurogen Corporation Aryl acid pyrimidinyl methyl amides, pyridazinyl methyl amides and related compounds
WO2005007627A1 (en) * 2003-07-18 2005-01-27 Nihon Nohyaku Co., Ltd. Phenylpyridine derivative, intermediate therefor, and herbicide containing the same as active ingredient
US8022225B2 (en) 2004-08-04 2011-09-20 Taisho Pharmaceutical Co., Ltd Triazole derivative
JP5035752B2 (en) 2006-02-03 2012-09-26 大正製薬株式会社 Triazole derivative
WO2007091570A1 (en) 2006-02-06 2007-08-16 Taisho Pharmaceutical Co., Ltd. Binding inhibitor of sphingosine-1-phosphate
PL2010493T3 (en) * 2006-04-12 2016-08-31 Merck Sharp & Dohme Pyridyl amide t-type calcium channel antagonists
US8048898B2 (en) 2007-08-01 2011-11-01 Taisho Pharmaceutical Co., Ltd Inhibitor of binding of S1P1
US8097712B2 (en) 2007-11-07 2012-01-17 Beelogics Inc. Compositions for conferring tolerance to viral disease in social insects, and the use thereof
US8962584B2 (en) 2009-10-14 2015-02-24 Yissum Research Development Company Of The Hebrew University Of Jerusalem, Ltd. Compositions for controlling Varroa mites in bees
SG183407A1 (en) 2010-03-08 2012-09-27 Monsanto Technology Llc Polynucleotide molecules for gene regulation in plants
UA116088C2 (en) 2011-09-13 2018-02-12 Монсанто Текнолоджи Ллс Method and compositions for weed control
CA2848695A1 (en) 2011-09-13 2013-03-21 Monsanto Technology Llc Methods and composition for weed control comprising inhibiting ppg oxidase
US10760086B2 (en) 2011-09-13 2020-09-01 Monsanto Technology Llc Methods and compositions for weed control
US10829828B2 (en) 2011-09-13 2020-11-10 Monsanto Technology Llc Methods and compositions for weed control
AU2012308686B2 (en) 2011-09-13 2018-05-10 Monsanto Technology Llc Methods and compositions for weed control
CA2848680C (en) 2011-09-13 2020-05-19 Monsanto Technology Llc Methods and compositions for weed control
AU2012308694B2 (en) 2011-09-13 2018-06-14 Monsanto Technology Llc Methods and compositions for weed control
MX348495B (en) 2011-09-13 2017-06-14 Monsanto Technology Llc Methods and compositions for weed control.
US10806146B2 (en) 2011-09-13 2020-10-20 Monsanto Technology Llc Methods and compositions for weed control
EP2570406A1 (en) * 2011-09-16 2013-03-20 Syngenta Participations AG. Plant growth regulating compounds
GB201121539D0 (en) * 2011-12-14 2012-01-25 Syngenta Participations Ag Plant growth regulating compounds
CA2873828A1 (en) 2012-05-24 2013-11-28 A.B. Seeds Ltd. Naked dsrna for silencing target molecules in plant seeds
EP2866562B1 (en) * 2012-06-30 2019-12-18 Dow AgroSciences LLC Pyridine n-oxides and processes for their preparation
CN104582488A (en) * 2012-06-30 2015-04-29 美国陶氏益农公司 Production of N-substituted sulfoximine pyridine N-oxides
CN105025870B (en) * 2012-12-12 2018-02-02 西姆莱斯股份公司 Composition comprising a metal oxide and a metal oxide
US10683505B2 (en) 2013-01-01 2020-06-16 Monsanto Technology Llc Methods of introducing dsRNA to plant seeds for modulating gene expression
EP2941487A2 (en) 2013-01-01 2015-11-11 A.B. Seeds Ltd. ISOLATED dsRNA MOLECULES AND METHODS OF USING SAME FOR SILENCING TARGET MOLECULES OF INTEREST
CN105263329B (en) 2013-03-13 2020-09-18 孟山都技术公司 Methods and compositions for weed control
CN105074008A (en) 2013-03-13 2015-11-18 孟山都技术有限公司 Methods and compositions for weed control
US10568328B2 (en) 2013-03-15 2020-02-25 Monsanto Technology Llc Methods and compositions for weed control
US9850496B2 (en) 2013-07-19 2017-12-26 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
UA122662C2 (en) 2013-07-19 2020-12-28 Монсанто Текнолоджі Ллс Compositions and methods for controlling leptinotarsa
RU2694950C2 (en) 2013-11-04 2019-07-18 Монсанто Текнолоджи Ллс Compositions and methods for controlling arthropod parasites and pest infestations
UA119253C2 (en) 2013-12-10 2019-05-27 Біолоджикс, Інк. METHOD FOR VARROA TREATMENT AND VEGETABLES
WO2015108982A2 (en) 2014-01-15 2015-07-23 Monsanto Technology Llc Methods and compositions for weed control using epsps polynucleotides
CN106413390B (en) 2014-04-01 2019-09-27 孟山都技术公司 Compositions and methods for controlling pests
CA2953347A1 (en) 2014-06-23 2015-12-30 Monsanto Technology Llc Compositions and methods for regulating gene expression via rna interference
US11807857B2 (en) 2014-06-25 2023-11-07 Monsanto Technology Llc Methods and compositions for delivering nucleic acids to plant cells and regulating gene expression
RU2021123470A (en) 2014-07-29 2021-09-06 Монсанто Текнолоджи Ллс COMPOSITIONS AND METHODS FOR COMBATING PESTS
JP6942632B2 (en) 2015-01-22 2021-09-29 モンサント テクノロジー エルエルシー LEPTINOTARSA control composition and its method
UY36703A (en) 2015-06-02 2016-12-30 Monsanto Technology Llc COMPOSITIONS AND METHODS FOR THE ADMINISTRATION OF A POLINUCLEOTIDE ON A PLANT
WO2016196782A1 (en) 2015-06-03 2016-12-08 Monsanto Technology Llc Methods and compositions for introducing nucleic acids into plants
CN108430972B (en) 2015-12-24 2022-12-27 协和麒麟株式会社 Alpha, beta-unsaturated amide compound
EP3647308B1 (en) 2017-06-26 2023-05-31 Nippon Soda Co., Ltd. Heteroaryl pyrimidine compound and pest control agent
CN107382847A (en) * 2017-07-21 2017-11-24 南通嘉禾化工有限公司 A kind of synthetic method of fluorine metazachlor
CN110639487A (en) 2019-09-30 2020-01-03 京东方科技集团股份有限公司 Preparation method of coating material, catalyst and three-way catalyst

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4030910A (en) * 1974-01-22 1977-06-21 The Dow Chemical Company Substituted pyridinyloxy(thio)phenyl -acetamides, -ureas and urea derivatives, herbicidal compositions and methods containing same
NZ215487A (en) 1985-03-16 1990-01-29 Wellcome Found Aryl derivatives, pharmaceutical compositions thereof and preservation of cut flowers
GB8820185D0 (en) * 1988-08-25 1988-09-28 Wellcome Found New medical use
GB9005965D0 (en) * 1990-03-16 1990-05-09 Shell Int Research Herbicidal carboxamide derivatives
GB9025828D0 (en) * 1990-11-28 1991-01-09 Shell Int Research Herbicidal carboxamide derivatives
TW212792B (en) * 1991-09-13 1993-09-11 Shell Internat Res Schappej B V
IL107335A (en) * 1992-10-22 1997-09-30 Shell Int Research Picolinamide derivatives, their preparation and their use as herbicides
GB2277930A (en) * 1993-05-11 1994-11-16 Shell Int Research Herbicidal picolinamide derivatives
EP0692474B1 (en) * 1994-07-14 1997-10-29 Kureha Kagaku Kogyo Kabushiki Kaisha 2- (unsubstituted or substituted) (benzyloxy or phenoxy)-4-substituted-6-(meta-substituted phenoxy) pyridine, process for producing the same, and herbicidal composition
EP0723960B1 (en) * 1995-01-26 2003-04-02 Basf Aktiengesellschaft Herbicidal 2,6-disubstituted pyridines and 2,4-disubstituted pyrimidines
JPH08277287A (en) * 1995-02-09 1996-10-22 Mitsubishi Chem Corp Indazoles and their uses
US5807804A (en) * 1996-02-22 1998-09-15 American Cyanamid Company Substituted pyridine herbicidal agents
ATE323696T1 (en) * 1996-07-30 2006-05-15 HERBICIDE-ACTIVE SUBSTITUTED PYRIDINE DERIVATIVES
US5869426A (en) * 1997-11-07 1999-02-09 American Cyanamid Company Herbicidal 6-thienyloxypyrid-2-carboxamides
AU1303099A (en) * 1997-11-07 1999-05-31 American Cyanamid Company Herbicidal furanyl- and thienyloxyazines
CA2309260C (en) * 1997-12-03 2011-09-13 E.I. Du Pont De Nemours And Company 2,4-substituted pyrimidines and their use in herbicidal compositions
DK1068194T3 (en) * 1998-04-01 2004-03-15 Janssen Pharmaceutica Nv PDE IV inhibiting pyridine derivatives
EP0955292A1 (en) * 1998-05-05 1999-11-10 American Cyanamid Company Herbicidal 2-(cycloalk(en)yloxy)-6-(hetero)aryloxy(thio)pyridines
AU753594B2 (en) * 1998-05-05 2002-10-24 American Cyanamid Company Herbicidal pyridine compounds
WO2000075112A1 (en) * 1999-06-09 2000-12-14 Kureha Kagaku Kogyo Kabushiki Kaisha Novel n-(2,2,2-trifluoroethyl)-4-methoxy-6-[(substituted or unsubstituted) m-cyanophenoxy]-2-pyridinecarboxamide derivatives, process for the preparation thereof and herbicides
WO2001000580A1 (en) * 1999-06-29 2001-01-04 Kureha Kagaku Kogyo Kabushiki Kaisha 2-(optionally substituted benzoylamino)-6-(optionally substituted phenoxy)pyridine derivatives, process for the preparation thereof and herbicides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03000679A2 *

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