EP1322604A1 - Delta 1-pyrrolines utilisees comme pesticides - Google Patents

Delta 1-pyrrolines utilisees comme pesticides

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Publication number
EP1322604A1
EP1322604A1 EP01967323A EP01967323A EP1322604A1 EP 1322604 A1 EP1322604 A1 EP 1322604A1 EP 01967323 A EP01967323 A EP 01967323A EP 01967323 A EP01967323 A EP 01967323A EP 1322604 A1 EP1322604 A1 EP 1322604A1
Authority
EP
European Patent Office
Prior art keywords
formula
butyl
spp
haloalkyl
alkyl
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Withdrawn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
EP01967323A
Other languages
German (de)
English (en)
Inventor
Andrew Plant
Albrecht Marhold
Rolf Grosser
Christoph Erdelen
Andreas Turberg
Olaf Hansen
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
Priority claimed from DE10051395A external-priority patent/DE10051395A1/de
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Publication of EP1322604A1 publication Critical patent/EP1322604A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C07D207/18—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 one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—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 one double bond between ring members or between a ring member and a non-ring member 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
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C307/00—Amides of sulfuric acids, i.e. compounds having singly-bound oxygen atoms of sulfate groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C307/02—Monoamides of sulfuric acids or esters thereof, e.g. sulfamic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • 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
    • C07D207/18—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 one double bond between ring members or between a ring member and a non-ring member
    • C07D207/20—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 one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms

Definitions

  • the present invention relates to new ⁇ '-pyrrolines, several ner processes for their preparation and their use as pesticides.
  • n 0 or 1
  • r and s independently of one another represent 0, 1 or 2
  • R ' represents halogen or methyl
  • R 2 represents hydrogen or halogen.
  • R 3 and R 1 independently of one another for halogen.
  • Al yl Haloalkyl, alkoxy or
  • Halogenalkoxy stand.
  • R 5 represents alkyl, haloalkyl, in each case optionally singly or multiply, identical or different phenyl substituted by radicals from the list W 'or represents -NR 6 R 7 ,
  • R 6 represents alkyl or haloalkyl
  • R 7 represents hydrogen, alkyl or haloalkyl
  • R 6 and R 7 also together represent alkylene or alkoxyalkylene
  • R 8 represents alkyl or haloalkyl
  • q 0, 1 or 2.
  • R, R, R, R, n, r and s have the meanings given above,
  • R, R, R and r have the meanings given above and
  • X represents Br, Cl, I, -OSO 2 CF 3 or -OSO 2 (CF 2 ) 3 CF 3 ,
  • R, R, R and r have the meanings given above and
  • R 4 , R 5 and s have the meanings given above,
  • (I) have very good insecticidal properties and can be used both in crop protection and in material protection to combat unwanted pests, such as insects.
  • the ⁇ '-pyrrolines of the formula (I) according to the invention show a substantially better insecticidal activity than the constitutionally most similar, previously known ⁇ '-pyrrolines of the same action.
  • n is preferably 0 or 1.
  • r and s independently of one another are preferably 0, 1 or 2.
  • R ' preferably represents fluorine, chlorine, bromine or methyl.
  • R " preferably represents hydrogen. Fluorine. Chlorine or bromine.
  • R 3 and R 4 independently of one another preferably represent fluorine, chlorine, bromine, C, -C 6 -alkyl, C r C 6 -haloalkyl, C, -C 6 -alkoxy or C, -C 6 -haloalkoxy.
  • R 5 preferably represents C, -C 6 -alkyl, C, -C 6 -haloalkyl, in each case optionally one to four times, identical or different phenyl substituted by radicals from the list W 'or -NR 6 R 7 .
  • W ' preferably represents fluorine, chlorine, bromine, C, -C 6 -alkyl, C r C 6 -haloalkyl, C, - C 6 -alkoxy, C, -C 6 -haloalkoxy, C, -C 6 -alkylcarbonyl, C r C 6 alkoxycarbonyl or -S (O) q R 8 .
  • R 6 preferably represents C r C 6 alkyl or C, -C 6 haloalkyl.
  • R 7 preferably represents hydrogen, C, -C 6 alkyl or C r C 6 haloalkyl.
  • R 6 and R 7 together also preferably represent C 3 -C 6 alkylene or C r C 4 alkoxy-C, -C 4 alkylene.
  • R 8 preferably represents C, -C 6 alkyl or C, -C 6 haloalkyl.
  • q is preferably 0, 1 or 2.
  • n particularly preferably represents 0 or 1.
  • r and s independently of one another are particularly preferably 0, 1 or 2.
  • R 1 particularly preferably represents fluorine, chlorine or methyl.
  • R 2 particularly preferably represents hydrogen, fluorine or chlorine.
  • R 'and R 4 independently of one another are particularly preferably fluorine, chlorine, C, -
  • R 5 particularly preferably represents C, -C 4 -alkyl, C, -C 4 -haloalkyl, in each case optionally mono- to triple, the same or different phenyl substituted by radicals from the list W 'or -NR 6 R 7 .
  • W ' is more preferably fluorine, chlorine, C, -C 4 -alkyl, C 4 haloalkyl,
  • R 6 particularly preferably represents C, -C 4 -alkyl or C, -C 4 -haloalkyl.
  • R 7 particularly preferably represents hydrogen, C, -C 4 -alkyl or C, -C 4 -haloalkyl.
  • R 6 and R 7 together also particularly preferably represent C 4 -C 5 alkylene or - (CH 2 ) 2 -O- (CH 2 ) 2 -.
  • R 8 particularly preferably represents C r C 4 - alkyl or C r C 4 haloalkyl.
  • q particularly preferably represents 0, 1 or 2.
  • n very particularly preferably represents 0 or 1.
  • r and s independently of one another very particularly preferably represent 0 or 1.
  • R 2 very particularly preferably represents hydrogen or fluorine.
  • R 'and R 4 independently of one another very particularly preferably represent fluorine, chlorine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, Trifluoromethyl, trifluoroethyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, trifluoromethoxy or trifluoroethoxy.
  • R 5 very particularly preferably represents methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, trifluoromethyl, trifluoroethyl, nonafluorobutyl, in each case, if appropriate, once or twice, the same or phenyl substituted by radicals from the list W 'or for -NR 6 R 7 .
  • R 6 very particularly preferably represents methyl, ethyl, n-propyl, i-propyl, n-
  • R 7 very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, i-
  • R ', R 2 , R 4 , R 5 and s have the meanings given above.
  • R 1 , R 2 , R 4 , R 5 and s have the meanings given above. Furthermore, (R) -configured compounds of the formulas (Id) are very particularly preferred.
  • R ', R 2 , R 3 , R 4 , R 5 , r and s have the meanings given above.
  • Enantiomerically pure compounds of the formulas (I-c) and (I-d) are obtained by customary processes for resolving racemates, for example by chromatography of the corresponding racemates on a chiral stationary phase. It is possible to break down both the racemic end products or racemic intermediates into the two enantiomers in this way.
  • Saturated hydrocarbon radicals such as alkyl
  • heteroatoms e.g. in alkoxy, where possible, be straight-chain or branched.
  • Optionally substituted radicals can be mono- or polysubstituted, whereby in the case of multiple substitutions the substituents can be the same or different.
  • Formula (II) provides a general definition of the amino ketones required as starting materials when carrying out process (A) according to the invention.
  • R 1, R 2, R 3, R 4, R 5, n, r and s being preferred, particularly preferred and very particularly preferably has those meanings which have already in connection with the description of the substances according to the invention of the formula ( I) were mentioned as preferred, particularly preferred etc. for these radicals.
  • amino ketones of formula (II) are new. They can be made by
  • R, R, R, n, r and s have the meanings given above,
  • M represents Li, MgCl, MgBr, Mgl or ZnCl
  • a diluent e.g. tetrahydrofuran
  • a diluent e.g. tetrahydrofuran
  • Formula (VII) provides a general definition of the N-Boc lactams required as starting materials when carrying out process (a).
  • R 3 , R 4 , R 5 , n, r and s are preferred, particularly preferred or very particularly preferred for those meanings which are already in connection with the description of the substances of the formula (I) according to the invention for these radicals preferred, particularly preferred, etc. were mentioned.
  • N-Boc lactams of the formula (VII) are new. They can be made, for example, by
  • R, R, R, n, r and s have the meanings given above,
  • Formula (VIII) provides a general definition of the metallated aromatics required as starting materials when carrying out process (a).
  • R 'and R 2 are preferred, particularly preferred or very particularly preferred for those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention were.
  • M preferably represents Li, MgCl, MgBr, Mgl, ZnCl, particularly preferably Li, MgCl, MgBr, Mgl, very particularly preferably Li, MgCl, MgBr.
  • Metallized aromatics of the formula (VIII) are known in some cases or can be prepared by known methods, e.g. Lithiation or Grignard reaction, can be prepared from the corresponding aromatics or halogen aromatics.
  • lactams required as starting materials in carrying out process (b) are generally defined by the formula (IX).
  • R 3 , R 4 , R 5 , n, r and s are preferred, particularly preferred or very particularly preferred for those meanings which are already in connection with the description of the substances of the formula (I) according to the invention for these radicals preferred, particularly preferred, etc. were mentioned.
  • Lactams of the formula (IX) are new.
  • R 4 , R ⁇ r and s have the meanings given above, can be made, for example, by
  • R 5 has the meanings given above and
  • Y represents halogen
  • R 3 , R 4 , R 5 , n, r and s have the meanings given above,
  • R 3 , R 4 , R 5 , r and s have the meanings given above,
  • lactams required as starting materials in carrying out process (c) are generally defined by the formula (X).
  • R 4 and s are preferably, particularly preferably or very particularly preferably, those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention ,
  • Lactams of the formula (X) are known and / or can be prepared by known processes (cf. WO 98/22438).
  • Formula (XI) provides a general definition of the sulfonic acid halides required as starting materials when carrying out process (c).
  • R 5 is preferably, particularly preferably or very particularly preferably, those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention.
  • Y preferably represents fluorine or chlorine.
  • Formula (XII) generally defines sulfonic anhydrides.
  • R 5 is preferably, particularly preferably or very particularly preferably, those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention.
  • Formula (XIII) provides a general definition of the biphenyls required as starting materials when carrying out process (d). Stand in this formula
  • R 4 , R 5 , r and s are preferred, particularly preferred or very particularly preferred for those meanings which have already been mentioned as preferred, particularly preferred etc. in connection with the description of the substances of the formula (I) according to the invention for these radicals.
  • Biphenyls of the formula (XIII) are known. They can e.g. manufacture by
  • R 3 , R 4 , r and s have the meanings given above,
  • R 5 has the meanings given above and
  • Y represents halogen
  • R 5 has the meanings given above
  • a base e.g. potassium carbonate
  • a diluent e.g. acetonitrile
  • Formula (XIV) provides a general definition of the hydroxybiphenyls required as starting materials when carrying out process (e).
  • R 3 , R 4 , r and s are preferably, particularly preferably or very particularly preferably those meanings which, in connection with the description of the substances of the formula (I) according to the invention, are preferred, particularly preferred, etc. for these radicals . were called.
  • Suitable diluents for carrying out process (A) according to the invention are all customary inert, organic solvents.
  • Halogenated aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin, may optionally be used; Chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole;
  • Nitriles such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide or sulfones such as sulfolane. Methylene chloride, chloroform, toluene, methanol or ethanol are particularly preferably used. When carrying out process (A) according to the invention, all customary Lewis acids or protonic acids are suitable.
  • Boc elimination methods are generally known (cf., for example, TW Greene, PGM Wuts, Protective Groups in Organic Synthesis, Ed. 3, New York, Wiley & Sons, 1999, pp. 520-525). Trifluoroacetic acid, HC1 or HBr are preferably used to split off the Boc protective group.
  • reaction temperatures can in each case be varied within a substantial range. In general, temperatures between -20 ° C and + 120 ° C, preferably between -10 ° C and 60 ° C.
  • reaction mixture is concentrated, taken up in a suitable solvent, adjusted to pH 12 with sodium hydroxide and the organic phase is washed with water, dried over sodium sulfate, filtered and concentrated.
  • the residue is optionally freed of any impurities that may still be present, using customary methods, such as chromatography or recrystallization.
  • the lactams of the formula (IX) can be subjected to racemate resolution.
  • preparative chromatography preferably high performance liquid chromatography (HPLC)
  • HPLC high performance liquid chromatography
  • a chiral stationary silica gel phase is used.
  • a silica gel derivative for example mercaptopropyl silica gel
  • N-methacryloyl-L-leucine-D-menthylamide has proven to be particularly suitable for the separation of the compounds of the formula (IX).
  • This separating material is known (cf. EP-A 0 379 917). All customary inert, organic solvents and mixtures of these can be considered as eluents.
  • Halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether may preferably be used.
  • Hydrocarbons such as hexane or heptane
  • alcohols such as methanol or
  • Propanol very particularly preferably n-heptane or isopropanol or mixtures of these.
  • the (R) -configured enantiomers obtained are then used as starting materials for the synthetic route described.
  • Formula (III) provides a general definition of the (bi) phenols required as starting materials when carrying out process (B) according to the invention.
  • R 1 , R 2 , R 3 , R 4 , n, r and s are preferably, particularly preferably or very particularly preferably, those meanings which have already been associated with the description of the substances of the formula (I) according to the invention were mentioned as preferred, particularly preferred etc. for these radicals.
  • sulfonylation halides of the formula (XI) and anhydrides of the formula (XII) are suitable as sulfonation reagents.
  • Suitable diluents for carrying out process (B) according to the invention are all customary inert, organic solvents.
  • Halogenated aliphatic, alicyclic or U (hetero) aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, pyridine or decalin; Chlorobenzene, Dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane or anisole; Nitriles, such as acet
  • Methylformanilide N-methylpyrrolidone or hexamethylphosphoric triamide
  • Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide or sulfones such as sulfolane.
  • Pyridine, dichloromethane, chloroform, tetrahydrofuran or toluene are particularly preferably used. If appropriate, mixtures with water can be used and the reaction can be carried out in a two-phase system.
  • Suitable acid binders for carrying out process (B) according to the invention are all inorganic and organic bases customary for such reactions.
  • Alkaline earth metal or alkali metal hydroxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide, or also ammonium hydroxide
  • alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, alkali metal or alkaline earth metal acetate such as sodium acetate, potassium acetate, calcium acetate
  • tertiary amines are preferably usable Trimethylamine, triethylamine, tributylamine, diethylisopropylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).
  • DABCO di
  • reaction temperatures can be varied within a substantial range when carrying out process (B) according to the invention. In general, temperatures between -70 ° C and + 110 ° C, preferably between -20 ° C and + 40 ° C.
  • 1 mol or a slight excess of sulfonylation reagent and 0.5 to 3 mol of acid binder are generally employed per mol of compound of the formula (III).
  • the processing takes place according to usual methods. The general procedure is to decant, wash, dry, filter and concentrate the reaction mixture. The residue is optionally freed of any impurities that may still be present, using customary methods, such as chromatography or recrystallization.
  • Formula (IV) provides a general definition of the pyrrolines required as starting materials when carrying out process (C) according to the invention.
  • R 1 , R 2 , R 3 and r are preferred, particularly preferred or very particularly preferred for those meanings which, in connection with the description of the substances of the formula (I) according to the invention, are preferred for these radicals, particularly preferred etc. were mentioned.
  • R ', R 2 , R 3 and r have the meanings given above and
  • X 1 represents chlorine, bromine and iodine, are known and can be produced by known processes (cf. WO 98/22438).
  • R, R, R and r have the meanings given above and
  • X 2 represents -OSO 2 CF 3 or -OSO 2 (CF 2 ) 3 CF 3 ,
  • Formula (VI) provides a general definition of the iodides required as starting materials when carrying out process (C) according to the invention.
  • R 4 , R 5 and s are preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention were.
  • Iodides of the formula (VI) are generally known or are commercially available.
  • a palladium catalyst is generally used, which in turn can be used with or without the addition of further ligands.
  • Triarylphosphines, trialkylphosphines or arsines are suitable as ligands.
  • Dppf, PPh 3 , P (t-Bu) 3 , Pcy 3 or AsPh 3 are preferably used, particularly preferably dppf.
  • Suitable acid binders for carrying out process (C) according to the invention are all inorganic and organic bases which are customary for such reactions.
  • Alkaline earth metal or alkali metal hydroxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide, or also ammonium hydroxide
  • alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, alkali metal or alkaline earth metal acetates such as sodium acetate, potassium acetate, calcium acetate, alkali metal and alkali metal
  • Tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).
  • DABCO diazabic
  • Suitable diluents for carrying out process (C) according to the invention are all customary inert, organic solvents.
  • Halogenated aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; Chlorobenzene, dichlorobenzene,
  • Methylpyrrolidone or hexamethylphosphoric triamide Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide or sulfones such as sulfolane. Acetone, dimethoxyethane, dioxane, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethanol, toluene or, if appropriate, mixtures of these diluents with water are particularly preferably used.
  • reaction temperatures can in each case be varied within a substantial range. In general, temperatures between 0 ° C and 140 ° C, preferably between
  • the process (C) according to the invention can be carried out in two variants.
  • a compound of the formula (IV) is first reacted with a diboronic ester.
  • the intermediates of the formula (V) are obtained, which are then reacted in a second stage with iodides of the formula (VI).
  • the intermediates of the formula (V) are not isolated, but instead reacted in situ with iodides of the formula (VI).
  • the procedure is generally carried out under atmospheric pressure. However, it is also possible to work under increased or reduced pressure.
  • the active compounds according to the invention are suitable, with good plant tolerance and favorable warm-blood toxicity, for combating animal pests, in particular insects, arachnids and nematodes which occur in agriculture, in forests, in the protection of stored products and materials, and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • the pests mentioned above include:
  • Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber. From the order of the Diplopoda e.g. Blaniulus guttulatus.
  • Chilopoda for example, Geophilus carpophagus and Scutigera spp.
  • Symphyla for example, Scutigerella immaculata.
  • Thysanura for example Lepisma saccharina.
  • Collembola for example Onychiurus armatus.
  • Orthoptera e.g. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis.
  • Heteroptera e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
  • Lepidoptera for example Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella x
  • Feltia spp. Earias insulana, Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonellella, Galleria mellonellaella, Galleria mellonellaella, Galleria mellonellaella, Galleria mellonellaella Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fu- miferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.
  • Conoderus spp. Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp. From the order of the Diptera e.g.
  • Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp.
  • Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp.
  • Arachnida e.g. Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllo-coptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommodes spp., I ., Chorioptes spp., Sarcoptes spp., Tarsonemus spp.,
  • Bryobia praetiosa Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevi palpus spp.
  • Plant-parasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp.
  • the compounds of the formula (I) according to the invention are distinguished in particular by an excellent action against caterpillars, beetle larvae, spider mites, aphids and leaf miners.
  • the compounds according to the invention can also be used in certain concentrations or application rates as herbicides and microbicides, for example as fungicides, antifungal agents and bactericides. If appropriate, they can also be used as intermediates or precursors for the synthesis of further active compounds.
  • plants and parts of plants can be treated.
  • Plants are understood here to mean all plants and plant populations, such as desired and undesirable 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 those by
  • Plant variety rights of protectable or non-protectable plant varieties Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, 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, offshoots and seeds.
  • Storage room according to the usual treatment methods, e.g. by dipping, spraying, Vaping, atomizing, scattering, spreading and, in the case of propagation material, in particular seeds, furthermore by means of single or multi-layer coating.
  • the active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and also female encapsulations in polymeric substances ,
  • formulations are made in a known manner, e.g. by mixing the active compounds according to the invention with extenders, that is to say liquid solvents and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.
  • extenders that is to say liquid solvents and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can also be used as auxiliary solvents.
  • auxiliary solvents e.g. organic solvents
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
  • Petroleum fractions mineral and vegetable oils, 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.
  • 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.
  • ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, as solid carriers for granules are possible: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and syn- synthetic granules made from inorganic and organic flours and granules made from organic material such as sawdust, coconut shells, corn cobs and tobacco stems;
  • natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, as solid carriers for granules are possible: eg broken and fractionated natural rocks such as calcite, marble, pumice
  • nonionic 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;
  • Possible dispersants are: e.g. Lignin sulfite waste liquors and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
  • 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% 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 other, also known active compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides, for example the
  • the insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenyl ureas, substances produced by microorganisms and others
  • Fungicides Aldimo ⁇ h, Ampropylfos, Ampropylfos Potassium, Andoprim, Anilazine, Azaconazole,
  • Debacarb dichlorophene, diclobutrazole, diclofluanide, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomo ⁇ h, diniconazole, dinicenazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon
  • copper preparations such as: copper hydroxide, copper phthalate, copper oxychloride, copper sulfate, copper oxide, oxy-copper and
  • Mancopper Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazole, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin, Nickel-dimethyldithiochalamopropyl, Nitrile
  • Tebuconazole Tecloftalam, Tecnazen, Tetcyclacis, Tetraconazole, Thiabendazole, Thicyofen, Thifluzamide, Thiophanate-methyl, Thiram, Tioxymid, Tolclofos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazbutichlamidid, Triazoxid, Triazoxid
  • Tricyclazol Tridemo ⁇ h
  • Trifloxystrobin Triflumizol
  • Triforin Triticonazol
  • Uniconazol Tricyclazol, Tridemo ⁇ h, Trifloxystrobin, Triflumizol, Triforin, Triticonazol, Uniconazol,
  • Validamycin A, vinclozolin, viniconazole, zarilamide, zineb, ziram and Dagger G OK-8705, OK-8801, ⁇ - (1, 1-dimethylethyl) -ß- (2-phenoxyethyl) - 1 H-1, 2.4 -triazole-1-ethanol, ⁇ - (2,4-dichloro-phenyl) -ß-fluoro-b-propyl-1 H-1, 2,4-triazole-1-ethanol, ⁇ - (2,4-dichloro-phenyl) - ß-methoxy-a-methyl-lH-l, 2,4-triazol-l-ethanol, ⁇ - (5-methyl-l, 3-dioxan-5-yl) -ß - [[4- (trifluoromethyl) - phenyl] methylene] -IH-l, 2,4-triazole-1-ethanol,
  • Fenamiphos Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fi- pronil, Fluazinam, Fluazuron, Flubrocythrinate, Flucycloxoxinon, Fluvalinoxuron, Flucythrinurin, Flucythrinurin, Flucytinurin, Flucytinurin, Flucytinurin, Flucytinurin, Flucytinurin, Flucytinurin, Flucytinurin, Flucytinurin, Flucyinhrin, Flucyinhrin, Flucyinhroxinon, Fluuminoxuron, Flucythrin, Flucyinhrin, Flucythrinur, Flu
  • Halofenozide HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene, imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion, ivermectin, kempolyederviruses lambda-cyhalothrin, lufenuron malathion, mecarbam, metaldehyde, methamidophosphate, methamidophosphate, methamidophosphate
  • Metharhilic flavoviride methidathione, methiocarb, methoprene, methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, milbemycin, monocrotophos, naled, nitenpyram, nithiazine, novaluron omethoat, oxamyl mydyd
  • Paecilomyces fumosoroseus Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propargite, Propoxur, Prothiofos, Prothrohrinos, Pothrohrinos, Pothrohrinate, Pothrohrinate , Pyridaben, pyridathione, pyrimidifene, pyriproxyfen,
  • the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists.
  • Synergists are compounds which increase the activity of the active compounds according to the invention without the added synergist itself having to be active.
  • the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
  • the active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.
  • the application takes place in a customary manner adapted to the application forms
  • the active ingredient When used against hygiene pests and pests of stored products, the active ingredient is distinguished by an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.
  • plants and their parts can be treated according to the invention.
  • transgenic plants and plant cultivars which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetic modified organisms) and their parts are treated.
  • the term “parts” or “parts of plants” or “parts of plants” was explained above. Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention. Plant cultivars are understood to mean plants with certain properties (“traits”) which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- and genotypes.
  • the treatment according to the invention can also have additive (“synergistic”) effects. For example, reduced application rates and / or extensions of the
  • the preferred transgenic (genetically engineered) plants or plant cultivars to be treated according to the invention include all plants which have received genetic material through the genetic modification which gives these plants particularly advantageous valuable 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, acceleration of ripeness, higher harvest yields, higher quality and or higher nutritional value of the crop products, higher storability and / or workability Further and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance of the plants to certain herbicides Agents.
  • transgenic plants As examples of transgenic plants, the important cultivated plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed and fruit plants (with the fruits apples, bims, citrus fruits and grapes) are mentioned, with corn, soybeans, potatoes and cotton and rapeseed are highlighted.
  • the properties (“traits”) which are particularly emphasized are the plants' increased defense against insects by toxins arising in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (for example by the genes Cry ⁇ A (a), Cry ⁇ A (b), Cry ⁇ A (c), CryllA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF as well as their combinations) are produced in the plants (hereinafter "Bt plants”).
  • Bt plants 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 are also particularly emphasized as properties (“traits").
  • traits are also particularly emphasized the increased tolerance of the plants to certain herbicidal active ingredients, for example imidazoline, sulfonylureas, glyphosate or phosphinotricin (for example "PAT” gene).
  • herbicidal active ingredients for example imidazoline, sulfonylureas, glyphosate or phosphinotricin (for example "PAT” gene).
  • the genes which confer the desired properties (“traits”) can also be found in Combinations with each other occur in the transgenic plants.
  • Examples of “Bt plants” are corn varieties, cotton varieties, soy varieties and potato varieties that are sold under the trade names YIELD GARD ® (e.g.
  • herbicide-tolerant plants are maize varieties, cotton varieties and soy varieties which are sold under the trade names Roundup Ready ® (tolerance against glyphosate, for example corn, cotton, soybeans), Liberty Link ® (tolerance against
  • Phosphinotricin such as rapeseed
  • IMI ® tolerance to imidazolinones
  • STS ® tolerance to sulfonylureas, such as corn
  • Herbicide-resistant plants (bred conventionally for herbicide tolerance) plants also sold under the name Clearfield ® varieties (eg maize) are mentioned. Of course, these statements also apply to those developed in the future or to the future Coming plant varieties with these or future-developed genetic 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 substances 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 active compounds according to the invention act not only against plant, hygiene and stored-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair linge, featherlings and fleas.
  • animal parasites ectoparasites
  • tick ticks leather ticks
  • mites running mites
  • flies stinging and licking
  • parasitic fly larvae lice, hair linge, featherlings and fleas.
  • Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
  • Ischnocerina e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
  • Nematocerina and Brachycerina e.g. 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 ..
  • Amblyomma spp. Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumoniassus spp., Stemostoma spp., Varroa spp.
  • Actinedida Prostigmata
  • Acaridida e.g. Acarapis spp., Cheyletiella spp., Omithocheyletia 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.
  • ticks such as Amblyomma hebraeum
  • parasitic flies such as against Lucilia cuprina.
  • the active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which are used in agricultural animals, e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens. Turkeys, ducks, geese, bees, other pets such as Dogs, cats. Caged birds.
  • agricultural animals e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens. Turkeys, ducks, geese, bees, other pets such as Dogs, cats. Caged birds.
  • aquarium fish and so-called experimental animals such as Hamsters, guinea pigs, rats and
  • 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 (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), 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 pumping in and with the help of shaped articles containing active ingredients, such as necklaces, ear tags, tail tags, limb tapes, holsters, marking devices, etc.
  • the active compounds of the formula (I) according to the invention can be used as formulations (for example powders, emulsions, flowable agents) which contain the active compounds according to the invention in an amount of 1 to 80% by weight, apply directly or after 100 to 10,000-fold dilution or use it as a chemical bath.
  • formulations for example powders, emulsions, flowable agents
  • Lyctus brunneus Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes mgicollis, Xyleboms spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus bmnneus, Sinoxylon spec. Dinoderus minutus.
  • Kalotermes flavicollis Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
  • Bristle tails such as Lepisma saccharina.
  • the material to be protected against insect infestation is very particularly preferably wood and wood processing products.
  • Wood and wood processing products which can be protected by the agent according to the invention or mixtures containing it are to be understood as examples:
  • the active compounds according to the invention can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.
  • the formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active compounds according to the invention with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellants, optionally siccatives and UV stabilizers and optionally dyes and pigments and further processing aids.
  • 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 optimal amount 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.
  • Water and optionally an emulsifier and / or wetting agent optionally an emulsifier and / or wetting agent.
  • 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 are used as such low-volatility, water-insoluble, oily and oily solvents or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene.
  • 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 of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C are advantageous. Te ⁇ entinöl and the like. For use.
  • 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.
  • the known organic-chemical binders are the water-thinnable and / or synthetic resins 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 is used.
  • 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
  • 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-repellents, odor correctors and
  • Inhibitors or anticorrosive agents and the like are 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 with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are used.
  • binder All or part of the binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additions are said to be one
  • Prevent volatilization of the active ingredients and crystallization or precipitation are 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
  • phosphoric acid esters such as tributyl phosphate phate
  • adipic acid esters such as di- (2-ethylhexyl) adipate
  • stearates such as butyl stearate or amyl stearate
  • oleates such as butyl oleate, glycerol ether or higher molecular weight glycol
  • Fixatives are chemically based on polyvinyl alkyl ethers such as Polyvinyl methyl ether or ketones such as benzophenone, 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 processes.
  • the ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides.
  • insecticides and fungicides mentioned in WO 94/29 268 are preferably suitable as additional admixing partners.
  • the compounds mentioned in this document are an integral part of the present application.
  • Insecticides such as chlo ⁇ yriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthronid, as well as thifloxiduron, and methifluorideuron, fifluorideuron, and methifluorideuron, as well as thifluorideuron, as well as fungloxidonuron, as well as fungloxidonuron, as well as fungloxidonuron, as well as fungalidium clonid, as well as Funglumidopuron, as well epoxyconazole,
  • the compounds according to the invention can be used to protect objects, in particular hulls, sieves, nets, structures, Quays and signaling systems that come into contact with sea or brackish water are used.
  • heavy metals such as in bis (trialkyltin) sulfides, tri- / ⁇ -butyltin laurate, tri- / ⁇ -butyltin chloride, copper (I) - oxide, triethyltin chloride, tri- ⁇ -butyl (2-phenyl-4-chlo ⁇ henoxy) tin, tributyltin oxide.
  • 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 are preferably:
  • Molluscicides such as fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb and trimethacarb; or conventional antifouling agents such as
  • 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.
  • the 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 a solvent system, in particular 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, small amounts of chlorinated rubber, chlorinated polypropylene and vinyl resins.
  • Paints may also contain inorganic pigments, organic pigments or dyes, which are preferably insoluble in sea water. Paints may also contain materials such as rosin to enable controlled release of the active ingredients. The paints may also contain plasticizers, modifiers that affect the rheological properties, 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 compounds according to the invention are also suitable for controlling animal pests, in particular insects, arachnids and mites, which occur in closed rooms, such as, for example, apartments, factory halls, offices, vehicle cabins and the like. You can fight these pests alone or in combination with other active ingredients in household insecticide products be used. They are effective against sensitive and resistant species and against all stages of development. These pests include:
  • Sco ⁇ ionidea e.g. Buthus occitanus.
  • Acarina e.g. Argas persicus, Argas reflexus, Bryobia ssp.
  • Dermanyssus gallinae Glyciphagus domesticus, Omithodoms moubat, Rhipice- phalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagides pteronissimus, Dermatophagoides forinae.
  • Diplopoda e.g. Blaniulus guttulatus, Polydesmus spp.
  • Aedes aegypti Aedes albopictus, Aedes taeniorhynchus, Anopheles spp. Calliphora erythrocephala. Chrysozona pluvialis. Culex quinquefasciatus, Culex pipiens. Culex tarsalis, Drosophila spp., Fannia canicularis. Musca domestica, Phlebotomus spp., Sarcophaga camaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.
  • Lepidoptera e.g. Achroia grisella, Galleria mellonella, Plodia inte ⁇ unctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
  • Siphonaptera e.g. 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.
  • anoplura e.g. Pediculus humanus capitis, Pediculus humanus co ⁇ oris, Phthims pubis.
  • Trifluoroacetic acid (185.37 g, 1.63 mol) is placed at 5 ° C. At this temperature a solution of 4- [l - [(tert-butoxycarbonyl) amino] -4- (2,6-difluo ⁇ henyl) -
  • 1,3-difluorobenzene (11.04 g, 96.7 mmol) is placed in tetrahydrofuran (100 ml) and cooled to -70 ° C. At this temperature, n-butyllithium (61.3 ml, 96.7 mmol) is added dropwise. The reaction mixture is allowed to warm to -30 ° C. and a solution of tert-butyl-2-oxo-5- (4 - ⁇ [(trifluoromethyl) sulfonyl] oxy ⁇ phenyl) -l-pyrrolidinecarboxylate (VI -1) (36.0 g, 87.9 mmol) in tetrahydrofuran (100 ml).
  • the reaction mixture is left to stir for 4 hours at -30 ° C. and then for 16 hours at room temperature.
  • the reaction mixture is stirred into water (1000 ml) and extracted with ethyl acetate (2 x 500 ml).
  • the combined organic phases are washed successively with 1N HCl, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution.
  • the organic phase is dried over sodium sulfate, filtered and concentrated.
  • a solution of 40 g of the racemate in 1 l of ethyl acetate is prepared for chromatography.
  • the determination is carried out in the acidic range at pH 2.3 with 0.1% aqueous phosphoric acid and acetonitrile as eluents; linear gradient from 10% acetonitrile to 90% acetonitrile.
  • Phosphate buffer solution and acetonitrile as eluents linear gradient from 10% acetonitrile to 90% acetonitrile.
  • the calibration is carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values using the
  • the lambda max values were determined on the basis of the UN spectra from 200 ⁇ m to 400 nm in the maxima of the chromatographic signals.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Cotton leaves which are heavily infested with the cotton aphid (Aphis gossypii), are treated by dipping into the active ingredient preparation of the desired concentration.
  • the kill is determined in%. 100% means that all of the aphids have been killed; 0% means that no aphids have been killed.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Soybean shoots (Glycine max) are treated by immersing them in the active ingredient preparation of the desired concentration and populating them with Heliothis virescens caterpillars 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.
  • Solvent .30 parts by weight of dimethylformamide 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 and emulsifier and the concentrate is diluted to the desired concentration with water containing emulsifier.
  • Cabbage leaves (Brassica oleracea), which are heavily infested with peach aphids (Myzus persicae), are treated by being dipped into the preparation of active compound of the desired concentration.
  • the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids 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 and emulsifier and the concentrate is diluted with water to the desired concentration.
  • Vessels are filled with sand, active ingredient solution, Meloidogyne incognita egg larva 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.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with larvae of the horseradish leaf beetle (Phaedon cochleariae) while the leaves are still moist.
  • the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • 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 cockroach (Plutella xylostella) 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
  • 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 exigua) 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 and emulsifier, and 1.0 is diluted to the desired amount 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 army worm 15 (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. 20
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • 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.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Amount of emulsifier and dilute the concentrate with water to the desired concentration is required.
  • the active ingredient preparation is poured onto the floor.
  • the concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm (mg / 1). You fill the bottom in 0.25 1 pots and let them stand at 20 ° C.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Soybean shoots (Glycine max) of the Roundup Ready variety (trademark of Monsanto Comp. USA) are treated by dipping into the preparation of active compound of the desired concentration and populated with the tobacco bud caterpillar Heliothis virescens 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.
  • Test animals Lucilia cuprina larvae
  • the active ingredient solution is diluted with water to the desired concentration.
  • Lucilia cuprina larvae About 20 Lucilia cuprina larvae are placed in a test tube containing approx. 1 cm 3 horse meat and 0.5 ml of the active ingredient preparation to be tested. After 48 hours, the effectiveness of the active ingredient preparation is determined as% larval mortality.
  • test tubes are then transferred to beakers with a bottom covered with sand. After a further 12 days, the test tubes are removed and the dolls and flies are counted.
  • the development inhibitory effect is the
  • Test animals sucked nymphs from Amblyomma hebraeum
  • the active ingredient solution is diluted with water to the desired concentration.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pyrrole Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne de nouvelles Δ1-pyrrolines de formule (I), dans laquelle R?1, R2, R3, R4, R5¿, n, r et s ont les significations indiquées dans la description. L'invention concerne également plusieurs procédés pour la production de ces substances, leur utilisation pour lutter contre des parasites, ainsi que de nouveaux produits intermédiaires.
EP01967323A 2000-09-22 2001-09-10 Delta 1-pyrrolines utilisees comme pesticides Withdrawn EP1322604A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10047119 2000-09-22
DE10047119 2000-09-22
DE10051395 2000-10-17
DE10051395A DE10051395A1 (de) 2000-09-22 2000-10-17 DELTA·1·-Pyrroline
PCT/EP2001/010430 WO2002024644A1 (fr) 2000-09-22 2001-09-10 Delta1-pyrrolines utilisees comme pesticides

Publications (1)

Publication Number Publication Date
EP1322604A1 true EP1322604A1 (fr) 2003-07-02

Family

ID=26007146

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01967323A Withdrawn EP1322604A1 (fr) 2000-09-22 2001-09-10 Delta 1-pyrrolines utilisees comme pesticides

Country Status (10)

Country Link
US (1) US20030220386A1 (fr)
EP (1) EP1322604A1 (fr)
JP (1) JP2004509864A (fr)
CN (1) CN1476428A (fr)
AU (1) AU2001287722A1 (fr)
BR (1) BR0114096A (fr)
HU (1) HUP0302964A3 (fr)
IL (1) IL154920A0 (fr)
MX (1) MXPA03002363A (fr)
WO (1) WO2002024644A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10243939A1 (de) * 2002-09-24 2004-04-01 Bayer Cropscience Ag Pyrroline
GB0412492D0 (en) * 2004-06-04 2004-07-07 Sterix Ltd Compound
US8329159B2 (en) * 2006-08-11 2012-12-11 Bristol-Myers Squibb Company Hepatitis C virus inhibitors
JP5643121B2 (ja) * 2010-02-18 2014-12-17 東ソー株式会社 アリール（ジオラート）ボラン類の製造方法
CN114369051B (zh) * 2022-01-06 2023-05-05 青岛农业大学 吡咯烷醇类化合物及其制备方法与应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19648011A1 (de) * 1996-11-20 1998-05-28 Bayer Ag Cyclische Imine
DE19822245A1 (de) * 1998-05-18 1999-11-25 Bayer Ag 2-(2-Methylphenyl)-3,4-dihydro-2H-pyrrol- Derivate
DE19822247A1 (de) * 1998-05-18 1999-11-25 Bayer Ag 2-(2-Chlorphenyl)-3,4-dihydro-2H-pyrrol-Derivate
DE19847076A1 (de) * 1998-10-14 2000-04-20 Bayer Ag 2-Hetaryl-3,4-dihydro-2H-pyrrol-Derivate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0224644A1 *

Also Published As

Publication number Publication date
IL154920A0 (en) 2003-10-31
HUP0302964A2 (hu) 2004-01-28
BR0114096A (pt) 2003-08-19
US20030220386A1 (en) 2003-11-27
AU2001287722A1 (en) 2002-04-02
HUP0302964A3 (en) 2004-06-28
CN1476428A (zh) 2004-02-18
JP2004509864A (ja) 2004-04-02
MXPA03002363A (es) 2004-09-10
WO2002024644A1 (fr) 2002-03-28

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