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EP1590358A1 - Derives de 9-cetospinosyne - Google Patents

Derives de 9-cetospinosyne

Info

Publication number
EP1590358A1
EP1590358A1 EP04700669A EP04700669A EP1590358A1 EP 1590358 A1 EP1590358 A1 EP 1590358A1 EP 04700669 A EP04700669 A EP 04700669A EP 04700669 A EP04700669 A EP 04700669A EP 1590358 A1 EP1590358 A1 EP 1590358A1
Authority
EP
European Patent Office
Prior art keywords
amino
ethyl
methyl
group
carbonyl
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Withdrawn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
EP04700669A
Other languages
German (de)
English (en)
Inventor
Peter Lösel
Michael E. Beck
Ulrich Ebbinghaus-Kintscher
Robert Velten
Peter Jeschke
Volker MÖHRLE
Rita FRÖDE
Günther EBERZ
Olga Malsam
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
Original Assignee
Bayer CropScience AG
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 CropScience AG filed Critical Bayer CropScience AG
Publication of EP1590358A1 publication Critical patent/EP1590358A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/14—Ectoparasiticides, e.g. scabicides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P43/00—Drugs for specific purposes, not provided for in groups A61P1/00-A61P41/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
    • C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
    • C07H17/08—Hetero rings containing eight or more ring members, e.g. erythromycins
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/44—Preparation of O-glycosides, e.g. glucosides
    • C12P19/60—Preparation of O-glycosides, e.g. glucosides having an oxygen of the saccharide radical directly bound to a non-saccharide heterocyclic ring or a condensed ring system containing a non-saccharide heterocyclic ring, e.g. coumermycin, novobiocin
    • C12P19/62—Preparation of O-glycosides, e.g. glucosides having an oxygen of the saccharide radical directly bound to a non-saccharide heterocyclic ring or a condensed ring system containing a non-saccharide heterocyclic ring, e.g. coumermycin, novobiocin the hetero ring having eight or more ring members and only oxygen as ring hetero atoms, e.g. erythromycin, spiramycin, nystatin

Definitions

  • the spinosyns are known compounds.
  • Spinosyns are fermentation products made from cultures of the Actinomycete Saccharopolyspora spinosa.
  • spinosyn-9 pseudoaglycone are disclosed in WO 97/00265 and US-A 6,001,981. It describes the production of further derivatives that can be obtained from natural products using semisynthetic processes.
  • the spinosyn-9 pseudoaglycone derivative, which is oxidized to the ketone at position C-9, is known, for example, as an insecticidal compound by chemical
  • the present invention relates to compounds of the general formula (I)
  • X represents O, NH or NR 4 ,
  • R 1 represents hydrogen or an amino sugar
  • R 2 represents hydrogen or optionally substituted alkyl, cycloalkyl, arylalkyl, hetarylalkyl, aryl or hetaryl, or, if X represents NH or NR 4 , represents CO-R 'or CS-R',
  • R ' for amino, for optionally substituted alkyl, alkylamino, dialkylamino, aryl, arylamino, hetarylamino, arylalkyl, hetaryl or
  • R 3 represents hydrogen or hydroxy
  • R 4 represents optionally substituted alkyl or forms a 3-, 4-, 5-, 6-, 7- or 8-membered ring with R 2 , which is formed by one or more heteroatoms (s) such as O, S, SO, SO 2 , NH or NR 5 can be interrupted and is optionally substituted, R 5 represents optionally substituted alkyl, cycloalkyl, arylalkyl, hetarylalkyl, aryl or hetaryl, and
  • Optionally substituted alkyl alone or as part of a radical in the general formulas means straight-chain or branched alkyl having preferably 1 to 6, in particular 1 to 4, carbon atoms.
  • Examples include optionally substituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylbutyl, 1,1 -Dimethylpropyl, 2,2-dimethylpropyl, 1-ethoxypropyl, hexyl, 1-
  • Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl may preferably be mentioned.
  • Optionally substituted cycloalkyl alone or as part of a radical in the general formulas means mono-, bi- and tricyclic cycloalkyl, preferably with 3 to 10, in particular with 3, 5 or 7 carbon atoms.
  • Examples include optionally substituted cyclopropyl, cyclobutyl,
  • Cyclopentyl cyclohexyl, cycloheptyl, cyclooctyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octyl and adamantyl.
  • Optionally substituted arylalkyl in the general formulas preferably means arylalkyl optionally substituted in the aryl part and / or alkyl part with an aryl part as defined below and preferably 1 to 4, in particular 1 or 2 carbon atoms in the alkyl part, where the alkyl part can be straight-chain or branched.
  • Substituted benzyl and phenylethyl may be mentioned as examples and preferably.
  • Optionally substituted hetarylalkyl in the general formulas preferably means hetarylalkyl optionally substituted in the hetaryl part and / or alkyl part with a hetaryl part as defined below and preferably 1 to 4, in particular 1 or 2 carbon atoms in the alkyl part, where the alkyl part can be straight-chain or branched.
  • Optionally substituted aryl alone or as part of a radical in the general formulas means, for example, a mononuclear, polynuclear or polynuclear aromatic radical such as phenyl, naphthyl, tetrahydronaphthyl, indanyl, fluorenyl, but preferably phenyl or naphthyl, in particular phenyl.
  • a mononuclear, polynuclear or polynuclear aromatic radical such as phenyl, naphthyl, tetrahydronaphthyl, indanyl, fluorenyl, but preferably phenyl or naphthyl, in particular phenyl.
  • Optionally substituted hetaryl alone or as part of a radical in the general formulas means 5- to 7-membered rings with preferably 1 to 3, in particular 1 or 2 identical or different heteroaromatics.
  • the heteroatoms in the heteroaromatics are oxygen, sulfur or nitrogen.
  • Exemplified and preferred are optionally substituted furyl, thienyl, pyrazolyl,
  • the optionally substituted radicals of the general formulas can carry one or more, preferably 1 to 3, in particular 1 to 2 identical or different substituents.
  • Examples of preferred substituents are:
  • Alkyl with preferably 1 to 4, in particular 1 to 2 carbon atoms, such as
  • halogen atoms being identical or different and being halogen atoms, preferably fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine, such as difluoromethyl, trifluoromethyl, trichloromethyl; Hydroxy, halogen, preferably fluorine, chlorine, bromine and iodine, especially fluorine and chlorine; cyano;
  • nitro amino; Monoalkyl- and dialkylamino with preferably 1 to 4, in particular 1 or 2 carbon atoms per alkyl group, such as methylamines, methylethylamino, dimethylamino, n-propylamino, isopropylamino, methyl-n-butylamino; Alkylcarbonyl radicals such as methylcarbonyl, alkoxycarbonyl preferably having 2 to 4, in particular 2 to 3 carbon atoms such as methoxycarbonyl and ethoxycarbonyl;
  • Suitable cyclic amino groups are heteroaromatic or aliphatic ring systems with one or more nitrogen atoms as the heteroatom, in which the heterocycles can be saturated or unsaturated, one ring system or more condensed ring systems, and optionally contain further heteroatoms such as nitrogen, oxygen and sulfur, etc.
  • cyclic amino groups can also mean a spiro ring or a bridged ring system.
  • the number of atoms which form cyclic amino groups is not restricted, for example in the case of a single ring system they consist of 3 to 8 atoms and im
  • cyclic amino groups are saturated and unsaturated monocyclic ring systems with a nitrogen atom as hetero atom, such as 1-azetidinyl, pyrrolidino, 2-pyrrolin-l-yl, 1-pyrrolyl, piperidino, 1,4-dihydropyridin-1-yl, 1,2, 5,6-tetrahydropyridin-l-yl called homopiperidino;
  • cyclic amino groups are saturated and unsaturated monocyclic ring systems with two or more nitrogen atoms as heteroatoms, such as 1-imidazolidinyl, 1-imidazolyl, 1-pyrazolyl, 1-triazolyl, 1-tetrazolyl, 1-piperazinyl, 1-homopiperazinyl, 1, 2- Called dihydropyridazin-1-yl, 1, 2-dihydropyrimidin-1-yl, perhydropyrimidin-1-yl and
  • examples of cyclic amino groups include saturated and unsaturated condensed cyclic ring systems such as indol-1-yl, 1,2-dihydro-benzimidazol-l-yl, perhydropyrrolo [1,2] pyrazine Called 2-yl; examples of cyclic amino groups are spirocyclic ring systems such as 2-azaspiro [4,5] -decan-2-yl; bridged heterocyclic ring systems such as 2-azabicyclo [2,2, l] heptan-7-yl may be mentioned as examples of cyclic amino groups.
  • the compounds of the invention are generally defined by the formula (I).
  • X preferably represents O, NH or NMe. is preferred for hydrogen or for an amino sugar of the formula la is lg
  • R 2 preferably represents optionally substituted aryl-C 3 -C 3 -alkyl, in particular benzyl, 1-phenyl-ethyl, 2-phenyl-ethyl, 3-phenyl-propyl, 2-
  • Halogen especially bromine, chlorine.
  • Haloalkylthio especially trifluoromethylthio, alkylsulfonyl, especially methylsulfonyl, haloalkylsulfonyl, especially trifluoromethylsulfonyl, hetarylsulfonyl, especially N-morpholinosulfonyl or N-pyra zolylsulfonyl, nitro, amino, a suitable cyclic amino group, in particular N-pyrrolidino, N-piperidino, N-morpholino, N- (2,6-dimethyl-morpholino), N-methyl-piperazino, N-thiomorpholino or N-dioxothio- morpholino, AJ_kylamino, especially methylamino, ethylamino, propylamino, isopropylamino, butylamino, sec-butylamino, isobutylimino, tert-
  • alkylenamino especially propylenamino, dialkylamino, especially dimethylammo, diethylamino, carboxyl, carbamoyl, cyano, alkoxycarbonyl, especially methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, sec-butyloxycarbonyl, isobutyloxyoxyoxyyl, especially N-alkoxycarbonylamino, in particular N-methoxycarbonylamino, N-ethoxycarbonylamino, N-propyloxycarbonylamino, N-isopropyloxycarbonylamino, N-butyloxycarbonylamino, N-sec-butyloxy-c ⁇ irbonylamino, N-isobutyloxycarbonylamino, N-tert-butyloxyc -trbonylamino,
  • R 2 furthermore preferably for CO-R 'or CS-R',
  • R ' for amino, for optionally substituted C 1 -C 4 -alkyl, C 1 -C 4 -alkylamino, di-C ⁇ -C -alkyla ⁇ üno, aryl, arylamino, het-arylamino, aryl-C ⁇ -C 3 alkyl, hetaryl or hetaryl -C-C 3 alkyl is.
  • R 4 preferably represents optionally substituted C 1 -C 4 -alkyl or preferably forms a 6-membered ring with R, which may be interrupted by O, S or NR and is optionally substituted.
  • R 5 preferably represents optionally substituted C 1 -C 4 -alkyl.
  • X particularly preferably represents O or NH.
  • R 1 particularly preferably represents hydrogen or an amino sugar
  • aryl-C 3 -C 3 -alkyl is particularly preferably aryl-C 3 -C 3 -alkyl, in particular benzyl, 1-phenyl-ethyl, hetaryl-C 3 -C 3 -alkyl, hetarylmethyl, in particular pyridylmethyl, pyrimidylmethyl, pyridazinylmethyl, pyrazylmethyl, furylmethyl, thiazolylmethyl, pyrazolylmethyl , Oxazolylmethyl, Isoxazolyhnethyl, Thiazolylmethyl, Imidazolylmethyl, Triazolylmethyl, Tetrazolylmethyl, Dihydro-dioxazinylmethyl, 1-Hetaryl-ethyl, in particular 1-Pyridylethyl, 1-Pyrimidylethyl, 1-Pyridazinylethyl, 1-Pyrazylethyl, 1-Pyrazylethyl
  • Trifluoromethylsulfonyl nitro, amino, alkylamino, especially methylamino, ethylamino, N-alkoxycarbonylamino, especially N-methoxycarb- onylamino, N-ethoxycarbonylamino, N-propyloxycarbonylamino, N-isopropyloxycarbonylamino, N-butyloxycarbonylamino, N-sec-butyloxycarbonylamino, N-isobutyloxycarbonylamino, N-tert-butyloxycarbonylamino, N-alkyleneoxycarbonyl-aminooxy, in particular , N-alkylsmfonylamino, in particular N-methylsulfonylamino, N-ethylsulfonylamino, N-propylsulfonylamino, N-isopropylsulfonylamino, N-butylsul
  • Alkylcarbonyl-N-alkylsulfonyl-amino in particular N-methylcarbonyl-N-methylsulfonyl-amino, N-methylcarbonyl-N-ethylsulfonyl-amino, N-ethyl-c-irbonyl-N-me ylsulfonyl-amino, N-ethylcarbonyl-N- ethyl-sulfonyl-amino, N-cycloalkylcarbonyl-N-alkylsulfonyl-amino, in particular N-cyclopropyl-carbonyl-N-methylsulfonyl-amino, N-1-methylcycloprop-1 -yl-carbonyl-N-methylsulfonylamino, N-cyclobutyl-N -methylsulfonylamino, alkylamino- c-ffbonyl ⁇ tmino,
  • N, N-dimethylaminosulfonylamino may be substituted.
  • R furthermore particularly preferably for CO-R 'or CS-R'
  • R ' for amino, arylamino, in particular trifluoromethoxyphenylamino, trifluoromethylphenylamino, chlorophenylamino,
  • Hetarylamino especially bromopyridyl-tmino, trifluoromethyl-pyridylamino.
  • X very particularly preferably stands for O.
  • R 1 very particularly preferably represents hydrogen or an amino sugar of the formula Ia or Ie
  • R 2 very particularly preferably represents benzyl, 1-phenylethyl, hetarylmethyl, in particular pyridylmethyl, pyridazinylmethyl, thiazolylmethyl, pyrazolylmethyl, isoxazolylmethyl, imidazolylmethyl, dihydro-dioxazinylmethyl, 1-pyridylethyl, 1-thiazolylethyl, 1-dihydroethyl, 1-dihydroethyl, 1-dihydroethyl, 1-dihydroethyl optionally by residues from the series hydrogen, methyl, tert-butyl, trifluoromethyl, bromine, chlorine, fluorine, methoxy, trifluoromethoxy, nitro, amino, methylamino, ethylamino, N-methoxycarbonylamino, N-ethoxycarbonylamino, N- Propyloxycarbonylamino, N-isopropy
  • Ethoxycarbonyl-N-methyl-amino N-isopropyloxycarbonyl-N-methyl-amino, N-tert-butyloxycarbonyl-N-methyl-amino, N-propyleneoxy-carbonyl-N-methylamino, N-cyclopropyl-carbonylamino, N- 1 - Methylcycloprop-1 -yl-carbonyl-N-amino, N-methoxy-carbonyl-N-methylsulfonyl-amino, N-methoxycarbonyl-N-ethyl-sulfonylamino, N-isobutyloxycarbonyl-N-methylsulfonyl-amino, N-tert- Butyloxycarbonyl-N-methylsulfonyl-amino, N-tert-butyloxycarbonyl-N-methylsulfonyl-amino, N-propyleneoxycarbonyl-
  • the general or residual definitions or explanations given above or in the preferred area apply accordingly to the end products and to the starting and intermediate products. These residues can be combined with one another, that is, also between the respective preferred areas.
  • the 9-ketospinosyn derivatives according to the invention of the general formula (I) and their salts can exist in stereoisomeric forms which either behave like image and mirror image (enantiomers) or do not behave like image and mirror image (diastereomers).
  • the present invention relates to both the enantiomers and the diastereomers and their respective
  • racemic forms can be separated in a known manner into constituents which are uniform in the stereomers. If appropriate, the isomers can be converted into one another by methods known per se.
  • optically active, stereoisomeric forms of the compounds of the general formula (T) and their salts are preferably formed and used according to the invention.
  • the invention therefore relates both to the pure enantiomers and diastereomers and to their mixtures for use as crop protection agents.
  • R 1 represents an aminosugar of the formulas Ia to If and / or R represents a basic radical
  • Suitable non-toxic salts of the 9-ketospinosyn derivatives of the general formula (I) are customary non-toxic salts, ie salts with different bases and salts with added acids.
  • Salts with inorganic bases such as alkali metal salts, for example sodium, potassium or cesium salts, alkaline earth metal salts, for example calcium or magnesium salts, ammonium salts, salts with organic bases and with inorganic amines, for example triethylammomum, dicyclohexylammonium, N 3 N, are preferred '-Dibenzylethylendiammonium-,
  • inorganic acids for example hydrochlorides, hydrobromides, dihydrosulfates, trihydrosulfates, or phosphates
  • organic carboxylic acids or organic sulfonic acids for example formates, acetates, trifluoroacetates, maleates, tartrates, benzene sulfonates, methanesul
  • Salts are formed according to standard salt manufacturing processes.
  • the compounds of the invention are neutralized with appropriate acids to form acid addition salts.
  • Representatively usable acid addition salts are salts which are formed, for example, by the reaction with other inorganic acids, such as, for example, sulfuric acid, hydrochloric acid, hydrobromic acid, phosphoric acid or organic carboxylic acids such as acetic acid, trifluoroacetic acid, citric acid, succinic acid, lactic acid, formic acid, maleic acid, camphic acid, and Form glycolic acid, glutaric acid, stearic acid, salicylic acid, sorbic acid, cinnamic acid, picric acid, benzoic acid or organic sulfonic acids such as methanesulfonic acids and para-toluenesulfonic acid or with basic amino acids such as aspartic acid, glutamic acid, arginine or the like.
  • inorganic acids such as, for example, sulfuric acid, hydrochloric acid,
  • Boc tert-butyloxycarbonyl
  • Cpr cyclopropyl
  • Chx cyclohexyl
  • MCpr 1-methyl-cycloprop-l-yl
  • Ph phenyl
  • R 3 is hydrogen, X is O and R 2 are those listed in Table 1
  • R 3 is hydrogen, X is O and R 2 are those listed in Table 1
  • Group 11 compounds correspond to the general formula (I) in which A-
  • R 1 represents an amino sugar of the formula la
  • R is hydrogen, X is O and R has the meanings listed in Table 1.
  • B represents a group -H 2 C-CH (CH 3 ) -
  • R 1 represents an amino sugar of the formula la
  • R 3 represents hydrogen, X represents O and R 2 has the meanings listed in Table 1.
  • R 3 represents hydrogen, X represents O and R 2 has the meanings listed in Table 1.
  • R 3 represents hydrogen, X represents O and R 2 has the meanings listed in Table 1.
  • Group 15 compounds correspond to the general formula (I) in which A-
  • R 1 represents an amino sugar of the formula Ib
  • R 3 represents hydrogen, X represents O and R 2 has the meanings listed in Table 1.
  • R 1 represents an amino sugar of the formula Ib
  • R 3 represents hydrogen, X represents O and R 2 those listed in Table 1
  • R 3 represents hydrogen, X represents O and R 2 has the meanings listed in Table 1.
  • Group 18 compounds correspond to the general formula (£) in which A-
  • B represents a group -H 2 C-CH (CH 3 ) -
  • R 1 represents an amino sugar of the formula lc
  • R 3 is hydrogen, X is O and R 2 are those listed in Table 1
  • Group 19 compounds correspond to the general formula (I) in which A-
  • R 1 represents an aminosugar of the formula Ic
  • R 3 represents hydrogen, X represents O and R 2 has the meanings listed in Table 1.
  • R 1 stands for an amino sugar of the formula lc
  • R 3 represents hydrogen, X represents O and R 2 has the meanings listed in Table 1.
  • R 3 represents hydrogen, X represents O and R 2 has the meanings listed in Table 1.
  • R represents hydrogen, X represents O and R has the meanings listed in Table 1.
  • R 3 is hydrogen, X is O and R 2 are those listed in Table 1
  • R represents hydrogen, X represents O and R has the meanings listed in Table 1.
  • Group 25 compounds correspond to the general formula (I) in which A-
  • R 3 represents hydrogen, X represents O and R 2 has the meanings listed in Table 1.
  • R is hydrogen, X is O and R is those listed in Table 1
  • R 3 represents hydrogen, X represents O and R 2 has the meanings listed in Table 1.
  • R 3 represents hydrogen, X represents O and R 2 has the meanings listed in Table 1.
  • Group 29 compounds correspond to the general formula (I) in which A-
  • R 3 represents hydrogen, X represents O and R 2 has the meanings listed in Table 1.
  • R represents hydrogen
  • X represents O
  • R 2 has the meanings listed in Table 1.
  • R 3 represents hydrogen, X represents O and R 2 has the meanings listed in Table 1.
  • B represents a group -H 2 C-CH (CH 3 ) -
  • R 1 represents an aminosugar of formula lf
  • R is hydrogen, X is O and R is those listed in Table 1
  • Group 33 compounds correspond to the general formula (I) in which A-
  • R 3 represents hydrogen, X represents O and R 2 has the meanings listed in Table 1.
  • R 1 represents an amino sugar of the formula Ig
  • R 3 is hydrogen, X is O and R 2 are those listed in Table 1
  • R 3 represents hydrogen, X represents O and R has the meanings listed in Table 1.
  • R represents hydrogen, X represents O and R has the meanings listed in Table 1.
  • Boc tert-butyloxycarbonyl
  • Cpr cyclopropyl
  • Cbu cyclobutyl
  • Ph phenyl Group 38
  • R 3 represents hydrogen, X represents NH and R 2 those listed in Table 2
  • R 3 represents hydrogen, X represents NH and R 2 has the meanings listed in Table 2.
  • AB stands for a group -H 2 C-CH 2 -
  • R 1 stands for an amino sugar of the formula la
  • R 3 represents hydrogen, X represents NH and R 2 has the meanings listed in Table 2.
  • AB stands for a group -H 2 C-CH (CH 3 ) -
  • R 1 stands for an amino sugar of the formula la
  • R 3 represents hydrogen, X represents NH and R 2 those listed in Table 2
  • R represents hydrogen, X represents NH and R has the meanings listed in Table 2.
  • R 3 represents hydrogen, X represents NH and R 2 has the meanings listed in Table 2.
  • Group 51 compounds correspond to the general formula (I) in which A-
  • R 1 represents an amino sugar of the formula Ib
  • R is hydrogen, X is NH and R has the meanings listed in Table 2.
  • AB stands for a group -H 2 C-CH (CH 3 ) -
  • R 1 stands for an amino sugar of the formula Ib
  • R 3 represents hydrogen, X represents NH and R 2 has the meanings listed in Table 2.
  • R 3 represents hydrogen, X represents NH and R 2 has the meanings listed in Table 2.
  • AB stands for a group -H 2 C-CH (CH 3 ) -
  • R 1 stands for an amino sugar of the formula lc
  • R represents hydrogen, X represents NH and R has the meanings listed in Table 2.
  • Group 55 compounds correspond to the general formula (I), in which
  • R is hydrogen, X is NH and R has the meanings listed in Table 2.
  • R 3 is hydrogen, X is NH and R 2 are those listed in Table 2
  • R 3 represents hydrogen, X represents NH and R 2 has the meanings listed in Table 2.
  • R represents hydrogen, X represents NH and R has the meanings listed in Table 2.
  • R 3 represents hydrogen, X represents NH and R 2 has the meanings listed in Table 2.
  • Group 60 compounds correspond to the general formula (I), in which
  • R 3 represents hydrogen, X represents NH and R 2 has the meanings listed in Table 2.
  • AB stands for a group -H 2 C-CH 2 -
  • R 1 stands for an amino sugar of the formula le
  • R 3 represents hydrogen, X represents NH and R 2 has the meanings listed in Table 2.
  • R 3 represents hydrogen, X represents NH and R 2 has the meanings listed in Table 2.
  • R 3 is hydrogen, X is NH and R 2 are those listed in Table 2
  • R is hydrogen, X is NH and R has the meanings listed in Table 2.
  • R 3 represents hydrogen
  • X represents NH
  • R 2 has the meanings listed in Table 2.
  • Group 66 Group 66 compounds correspond to the general formula (T), in which
  • R 1 and R 3 stand for hydrogen
  • X stands for NMe
  • R 2 has the meanings listed in Table 2.
  • Group 67 Group 67 compounds correspond to the general formula (I), in which
  • AB stands for a group -H 2 C-CH 2 -
  • R 1 and R 3 stand for hydrogen
  • X stands for NMe
  • R 2 has the meanings listed in Table 2.
  • Group 69 compounds correspond to the general formula (I), in which
  • AB stands for a group -H 2 C-CH (CH 3 ) -
  • R 1 and R 3 stand for hydrogen
  • X stands for NMe
  • R 2 has the meanings listed in Table 2.
  • Group 70 compounds correspond to the general formula (I), in which
  • R 3 stands for hydrogen
  • X stands for NMe
  • R 2 those listed in Table 2
  • R 3 stands for hydrogen
  • X stands for NMe
  • R 2 has the meanings listed in Table 2.
  • R 3 stands for hydrogen
  • X stands for NMe
  • R 2 has the meanings listed in Table 2.
  • R 3 stands for hydrogen
  • X stands for NMe
  • R 2 has the meanings listed in Table 2.
  • Group 78 compounds correspond to the general formula (I), in which
  • R 3 is hydrogen, X is NMe and R 2 are those listed in Table 2
  • R 3 is hydrogen, X is NMe and R 2 are those listed in Table 2
  • R 3 represents hydrogen, X represents NMe and R 2 has the meanings listed in Table 2.
  • Group 81 compounds correspond to the general formula (I), in which
  • AB stands for a group -H 2 C-CH (CH 3 ) -
  • R 1 stands for an amino sugar of the formula Ib
  • R 3 is hydrogen, X is NMe and R 2 has the meanings listed in Table 2.
  • R represents hydrogen, X represents NMe and R has the meanings listed in Table 2.
  • Group ⁇ 3 compounds of group 83 correspond to the general formula (I), in which
  • AB stands for a group -H 2 C-CH (CH 3 ) -
  • R 1 stands for an amino sugar of the formula lc 1c
  • R 3 is hydrogen, X is NMe and R 2 are those listed in Table 2
  • Group 84 compounds correspond to the general formula (I), in which
  • R represents hydrogen, X represents NMe and R has the meanings listed in Table 2.
  • R 3 represents hydrogen, X represents NMe and R 2 has the meanings listed in Table 2.
  • Group 86 Group 86 compounds correspond to the general formula (I), in which
  • R stands for hydrogen
  • X stands for NMe
  • R has the meanings listed in Table 2.
  • R 3 represents hydrogen, X represents NMe and R 2 has the meanings listed in Table 2.
  • Group 88 Group 88 compounds correspond to the general formula (I), in which
  • R stands for hydrogen
  • X stands for NMe
  • R has the meanings listed in Table 2.
  • R is hydrogen, X is NMe and R is those listed in Table 2
  • R 3 represents hydrogen, X represents NMe and R 2 has the meanings listed in Table 2.
  • Group 92 Group 92 compounds correspond to the general formula (I), in which
  • R 1 stands for an amino sugar of the formula lf
  • R stands for hydrogen
  • X stands for NMe
  • R has the meanings listed in Table 2.
  • R 1 stands for an amino sugar of the formula lf
  • R 3 represents hydrogen, X represents NMe and R has the meanings listed in Table 2.
  • R stands for hydrogen
  • X stands for NMe
  • R has the meanings listed in Table 2.
  • the present invention also relates to a process for the preparation of the new 9-ketospinosyn derivatives of the general formula (I),
  • R, R and A-B have the meanings given above,
  • the compounds of the general formula (Ia) can be formed in the process according to the invention as a mixture of (E) -isomer ( ⁇ tt-form) and (Z) -isomer (syn-Vo ⁇ m).
  • the compounds of the general formula (Ia) can be formed in the process according to the invention as a mixture of (E) -isomer (anti-form) and (Z) -isomer (syn-form).
  • Formula (II) provides a general definition of the 9-ketospinosyn derivatives required as starting materials for carrying out the process according to the invention.
  • R 1 and AB preferably represent those radicals which have already been described in connection with the description of the compounds of the invention general formula (I) can be mentioned as preferred for this substituent or the group.
  • the 9-ketospinosyn derivatives of the general formula (Et) used as starting materials, in which R 3 stands for hydroxy, can be obtained, for example, via selective and / or stereospecific hydroxylation, ie by means of bioconversion, using suitable microorganisms or their enzymes.
  • A-B and R have the meanings given above,
  • strains for example, which are deposited with the German Collection of Microorganisms and Cell Cultures GmbH (DSMZ), Mascheroder Weg lb, D-38124 Braunschweig, Germany, in accordance with the provisions of the Budapest Treaty:
  • the aqueous nutrient medium typically contains an assimilable carbon source and an assimilable nitrogen source.
  • the compounds of formula (Ha) are produced, for example, when a strain from the species Streptomyces dja Actuallysis, S. griseofuscus, S. caelestis, S. antibioticus, S. griseus or S. aureofaciens in an aqueous nutrient medium under aerobic conditions in the presence of Compounds of formula (Ilb) are fermented.
  • the microorganisms are fermented in a nutrient medium which contains a carbon source and optionally a proteinaceous material.
  • Preferred carbon sources include glucose, brown sugar, sucrose, glycerin, starch, corn starch, lactose, dextrin, molasses, etc.
  • Preferred nitrogen sources include cottonseed flour, yeast, autolysed
  • the preparation of the compounds of the general formula (Ha) can be induced at any temperature which ensures sufficient growth of the microorganisms.
  • the temperature is preferably between 21 ° C. and 32 ° C., particularly preferably approximately 28 ° C.
  • optimal production of the compounds of formula (Ha) is obtained within 2 to 4 days after adding the compounds of formula (Hb) to the culture.
  • the compounds according to the invention can be produced both in shake bottles and in stirred fermenters.
  • Isolate and clean fermentation broth e.g. preparative gel chromatography, preparative chromatography on reversed phase or preparative absorption chromatography.
  • the detection can e.g. by UV absorption or mass spectrometry.
  • amino compounds also to be used as starting materials for carrying out the process according to the invention are defined by the general formula (HI).
  • Formula (I) can be mentioned as preferred for this substituent.
  • the amino compounds of formula (HI) are e.g. T. commercially available, some are known and can be prepared by known methods (see, for example, hetaryl methoxamine: US Pat. No. 5,489,680; DE-A 21 19 012, alkoxy amines: EP-A 495 750; DE-A 22 06 890; D. Favara et al., Farmaco, Ed. Sci. 42 (10), 1987, p. 697).
  • R 2 has the same meaning as given above and E represents a nucleofugic leaving group, for example aliphatic or aromatic substituted sulfonyloxy, for example methanesulfonyloxy, salts of sulfonic acid, p-toluenesulfonyloxy (tosyloxy), but also, for example, halogen, especially bromine, chlorine or iodine. (see O-alkylation).
  • the compounds of the formula (HI) can expediently be released in the following manner:
  • the hydrazinolysis can preferably take place in a diluent, for example alcohol, at the boiling point.
  • the hydrolysis can preferably be carried out in an aqueous, aqueous-alcoholic or alcoholic solution by heating for several hours.
  • R 'and R together represent an isopropylidene group
  • acid hydrolysis and, in the event that R' and R" together represent an ⁇ -hydroxy-benzylidene
  • R "is a carbethoxy group both alkaline and acidic hydrolysis can be used (cf. DE-A 21 19 012; D. Favara et al., Farmaco, Ed. Sci. 42 (10) , (1987) p. 697).
  • Inorganic salts such as hydrochloric acid or sulfuric acid in ethanolic or isopropanolic solution are preferably used to prepare the salts.
  • an optionally substituted aryl radical or arylalkyl radical can optionally also stand for the radical R.
  • the aromatic NH 2 group can be modified by generally known methods.
  • the acylation reactions, alkylation reactions or sulfonylation reactions can advantageously be carried out already in the protected Indian medium R'R "NOR 2 and in the presence of basic reaction auxiliaries and in the presence of suitable diluents.
  • the compounds of the general formula (IHa) can be released according to those mentioned above Methods are used (see also Scheme 5): Scheme 5
  • N- (boc-amino) phthalimide or N- ( ⁇ enzyloxycarbonylamino) phthalimide can also be used as a suitable starting component (N. Brosse et al., J. Org. Chem. 2001, 66, 2869).
  • the radical R 2 can be introduced by means of a Mitsunobu reaction or N-alkylation.
  • acid binders such as amines, in particular tertiary amines, and alkali and alkaline earth compounds can be used as basic reaction auxiliaries for carrying out the process according to the invention.
  • Examples include the hydroxides, oxides and carbonates of lithium,
  • guanidine bases such as 7-methyl-l, 5,7-triazabicyclo (4.4.0) dec-5-ene (MTBD); Diazabicyclo (4.3.0) nonene (DBN), diazabicyclo- (2.2.2) octane (DABCO), 1,8-diaza-bicyclo (5.4.0) undecene (DBU) cyclohexyl-tetra-butylguanidine (CyTBG), cyclohexyltelramethylguanidm (CyTMG), N, N, N, N-tetramethyl-l, 8-naphthalenediamine, pentamethylpiperidine, tertiary amines such as triethylamine, trimethylamine, tribenzylamine, triisopropylamine, tributylamine, tribenzylamine, tricyclohexylamine, triamy
  • Aromatic amines in particular pyridine, or tertiary amines, in particular trialkylamines, such as triethylamine, N, N-diisopropylethylamine, N-propyldiisopropylamine, N, N'-dimethylcyclohexylamine or N-methylmorpholine, are preferably found,
  • diluents are advantageously used in an amount such that the reaction mixture remains readily stirrable throughout the process.
  • Suitable diluents for carrying out the process according to the invention are all inert organic solvents.
  • halogenated hydrocarbons especially chlorinated hydrocarbons, such as tetrachlorethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, carbon tetrachloride, trichloroethane, trichlorethylene, pentachloroethane, difluorobenzene, 1,2-dichloroethane, bromine, chlorobenzene Dichlorobenzene, chlorotoluene, trichlorobenzene; Alcohols such as methanol, ethanol, isopropanol, butanol; Ethers such as ethyl propyl ether, methyl tert-butyl ether, n-
  • chlorinated hydrocarbons such as tetrachlorethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, carbon te
  • mixtures of the solvents and diluents mentioned can also be used in the process according to the invention.
  • preferred diluents for carrying out the process according to the invention are amines such as trimethyl-, triethyl-, tripropyl-, tributylamine, N-methylmorpholine and pyridine, amides such as N, N-dimethylformamide, N, N-dipropylformamide, N, N- Dibutylformamide or N-methyl-pyrrolidine.
  • the reaction of amino compounds of the general formula (HI) can be carried out by using 17- ⁇ -desosaminyl-9-ketospinosyn and the 9-ketospinosyn aglycone derivatives of the general formula (H) in the presence of an amino compound of the general formula (IH ) in the presence of a specified basic reaction auxiliary and optionally in one of the specified diluents.
  • the reaction time is preferably between 10 minutes and 48 hours.
  • the reaction is preferably carried out at temperatures between -10 ° C and + 200 ° C, preferably between + 10 ° C and + 180 ° C, particularly preferably at room temperature. You can always work under normal pressure.
  • the process is preferably carried out at normal pressure or at pressures of up to 15 bar and, if appropriate, under a protective gas atmosphere (nitrogen or helium).
  • reaction mixture is concentrated in vacuo and purified in the customary manner by means of column chromatography (cf. also the preparation examples).
  • the active ingredients are suitable for protecting plants and plant organs, for increasing crop yields, improving the quality of the crop and for controlling animal pests, in particular insects, arachnids and nematodes, which are used in agriculture , occur in forests, in gardens and leisure facilities, in the protection of supplies and materials as well as in the hygiene sector. They can preferably be used as pesticides. she are effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • the pests mentioned above include:
  • Thysanura e.g. Lepisma saccharina.
  • Orthoptera e.g. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.
  • Phthiraptera e.g. Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp.
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci
  • Thrips palmi Frankliniella accidentalis. From the order of the Heteroptera, for example Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
  • Trialeurodes vaporariorum Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phoropalosumum , Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
  • Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.,
  • Leptinotarsa decemlineata Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sultusorrimushmpphppm, spp.
  • Anthrenus spp. Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, AmphimaUon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Plant parasitic nematodes include e.g. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp.,
  • the substances according to the invention have a strong microbicidal action and can be used to control unwanted microorganisms, such as fungi and bacteria, in crop protection and in material protection.
  • Fungicides can be used in crop protection to combat Plasmodiophoromyces, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
  • Bactericides can be used in plant protection to combat Pseudomonadaceae,
  • Xanthomonas species such as, for example, Xanthomonas campestris pv. Oiyzae;
  • Pseudomonas species such as, for example, Pseudomonas syringae pv. Lachrymans;
  • Erwinia species such as, for example, Erwinia amylovora;
  • 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 Pseudoperonospora cubensis;
  • Plasmopara species such as, for example, Plasmopara viticola
  • Bremia species such as, for example, Brernia lactucae
  • 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. gr-tminea (conidial form: Drechslera, Syn: Helminthosporium);
  • Cochliobolus species such as, for example, Cochliobolus sativus (conidial form: Drechslera, Syn: Helminthosporium);
  • Uromyces species such as, for example, Uromyces appendiculatus
  • Puccinia species such as, for example, Puccinia recondita
  • Sclerotinia species such as, for example, Sclerotinia sclerotiorum
  • 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, PseudocercosporeUa herpotrichoides.
  • the active compounds according to the invention also have a strengthening effect in plants. They are therefore suitable for mobilizing the plant's own defenses against attack by unwanted microorganisms.
  • Plant-strengthening (resistance-inducing) substances are to be understood in the present context as those substances which are able to stimulate the defense system of plants in such a way that the treated plants develop extensive resistance to these microorganisms when subsequently inoculated with undesirable microorganisms.
  • Undesired microorganisms are to be understood in the present case as phytopathogenic fungi, bacteria and viruses.
  • the substances according to the invention can thus be used to protect plants against attack by the pests mentioned within a certain period of time after the treatment.
  • the period within which protection is brought about generally extends from 1 to 10 days, preferably 1 to 7 days after the treatment of the plants with the active compounds.
  • Plants are understood here as plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Cultivated plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be protected by plant breeders' rights.
  • Plants such as sprout, leaf, flower and root are understood, with examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes.
  • the plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, cuttings and seeds.
  • Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention.
  • Plant varieties are understood to mean plants with new properties ("traits"), which are produced both by conventional breeding, by mutagenesis or by recombinant DNA
  • the treatment according to the invention can also cause superadditive (“synergistic") effects.
  • superadditive for example, reduced application rates and / or widening of the spectrum of action and / or an increase in the action of the substances and agents which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or Soil salinity, increased flowering performance, easier harvesting, loading acceleration of ripeness, higher crop yields, higher quality and or higher nutritional value of the harvested products, higher shelf life and / or workability of the harvested products possible, which go beyond the effects to be expected.
  • the preferred transgenic (genetically engineered) plants or plant cultivars to be treated according to the invention include all plants which, by virtue of the genetic engineering modification, have received genetic material which gives these plants particularly advantageous properties (“traits”). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated ripening, higher harvest yields, higher quality and / or higher nutritional value of the harvested products , higher shelf life and / or workability of the harvested products.
  • transgenic plants are the important crop plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, tobacco, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and
  • Grapes mentioned, with corn, soy, potato, cotton, tobacco and rapeseed being particularly emphasized.
  • the traits are particularly emphasized as the plants' increased defense against insects, arachnids, nematodes and snails due to the toxins produced in the plants, especially those caused by the genetic material from Bacillus thuringiensis (e.g. by the
  • Bt plants Gene Cry ⁇ A (a), CryIA (b), CryIA (c), CryHA, CrylHA, CryHIB2, Cry9c Cry2Ab, Cry3Bb and CrylF as well as their combinations) are produced in the plants (hereinafter "Bt plants”.
  • the properties (“traits”) also particularly emphasize the increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins.
  • the traits are also particularly emphasized the increased tolerance of the plants to certain herbicidal active ingredients, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example "PAT” gene).
  • herbicidal active ingredients for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example "PAT” gene).
  • the genes conferring the desired properties can also occur in combinations with one another in the transgenic plants.
  • Bt plants are corn varieties, cotton varieties, soy varieties and potato varieties that are sold under the trade names YIELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard® ( Cotton), Nucotn® (cotton) and NewLeafD (potato).
  • YIELD GARD® e.g. corn, cotton, soy
  • KnockOut® e.g. corn
  • StarLink® e.g. corn
  • Bollgard® Cotton
  • Nucotn® cotton
  • NewLeafD NewLeafD
  • Soybean varieties named under the trade names Roundup Ready® tolerance to glyphosate e.g. corn, cotton, soy
  • Liberty Link® tolerance to phosphinotricin, e.g. rapeseed
  • EVA® to imidazolinones
  • STS® tolerance to sulfonylureas e.g. corn
  • the herbicide-resistant plants include the varieties sold under the name Clearfield® (e.g. maize). Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties ("traits").
  • plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active compound mixtures according to the invention.
  • the preferred ranges given above for the active ingredients or mixtures also apply to the treatment of these plants. Plant treatment with the compounds or mixtures specifically listed in the present text should be particularly emphasized.
  • the treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space using the customary treatment methods, for example by dipping, spraying, Evaporation, nebulization, scattering, spreading and, in the case of propagation material, in particular seeds, also by means of single- or multi-layer coating.
  • the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms.
  • technical materials are understood to mean non-living materials that have been prepared for use in technology.
  • technical materials that are to be protected against microbial change or destruction by active substances according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, plastics and plastic articles, cooling lubricants and other materials that can be attacked or decomposed by microorganisms .
  • parts of production systems for example cooling water circuits, are also mentioned which can be impaired by the multiplication of microorganisms.
  • technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably wood.
  • Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials.
  • the active compounds according to the invention preferably act against fungi, in particular narrow pulp, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.
  • Microorganisms of the following genera may be mentioned, for example:
  • Alternaria such as Alternaria tenuis
  • Aspergillus such as Aspergillus niger
  • Chaetomium such as chaetomium globosum
  • Coniophora such as Coniophora puetana
  • Lentinus such as Lentinus tigrinus
  • Penicillium such as Penicillium glaucum
  • Polyporus such as Polyporus versicolor
  • Aureobasidium such as aureobasidium pullulans
  • Sclerophoma such as Sclerophoma pityophila
  • Trichoderma such as Trichoderma viride
  • Escherichia such as Escherichia coli
  • Pseudomonas such as Pseudomonas aeruginosa
  • Staphylococcus such as Staphylococcus aureus.
  • the active compounds can be converted into the customary formulations, such as
  • formulations are prepared in a known manner, for example by mixing the active ingredients with srecking agents, that is to say liquid solvents, under pressure liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and or dispersants and / or foam-generating agents.
  • srecking agents that is to say liquid solvents
  • surface-active agents that is to say emulsifiers and or dispersants and / or foam-generating agents.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • 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, e.g. 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.
  • chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins
  • alcohols such as butanol or glycol and their ethers and esters
  • ketones such as ace
  • Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and pressure, e.g. Aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
  • Possible solid carriers are: e.g. natural stone powder such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic stone powder such as highly disperse silica, aluminum oxide and silicates. The following are suitable as solid carriers for granules: e.g.
  • emulsifiers and / or foaming agents are: e.g. non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates.
  • dispersants come in
  • adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholi- pide, such as cephalins and lecithins, and synthetic phospholipids.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes 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 also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to to broaden the spectrum of uses or to prevent the development of resistance.
  • synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.
  • amidoflumet amidoflumet; Ampropylfos; Ampropylfos-potassium; andoprim; anilazine; azaconazole; azoxystrobin; benalaxyl; Benodanil; benomyl; Benthiavalicarbisopropyl; Benzamacril; Benzamacril-isobutyl; bilanafos; binapacryl; biphenyl:
  • bitertanol Blasticidin-S; bromuconazole; Bupirimate; Buthiobate; butylamine;
  • Furcarbanil Furmecyclox; guazatine; Hexachlorobenzene; Hexaconazole hymexazole; imazalil; Imibenconazole; Iminoctadine triacetate; Iminoctadine tris (albesil; iodocarb; Ipconazole; Iprobefos; Iprodione; Iprovalicarb; Irumamycin; Isoprothiolane; Isovaledione; Kasugamycin; Kresoxim-methyl; Mancozeb; Maneb Meferimzone; Mepanipyrim; Mepronil; Metalaxyl; Metalaxyl; Metalaxyl; Metalaxyl; Metalconyl
  • Thicyofen Thifluzamide; Thiophanate-methyl; thiram; Tioxymid; Tolclofos-methyl tolylfluanid; triadimefon; triadimenol; Triazbutil; triazoxide; Tricyclamides: tricyclazole; tridemorph; trifloxystrobin; triflumizole; triforine; triticonazole; Uniconazole; Validamycin A; vinclozolin; Zineb; ziram; zoxamide; (2S) -N- [2- [4- [[3- (4-chlorophenyl) -2-propynyl] oxy] -3-methoxyphenyl] ethyl] -3-methyl- 2-
  • copper salts and preparations such as Bordeaux mixture; Copper hydroxide; Copper naphthenate; Copper oxychloride; Copper sulfate; Cufraneb; Cuprous oxide;
  • Cadusafos camphechlor, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, CGA-50439, Chi ⁇ omethionat, Chlordane, Chlordimeform, Chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, Chlorobenzilate, Chloropicrin, Chlorproxyfen, chlorpyrifos-methyl, chlorpyrifos (-ethyl ), CMovaporthrin, Chromafenozide, Cis-Cypermethrin, Cis-Resmethrin, Cis-
  • DDT Deltamethrin, Demeton-S-methyl, Demeton-S-methylsulphone, Diafenthiuron, Dialifos, Diazinon, Dichlofenthion, Dichlorvos, Dicofol, Dicrotophos, Dicyclanil, Diflubenzuron, Dimethoate, Dimethylvinphos, Diobutonefone, Dinobutonefinofocus sodium, dofenapyn, DOWCO-439,
  • Halofenozide HCH, HCN-801, Heptenophos, Hexaflumuron, Hexythiazox, Hydramethylnone, Hydroprene,
  • IKA-2002 Imidacloprid, Imiprothrin, Indoxacarb, Iodofenphos, Iprobefos, Isazofos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
  • Mecarbam Malathion, Mecarbam, Mesulfenfos, Metaldehyde, Metam-sodium, Metiiacrifos, Methamidophos, Metharhician Anisopliae, Metharhician Flavoviride, Methidathione, Methiocarb, Methomyl, Methoprene, Methoxychlor, Methoxyfenozide, Metolcarb, Metoxadoszone, Milbinphin, MilbinMincinphonone, Mbemininphonone, Mevinphinin, Mbmininin, Mevin 45700, monocrotophos, moxidectin, MTI-800,
  • NC-104 NC-170, NC-184, NC-194, NC-196, Niclosamide, Nicotine, Nitenpyra, Nithiazine, NNI-0001, NNI-0101, NNI-0250, NNI-9768, Novaluron, Noviflumuron,
  • Paecilomyces fumosoroseus Parathion-methyl, Parathion (-ethyl), Permethrin (eis, trans-), Petroleum, PH-6045, Phenothrin (lR-trans isomer), Phenthoate, Phorate,
  • Phosalones Phosmet, Phosphamidon, Phosphocarb, Phoxim, Piperonyl butoxide, Pirimicarb, pirimiphos-methyl, pirimiphos-ethyl, Pr dlethrin, profenofos, promecarb, propaphos, propargite, propetamphos, propoxur, prothiofos, Prothoate, Protrifen- bute, pymetrozine, pyraclofos, Pvresmethrin, pyrethrum, pyridaben, pyridalyl, pyridaphenthion, Pyridathion, Pyrimidifen, pyriproxyfen,
  • the compounds of the formula (I) according to the invention also have very good antifungal effects. They have a very broad antifungal spectrum, especially against dermatophytes and shoot fungi, mold and diphasic fungi (e.g. against Candida species such as Candida albicans, Candida glabrata) and Epidermophyton floccosum, Aspergillus species such as
  • the application rates can be varied within a relatively wide range, depending on the type of application.
  • the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha.
  • the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed.
  • the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.
  • the active compounds according to the invention can also be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists.
  • Synergists are compounds that increase the effectiveness of the active ingredients without the added synergist itself having to be active.
  • the active compounds according to the invention can also be present in commercial formulations and in the use forms prepared from these formulations in mixtures with inhibitors which break down the active compound after use in the environment of the plant on which
  • the application takes place in a customary manner adapted to the application forms.
  • the active substance When used against hygiene pests and pests of stored products, the active substance is distinguished by an excellent residual action on wood and clay and by a good stability to alkali on limed substrates.
  • the active compounds according to the invention act not only against plant, hygiene and
  • animal parasites such as shield ticks, leather ticks, space mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, featherlings and fleas.
  • ectoparasites animal parasites
  • shield ticks leather ticks, space mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, featherlings and fleas.
  • Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
  • Nematocerina and Brachycerina from the order Diptera and the subordinates Nematocerina and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp.
  • Atylotus spp. Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.
  • Siphonaptrida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
  • Mesostigmata e.g. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietssus spp.,. Pneumon ., Sternostoma spp., Varroa spp.
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp.
  • Tyrophagus spp. Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.
  • the active compounds of the formula (I) according to the invention are also suitable for combating arthropods which are farm animals, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as dogs, cats, house birds, aquarium fish and so-called experimental animals such as hamsters, guinea pigs, rats and mice.
  • arthropods are farm animals, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as dogs, cats, house birds, aquarium fish and so-called experimental animals such as hamsters, guinea pigs, rats and mice.
  • the active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral administration, for example by injections
  • implants by nasal application, by dermal application in the form of, for example, diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), washing, powdering and with the help of shaped articles containing active ingredients, such as collars, ear tags, tail tags, limb tapes, holsters, marking devices, etc.
  • active ingredients such as collars, ear tags, tail tags, limb tapes, holsters, marking devices, etc.
  • the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowable agents) which contain the active compounds in an amount of 1 to 80% by weight, directly or apply after 100 to 10,000-fold dilution or use it as a chemical bath.
  • formulations for example powders, emulsions, flowable agents
  • insects which destroy industrial materials.
  • insects may be mentioned by way of example and preferably, but without limitation:
  • Hymenoptera such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur;
  • Termites such as, for example, Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis,
  • Reticulitermes lucifugus Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus;
  • Bristle tails such as Lepisma saccharina
  • non-living materials such as preferably plastics, adhesives, glues, papers and cartons, leather, wood, wood processing products and paints.
  • the one to be protected against insect attack is very particularly preferably
  • Wood and wood processing products that can be protected by the agent according to the invention or mixtures containing it are to be understood as examples: Building timber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wooden cladding, wooden windows and doors, plywood, chipboard, carpentry or wooden products that are generally used in house construction or joinery.
  • the insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.
  • the amount of the agents or concentrates used depends on the type and occurrence of the insects and on the medium. The optimum amount of use can be determined in each case by test series. In general, however, it is sufficient to use 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.
  • the organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C.
  • Corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used as such low-volatility, water-insoluble, oily and oily solvents.
  • Mineral oils with a boiling range of 170 to 220 ° C, test gasoline with a boiling range of 170 to 220 ° C, spindle oil with a boiling range are advantageous from 250 to 350 ° C, petroleum or aromatics with a boiling range from 160 to 280 ° C, turpentine oil and the like.
  • organic low-volatility oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture.
  • part of the organic chemical solvent or solvent mixture or an aliphatic polar organic chemical solvent or solvent mixture is replaced.
  • Aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups, such as, for example, glycol ethers, esters or the like, are preferably used.
  • the organic-chemical binders used are the water-thinnable synthetic resins which are known per se and / or which are soluble or dispersible or emulsifiable in the organic chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or synthetic resin.
  • binders consisting of or containing an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-cou
  • the synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In addition, known dyes, pigments, water-repellants, odor correctors and inhibitors or anticorrosive agents and the like can be used.
  • At least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder.
  • Alkyd resins having an oil content of more than 45% by weight, preferably 50 to, are preferred according to the invention
  • binder mentioned can be replaced by a fixative (mixture) or a plasticizer (mixture).
  • fixative mixture
  • plasticizer mixture
  • additives are intended to volatilize the active ingredients and crystallize or precipitate! prevent. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).
  • the plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, higher glycerol glycerol or glycerol ether - Kolether, glycerol ester and p-toluenesulfonic acid ester.
  • phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate
  • phosphoric acid esters such as tributyl phosphate
  • adipic acid esters such as di- (2-ethylhexyl) adipate
  • Fixing agents are chemically based on polyvinyl alkyl ethers such as polyvinyl methyl ether or ketones such as benzophenone and ethylene benzophenone.
  • Water is also particularly suitable as a solvent or diluent, if appropriate in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.
  • a particularly effective wood protection is achieved through industrial impregnation processes, e.g. Vacuum, double vacuum or pressure process.
  • the ready-to-use compositions may optionally contain further insecticides and, if appropriate, one or more fungicides.
  • insecticides and fungicides mentioned in WO 94/29268 are preferably suitable as additional admixing partners.
  • the compounds mentioned in this document are an integral part of the present application.
  • Insecticides such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthrin, trifluorophenoid, trifluoropurid, trifluoridophen, methanophenolidophenol, trifluorophenol, trifluoric acid , Tefluthrin and fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole,
  • the compounds according to the invention can be used to protect objects, in particular ship hulls, sieves, nets, structures, quay systems and signaling systems which come into contact with sea or brackish water.
  • group Ledamorpha such as various Lepas and Scalpellum species
  • Balanomorpha (barnacles) such as Baianus or PoUicipes species
  • heavy metals such as e.g. in bis (trialkyltin) sulfides, tri-butyltin laurate, tri-butyltin chloride, copper (I) oxide, triethyltin chloride, tri-n-butyl (2-phenyl-4-chlorophenoxy) tin, tributyltin oxide, molybdenum disulfide, Antimony oxide, polymeric butyl titanate, phenyl (bispyridine) bismuth chloride, tri-butyltin fluoride, manganese ethylene bisthiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisthiocarbamate, zinc and copper salts of 2-pyridinethiol-1-oxide, bisdimethyldihoxydiamethyldihamidoxydiamethyldihydoxydiamethyldi
  • the ready-to-use antifouling paints may also contain other active ingredients, preferably algicides, fungicides, herbicides, molluscicides or other antifouling active ingredients.
  • Suitable combination partners for the antifouling agents according to the invention preferably:
  • Algicides such as 2-tert-butylamino-4-cyclopropylamino-6-methylthio-l, 3,5-triazine, dichlorophene, diuron, endothal, fentin acetate, isoproturon, methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;
  • Fungicides such as benzo [b] thiophenecarboxylic acid cyclohexylamide-S, S-dioxide, dichlorofluoranide, fluorofolpet, 3-iodo-2-propynyl butyl carbamate, tolylfluanid and azoles such as azaconazole, cyproconazole, epoxyconazole, hexaconazole, conconazole, metconazole, metconazole ;
  • MoUuscicides such as fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb and trimethacarb;
  • antifouling agents such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulfone, 2- (N, N-dimethylthiocarbamoylti io) -5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridinthiol-l-oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine,
  • antifouling agents such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulfone, 2- (N, N-dimethylthiocarbamoylti io) -5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridinthiol-l
  • the antifouling agents used contain the active compound according to the invention of the compounds according to the invention in a concentration of 0.001 to 50% by weight, in particular of 0.01 to 20% by weight.
  • antifouling agents according to the invention furthermore contain the usual constituents as described, for example, in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.
  • antifouling paints contain in particular binders.
  • Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in one
  • Solvent system especially in an aqueous system, vinyl chloride / vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene / styrene / acrylonitrile rubbers, drying oils, such as linseed oil, resin esters or modified hard resins in combination with tar or bitumen, Asphalt and epoxy compounds, minor
  • Paints may also contain inorganic pigments, organic pigments or dyes, which are preferably insoluble in seawater. Furthermore, paints can contain materials such as rosin in order to be controlled
  • the paints may also contain plasticizers, theological properties modifiers and other conventional ingredients.
  • the compounds according to the invention or the abovementioned mixtures can also be incorporated into self-polishing antifouling systems.
  • the active ingredients are also suitable for combating animal pests, in particular insects, arachnids and mites, which live in closed rooms, such as apartments, factory halls, offices, vehicle cabins, etc. occurrence. They can be used to control these pests on their own or in combination with other active ingredients and auxiliaries in household insecticide products. They are effective against sensitive and resistant species and against all stages of development. These pests include:
  • Scorpionidea for example Buthus occitanus.
  • Acarina for example, argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Omithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimides for Dina- phophisides, Dermatophago.
  • Opiliones e.g. Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.
  • Diplopoda e.g. Blaniulus guttulatus, Polydesmus spp.
  • Psocoptera for example Lepinatus spp., Liposcelis spp.
  • Coleptera for example, Anthrenus spp., Attagenus spp., De mestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.
  • Aedes aegypti Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, ' Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila domppica, Musannotiapppp carnaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.
  • Lepidoptera e.g. Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
  • Ctenocephalides canis Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
  • Hymenoptera e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
  • Rhodinus prolixus Triatoma infestans.
  • the application in the field of household insecticides is carried out alone or in combination with other suitable active compounds such as phosphoric acid esters, carbamates, pyrethroids, neonicotoids, growth regulators or active compounds from other known classes of insecticides. They are used in aerosols, unpressurized sprays, e.g. pump and atomizer sprays, automatic fog machines, foggers, foams, gels, evaporator products with evaporator plates made of cellulose or plastic, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-free or passive evaporation systems, moth papers, moth bags and moth gels, as granules or dusts, in lures or bait stations.
  • suitable active compounds such as phosphoric acid esters, carbamates, pyrethroids, neonicotoids, growth regulators or active compounds from other known classes of insecticides. They are used in aerosols, unpressurized sprays, e.g. pump and
  • Emulsifier 2 parts by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.
  • Vessels are filled with sand, active ingredient solution, Meloidogyne incognita egg larvae suspension and lettuce seeds.
  • the lettuce seeds germinate and the plantlets develop.
  • the galls develop at the roots.
  • the nematicidal effect is determined in% using the formation of bile. 100% means that no galls were found; 0% means that the number of galls on the treated plants corresponds to that of the untreated control.
  • dimethylformamide emulsifier 1.5 parts by weight of dimethylformamide emulsifier: 0.5 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 emulsifier and the concentrate is diluted to the desired concentration with water containing emulsifier.
  • Chinese cabbage leaf slices (Brassica peldnensis), which are affected by all stages of the green peach aphid (Myzus persicae), are sprayed with an active ingredient preparation of the desired concentration.
  • the effect is determined in%. 100% means that all the aphids have been killed; 0% means that no aphids have been killed.
  • dimethylformamide emulsifier 1.5 parts by weight of dimethylformamide emulsifier: 0.5 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 emulsifier and the concentrate is diluted to the desired concentration with water containing emulsifier.
  • Chinese cabbage leaf slices (Brassica peldnensis) are sprayed with an active ingredient preparation of the desired concentration and, after drying, with larvae of the
  • Horseradish leaf beetle (Phaedon cochleariae) occupied.
  • the effect is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.
  • Example D the compound of preparation example 1-105 shows good activity.
  • Emulsifier 2 parts by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted to the desired concentration with water containing emulsifier.
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the army worm (Spodoptera frugiperda) while the leaves are still moist.
  • the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent emulsifier and the concentrate is diluted to the desired concentration with water containing emulsifier.
  • a specified amount of active compound preparation of the desired concentration is pipetted onto a standardized amount of synthetic feed.
  • one larva (L3) of the army worm (Spodoptera frugiperda) is placed on the feed.
  • the kill is determined in%. 100% means that all animals have been killed; 0% means that no animals have been killed.
  • the compound of preparation example 1-22 shows good activity.
  • dimethylformamide emulsifier 1.5 parts by weight of dimethylformamide emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
  • Bean leaf slices Phaseolus vulgaris
  • Triticae Tricholine dexase
  • Bean leaf slices Phaseolus vulgaris
  • which are affected by all stages of the common spider mite Tetranychus urticae
  • an active ingredient preparation of the desired concentration is sprayed with an active ingredient preparation of the desired concentration.
  • the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
  • Emulsifier 2 parts by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted to the desired concentration with water containing emulsifier.
  • Bean plants Phaseolus vulgaris
  • Tetranychus urticae which are heavily infested with all stages of the common spider mite (Tetranychus urticae), are immersed in an active ingredient preparation of the desired concentration.
  • the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
  • the 9-ketospinosynA aglycone (11-1) is enriched to> 98% by primary crystallization of the mixture in cyclohexane / ethyl acetate. 20.78 g of 9-ketospinosynA aglycone (II-1) are obtained as colorless crystals.
  • the 5,6-dihydro-9-ketospinosyn A-aglycon (Ila) [Nerbinding of the general formula (II), wherein R 1 is hydrogen and AB stands for the group -H 2 C-CH 2 -] can be analogous to WO 02/079184 described by means of pyridinium dichromate oxidation from which the 5,6-dihydro-spinosyn A-aglycone (cf. WO 01/16303) are produced.
  • N- [4- (N'-methylsulfonylaminophenethoxy)] phthalimide 24.0 g (60.2 mmol) of N- (4-aminophenethoxy) phthalimide hydrochloride are placed in 400 ml of dichloromethane and mixed with 14.6 ml of pyridine. After dropwise addition of 6.9 g (60.2 mmol) of methanesulfonyl chloride at 0 ° C., the reaction mixture is stirred at room temperature for about 18 hours. The reaction solution is then shaken once against 5% aqueous hydrochloric acid and twice against distilled water. The organic phase is separated off, dried and evaporated down in vacuo.

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Abstract

L'invention concerne des dérivés de 9-cétospinosynes, substitués par un reste =N-(O, NH oder NRx)-Ry en position C-9, ainsi que leur procédé de production et leur utilisation dans la lutte contre les nuisibles.
EP04700669A 2003-01-17 2004-01-08 Derives de 9-cetospinosyne Withdrawn EP1590358A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10301519 2003-01-17
DE10301519A DE10301519A1 (de) 2003-01-17 2003-01-17 9-Ketospinosyn-Derivate
PCT/EP2004/000058 WO2004065402A1 (fr) 2003-01-17 2004-01-08 Derives de 9-cetospinosyne

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EP1590358A1 true EP1590358A1 (fr) 2005-11-02

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EP04700669A Withdrawn EP1590358A1 (fr) 2003-01-17 2004-01-08 Derives de 9-cetospinosyne

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EP (1) EP1590358A1 (fr)
JP (1) JP2006517538A (fr)
KR (1) KR20050093828A (fr)
CN (1) CN100404544C (fr)
AU (1) AU2004205353A1 (fr)
BR (1) BRPI0406802A (fr)
DE (1) DE10301519A1 (fr)
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WO (1) WO2004065402A1 (fr)

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JP5315818B2 (ja) * 2007-07-12 2013-10-16 住友化学株式会社 有害生物防除組成物
CA2932121A1 (fr) 2007-11-30 2009-06-11 Newlink Genetics Corporation Inhibiteurs de l'ido
CA2737875C (fr) * 2008-09-22 2015-11-24 Christine Kritikou Compositions anticolmatage contenant de la spinosyne, procedes pour les utiliser et articles proteges contre l'attachement d'organismes de biocolmatage
CN102190694B (zh) * 2010-03-12 2015-09-09 中南大学 多杀菌素衍生物、制备方法及其作为杀虫剂的用途
CN114181201B (zh) * 2020-09-15 2023-12-01 香港科技大学 作为针对各种神经退行性疾病的潜在治疗剂的新化合物

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MXPA05007579A (es) 2005-12-15
BRPI0406802A (pt) 2006-01-17
AU2004205353A1 (en) 2004-08-05
WO2004065402A1 (fr) 2004-08-05
CN1784416A (zh) 2006-06-07
KR20050093828A (ko) 2005-09-23
JP2006517538A (ja) 2006-07-27
US20060128642A1 (en) 2006-06-15
CN100404544C (zh) 2008-07-23
DE10301519A1 (de) 2004-07-29
US7312200B2 (en) 2007-12-25

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