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EP0730592A1 - Derivatives of 2,3,5,6-tetrafluorobenzoic acid and their use in combating pests - Google Patents

Derivatives of 2,3,5,6-tetrafluorobenzoic acid and their use in combating pests

Info

Publication number
EP0730592A1
EP0730592A1 EP95901380A EP95901380A EP0730592A1 EP 0730592 A1 EP0730592 A1 EP 0730592A1 EP 95901380 A EP95901380 A EP 95901380A EP 95901380 A EP95901380 A EP 95901380A EP 0730592 A1 EP0730592 A1 EP 0730592A1
Authority
EP
European Patent Office
Prior art keywords
substituted
carbon atoms
alkyl
unsubstituted
ethyl
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Withdrawn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
EP95901380A
Other languages
German (de)
French (fr)
Inventor
Udo Kraatz
Gerd Hänssler
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 AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0730592A1 publication Critical patent/EP0730592A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
    • C07D295/182—Radicals derived from carboxylic acids
    • C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group, wherein Cn means a carbon skeleton not containing a 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group, wherein Cn means a carbon skeleton not containing a 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
    • A01N37/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides containing at least one oxygen or sulfur atom being directly attached to the same aromatic ring system
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/46—N-acyl derivatives
    • 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
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/65—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/66—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/77—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/78—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/81—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • C07C233/82—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/83—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/81—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • C07C233/82—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/87—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom of a carbon skeleton containing six-membered aromatic rings
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/04—Systems containing only non-condensed rings with a four-membered ring

Definitions

  • the invention relates to new derivatives of 2,3,5,6-tetrafluorobenzoic acid, a process for their preparation and their use for controlling pests.
  • Y stands for oxygen or sulfur
  • R 1 and R 2 independently of one another are optionally substituted alkyl, cycloalkyl and aryl, R 3 is alkyl with at least 2 carbon atoms, substituted alkyl and optionally substituted cycloalkyl, aryl and aralkyl,
  • R 4 , R 5 and R 6 independently of one another are hydrogen and optionally substituted alkyl, aryl and aralkyl, or
  • R 5 and R 6 together with the nitrogen atom to which they are attached form an optionally substituted ring, or
  • R 7 and R 8 independently of one another are hydrogen and optionally substituted alkyl, cycloalkyl, aryl, aralkyl, alkylheteroaryl and heteroaryl, or represent the groups -CHR 4 -COOH and -CHR 4 -COOCH 3 , where R 7 and R 8 are not simultaneously stand for hydrogen, or
  • R 7 and R 8 together with the nitrogen atom to which they are attached form an optionally substituted ring
  • the new derivatives of 2,3,5,6-tetrafluorobenzoic acid of the general formula (I) have an excellent microbicidal activity, in particular against microorganisms which are pathogenic to plants.
  • the active compounds according to the invention have an excellent resistance-inducing activity in plants against attack by undesired microorganisms.
  • Alkyl individually or in composite radicals, straight-chain or branched alkyl having 1 to 8, in particular 1 to 4, carbon atoms. Examples include methyl, ethyl, n.- and i.-propyl, n-, i-, s- and t-butyl.
  • Cycloalkyl - a 3- to 7-membered ring, in particular a ring with 3, 5 or 6 carbon atoms. Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl may be mentioned by way of example and preferably.
  • Aryl unsubstituted or substituted aryl having 6 to 10 carbon atoms examples are unsubstituted or substituted
  • Aralkyl unsubstituted or substituted aralkyl having 1 to 4, in particular 1 or 2, carbon atoms in the straight-chain or branched alkyl part and 6 to
  • Preferred heteroatoms are oxygen, sulfur and nitrogen.
  • heteroarylalkyl the heteroaryl part corresponds to the definitions and preferred ranges given above.
  • the alkyl part is straight-chain or branched and contains 1 to
  • 4 especially 1 or 2 carbon atoms.
  • exemplary and preferred are heteroarylmethyl, 1,1- and 1,2-heteroarylethyl and 1,1-, 1,2-, 1,3- and 2,2-heteroarylpropyl.
  • the optionally substituted radicals of the general formulas can carry one or more, preferably 1 to 3, in particular 1 or 2, identical or different substituents.
  • substituents are: alkyl having preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methyl, ethyl, n.- and i.-propyl and n.-, i.-, sea and t.
  • Alkoxy preferably having 1 to 4, in particular 1 or 2, carbon atoms, such as methoxy, ethoxy, n.- and i.-propyloxy and n.-, L-, see- and t.-butyloxy
  • Alkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio, n.- and i.-propylthio and n.-, i.-, see- and t.-butylthio
  • Haloalkyl, haloalkoxy and haloalkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms and preferably 1 to 9, in particular 1 to 5 halogen atoms, where the halogen atoms are identical or different and are halogen atoms, preferably fluorine, chlorine or bromine, in particular fluorine, such as trifluoromethyl, difluoromethyl, pentafluoroe
  • R 1 and R 2 are the same or different and each represents unsubstituted or substituted alkyl having 1 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms or phenyl,
  • R 3 represents alkyl with 2 to 8 carbon atoms, substituted alkyl with 1 to 8 carbon atoms, each unsubstituted or substituted cycloalkyl with 3 to 7 carbon atoms, phenyl or phenylalkyl with 1 to 4 carbon atoms in the alkyl part,
  • R 4 , R 5 , R 6 , R 7 and R 8 are the same or different and represent hydrogen, in each case unsubstituted or substituted alkyl having 1 to 8 carbon atoms, phenyl or phenylalkyl having 1 to 4 carbon atoms in the alkyl part, where R and R 8 does not simultaneously represent hydrogen,
  • R 7 and R 8 independently of one another, in addition, each for unsubstituted or substituted cycloalkyl having 3 to 7 carbon atoms, 5- to 9-membered heteroaryl which contains 1 to 4 identical or different heteroatoms such as oxygen, nitrogen and sulfur, or corresponding heteroarylalkyl having 1 to 4 carbon atoms in the alkyl part, or
  • R 8 represents the groups -CHR 4 -COOH and -CHR 4 -COOCH 3 or
  • R 5 and R 6 together with the nitrogen atom to which they are attached form an unsubstituted or substituted 5- to 7-membered ring which can additionally contain 1 or 2 identical or different heteroatoms such as oxygen, nitrogen and sulfur, or
  • R 7 and R 8 together with the nitrogen atom to which they are attached form an unsubstituted or substituted 5- to 7-membered ring which can additionally contain 1 or 2 identical or different heteroatoms such as oxygen, nitrogen and sulfur.
  • R 1 and R 2 are the same or different and each represents unsubstituted branched alkyl having 4 to 6 carbon atoms or substituted alkyl having 1 to 6 carbon atoms, each unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopropyl, cyclohexyl or phenyl,
  • R 3 represents alkyl having 2 to 6 carbon atoms, substituted alkyl having 1 to 6 carbon atoms, in each case unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or
  • R 4 represents hydrogen or alkyl having 1 to 4 carbon atoms or optionally substituted phenyl or benzyl,
  • R 5 and R 6 are the same or different and represent hydrogen, alkyl having 1 to 8 carbon atoms and unsubstituted or substituted phenyl, the preferred substituents being halogen, alkyl, alkoxy, Alkylthio, haloalkyl, haloalkoxy and haloalkylthio may be mentioned,
  • R 7 and R 8 are identical or different and represent hydrogen, in each case unsubstituted or substituted alkyl having 1 to 6 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl and benzyl, the substituents preferably being halogen, alkyl, alkoxy, alkylthio, Haloalkyl, haloalkoxy, haloalkylthio and dialkylamino may be mentioned, but R 7 and R 8 do not simultaneously represent hydrogen, and
  • R 8 additionally stands for the groups -CHR 4 -COOH and -CHR 4 -COOCH 3 or
  • R 3 and R 6 together with the nitrogen atom to which they are attached represent an unsubstituted or substituted piperidine
  • R 7 and R 8 together with the nitrogen atom to which they are attached are in each case an unsubstituted or substituted piperidine,
  • R 1 represents methyltriazolyl
  • R 2 represents butyl, pentyl, hexyl and heptyl which is optionally substituted by unsubstituted or halogen-substituted phenoxy, or in each case optionally one to three times by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy,
  • R 3 stands for ethyl, n- and i-propyl, n-, i-, s- and t-butyl, or for methyl, ethyl, n- and i-propyl substituted by dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl , n.-, i.-, s.- and t.-butyl, or for each optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy or phenyl, benzyl or
  • R 5 represents hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl,
  • R 6 represents hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl, or
  • R 5 and R 6 together with the nitrogen atom to which they are attached form a piperidine, morpholine, hexahydroazepine or piperazine ring,
  • R 7 represents hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl,
  • R 8 represents methyl, ethyl, n.- and i.-propyl, n.-, i.-, s.- and t.-butyl, optionally substituted by dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, or each in each case optionally monosubstituted to trisubstituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy
  • R 4 represents hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl, phenyl, biphenyl and hydroxybiphenyl and benzyl, or R 7 and R 8 together with the nitrogen atom to which they are bonded form a piperidine, pyrrolidine, morpholine or piperazine ring, which are optionally mono- or disubstituted by methyl, ethyl, hydroxymethyl and hydroxyethyl
  • Preferred compounds are also addition products of acids and those derivatives of the formula (I) in which the substituents R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 have the meanings which are already preferred for these substituents
  • the acids which can be added preferably include hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono-, bi- and trifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, Fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, sulfonic acids such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid as well as saccharin or thiosaccharin
  • hydrohalic acids such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono-, bi- and trifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic
  • preferred compounds are addition products of salts and metals of main groups II to IV and groups I and II as well as groups IV to VIII and those derivatives of formula (I) in which the substituents R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 have the meanings which have already been mentioned preferably for these substituents
  • Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred.
  • Anions of these salts are those which are derived from acids which lead to environmentally compatible addition products.
  • Particularly preferred acids in this context are Hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, nitric acid and sulfuric acid
  • the new derivatives of tetrafluorobenzoic acid of the formula (I) can be prepared in an analogous manner by known processes.
  • the starting compounds required for the preparation of the compounds of the formula (I) are known or can be prepared by generally known methods
  • the starting compounds are preferably reacted in an inert water-immiscible diluent, such as aromatic, non-aromatic or halogenated hydrocarbons such as: esters, such as ethyl acetate; Chlorinated hydrocarbons, such as dichloromethane, trichloroethane; Aromatics such as toluene; Hydrocarbons such as cyclohexane or their mixtures and / or in the presence of an acid binder such as potassium carbonate, triethylamine, pyridine, N-methylpiperidine or potassium or sodium hydroxide, at temperatures from 0 ° C to 100 ° C, preferably 20 ° C to 40 ° C and under normal pressure.
  • the invention encompasses both the pure isomers and the mixtures. These mixtures can be prepared using common methods, e.g. selective crystallization from suitable solvents or chromatography on silica gel or aluminum oxide are separated into the components. Racemates can be separated into the individual enantiomers by conventional methods, e.g. by salt formation with optically active acids such as champhersulfonic acid or dibenzoyl acid and selective crystallization or by derivatization with suitable, optically active reagents, separation of the diastereomeric derivatives and cleavage or separation on optically active column material.
  • optically active acids such as champhersulfonic acid or dibenzoyl acid
  • suitable, optically active reagents separation of the diastereomeric derivatives and cleavage or separation on optically active column material.
  • the active compounds of the formula (I) according to the invention have a strong action against pests and can be used practically to combat unwanted harmful organisms.
  • the active ingredients are suitable for use as crop protection agents, in particular as fungicides.
  • Fungicidal agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
  • Pythium species such as, for example, Pythium ultimum
  • Phytophthora species such as, for example, Phytophthora infestans
  • Pseudoperonospora species such as, for example, Pseudoperonospora humuli or
  • Plasmopara species such as, for example, Plasmopara viticola
  • Peronospora species such as, for example, Peronospora pisi or P. brassicae
  • Erysiphe species such as, for example, Erysiphe graminis
  • Sphaerotheca species such as, for example, Sphaerotheca fuliginea
  • Podosphaera species such as, for example, Podosphaera leucotricha
  • Venturia species such as, for example, Venturia inaequalis
  • Pyrenophora species such as, for example, Pyrenophora teres or P. graminea (conidia form: Drechslera, Syn: Helminthosporium);
  • Cochliobolus species such as, for example, Cochliobolus sativus
  • Drechslera (Coni form: Drechslera, Syn: Helminthosporium);
  • Uromyces species such as, for example, Uromyces appendiculatus
  • Puccinia species such as, for example, Puccinia recondita
  • Tilletia species such as, for example, Tilletia caries
  • Ustilago species such as, for example, Ustilago nuda or Ustilago avenae;
  • Pellicularia species such as, for example, Pellicularia sasakii;
  • Pyricularia species such as, for example, Pyricularia oryzae
  • Fusarium species such as, for example, Fusarium culmorum
  • Botrytis species such as, for example, Botrytis cinerea
  • Septoria species such as, for example, Septoria nodorum
  • Leptosphaeria species such as, for example, Leptosphaeria nodorum;
  • Cercospora species such as, for example, Cercospora canescens
  • Alternaria species such as, for example, Alternaria brassicae
  • Pseudocercosporella species such as, for example, Pseudocercosporella herpotrichoides.
  • the active compounds according to the invention can be used with particular good protection for controlling Pyricularia species on rice.
  • the active compounds according to the invention furthermore have a strong resistance-inducing action in plants. They are therefore suitable for generating resistance in plants against attack by undesired microorganisms
  • resistance-inducing substances are to be understood as those substances which, on the one hand, show only a low activity when directly affected by the undesired microorganisms, but on the other hand are able to stimulate the immune system of plants in such a way that the affected If the plants are subsequently inoculated with undesirable microorganisms, they will develop extensive resistance to these microorganisms
  • Undesired microorganisms are to be understood in the present case as phytopathogenic fungi, bacteria and viruses.
  • the substances according to the invention can therefore be used to produce resistance to the attack by the named pathogens in plants within a certain period of time after the treatment.
  • the period within which resistance is brought about is generally from 1 to 10 days, preferably 1 to 7 days after the treatment of the plants with the active compounds
  • Unwanted microorganisms in crop protection include fungi from the classes of the Plasmodiophoromycetes, Oomycetes and Chytridiomycetes. Zygomycetes. Ascomycetes. Basidiomycetes and Deuteromycetes
  • the active compounds can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV Cold and warm mist shapes
  • formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents If water is used as an extender, organic solvents can also be used, for example Auxiliary solvents are used.
  • extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents
  • surface-active agents ie emulsifiers and / or dispersants and / or foam-generating agents
  • organic solvents can also be used, for example Auxiliary solvents are used.
  • Liquid solvents are essentially aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions Alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide and water; Liquefied gaseous extenders or carriers are liquids that are gaseous at normal temperature and pressure, e.g.
  • aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide
  • solid rock materials can be considered, for example, natural rock powder , such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flours, such as highly disperse silicic acid, aluminum oxide and silicates, as solid carriers for granules are, for example, broken and fractionated natural rocks such as calcite, marble, pumice , Sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks, as emulsifiers and / or foam-generating agents, for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters , Poly oxyethylene fatty alcohol ethers, for example alkylaryl polygly
  • adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phosphophides, such as wafers and lecithins, and synthetic phospholipids, and other additives can be mineral and vegetable oils
  • Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as Aliza ⁇ n, azo and metal phthalocyanine substances and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and in mixtures with fertilizers and growth regulators.
  • the active compounds according to the invention can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the spectrum of activity or to prevent the development of resistance.
  • fungicides bactericides
  • acaricides nematicides or insecticides
  • synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.
  • the following compounds are particularly favorable mixing partners.
  • Difenoconazole dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
  • Fludioxonil fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl aluminum, fthalides, fuberidazole, furalaxyl, furmecyclox,
  • copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
  • Mancopper Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol,
  • Oxadixyl Oxamocarb, Oxycarboxin, Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin,
  • Amitraz Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M,
  • Bacillus thuringiensis Bendiocarb, Benfuracarb, Bensultap, Betacyluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin,
  • Cadusafos Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap,
  • Chlorfenvinphos Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis- Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin,
  • Fenamiphos fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,
  • Fenoxycarb fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil,
  • Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyraclhrhos, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclof
  • Tebufenozid Tebufenpyrad, Tebupirimiphos, Teflubenuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralometonium, Triaromenoriazonium, Triaromenoriazonium YI 5301/5302, zetamethrin.
  • the active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of plants can also be treated.
  • the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%. In the seed treatment, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
  • active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.
  • the active substance concentrations for the treatment of parts of plants in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001 percent by weight, preferably between 0.5 and 0.001%.
  • Solvent 12.5 parts by weight of acetone emulsifier: 0.3 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and the concentrate is diluted to the desired concentration with water and the stated amount of emulsifier.
  • the disease infestation is evaluated 4 days after the inoculation.
  • the compounds according to the manufacturing examples 1, 2, 3 and 37 show 100% efficiency at an application rate of 100 mg of active ingredient per 100 cm 3 .

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Abstract

The application relates to derivatives of 2,3,5,6-tetrafluorobenzoic acid of formula (I) wherein Y represents oxygen or sulphur and X represents the groups -O- N=CR?1R2, -OR3, -OCHR4-CO-NR5R6 or -NR7R8¿ as well as a process for manufacturing the said substance and uses thereof in combating pests.

Description

DERIVATE DER 2 , 3 , 5 , 6-TETRAFLUOROBENZOESAURE UND IHRE VERWENDUNG ZUR BEKÄMPFUNG VON SCHÄDLINGEN DERIVATIVES OF THE 2, 3, 5, 6-TETRAFLUOROBENZOESAURE AND THEIR USE FOR CONTROLLING Pests
Die Erfindung betrifft neue Derivate der 2,3,5,6-Tetrafluorbenzoesäure, ein Verfahren zu deren Herstellung sowie deren Verwendung zur Bekämpfung von Schädlingen.The invention relates to new derivatives of 2,3,5,6-tetrafluorobenzoic acid, a process for their preparation and their use for controlling pests.
Gegenstand der Anmeldung sind Derivate der 2,3,5,6-Tetrafluorbenzoesäure der all¬ gemeinen Formel (I)The application relates to derivatives of 2,3,5,6-tetrafluorobenzoic acid of the general formula (I)
in welcherin which
Y für Sauerstoff oder Schwefel steht undY stands for oxygen or sulfur and
X für die Gruppen -O-N=CR- -R2, -OR3, -OCHR4-CO-NR5R6 oder -NR7R8 stehtX represents the groups -ON = CR- -R 2 , -OR 3 , -OCHR 4 -CO-NR 5 R 6 or -NR 7 R 8
worinwherein
R1 und R2 unabhängig voneinander gegebenenfalls substituiertes Alkyl, Cycloalkyl und Aryl bedeuten, R3 Alkyl mit mindestens 2 Kohlenstoffatomen, substituiertes Alkyl und gegebenenfalls substituiertes Cycloalkyl, Aryl und Aralkyl bedeuten,R 1 and R 2 independently of one another are optionally substituted alkyl, cycloalkyl and aryl, R 3 is alkyl with at least 2 carbon atoms, substituted alkyl and optionally substituted cycloalkyl, aryl and aralkyl,
R4, R5 und R6 unabhängig voneinander Wasserstoff und gegebenenfalls substituiertes Alkyl, Aryl und Aralkyl bedeuten, oderR 4 , R 5 and R 6 independently of one another are hydrogen and optionally substituted alkyl, aryl and aralkyl, or
R5 und R6 gemeinsam mit dem Stickstoffatom an das sie gebunden sind einen gegebenenfalls substituierten Ring bilden, oderR 5 and R 6 together with the nitrogen atom to which they are attached form an optionally substituted ring, or
R7 und R8 unabhängig voneinander Wasserstoff und gegebenenfalls substituiertes Alkyl, Cycloalkyl, Aryl, Aralkyl, Alkylheteroaryl und Heteroaryl bedeuten, oder für die Gruppen -CHR4-COOH und -CHR4-COOCH3 stehen, wobei R7 und R8 nicht gleichzeitig für Wasserstoff stehen, oderR 7 and R 8 independently of one another are hydrogen and optionally substituted alkyl, cycloalkyl, aryl, aralkyl, alkylheteroaryl and heteroaryl, or represent the groups -CHR 4 -COOH and -CHR 4 -COOCH 3 , where R 7 and R 8 are not simultaneously stand for hydrogen, or
R7 und R8 gemeinsam mit dem Stickstoff atom an das sie gebunden sind einen gegebenenfalls substituierten Ring bildenR 7 and R 8 together with the nitrogen atom to which they are attached form an optionally substituted ring
sowie deren Säureadditions-Salze und Metallsalz-Komplexe.as well as their acid addition salts and metal salt complexes.
Weiterhin wurde gefunden, daß man die Derivate der 2,3,5,6-Tetrafluorbenzoesäure der Formel (I) erhält, wenn man 2,3,5,6-Tetrafluorbenzoylchlorid oder -anhydrid mit einem entsprechenden Oxim, Alkohol oder Amin gegebenenfalls in Gegenwart eines Lösungsmittels und/oder einer Base umsetzt.Furthermore, it has been found that the derivatives of 2,3,5,6-tetrafluorobenzoic acid of the formula (I) are obtained if 2,3,5,6-tetrafluorobenzoyl chloride or anhydride with a corresponding oxime, alcohol or amine, if appropriate in the presence a solvent and / or a base.
Schließlich wurde gefunden, daß die neuen Derivate der 2,3,5,6-Tetrafluorbenzoe- säure der allgemeinen Formel (I) eine hervorragende mikrobizide Wirksamkeit, ins¬ besondere gegen pflanzenpathogene Mikroorganismen besitzen. Darüber hinaus besitzen die erfindungsgemäßen Wirkstoffe eine hervorragende resistenzinduzierende Wirksamkeit in Pflanzen gegen den Befall durch unerwünschte Mikroorganismen.Finally, it was found that the new derivatives of 2,3,5,6-tetrafluorobenzoic acid of the general formula (I) have an excellent microbicidal activity, in particular against microorganisms which are pathogenic to plants. In addition, the active compounds according to the invention have an excellent resistance-inducing activity in plants against attack by undesired microorganisms.
Im folgenden wird der Einfachheit halber stets von Verbindungen der Formel (I) gesprochen, obwohl sowohl die reinen Verbindungen, als auch die Gemische mit unterschiedlichen Anteilen an isomeren, enantiomeren und diastereomeren Verbin¬ dungen gemeint sind. Die erfindungsgemäßen Derivate der 2,3,5,6-Tetrafluorbenzoesäure sind durch die Formel (I) allgemein definiert.For the sake of simplicity, the following always refers to compounds of the formula (I), although both the pure compounds and the mixtures are meant with different proportions of isomeric, enantiomeric and diastereomeric compounds. The derivatives of 2,3,5,6-tetrafluorobenzoic acid according to the invention are generally defined by the formula (I).
Vorzugsweise bedeutet in den allgemeinen Formeln im folgenden, falls nicht anders definiert:Unless otherwise defined, the following preferably means in the general formulas:
Alkyl, einzeln oder in zusammengesetzten Resten geradkettiges oder verzweigtes Alkyl mit 1 bis 8, insbesondere 1 bis 4 Kohlenstoffatomen. Beispielhaft und vorzugsweise seien Methyl, Ethyl, n.- und i.-Propyl, n-, i-, s- und t-Butyl, genannt.Alkyl, individually or in composite radicals, straight-chain or branched alkyl having 1 to 8, in particular 1 to 4, carbon atoms. Examples include methyl, ethyl, n.- and i.-propyl, n-, i-, s- and t-butyl.
Cycloalkyl - ein 3- bis 7-gliedriger Ring, insbesondere ein Ring mit 3, 5 oder 6 Kohlen¬ stoffatomen. Beispielhaft und vorzugsweise seien Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl und Cycloheptyl genannt.Cycloalkyl - a 3- to 7-membered ring, in particular a ring with 3, 5 or 6 carbon atoms. Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl may be mentioned by way of example and preferably.
Aryl unsubstituiertes oder substituiertes Aryl mit 6 bis 10 Kohlenstoffatomen. Beispielhaft und vorzugsweise sei jeweils unsubstituiertes oder substituiertesAryl unsubstituted or substituted aryl having 6 to 10 carbon atoms. Examples are unsubstituted or substituted
Phenyl und Naphthyl, insbesondere unsubstituiertes oder substituiertes Phenyl genannt.Phenyl and naphthyl, especially unsubstituted or substituted phenyl called.
Aralkyl unsubstituiertes oder substituiertes Aralkyl mit 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatomen im geradkettigen oder verzweigten Alkylteil und 6 bisAralkyl unsubstituted or substituted aralkyl having 1 to 4, in particular 1 or 2, carbon atoms in the straight-chain or branched alkyl part and 6 to
10 Kohlenstoffatomen, vorzugsweise Phenyl im Arylteil. Beispielhaft und vorzugsweise seien Benzyl, 1,1- und 1,2-Phenethyl und 1,1-, 1,2-, 1,3- und 2,2-Phenylpropyl genannt.10 carbon atoms, preferably phenyl in the aryl part. Exemplary and preferred are benzyl, 1,1- and 1,2-phenethyl and 1,1-, 1,2-, 1,3- and 2,2-phenylpropyl.
Heteroaryl - unsubstituierter oder substituierter 5- bis 9-gliedriger Ring, insbesondere 5- bis 7-gliedriger Ring, der 1 bis 4, bevorzugt 1 bis 3, gleiche oder ver¬ schiedene Heteroatome enthält. Als Heteroatome seien vorzugsweise Sauer¬ stoff, Schwefel und Stickstoff genannt. Beispielhaft und vorzugsweise seien Pyrimidinyl, Pyrrolyl, Isothiazolyl, Oxazolyl, Thienyl, Furyl, Pyridazinyl, Pyrazinyl, Isooxazolyl, Thiazolyl und insbesondere Pyridyl genannt.Heteroaryl - unsubstituted or substituted 5- to 9-membered ring, in particular 5- to 7-membered ring, which contains 1 to 4, preferably 1 to 3, identical or different heteroatoms. Preferred heteroatoms are oxygen, sulfur and nitrogen. Be exemplary and preferred Pyrimidinyl, pyrrolyl, isothiazolyl, oxazolyl, thienyl, furyl, pyridazinyl, pyrazinyl, isooxazolyl, thiazolyl and especially pyridyl.
Heteroarylalkyl der Heteroarylteil entspricht den oben angegebenen Definitionen und Vor- zugsbereichen. Der Alkylteil ist geradkettig oder verzweigt und enthält 1 bisHeteroarylalkyl the heteroaryl part corresponds to the definitions and preferred ranges given above. The alkyl part is straight-chain or branched and contains 1 to
4 insbesondere 1 oder 2 Kohlenstoffatome. Beispielhaft und vorzugsweise seien Heteroarylmethyl, 1,1- und 1,2-Heteroarylethyl und 1,1-, 1,2-, 1,3- und 2,2-Heteroarylpropyl genannt.4 especially 1 or 2 carbon atoms. Exemplary and preferred are heteroarylmethyl, 1,1- and 1,2-heteroarylethyl and 1,1-, 1,2-, 1,3- and 2,2-heteroarylpropyl.
Die gegebenenfalls substituierten Reste der allgemeinen Formeln können einen oder mehrere, vorzugsweise 1 bis 3, insbesondere 1 oder 2, gleiche oder verschiedene Substituenten tragen. Als Substituenten seien beispielhaft und vorzugsweise aufgeführt: Alkyl mit vorzugsweise 1 bis 4, insbesondere 1 oder 2 Kohlenstoff¬ atomen, wie Methyl, Ethyl, n.- und i.-Propyl und n.-, i.-, see- und t.-Butyl; Alkoxy mit vorzugsweise 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatomen, wie Methoxy, Ethoxy, n.- und i.-Propyloxy und n.-, L-, see- und t.-Butyloxy; Alkylthio mit vorzugsweise 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatomen, wie Methylthio, Ethylthio, n.- und i.-Propylthio und n.-, i.-, see- und t.-Butylthio; Halogenalkyl, Halogenalkoxy und Halogenalkylthio mit vorzugsweise 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatomen und vorzugsweise 1 bis 9, insbesondere 1 bis 5 Halogenatomen, wobei die Halogenatome gleich oder verschieden sind und als Halogenatome, vorzugsweise Fluor, Chlor oder Brom, insbesondere Fluor stehen, wie Trifluormethyl, Difluormethyl, Pentafluorethyl, Tetrafluorethyl, Trifluorchlorethyl, Trifluorethyl, Trifluorethoxy, Difluormethoxy, Pentafluorethoxy, Tetrafluorethoxy, Trifluorchlorethoxy, Trifluormethoxy und Trifluormethylthio; Hydroxy; Halogen, vorzugsweise Fluor, Chlor, Brom und Jod, insbesondere Fluor, Chlor und Brom; Cyano; Nitro; Dialkylamino mit vorzugsweise 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatomen je Alkylgruppe, wie Dimethylamino und Diethylamino; Carboxy; Alkylalkoxy mit 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatomen in jedem Alkylteil; Carbonylalkoxy mit 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatomen im Alkylteil, wie Carbonylmethoxy und Carbonylethoxy; Carbonylalkyl mit 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatomen im Alkylteil, wie Acetyl und Propionyl; Formyl; Carbonylaryloxy mit 5 bis 10 Kohlenstoffatomen im Arylteil, wie Carbonyl- phenoxy; Carbonylaryl mit 6 bis 10 Kohlenstoffatomen im Arylteil, wie Benzoyl; Oxycarbonylalkyl mit 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatomen im Alkylteil, wie Acetoxy; Oxycarbonylaryl mit 6 bis 10 Kohlenstoffatomen im Arylteil, wie Benzoyloxy; Carboxylamino, Carbonylaminoalkyl, Carbonylaminodialkyl, Aminocarbonyl, Alkylaminocarbonyl, Aminocarbonylalkyl und Alkylamino- carbonylalkyl mit jeweils 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatomen im Alkylteil; Sulfonamido; Sulfonalkyl; Sulfonylalkyl und Sulfonylalkoxy mit jeweils 1 bis 4, insbesondere 1 oder 2 Kohlenstoffatomen; jeweils unsubstituiertes oder durch Halogen, insbesondere Fluor, Chlor und/oder Brom substituiertes Phenyl oder Phenoxy.The optionally substituted radicals of the general formulas can carry one or more, preferably 1 to 3, in particular 1 or 2, identical or different substituents. Examples of preferred substituents are: alkyl having preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methyl, ethyl, n.- and i.-propyl and n.-, i.-, sea and t. Butyl; Alkoxy preferably having 1 to 4, in particular 1 or 2, carbon atoms, such as methoxy, ethoxy, n.- and i.-propyloxy and n.-, L-, see- and t.-butyloxy; Alkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms, such as methylthio, ethylthio, n.- and i.-propylthio and n.-, i.-, see- and t.-butylthio; Haloalkyl, haloalkoxy and haloalkylthio with preferably 1 to 4, in particular 1 or 2 carbon atoms and preferably 1 to 9, in particular 1 to 5 halogen atoms, where the halogen atoms are identical or different and are halogen atoms, preferably fluorine, chlorine or bromine, in particular fluorine, such as trifluoromethyl, difluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluorochloroethyl, trifluoroethyl, trifluoroethoxy, difluoromethoxy, pentafluoroethoxy, tetrafluoroethoxy, trifluorochloroethoxy, trifluoromethoxy and trifluoromethylthio; Hydroxy; Halogen, preferably fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine; Cyano; Nitro; Dialkylamino with preferably 1 to 4, in particular 1 or 2, carbon atoms per alkyl group, such as dimethylamino and diethylamino; Carboxy; Alkylalkoxy having 1 to 4, in particular 1 or 2, carbon atoms in each alkyl part; Carbonylalkoxy with 1 to 4, especially 1 or 2 carbon atoms in the alkyl part, such as carbonylmethoxy and carbonylethoxy; Carbonylalkyl having 1 to 4, in particular 1 or 2, carbon atoms in the alkyl part, such as acetyl and propionyl; Formyl; Carbonylaryloxy with 5 to 10 carbon atoms in the aryl part, such as carbonylphenoxy; Carbonylaryl having 6 to 10 carbon atoms in the aryl part, such as benzoyl; Oxycarbonylalkyl having 1 to 4, in particular 1 or 2, carbon atoms in the alkyl part, such as acetoxy; Oxycarbonylaryl having 6 to 10 carbon atoms in the aryl part, such as benzoyloxy; Carboxylamino, carbonylaminoalkyl, carbonylaminodialkyl, aminocarbonyl, alkylaminocarbonyl, aminocarbonylalkyl and alkylaminocarbonylalkyl each having 1 to 4, in particular 1 or 2, carbon atoms in the alkyl part; Sulfonamido; Sulfonalkyl; Sulfonylalkyl and sulfonylalkoxy each having 1 to 4, in particular 1 or 2, carbon atoms; in each case unsubstituted or substituted by halogen, in particular fluorine, chlorine and / or bromine, phenyl or phenoxy.
Die hier aufgeführten Definitionen gelten in entsprechender Weise auch für die Definitionen in den folgenden bevorzugten Kombinationen von Resten.The definitions listed here apply in a corresponding manner to the definitions in the following preferred combinations of radicals.
Bevorzugt sind die Verbindungen der Formel (I), in welcherPreferred are the compounds of formula (I) in which
R1 und R2 gleich oder verschieden sind und für jeweils unsubstituiertes oder substituiertes Alkyl mit 1 bis 4 Kohlenstoffatomen, Cycloalkyl mit 3 bis 7 Kohlenstoffatomen oder Phenyl stehen,R 1 and R 2 are the same or different and each represents unsubstituted or substituted alkyl having 1 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms or phenyl,
R3 für Alkyl mit 2 bis 8 Kohlenstoffatomen, substituiertes Alkyl mit 1 bis 8 Kohlenstoffatomen, jeweils unsubstituiertes oder substituiertes Cycloalkyl mit 3 bis 7 Kohlenstoffatomen, Phenyl oder Phenylalkyl mit 1 bis 4 Kohlenstoffatomen im Alkylteil stehen,R 3 represents alkyl with 2 to 8 carbon atoms, substituted alkyl with 1 to 8 carbon atoms, each unsubstituted or substituted cycloalkyl with 3 to 7 carbon atoms, phenyl or phenylalkyl with 1 to 4 carbon atoms in the alkyl part,
R4, R5, R6, R7 und R8 gleich oder verschieden sind und für Wasserstoff, jeweils unsubstituiertes oder substituiertes Alkyl mit 1 bis 8 Kohlenstoff¬ atomen, Phenyl oder Phenylalkyl mit 1 bis 4 Kohlenstoffatomen im Alkylteil stehen, wobei R und R8 nicht gleichzeitig für Wasserstoff stehen,R 4 , R 5 , R 6 , R 7 and R 8 are the same or different and represent hydrogen, in each case unsubstituted or substituted alkyl having 1 to 8 carbon atoms, phenyl or phenylalkyl having 1 to 4 carbon atoms in the alkyl part, where R and R 8 does not simultaneously represent hydrogen,
R7 und R8 unabhängig voneinander zusätzlich auch für jeweils unsubstituiertes oder substituiertes Cycloalkyl mit 3 bis 7 Kohlenstoffatomen, 5- bis 9-gliedriges Heteroaryl, welches 1 bis 4 gleiche oder verschiedene Heteroatome wie Sauerstof, Stickstoff und Schwefel enthält, oder entsprechendes Heteroarylalkyl mit 1 bis 4 Kohlenstoffatomen im Alkylteil stehen, oderR 7 and R 8 independently of one another, in addition, each for unsubstituted or substituted cycloalkyl having 3 to 7 carbon atoms, 5- to 9-membered heteroaryl which contains 1 to 4 identical or different heteroatoms such as oxygen, nitrogen and sulfur, or corresponding heteroarylalkyl having 1 to 4 carbon atoms in the alkyl part, or
R8 für die Gruppen -CHR4-COOH und -CHR4-COOCH3 steht oderR 8 represents the groups -CHR 4 -COOH and -CHR 4 -COOCH 3 or
R5 und R6 zusammen mit dem Stickstoffatom an welches sie gebunden sind einen unsubstituierten oder substituierten 5- bis 7-gliedrigen Ring bilden der zusätzlich 1 oder 2 gleiche oder verschiedene Heteroatome wie Sauerstoff, Stickstoff und Schwefel enthalten kann, oderR 5 and R 6 together with the nitrogen atom to which they are attached form an unsubstituted or substituted 5- to 7-membered ring which can additionally contain 1 or 2 identical or different heteroatoms such as oxygen, nitrogen and sulfur, or
R7 und R8 zusammen mit dem Stickstoffatom an welches sie gebunden sind einen unsubstituierten oder substituierten 5- bis 7-gliedrigen Ring bilden der zusätzlich 1 oder 2 gleiche oder verschiedene Heteroatome wie Sauerstoff, Stickstoff und Schwefel enthalten kann.R 7 and R 8 together with the nitrogen atom to which they are attached form an unsubstituted or substituted 5- to 7-membered ring which can additionally contain 1 or 2 identical or different heteroatoms such as oxygen, nitrogen and sulfur.
Besonders bevorzugt sind diejenigen Verbindungen der Formel (I), in welcherThose compounds of the formula (I) in which
R1 und R2 gleich oder verschieden sind und für jeweils unsubstituiertes ver¬ zweigtes Alkyl mit 4 bis 6 Kohlenstoffatomen oder substituiertes Alkyl mit 1 bis 6 Kohlenstoffatomen, jeweils unsubstituiertes oder substituiertes Cyclopropyl, Cyclobutyl, Cyclopropyl, Cyclohexyl oder Phenyl stehen,R 1 and R 2 are the same or different and each represents unsubstituted branched alkyl having 4 to 6 carbon atoms or substituted alkyl having 1 to 6 carbon atoms, each unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopropyl, cyclohexyl or phenyl,
R3 für Alkyl mit 2 bis 6 Kohlenstoffatomen, substituiertes Alkyl mit 1 bis 6 Kohlenstoffatomen, jeweils unsubstituiertes oder substituiertes Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Phenyl oderR 3 represents alkyl having 2 to 6 carbon atoms, substituted alkyl having 1 to 6 carbon atoms, in each case unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or
Benzyl steht,Benzyl stands,
R4 für Wasserstoff oder Alkyl mit 1 bis 4 Kohlenstoffatomen oder gegebenenfalls substituiertes Phenyl oder Benzyl steht,R 4 represents hydrogen or alkyl having 1 to 4 carbon atoms or optionally substituted phenyl or benzyl,
R5 und R6 gleich oder verschieden sind und für Wasserstoff, Alkyl mit 1 bis 8 Kohlenstoffatomen und unsubstituiertes oder substituiertes Phenyl stehen wobei als Substituenten vorzugsweise Halogen, Alkyl, Alkoxy, Alkylthio, Halogenalkyl, Halogenalkoxy und Halogenalkylthio ge¬ nannt seien,R 5 and R 6 are the same or different and represent hydrogen, alkyl having 1 to 8 carbon atoms and unsubstituted or substituted phenyl, the preferred substituents being halogen, alkyl, alkoxy, Alkylthio, haloalkyl, haloalkoxy and haloalkylthio may be mentioned,
R7 und R8 gleich oder verschieden sind und für Wasserstoff, jeweils unsubsti¬ tuiertes oder substituiertes Alkyl mit 1 bis 6 Kohlenstoffatomen, Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Phenyl und Benzyl stehen wobei als Substituenten vorzugsweise Halogen, Alkyl, Alkoxy, Alkylthio, Halogenalkyl, Halogenalkoxy, Halogenalkylthio und Dialkylamino genannt seien, wobei jedoch R7 und R8 nicht gleich¬ zeitig für Wasserstoff stehen, undR 7 and R 8 are identical or different and represent hydrogen, in each case unsubstituted or substituted alkyl having 1 to 6 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl and benzyl, the substituents preferably being halogen, alkyl, alkoxy, alkylthio, Haloalkyl, haloalkoxy, haloalkylthio and dialkylamino may be mentioned, but R 7 and R 8 do not simultaneously represent hydrogen, and
R8 zusätzlich für die Gruppen -CHR4-COOH und -CHR4-COOCH3 steht oderR 8 additionally stands for the groups -CHR 4 -COOH and -CHR 4 -COOCH 3 or
R3 und R6 zusammen mit dem Stickstoffatom an welches sie gebunden sind einen jeweils unsubstituierten oder substituierten Piperidin-,R 3 and R 6 together with the nitrogen atom to which they are attached represent an unsubstituted or substituted piperidine,
Morpholin-, Hexahydroazepin- oder Piperazinring bilden, wobei als Substituenten vorzugsweise Alkyl und Hydroxyalkyl genannt seien, oderForm morpholine, hexahydroazepine or piperazine ring, alkyl and hydroxyalkyl preferably being mentioned as substituents, or
R7 und R8 zusammen mit dem Stickstoffatom an welches sie gebunden sind einen jeweils unsubstituierten oder substituierten Piperidin-,R 7 and R 8 together with the nitrogen atom to which they are attached are in each case an unsubstituted or substituted piperidine,
Pyrrolidin-, Morpholin-, Hexahydroazepin- oder Piperazinring bilden, wobei als Substituenten vorzugsweise Alkyl und Hydroxyalkyl genannt seien.Form pyrrolidine, morpholine, hexahydroazepine or piperazine ring, alkyl and hydroxyalkyl preferably being mentioned as substituents.
Ganz besonders bevorzugt sind diejenigen Verbindungen der Formel (I), in welcherThose compounds of the formula (I) in which
R1 für Methyltriazolyl steht,R 1 represents methyltriazolyl,
R2 für gegebenenfalls durch unsubstituiertes oder halogensubstituiertes Phenoxy substituiertes Butyl, Pentyl, Hexyl und Heptyl, oder jeweils gegebenenfalls ein- bis dreifach durch Fluor, Chlor, Brom, Methyl, Ethyl, Methoxy, Ethoxy,R 2 represents butyl, pentyl, hexyl and heptyl which is optionally substituted by unsubstituted or halogen-substituted phenoxy, or in each case optionally one to three times by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy,
Trifluormethyl oder Trifluormethoxy substituiertes Phenyl oder Cyclopropyl steht, R3 für Ethyl, n- und i-Propyl, n-, i-, s- und t-Butyl steht, oder für durch Dimethylamino, Diethylamino, Methoxycarbonyl, Ethoxycarbonyl substitu¬ iertes Methyl, Ethyl, n - und i.-Propyl, n.-, i.-, s.- und t.-Butyl steht, oder für jeweils gegebenenfalls durch Fluor, Chlor, Brom, Methyl, Ethyl, Methoxy, Ethoxy, Trifluormethyl, Trifluormethoxy substituiertes Phenyl, Benzyl oderTrifluoromethyl or trifluoromethoxy substituted phenyl or cyclopropyl, R 3 stands for ethyl, n- and i-propyl, n-, i-, s- and t-butyl, or for methyl, ethyl, n- and i-propyl substituted by dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl , n.-, i.-, s.- and t.-butyl, or for each optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy or phenyl, benzyl or
Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl steht,Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,
R4 für Wasserstoff, Methyl, Ethyl, n.-, i.-Propyl, n.-, i.-, s.- und t. -Butyl steht,R 4 for hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t. -Butyl stands,
R5 für Wasserstoff, Methyl, Ethyl, n.-, i.-Propyl, n.-, i.-, s.- und t.-Butyl steht,R 5 represents hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl,
R6 für Wasserstoff, Methyl, Ethyl, n.-, i.-Propyl, n.-, i.-, s.- und t.-Butyl steht, oderR 6 represents hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl, or
R5 und R6 zusammen mit dem Stickstoffatom an welches sie gebunden sind einen Piperidin-, Morpholin-, Hexahydroazepin- oder Piperazinring bilden,R 5 and R 6 together with the nitrogen atom to which they are attached form a piperidine, morpholine, hexahydroazepine or piperazine ring,
R7 für Wasserstoff, Methyl, Ethyl, n.-, i.-Propyl, n.-, i.-, s.- und t.-Butyl steht,R 7 represents hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl,
R8 für gegebenenfalls durch Dimethylamino, Diethylamino, Methoxycarb¬ onyl, Ethoxycarbonyl substituiertes Methyl, Ethyl, n.- und i.-Propyl, n.-, i.-, s.- und t.-Butyl steht, oder für jeweils gegebenenfalls einfach bis dreifach durch Fluor, Chlor, Brom, Methyl, Ethyl, Methoxy, Ethoxy, Trifluormethyl und/oder Trifluormethoxy substituiertesR 8 represents methyl, ethyl, n.- and i.-propyl, n.-, i.-, s.- and t.-butyl, optionally substituted by dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, or each in each case optionally monosubstituted to trisubstituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy
Phenyl, Benzyl, Cyclopropyl, Cyclobutyl, Cyclopentyl und Cyclohexyl steht,Phenyl, benzyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl,
oder für die Gruppen -CHR4'-COOH und -CHR4'-COOCH3 steht, worinor represents the groups -CHR 4 ' -COOH and -CHR 4' -COOCH 3 , wherein
R4 für Wasserstoff, Methyl, Ethyl, n.-, i.-Propyl, n.-, i.-, s.- und t.-Butyl, Phenyl, Biphenyl und Hydroxybiphenyl und Benzyl steht, oder R7 und R8 zusammen mit dem Stickstoffatom an welches sie gebunden sind, einen jeweils gegebenenfalls einfach oder zweifach durch Methyl, Ethyl, Hydroxymethyl und Hydroxyethyl substituierten Piperidin-, Pyrrolidin-, Morpholin- oder Piperazinπng bildenR 4 represents hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl, phenyl, biphenyl and hydroxybiphenyl and benzyl, or R 7 and R 8 together with the nitrogen atom to which they are bonded form a piperidine, pyrrolidine, morpholine or piperazine ring, which are optionally mono- or disubstituted by methyl, ethyl, hydroxymethyl and hydroxyethyl
Bevorzugte Verbindungen sind auch Additionsprodukte aus Sauren und denjenigen Derivaten der Formel (I), in denen die Substituenten R1, R2, R3, R4, R5, R6, R7 und R8 die Bedeutungen haben, die bereits vorzugsweise für diese Substituenten genannt wurdenPreferred compounds are also addition products of acids and those derivatives of the formula (I) in which the substituents R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 have the meanings which are already preferred for these substituents
Zu den Sauren die addiert werden können, gehören vorzugsweise Halogenwasser- stoffsauren, wie z.B Chlorwasserstoffsaure und Bromwasserstoffsaure, insbesondere Chlorwasserstoff saure, ferner Phosphorsaure, Salpetersaure, Schwefelsaure, mono-, bi- und trifunktionelle Carbonsauren und Hydroxycarbonsauren, wie z.B Essigsaure, Maleinsäure, Bernsteinsaure, Fumarsaure, Weinsaure, Zitronensäure, Salicylsaure, Sorbinsaure und Milchsäure, Sulfonsäuren, wie z B p-Toluolsulfonsaure und 1,5- Napthalindisulfonsaure sowie Saccharin oder ThiosaccharinThe acids which can be added preferably include hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono-, bi- and trifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, Fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, sulfonic acids such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid as well as saccharin or thiosaccharin
Außerdem bevorzugte Verbindungen sind Additionsprodukte aus Salzen und Metallen der II bis IV Haupt- und der I. und II sowie IV bis VIII Nebengruppe und denjenigen Deπvaten der Formel (I), in denen die Substituenten R1, R2, R3, R4, R5, R6, R7 und R8 die Bedeutungen haben, die bereits vorzugsweise für diese Substituenten genannten wurdenIn addition, preferred compounds are addition products of salts and metals of main groups II to IV and groups I and II as well as groups IV to VIII and those derivatives of formula (I) in which the substituents R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 have the meanings which have already been mentioned preferably for these substituents
Hierbei sind Salze des Kupfers, Zinks, Mangans, Magnesiums, Zinns, Eisens und des Nickels besonders bevorzugt Als Anionen dieser Salze kommen solche in Betracht, die sich von solchen Sauren ableiten, die zu umweltvertraglichen Additionsprodukten fuhren Besonders bevorzugte derartige Sauren sind in diesem Zusammenhang die Halogenwasserstoffsauren, wie z B die Chlorwasserstoffsaure und die Bromwasserstoffsaure, Salpetersaure und SchwefelsaureSalts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Anions of these salts are those which are derived from acids which lead to environmentally compatible addition products. Particularly preferred acids in this context are Hydrogen halide acids, such as, for example, hydrochloric acid and hydrobromic acid, nitric acid and sulfuric acid
Die neuen Derivate der Tetrafluorbenzoesaure der Formel (I) lassen sich nach be¬ kannten Verfahren in analoger Weise herstellen Die zur Herstellung der Verbin¬ dungen der Formel (I) benotigten Ausgangsverbindungen sind bekannt bzw können nach allgemein bekannten Methoden hergestellt werden Die Umsetzung der Ausgangsverbindungen erfolgt vorzugsweise in einem inerten mit Wasser nicht mischbaren Verdünnungsmittel wie z.B. aromatische, nichtaromatische oder halogenierte Kohlenwasserstoffe wie: Ester, wie z.B. Essigester; Chlorkohlenwasserstoffen, wie z.B. Dichlormethan, Trichlorethan; Aromaten, wie z.B. Toluol; Kohlenwasserstoffe, wie z.B. Cyclohexan bzw. derer Mischungen und/oder in Gegenwart eines Säurebindemittels wie z.B. Kaliumcarbonat, Triethylamin, Pyridin, N-Methylpiperidin oder Kalium- oder Natriumhydroxid, bei Temperaturen von 0°C bis 100°C, vorzugsweise 20°C bis 40°C und unter Normaldruck. Bei der Reaktion mit Aminosäuren arbeitet man in wäßriger Lösung vorzugsweise mit Natronlauge als Hilfsbase bei 0°C bis 20°C.The new derivatives of tetrafluorobenzoic acid of the formula (I) can be prepared in an analogous manner by known processes. The starting compounds required for the preparation of the compounds of the formula (I) are known or can be prepared by generally known methods The starting compounds are preferably reacted in an inert water-immiscible diluent, such as aromatic, non-aromatic or halogenated hydrocarbons such as: esters, such as ethyl acetate; Chlorinated hydrocarbons, such as dichloromethane, trichloroethane; Aromatics such as toluene; Hydrocarbons such as cyclohexane or their mixtures and / or in the presence of an acid binder such as potassium carbonate, triethylamine, pyridine, N-methylpiperidine or potassium or sodium hydroxide, at temperatures from 0 ° C to 100 ° C, preferably 20 ° C to 40 ° C and under normal pressure. In the reaction with amino acids, an aqueous solution is preferably used with sodium hydroxide solution as an auxiliary base at 0 ° C. to 20 ° C.
Die Erfindung umfaßt sowohl die reinen Isomeren als auch die Gemische. Diese Gemische können nach gebräuchlichen Methoden, z.B. selektive Kristallisation aus geeigneten Lösungsmitteln oder Chromatographie an Kieselgel oder Aluminiumoxid in die Komponenten aufgetrennt werden. Racemate können nach üblichen Methoden in die einzelnen Enantiomeren aufgetrennt werden, so z.B. durch Salzbildung mit optisch aktiven Säuren wie Champhersulfonsäure oder Dibenzoyl einsäure und selektive Kristallisation oder durch Derivatisierung mit geeigneten, optisch aktiven Reagenzien, Trennung der diastereomeren Derivate und Rückspaltung oder Trennung an optisch aktivem Säulenmaterial.The invention encompasses both the pure isomers and the mixtures. These mixtures can be prepared using common methods, e.g. selective crystallization from suitable solvents or chromatography on silica gel or aluminum oxide are separated into the components. Racemates can be separated into the individual enantiomers by conventional methods, e.g. by salt formation with optically active acids such as champhersulfonic acid or dibenzoyl acid and selective crystallization or by derivatization with suitable, optically active reagents, separation of the diastereomeric derivatives and cleavage or separation on optically active column material.
Die erfindungsgemäßen Wirkstoffe der Formel (I) weisen eine starke Wirkung gegen Schädlinge auf und können zur Bekämpfung von unerwünschten Schadorganismen praktisch eingesetzt werden. Die Wirkstoffe sind für den Gebrauch als Pflanzenschutzmittel insbesondere als Fungizide geeignet.The active compounds of the formula (I) according to the invention have a strong action against pests and can be used practically to combat unwanted harmful organisms. The active ingredients are suitable for use as crop protection agents, in particular as fungicides.
Fungizide Mittel im Pflanzenschutz werden eingesetzt zur Bekämpfung von Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.Fungicidal agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
Beispielhaft aber nicht begrenzend seien einige Erreger von pilzlichen Erkrankungen, die unter die oben aufgezählten Oberbegriffe fallen, genannt:Some pathogens of fungal diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Pythium-Arten, wie beispielsweise Pythium ultimum; Phytophthora-Arten, wie beispielsweise Phytophthora infestans; Pseudoperonospora-Arten, wie beispielsweise Pseudoperonospora humuli oderPythium species, such as, for example, Pythium ultimum; Phytophthora species, such as, for example, Phytophthora infestans; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or
Pseudoperonospora cubensis;Pseudoperonospora cubensis;
Plasmopara-Arten, wie beispielsweise Plasmopara viticola;Plasmopara species, such as, for example, Plasmopara viticola;
Peronospora-Arten, wie beispielsweise Peronospora pisi oder P. brassicae; Erysiphe-Arten, wie beispielsweise Erysiphe graminis;Peronospora species, such as, for example, Peronospora pisi or P. brassicae; Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca-Arten, wie beispielsweise Sphaerotheca fuliginea;Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera-Arten, wie beispielsweise Podosphaera leucotricha;Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia-Arten, wie beispielsweise Venturia inaequalis;Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora-Arten, wie beispielsweise Pyrenophora teres oder P. graminea (Koni dienform: Drechslera, Syn: Helminthosporium);Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidia form: Drechslera, Syn: Helminthosporium);
Cochliobolus-Arten, wie beispielsweise Cochliobolus sativusCochliobolus species, such as, for example, Cochliobolus sativus
(Koni dienform: Drechslera, Syn: Helminthosporium);(Coni form: Drechslera, Syn: Helminthosporium);
Uromyces-Arten, wie beispielsweise Uromyces appendiculatus;Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia-Arten, wie beispielsweise Puccinia recondita; Tilletia- Arten, wie beispielsweise Tilletia caries;Puccinia species, such as, for example, Puccinia recondita; Tilletia species, such as, for example, Tilletia caries;
Ustilago-Arten, wie beispielsweise Ustilago nuda oder Ustilago avenae;Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia-Arten, wie beispielsweise Pellicularia sasakii;Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia-Arten, wie beispielsweise Pyricularia oryzae;Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium-Arten, wie beispielsweise Fusarium culmorum; Botrytis- Arten, wie beispielsweise Botrytis cinerea;Fusarium species, such as, for example, Fusarium culmorum; Botrytis species, such as, for example, Botrytis cinerea;
Septoria- Arten, wie beispielsweise Septoria nodorum;Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria-Arten, wie beispielsweise Leptosphaeria nodorum;Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora-Arten, wie beispielsweise Cercospora canescens;Cercospora species, such as, for example, Cercospora canescens;
Alternaria- Arten, wie beispielsweise Alternaria brassicae; Pseudocercosporella-Arten, wie beispielsweise Pseudocercosporella herpotrichoides.Alternaria species, such as, for example, Alternaria brassicae; Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.
Die gute Pflanzenverträglichkeit der Wirkstoffe in den zur Bekämpfung von Pflan¬ zenkrankheiten notwendigen Konzentrationen erlaubt eine Behandlung von oberirdischen Pflanzenteilen, von Pflanz- und Saatgut, und des Bodens.The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases allows treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.
Dabei lassen sich die erfindungsgemäßen Wirkstoffe mit besonders gutem Erfolg protektiv zur Bekämpfung von Pyricularia-Arten an Reis einsetzen. Die erfϊndungsgemaßen Wirkstoffe weisen desweiteren eine starke resistenz¬ induzierende Wirkung in Pflanzen auf Sie eignen sich daher zur Erzeugung von Resistenz in Pflanzen gegen Befall durch unerwünschte MikroorganismenThe active compounds according to the invention can be used with particular good protection for controlling Pyricularia species on rice. The active compounds according to the invention furthermore have a strong resistance-inducing action in plants. They are therefore suitable for generating resistance in plants against attack by undesired microorganisms
Unter resistenz-induzierenden Stoffen sind im vorliegenden Zusammenhang solche Substanzen zu verstehen, die einerseits bei direkter Einwirkung auf die uner¬ wünschten Mikroorganismen nur eine geringe Aktivität zeigen, andererseits aber in der Lage sind, das Abwehrsystem von Pflanzen so zu stimulieren, daß die behan¬ delten Pflanzen bei nachfolgender Inokulation mit unerwünschten Mikroorganismen weitgehende Resistenz gegen diese Mikroorganismen entfaltenIn the present context, resistance-inducing substances are to be understood as those substances which, on the one hand, show only a low activity when directly affected by the undesired microorganisms, but on the other hand are able to stimulate the immune system of plants in such a way that the affected If the plants are subsequently inoculated with undesirable microorganisms, they will develop extensive resistance to these microorganisms
Unter unerwünschten Mikroorganismen sind im vorliegenden Fall phytopathogene Pilze, Bakterien und Viren zu verstehen Die erfindungsgemaßen Stoffe können also eingesetzt werden, um in Pflanzen innerhalb eines gewissen Zeitraumes nach der Behandlung Resistenz gegen den Befall durch die genannten Schaderreger zu erzeugen Der Zeitraum, innerhalb dessen Resistenz herbeigeführt wird, erstreckt sich im allgemeinen von 1 bis 10 Tage, vorzugsweise 1 bis 7 Tage nach der Behandlung der Pflanzen mit den WirkstoffenUndesired microorganisms are to be understood in the present case as phytopathogenic fungi, bacteria and viruses. The substances according to the invention can therefore be used to produce resistance to the attack by the named pathogens in plants within a certain period of time after the treatment. The period within which resistance is brought about is generally from 1 to 10 days, preferably 1 to 7 days after the treatment of the plants with the active compounds
Zu den unerwünschten Mikroorganismen im Pflanzenschutz gehören Pilze aus den Klassen der Plasmodiophoromycetes, Oomycetes, Chytridiomycetes. Zygomycetes. Ascomycetes. Basidiomycetes und DeuteromycetesUnwanted microorganisms in crop protection include fungi from the classes of the Plasmodiophoromycetes, Oomycetes and Chytridiomycetes. Zygomycetes. Ascomycetes. Basidiomycetes and Deuteromycetes
Die Wirkstoffe können in Abhängigkeit von ihren jeweiligen physikalischen und/oder chemischen Eigenschaften in übliche Formulierungen übergeführt werden, wie Losungen, Emulsionen, Suspensionen, Pulver, Schaume, Pasten, Granulate, Aerosole, Feinstverkapselungen in polymeren Stoffen und in Hullmassen für Saatgut, sowie ULV-Kalt-und Warmnebel-FormuherungenDepending on their respective physical and / or chemical properties, the active compounds can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV Cold and warm mist shapes
Diese Formulierungen werden in bekannter Weise hergestellt, z B durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Losungsmitteln, unter Druck ste¬ henden verflüssigten Gasen und/oder festen Tragerstoffen, gegebenenfalls unter Verwendung von oberflachen-aktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln Im Falle der Benutzung von Wasser als Streckmittel können z B auch organische Losungsmittel als Hilfslosungsmittel verwendet werden Als flussige Lösungsmittel kommen im wesentlichen in Frage Aromaten, wie Xylol, Toluol, oder Alkylnaphthaline, chlo¬ rierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclo- hexan oder Paraffine, z B Erdolfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Ether und Ester, Ketone, wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclohexanon, stark polare Losungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasformigen Streckmitteln oder Tragerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Normal druck gasformig sind, z B Aerosol-Treibgase, wi e Halogenkohlenwasserstoffe sowie Butan, Propan, Stickstoff und Kohlendioxid, als feste Tragerstoffe kommen in Frage z B natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsaure, Aluminiumoxid und Silikate, als feste Tragerstoffe für Granulate kommen in Frage z B gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sagemehl, Kokosnußschalen, Maiskolben und Tabakstengel, als Emulgier- und/oder schaumerzeugende Mittel kommen in Frage z B nichüonogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsaure-Ester, Polyoxyethylen-Fettalkohol-Ether, z B Alkylarylpolyglykol-Ether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate, als Dispergiermittel kommen in Frage z B Lignin-Sulfitablaugen und MethylcelluloseThese formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents If water is used as an extender, organic solvents can also be used, for example Auxiliary solvents are used. Liquid solvents are essentially aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions Alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide and water; Liquefied gaseous extenders or carriers are liquids that are gaseous at normal temperature and pressure, e.g. aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; solid rock materials can be considered, for example, natural rock powder , such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flours, such as highly disperse silicic acid, aluminum oxide and silicates, as solid carriers for granules are, for example, broken and fractionated natural rocks such as calcite, marble, pumice , Sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks, as emulsifiers and / or foam-generating agents, for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters , Poly oxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and protein hydrolyzates, and dispersants are, for example, lignin sulfite liquors and methyl cellulose
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, naturliche und synthetische pulverige, kornige oder latexformige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie naturliche Phosphohpide, wie Kephahne und Lecithine, und synthetische Phospholipide Weitere Additive können mineralische und vegetabile Ole seinIn the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phosphophides, such as wafers and lecithins, and synthetic phospholipids, and other additives can be mineral and vegetable oils
Es können Farbstoffe wie anorganische Pigmente, z B Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizaπn-, Azo- und Metallphthalo- cyamnfarb Stoffe und Spurennahrstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 %.Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as Alizaπn, azo and metal phthalocyanine substances and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
Die erfindungsgemäßen Wirkstoffe können in den Formulierungen in Mischung mit anderen bekannten Wirkstoffen vorliegen wie Fungizide, Insektizide, Akarizide und Herbizide sowie in Mischungen mit Düngemitteln und Wachstumsregulatoren.The active compounds according to the invention can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and in mixtures with fertilizers and growth regulators.
Die erfindungsgemäßen Wirkstoffe können als solche oder in ihren Formulierungen auch in Mischung mit bekannten Fungiziden, Bakteriziden, Akariziden, Nematiziden oder Insektiziden verwendet werden, um so z.B. das Wirkungsspektrum zu verbreitern oder Resistenzentwicklungen vorzubeugen. In vielen Fällen erhält man dabei synergistische Effekte, d.h. die Wirksamkeit der Mischung ist größer als die Wirksamkeit der Einzelkomponenten.The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the spectrum of activity or to prevent the development of resistance. In many cases, synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.
Besonders günstige Mischpartner sind z.B. die folgenden Verbindungen. The following compounds are particularly favorable mixing partners.
Fungizide:Fungicides:
2-Aminobutan;2-Anilino-4-methyl-6-cyclopropyl-pyrimidin;2',6'-Dibromo-2-methyl-2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-
4'-tri-luoromethoxy-4'-trifluoro-methyl-l,3-thizole-5-carboxanilid?,6-Dichloro-N-(4- trifluoromethylbenzyl)benzamid; (E)-2-Methoxyimino-N-methyl-2-(2-phenoxyphenyl)- acetamid; 8-Hydroxyquinolinsulfat; Methyl-(E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4'-tri-luoromethoxy-4'-trifluoromethyl-1,3-thizole-5-carboxanilide?, 6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidine-
4-yloxy]phenyl}-3-methoxyacrylat; Methyl-(E)-methoximino[α-(o-tolyloxy)-o- tolyl]acetat; 2-Phenylphenol (OPP), Aldimorph, Ampropylfos, Anilazin, Azaconazol,4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [α- (o-tolyloxy) -otolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S,Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S,
Bromuconazole, Bupirimate, Buthiobate, Calciumpolysulfid, Captafol, Captan, Carbendazim, Carboxin, ChinomethionatBromuconazole, bupirimate, buthiobate, calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate
(Quinomethionat), Chloroneb, Chloropicrin, Chlorothalonil, Chlozolinat, Cufraneb,(Quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb,
Cymoxanil, Cyproconazole, Cyprofuram,Cymoxanil, cyproconazole, cyprofuram,
Dichlorophen, Diclobutrazol, Diclofluanid, Diclomezin, Dicloran, Diethofencarb.Dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb.
Difenoconazol, Dimethirimol, Dimethomorph, Diniconazol, Dinocap, Diphenylamin, Dipyrithion, Ditalimfos, Dithianon, Dodin, Drazoxolon,Difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, Epoxyconazole, Ethirimol, Etridiazol,Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin,Fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin,
Fenpropimorph, Fentinacetate, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam,Fenpropimorph, fentin acetates, fentin hydroxide, ferbam, ferim zone, fluazinam,
Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil, Flutriafol, Folpet, Fosetyl-Aluminium, Fthalide, Fuberidazol, Furalaxyl, Furmecyclox,Fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl aluminum, fthalides, fuberidazole, furalaxyl, furmecyclox,
Guazatine,Guazatine,
Hexachlorobenzol, Hexaconazol, Hymexazol,Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobenfos (IBP), Iprodion, Isoprothiolan,Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,
Kasugamycin, Kupfer-Zubereitungen, wie: Kupferhydroxid, Kupfernaphthenat, Kupferoxychlorid, Kupfersulfat, Kupferoxid, Oxin-Kupfer und Bordeaux-Mischung,Kasugamycin, copper preparations such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol,Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol,
Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil.Methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil.
Nickeldimethyldithiocarbamat, Nitrothal-isopropyl, Nuarimol,Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin, Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin,Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin, Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin,
Probenazol, Prochloraz, Procymidon, Propamocarb, Propiconazole, Propineb,Probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb,
Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon,Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon,
Quintozen (PCNB),Quintozen (PCNB),
Schwefel und Schwefel-Zubereitungen, Tebuconazol, Teclof alam, Tecnazen, Tetraconazol, Thiabendazol, Thicyofen, Thio- phanatmethyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflumizol, Triforin, Triticonazol, Validamycin A, Vinclozolin, Zineb, ZiramSulfur and sulfur preparations, Tebuconazole, Alam Teclof, tecnazene, tetraconazole, thiabendazole, Thicyofen, thio phanatmethyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, validamycin A, vinclozolin, zineb, Ziram
Bakterizide:Bactericides:
Bronopol, Dichlorophen, Nitrapyrin, Nickel, Dimethyldithiocarbamat, Kasugamycin, Octhilinon, Furancarbonsäure, Oxytetracyclin, Probenazol, Streptomycin, Tecloftalam, Kupfersulfat und andere Kupfer-Zubereitungen.Bronopol, dichlorophene, nitrapyrin, nickel, dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.
Insektizide / Akarizide / Nematizide:Insecticides / acaricides / nematicides:
Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin,Abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin,
Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M,Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M,
Azocyclotin,Azocyclotin,
Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin,Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin,
Butylpyridaben,Butyl pyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap,Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap,
CGA 157 419, CGA 184 699, Chloethocarb, Chlorethoxyfos, Chloretoxyfos,CGA 157 419, CGA 184 699, chloethocarb, chlorethoxyfos, chloretoxyfos,
Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis- Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin,Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis- Resmethrin, Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyfluthrin,
Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazin,Cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon,Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon,
Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron,Dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron,
Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton, Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox,Dimethoate, Dimethylvinphos, Dioxathion, Disulfoton, Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox,
Ethoprophos, Etofenprox, Etrimphos,Ethoprophos, Etofenprox, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb,Fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,
Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil,Fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil,
Floazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,Floazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,
HCH, Heptenophos, Hexaflumuron, Hexythiazox,HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobenfos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
Lambda-cyhalothrin, Lufenuron, Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyd, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin, Naled, NC 184, NI 25, Nitenpyram, Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos,Lambda cyhalothrin, lufenuron, Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathione, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin, Naled, NC 184, NI 25, Nitenpyram, Omethoat, Oxofonon, Oxamyl, Oxamyl, Oxydos
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyraclofos, Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos, RH 5992,Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyraclhrhos, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhium, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraclofhrin, Pyrraclofhion, Pyrraclofhion, Pyrraclofhion, Pyrraphofin, Pyrraclofhion, Pyrraclofhion, Pyrraclofhium, Pyrraclofhion, Pyrraclofhrin, Pyrraphofin, Pyrophone, Pyrophone, Pyrophone, Pyrophone, Pyrophone, Pyrophone, Pyrate, Pyrate Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos, RH 5992,
Salithion, Sebufos, Silafiuofen, Sulfotep, Sulprofos,Salithion, Sebufos, Silafiuofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflubenuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Triarathen, Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimethacarb, Vamidothion, XMC, Xylylcarb, YI 5301/5302, Zetamethrin.Tebufenozid, Tebufenpyrad, Tebupirimiphos, Teflubenuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralometonium, Triaromenoriazonium, Triaromenoriazonium YI 5301/5302, zetamethrin.
Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Herbiziden oder mit Düngemitteln und Wachstumsregulatoren ist möglich.A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus bereiteten Anwendungsformen wie gebrauchsfertige Lösungen, Suspensionen, Spritzpulver, Pasten, lösliche Pulver, Stäubemittel und Granulate angewendet werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Gießen, Verspritzen, Versprühen, Verstreuen, Verstäuben, Verschäumen, Bestreichen usw.. Es ist ferner möglich, die Wirkstoffe nach dem Ultra-Low- Volume- Verfahren auszubringen oder die Wirkstoffzubereitung oder den Wirkstoff selbst in den Boden zu injizieren. Es kann auch das Saatgut von Pflanzen behandelt werden.The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of plants can also be treated.
Bei der Behandlung von Pflanzenteilen können die Wirkstoffkonzentrationen in den Anwendungsformen in einem größeren Bereich variiert werden. Sie liegen im allge- meinen zwischen 1 und.0,0001 Gew.-%, vorzugsweise zwischen 0,5 und 0,001 %. Bei der Saatgutbehandlung werden im allgemeinen Wirkstoffmengen von 0,001 bis 50 g je Kilogramm Saatgut, vorzugsweise 0,01 bis 10 g benötigt.When treating parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%. In the seed treatment, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
Bei Behandlung des Bodens sind Wirkstoffkonzentrationen von 0,00001 bis 0,1 Gew.-%, vorzugsweise von 0,0001 bis 0,02 % am Wirkungsort erforderlich.When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.
Bei der Anwendung als Resistenzinduktoren können die Wirkstoffkonzentrationen für die Behandlung von Pflanzenteilen in den Anwendungsformen in einem größeren Bereich variiert werden. Sie liegen im allgemeinen zwischen 1 und 0,0001 Gewichtsprozent, vorzugsweise zwischen 0,5 und 0,001 %.When used as resistance inducers, the active substance concentrations for the treatment of parts of plants in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001 percent by weight, preferably between 0.5 and 0.001%.
Die Herstellung und die Verwendung der erfindungsgemäßen Stoffe wird durch die folgenden Beispiele veranschaulicht. The preparation and use of the substances according to the invention is illustrated by the following examples.
HerstellungsbeispieleManufacturing examples
Herstellungsbeispiel 1Production Example 1
Unter Ruhren tropft man bei 20° 55 g (0,26 Mol) 2,3,5,6-Tetrafluorbenzoylchlorid zu einer Losung von 42,4 g (0,27 Mol) l-Hydroxyacetyl-2,3,4,5,6,7-hexahydroazepin und 27 g (0,27 Mol) Triethylamin in 500 ml Methylenchlorid im Verlauf von 30 Minuten zu Nach Ruhren über Nacht arbeitet man mit Wasser/Dichlormethan auf, trennt die organische Phase ab und engt diese im Vakuum ein Man erhalt ein zähes Ol, das bald kristallisiert und mit Petrolether verrührt wird Ausbeute 67,5 g (77,9 % der Theorie) Fp 64 bis 66°55 g (0.26 mol) of 2,3,5,6-tetrafluorobenzoyl chloride are added dropwise at 20 ° to a solution of 42.4 g (0.27 mol) of l-hydroxyacetyl-2,3,4,5, 6,7-hexahydroazepine and 27 g (0.27 mol) of triethylamine in 500 ml of methylene chloride in the course of 30 minutes. After stirring overnight, work up with water / dichloromethane, separate the organic phase and concentrate it in vacuo a viscous oil, which soon crystallizes and is stirred with petroleum ether. Yield 67.5 g (77.9% of theory), mp 64 to 66 °
Herstellbeispiel 2Preparation example 2
Zur Losung von 8,08 g (49 mMol) L-Phenylalamn in 25 ml 2N-Natronlauge tropft man unter Eiskuhlung gleichzeitig 10,6 g (50 mMol) 2,3,5,6-Tetrafluorbenzoylchlorid und 25 ml 2N-Natronlauge zu Nach Ruhren über Nacht stellt man mit verdünnter Salzsaure auf pH 2 und saugt das ausgefallene Kπstallisat ab Ausbeute 15,6 g (93,4 % der Theorie) Fp 146 bis 147° In entsprechender Weise und gemäß den allgemeinen Angaben werden die folgenden Verbindungen der Formel (I) hergestellt:10.6 g (50 mmol) of 2,3,5,6-tetrafluorobenzoyl chloride and 25 ml of 2N sodium hydroxide solution are added dropwise to the solution of 8.08 g (49 mmol) of L-phenylalamn in 25 ml of 2N sodium hydroxide solution while cooling with ice Overnight stirring is adjusted to pH 2 with dilute hydrochloric acid and the precipitated precipitate is sucked from a yield of 15.6 g (93.4% of theory), mp 146 to 147 ° The following compounds of the formula (I) are prepared in a corresponding manner and in accordance with the general information:
AnwendungsbeispieleExamples of use
Beispiel AExample A
Pyricularia-Test (Reis) / systemischPyricularia test (rice) / systemic
Lösungsmittel: 12,5 Gewichtsteile Aceton Emulgator: 0,3 Gewichtsteile AlkylarylpolyglykoletherSolvent: 12.5 parts by weight of acetone emulsifier: 0.3 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Ge¬ wichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und verdünnt das Konzentrat mit Wasser und der angegebenen Menge Emulgator auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and the concentrate is diluted to the desired concentration with water and the stated amount of emulsifier.
Zur Prüfung auf systemische Eigenschaften werden 40 ml der Wirkstoffzubereitung auf Einheitserde gegossen, in der junge Reispflanzen angezogen wurden. 7 Tage nach der Behandlung werden die Pflanzen mit einer wäßrigen Sporensuspension von Pyricularia oryzae inokuliert. Danach verbleiben die Pflanzen in einem Gewächshaus bei einer Temperatur von 25°C und einer relativen Luftfeuchtigkeit von 100 % bis zur Auswertung.To test for systemic properties, 40 ml of the active ingredient preparation are poured onto common soil in which young rice plants have been grown. 7 days after the treatment, the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants then remain in a greenhouse at a temperature of 25 ° C. and a relative atmospheric humidity of 100% until evaluation.
4 Tage nach der Inokulation erfolgt die Auswertung des Krankheitsbefalls.The disease infestation is evaluated 4 days after the inoculation.
Die Verbindungen gemäß der Herstellungsb ei spiele 1, 2, 3 und 37 zeigen bei einer Aufwandmenge von 100 mg Wirkstoff pro 100 cm3 einen 100 %igen Wirkungsgrad. The compounds according to the manufacturing examples 1, 2, 3 and 37 show 100% efficiency at an application rate of 100 mg of active ingredient per 100 cm 3 .

Claims

PatentansprücheClaims
1. Derivate der 2,3,5,6-Tetrafluorbenzoesäure der allgemeinen Formel (I) First Derivatives of 2,3,5,6-tetrafluorobenzoic acid of the general formula (I)
in welcherin which
Y für Sauerstoff oder Schwefel steht undY stands for oxygen or sulfur and
X für die Gruppen -O-N=CR]R2, -OR3, -OCHR4-CO-NR5R6 oder -NR7R8 stehtX represents the groups -ON = CR ] R 2 , -OR 3 , -OCHR 4 -CO-NR 5 R 6 or -NR 7 R 8
worinwherein
R1 und R2 unabhängig voneinander gegebenenfalls substituiertes Alkyl, Cycloalkyl und Aryl bedeuten,R 1 and R 2 independently of one another are optionally substituted alkyl, cycloalkyl and aryl,
R3 Alkyl mit mindestens 2 Kohlenstoffatomen, substituiertes Alkyl und gegebenenfalls substituiertes Cycloalkyl, Aryl und Aralkyl bedeuten,R 3 is alkyl with at least 2 carbon atoms, substituted alkyl and optionally substituted cycloalkyl, aryl and aralkyl,
R4, R5 und R6 unabhängig voneinander Wasserstoff und gegebe- enfalls substituiertes Alkyl, Aryl und Aralkyl bedeuten, oderR 4 , R 5 and R 6 independently of one another are hydrogen and optionally substituted alkyl, aryl and aralkyl, or
R5 und R6 gemeinsam mit dem Stickstoffatom an das sie gebunden sind einen gegebenenfalls substituierten Ring bilden, oderR 5 and R 6 together with the nitrogen atom to which they are attached form an optionally substituted ring, or
R7 und R8 unabhängig voneinander Wasserstoff und gegebe¬ nenfalls substituiertes Alkyl, Cycloalkyl, Aryl, Aralkyl, Alkylheteroaryl und Heteroaryl bedeuten, oder für die Gruppen -CHR4-COOH und -CHR4-COOCH3 stehen, wobei R7 und R8 nicht gleichzeitig für Wasserstoff stehen, oderR 7 and R 8 independently of one another are hydrogen and optionally substituted alkyl, cycloalkyl, aryl, aralkyl, Alkylheteroaryl and heteroaryl mean, or stand for the groups -CHR 4 -COOH and -CHR 4 -COOCH 3 , where R 7 and R 8 are not simultaneously hydrogen, or
R7 und R8 gemeinsam mit dem Stickstoffatom an das sie ge¬ bunden sind einen gegebenenfalls substituierten Ring bildenR 7 and R 8 together with the nitrogen atom to which they are bound form an optionally substituted ring
sowie deren Säureadditions-Salze und Metallsalz-Komplexe.as well as their acid addition salts and metal salt complexes.
2. Verbindungen der Formel (I), gemäß Anspruch 1, in welcher2. Compounds of formula (I), according to claim 1, in which
R1 und R2 gleich oder verschieden sind und für jeweils unsub¬ stituiertes oder substituiertes Alkyl mit 1 bis 4 Kohlen¬ stoffatomen, Cycloalkyl mit 3 bis 7 Kohlenstoffatomen oder Phenyl stehen,R 1 and R 2 are the same or different and each represents unsubstituted or substituted alkyl having 1 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms or phenyl,
R3 für Alkyl mit 2 bis 8 Kohlenstoffatomen, substituiertes Alkyl mit 1 bis 8 Kohlenstoffatomen, jeweils unsubstituiertes oder substituiertesR 3 for alkyl with 2 to 8 carbon atoms, substituted alkyl with 1 to 8 carbon atoms, each unsubstituted or substituted
Cycloalkyl mit 3 bis 7 Kohlenstoffatomen, Phenyl oder Phenylalkyl mit 1 bis 4 Kohlenstoffatomen im Alkylteil stehen,Cycloalkyl having 3 to 7 carbon atoms, phenyl or phenylalkyl having 1 to 4 carbon atoms in the alkyl part,
R4, R5, R6, R7 und R8 gleich oder verschieden sind und für Wasserstoff, jeweils unsubstituiertes oder substituiertes Alkyl mit 1 bis 8 Koh- lenstoffatomen, Phenyl oder Phenylalkyl mit 1 bis 4 Kohlenstoff¬ atomen im Alkylteil stehen, wobei R und R8 nicht gleichzeitig für Wasserstoff stehen,R 4 , R 5 , R 6 , R 7 and R 8 are identical or different and represent hydrogen, in each case unsubstituted or substituted alkyl having 1 to 8 carbon atoms, phenyl or phenylalkyl having 1 to 4 carbon atoms in the alkyl part, where R and R 8 do not simultaneously represent hydrogen,
R7 und R8 unabhängig voneinander zusätzlich auch für jeweils unsubstituiertes oder substituiertes Cycloalkyl mit 3 bis 7 Kohlenstoffatomen, 5- bis 9-gliedriges Heteroaryl, welches 1 bis 4 gleiche oder verschiedene Heteroatome wie Sauerstoff, Stickstoff und Schwefel enthält, oder entsprechendes Heteroarylalkyl mit 1 bis 4 Kohlen¬ stoffatomen im Alkylteil stehen, oderR 7 and R 8 independently of one another, in addition, each for unsubstituted or substituted cycloalkyl having 3 to 7 carbon atoms, 5- to 9-membered heteroaryl which contains 1 to 4 identical or different heteroatoms such as oxygen, nitrogen and sulfur, or corresponding heteroarylalkyl having 1 to 4 carbon atoms in the alkyl part, or
R8 für die Gruppen -CHR4-COOH und -CHR4-COOCH3 steht oderR 8 represents the groups -CHR 4 -COOH and -CHR 4 -COOCH 3 or
R5 und R6 zusammen mit dem Stickstoffatom an welches die ge- bunden sind einen unsubstituierten oder substituiertenR 5 and R 6 together with the nitrogen atom to which they are attached are an unsubstituted or substituted one
5- bis 7-gliedrigen Ring bilden der zusätzlich 1 oder 2 gleiche oder verschiedene Heteroatome wie Sauerstoff, Stickstoff und Schwefel enthalten kann, oder5- to 7-membered ring form which can additionally contain 1 or 2 identical or different heteroatoms such as oxygen, nitrogen and sulfur, or
R7 und R8 zusammen mit dem Stickstoffatom an welches die gebunden sind einen unsubstituierten oder substi¬ tuierten 5- bis 7-gliedrigen Ring bilden der zusätzlich 1 oder 2 gleiche oder verschiedene Heteroatome wie Sauerstoff, Stickstoff und Schwefel enthalten kann.R 7 and R 8 together with the nitrogen atom to which they are attached form an unsubstituted or substituted 5- to 7-membered ring which can additionally contain 1 or 2 identical or different heteroatoms such as oxygen, nitrogen and sulfur.
3. Verbindungen der Formel (I), gemäß Anspruch 1, in welcher3. Compounds of formula (I), according to claim 1, in which
R1 und R2 gleich oder verschieden sind und für jeweils unsub¬ stituiertes verzweigtes Alkyl mit 4 bis 6 Kohlenstoff¬ atomen oder substituiertes Alkyl mit 1 bis 6 Kohlen¬ stoffatomen, jeweils unsubstituiertes oder substituiertes Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl oder Phenyl stehen,R 1 and R 2 are the same or different and each represents unsubstituted branched alkyl having 4 to 6 carbon atoms or substituted alkyl having 1 to 6 carbon atoms, each unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl,
R3 für Alkyl mit 2 bis 6 Kohlenstoffatomen, substituiertes Alkyl mit 1 bis 6 Kohlenstoffatomen, jeweils unsubstituiertes oder substituiertes Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Phenyl oder Benzyl steht,R 3 represents alkyl having 2 to 6 carbon atoms, substituted alkyl having 1 to 6 carbon atoms, in each case unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl or benzyl,
R4 für Wasserstoff oder Alkyl mit 1 bis 4 Kohlenstoffatomen oder gegebenenfalls Phenyl oder Benzyl steht, R5 und R6 gleich oder verschieden sind und für Wasserstoff,R 4 represents hydrogen or alkyl having 1 to 4 carbon atoms or optionally phenyl or benzyl, R 5 and R 6 are the same or different and are hydrogen,
Alkyl mit 1 bis 8 Kohlenstoffatomen und unsubsti¬ tuiertes oder substituiertes Phenyl stehen wobei als Substituenten vorzugsweise Halogen, Alkyl, Alkoxy, Alkylthio, Halogenalkyl, Halogenalkoxy und Halogen¬ alkylthio genannt seien,Alkyl having 1 to 8 carbon atoms and unsubstituted or substituted phenyl are preferably substituted by halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy and haloalkylthio,
R7 und R8 gleich oder verschieden sind und für Wasserstoff, jeweils unsubstituiertes oder substituiertes Alkyl mit 1 bis 6 Kohlenstoffatomen, Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Phenyl und Benzyl stehen wobei als Substituenten vorzugsweise Halogen, Alkyl, Alkoxy, Alkylthio, Halogenalkyl, Halogenalkoxy, Halogenalkylthio und Dialkylamino genannt seien, wobei jedoch R7 und R8 nicht gleichzeitig für Wasser- stoff stehen, undR 7 and R 8 are the same or different and represent hydrogen, in each case unsubstituted or substituted alkyl having 1 to 6 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl and benzyl, the substituents being preferably halogen, alkyl, alkoxy, alkylthio, haloalkyl, Haloalkoxy, haloalkylthio and dialkylamino may be mentioned, but R 7 and R 8 do not simultaneously represent hydrogen, and
R8 zusätzlich für die Gruppen -CHR4-COOH und -CHR4-COOCH3 steht oderR 8 additionally stands for the groups -CHR 4 -COOH and -CHR 4 -COOCH 3 or
R5 und R6 zusammen mit dem Stickstoff atom an welches sie gebunden sind einen jeweils unsubstituierten oder substituierten Piperidin-, Morpholin-, Hexahydroaze¬ pin- oder Piperazinring bilden, wobei als Substituenten vorzugsweise Alkyl und Hydroxyalkyl genannt seien, oderR 5 and R 6 together with the nitrogen atom to which they are attached form an unsubstituted or substituted piperidine, morpholine, hexahydroaze¬ pin or piperazine ring, alkyl and hydroxyalkyl preferably being mentioned as substituents, or
R7 und R8 zusammen mit dem Stickstoffatom an welches sie ge- bunden sind einen jeweils unsubstituierten oder substi¬ tuierten Piperidin-, Pyrrolidin-, Morpholin-, Hexa¬ hydroazepin- oder Piperazinring bilden, wobei als Substituenten vorzugsweise Alkyl und Hydroxyalkyl genannt seien.R 7 and R 8 together with the nitrogen atom to which they are attached form an unsubstituted or substituted piperidine, pyrrolidine, morpholine, hexahydroazepine or piperazine ring, alkyl and hydroxyalkyl preferably being mentioned as substituents.
Verbindungen der Formel (I), gemäß Anspruch 1, in welcher R1 für Methyltriazolyl steht,Compounds of formula (I) according to claim 1, in which R 1 represents methyltriazolyl,
R2 für gegebenenfalls durch unsubstituiertes oder halogensubstituiertesR 2 for optionally unsubstituted or halogen-substituted
Phenoxy substituiertes Butyl, Pentyl, Hexyl und Heptyl, oder jeweils gegebenenfalls ein- bis dreifach durch Fluor, Chlor, Brom, Methyl, Ethyl, Methoxy, Ethoxy, Trifluormethyl oder Trifluormethoxy substituiertes Phenyl oder Cyclopropyl steht,Phenoxy-substituted butyl, pentyl, hexyl and heptyl, or in each case optionally phenyl or cyclopropyl which is substituted once to three times by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,
R3 für Ethyl, n- und i-Propyl, n-, i-, s- und t-Butyl steht, oder für durch Dimethylamino, Diethylamino, Methoxycarbonyl, Ethoxycarbonyl substituiertes Methyl, Ethyl, n.- und i.-Propyl, n.-, i.-, s.- und t.-Butyl steht, oder für jeweils gegebenenfalls durch Fluor, Chlor, Brom,R 3 represents ethyl, n- and i-propyl, n-, i-, s- and t-butyl, or for methyl, ethyl, n.- and i.-propyl substituted by dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n.-, i.-, s.- and t.-butyl, or each optionally by fluorine, chlorine, bromine,
Methyl, Ethyl, Methoxy, Ethoxy, Trifluormethyl, Trifluormethoxy substituiertes Phenyl, Benzyl oder Cyclopropyl, Cyclobutyl, Cyclo¬ pentyl oder Cyclohexyl steht,Methyl, ethyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy substituted phenyl, benzyl or cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,
R4 für Wasserstoff, Methyl, Ethyl, n.-, i.-Propyl, n.-, i.-, s.- und t.-Butyl steht,R 4 represents hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl,
R5 für Wasserstoff, Methyl, Ethyl, n.-, i.-Propyl, n.-, L-, s.- und t.-Butyl steht,R 5 represents hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, L-, s.- and t.-butyl,
R6 für Wasserstoff, Methyl, Ethyl, n.-, i.-Propyl, n.-, L-, s.- und t.-Butyl steht, oderR 6 represents hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, L-, s.- and t.-butyl, or
R5 und R6 zusammen mit dem Stickstoff atom an welches sie gebunden sind einen Piperidin-, Morpholin-, Hexa¬ hydroazepin- oder Piperazinring bilden,R 5 and R 6 together with the nitrogen atom to which they are attached form a piperidine, morpholine, hexahydroazepine or piperazine ring,
R7 für Wasserstoff, Methyl, Ethyl, n.-, i.-Propyl, n.-, i.-, s.- und t.-Butyl steht,R 7 represents hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl,
R8 für gegebenenfalls durch Dimethylamino, Diethylamino, Methoxycarb¬ onyl, Ethoxycarbonyl substituiertes Methyl, Ethyl, n.- und i.-Propyl, n -, i.-, s.- und t.-Butyl steht, oder für jeweils gegebenenfalls einfach bis dreifach durch Fluor, Chlor, Brom, Methyl, Ethyl, Methoxy, Ethoxy, Trifluormethyl und/oder Trifluormethoxy substituiertes Phenyl, Benzyl, Cyclopropyl, Cyclobutyl, Cyclopentyl und Cyclohexyl steht,R 8 represents methyl, ethyl, n.- and i.-propyl, n -, i.-, s.- and t.-butyl which is optionally substituted by dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, or is in each case optionally simple is phenyl, benzyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl which is substituted three times by fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl and / or trifluoromethoxy,
oder für die Gruppen -CHR4'-COOH und -CHR '-COOCH3 steht, worinor represents the groups -CHR 4 ' -COOH and -CHR ' -COOCH 3 , wherein
R4' für Wasserstoff, Methyl, Ethyl, n.-, i.-Propyl, n.-, i.-, s.- und t.-Butyl, Phenyl, Biphenyl und Hydroxybiphenyl und Benzyl steht, oderR 4 'represents hydrogen, methyl, ethyl, n.-, i.-propyl, n.-, i.-, s.- and t.-butyl, phenyl, biphenyl and hydroxybiphenyl and benzyl, or
R7 und R8 zusammen mit dem Stickstoffatom an welches sie gebunden sind einen jeweils gegebenenfalls einfach oder zweifach durch Methyl, Ethyl, Hydroxymethyl und Hydroxyethyl substituierten Piperidin-, Pyrrolidin-, Morpholin- oder Piperazinring bilden.R 7 and R 8 together with the nitrogen atom to which they are attached form a piperidine, pyrrolidine, morpholine or piperazine ring which is optionally mono- or disubstituted by methyl, ethyl, hydroxymethyl and hydroxyethyl.
5. Schädlingsbekämpfungsmittel, gekennzeichnet durch einen Gehalt an mindestens einer Verbindung der Formel (I) nach Anspruch 1.5. pesticide, characterized by a content of at least one compound of the formula (I) according to claim 1.
6. Verfahren zur Bekämpfung von Schädlingen, dadurch gekennzeichnet, daß man Verbindungen der Formel (I) nach Anspruch 1 auf Schädlinge und/oder ihren Lebensraum einwirken läßt.6. A method for controlling pests, characterized in that compounds of the formula (I) according to Claim 1 are allowed to act on pests and / or their habitat.
7. Verfahren zur Herstellung von Verbindungen der Formel (I) nach7. Process for the preparation of compounds of formula (I) according to
Anspruch 1, dadurch gekennzeichnet, daß man 2,3,5,6-Tetrafluorbenzoyl- chlorid oder -anhydrid mit einem entsprechenden Oxim, Alkohol oder Amin gegebenenfalls in Gegenwart eines Verdünnungsmittels und/oder einer Base umsetzt.Claim 1, characterized in that 2,3,5,6-tetrafluorobenzoyl chloride or anhydride is reacted with a corresponding oxime, alcohol or amine, optionally in the presence of a diluent and / or a base.
8. Verwendung von Verbindungen der Formel (I) nach den Ansprüchen 1 bis 4 zur Bekämpfung von Schädlingen. Verfahren zur Herstellung von Schädlingsbekämpfungsmitteln, dadurch ge¬ kennzeichnet, daß man Verbindungen der Formel (I) nach den Ansprüchen 1 bis 4 mit Streckmitteln und/oder oberflächenaktiven Mitteln vermischt. 8. Use of compounds of formula (I) according to claims 1 to 4 for controlling pests. Process for the preparation of pesticides, characterized in that compounds of the formula (I) according to Claims 1 to 4 are mixed with extenders and / or surface-active agents.
EP95901380A 1993-11-25 1994-11-14 Derivatives of 2,3,5,6-tetrafluorobenzoic acid and their use in combating pests Withdrawn EP0730592A1 (en)

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DE19615452A1 (en) * 1996-04-19 1997-10-23 Bayer Ag 2,3,5,6-tetrafluorobenzoic acid amides
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DE1642224B2 (en) * 1967-04-28 1976-04-29 Basf Ag, 6700 Ludwigshafen USE OF SUBSTITUTED BENZOIC ANILIDES FOR CONTROL OF FUNGI FROM THE CLASS OF BASIDIOMYCETS
US4055663A (en) * 1974-06-27 1977-10-25 National Patent Development Corporation Halogenated acylamino acids as fungicides
DE2944446A1 (en) * 1979-11-03 1981-06-11 Bayer Ag, 5090 Leverkusen TRISUBSTITUTED BENZYL OXIMETERS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9514688A1 *

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BR9408162A (en) 1997-08-05
HU9601420D0 (en) 1996-07-29
PL314587A1 (en) 1996-09-16
CZ147396A3 (en) 1996-08-14
HUT74715A (en) 1997-02-28
TW258646B (en) 1995-10-01
SK65896A3 (en) 1996-11-06
JPH09511221A (en) 1997-11-11
DE4340180A1 (en) 1995-06-01
WO1995014688A1 (en) 1995-06-01
CN1141037A (en) 1997-01-22
AU1064995A (en) 1995-06-13

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