WO2000035285A1 - 4-haloalkyl-3-heterocyclylpyridines et 4-haloalkyl-5-heterocyclylpyrimidines et leur utilisation comme repulsifs - Google Patents

4-haloalkyl-3-heterocyclylpyridines et 4-haloalkyl-5-heterocyclylpyrimidines et leur utilisation comme repulsifs Download PDF

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WO2000035285A1
WO2000035285A1 PCT/EP1999/009949 EP9909949W WO0035285A1 WO 2000035285 A1 WO2000035285 A1 WO 2000035285A1 EP 9909949 W EP9909949 W EP 9909949W WO 0035285 A1 WO0035285 A1 WO 0035285A1
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radicals
alkyl
group
cycloalkyl
alkenyl
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PCT/EP1999/009949
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German (de)
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Werner Knauf
Andrew Charles Chapple
Eva Wojtech
Burkhard Rook
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Aventis Cropscience Gmbh
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Priority to AU26609/00A priority Critical patent/AU2660900A/en
Publication of WO2000035285A1 publication Critical patent/WO2000035285A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • 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
    • C07D417/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D417/14—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 three or more hetero rings

Definitions

  • repellents are understood to be agents that have a defensive or expelling effect on other living beings, in particular pests and nuisances. Many of the agents, due to their unpleasant taste or smell, cause the animals to move away from e.g. Keep food or certain places away.
  • the invention therefore relates to the use of compounds of the formula (I) as repellents,
  • X is CH or N; m 0 or 1;
  • Q is a 5-atom heterocyclic group "N ⁇ 3
  • R 1 is hydrogen
  • -S0 2 R 10 , -PW 2 R 10 2 and -PW 3 R 10 is substituted, heterocyclyl, which optionally with one or more radicals from the group
  • R 2 and R 3 independently of one another have the definitions given in R 1 or
  • R 2 and R 3 together form a 5- to 7-membered ring which can be partially or completely unsaturated and interrupted by one or more atoms from the group consisting of nitrogen, oxygen and sulfur, but not more than one oxygen atom may be directly adjacent and the Ring is optionally substituted by one or more, but at most 5, radicals R 1 ;
  • R 4 and R 6 independently of one another have the definitions given in R 1 or
  • R 4 and R 6 together form a 4- to 7-membered ring which can be partially or completely unsaturated and can be interrupted by one or more atoms from the group consisting of nitrogen, oxygen and sulfur, but not more than one oxygen atom may be directly adjacent, and the ring is optionally substituted by one or more, but at most 5, radicals R 1 ; R 5 and R 7 are independently hydrogen,
  • R 4 and R 5 together form a 4- to 7-membered ring which can be partially unsaturated and interrupted by one or more atoms from the group consisting of nitrogen, oxygen and sulfur, but not more than one oxygen atom may be directly adjacent, and the ring is optionally substituted by one or more but a maximum of 5 radicals R 1 or
  • R 8 is hydrogen
  • the fourteen latter radicals optionally having one or more radicals from the group
  • Aryl which may be one or more radicals from the group Halogen, cyano, nitro, hydroxy, thio, amino, formyl, (d-C ⁇ J-alkoxy, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyloxy, (d-CeJ-haloalkyloxy, (C 2 -C 6 ) haloalkenyloxy, (C 2 -C 6 ) haloalkynyloxy, (C 3 -C 8 ) cycloalkoxy, (C 4 -C 8 ) cycloalkenyloxy, (C 3 -C 8 ) halocycloalkoxy, (C 4 -C 8 ) halocyclo-alkenyloxy, carbamoyl, (dC 6 ) -mono- or dialkylcarbamoyl, (C ⁇ -C 6 ) -alkoxycarbonyl, (CrC 6 )
  • Cycloalkenyl (Cs-C ⁇ J-cycloalkyl-CCi-Ct ⁇ alkyl, (C 4 -C 8 ) -cycloalkenyl- (-C-C 4 ) -alkyl, (C 3 -C 8 ) -cycloalkyl- (C 2 -C 4 ) Alkenyl, (C 4 -C 8 ) cycloalkenyl (dC 4 ) alkenyl, the nine latter radicals optionally having one or more radicals from the group
  • Halogen, cyano, (dC 6 ) alkoxy, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyloxy and (-C-C 6 ) -haloalkyloxy are substituted;
  • Monoalkylamino and (dC- dialkylamino is substituted, NR 10 2l OR 10 or SR 10 .
  • Halogen includes fluorine, chlorine, bromine and iodine.
  • (C 1 -C 4 ) alkyl is an unbranched or branched
  • Hydrocarbon radical having 1, 2, 3 or 4 carbon atoms such as the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl radical.
  • alkyl radicals with a larger range of carbon atoms are to be understood as an unbranched or branched saturated hydrocarbon radical which contains a number of carbon atoms which corresponds to this range specification.
  • the expression "(C 1 -C 6 ) alkyl” accordingly encompasses the abovementioned alkyl radicals and, for example, the pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, hexyl radical.
  • (C 1 -C 10 ) alkyl means the abovementioned alkyl radicals and, for example, the nonyl, 1-decyl or 2-decyl radical and the expression "(C 1 -C 2 o) -Alkyl "means the abovementioned alkyl radicals and, for example, the undecyl, dodecyl, pentadecyl or eicosyl radical.
  • alkyl group in which one or more hydrogen atoms are replaced by the same number of identical or different halogen atoms, preferably chlorine or fluorine, such as the trifluoromethyl, the 1-fluoroethyl, the 2,2,2-trifluoroethyl, the chloromethyl -, Fluoromethyl, the difluoromethyl and the 1, 1, 2,2-tetrafluoroethyl group.
  • halogen atoms preferably chlorine or fluorine, such as the trifluoromethyl, the 1-fluoroethyl, the 2,2,2-trifluoroethyl, the chloromethyl -, Fluoromethyl, the difluoromethyl and the 1, 1, 2,2-tetrafluoroethyl group.
  • alkenyl and alkynyl with a prefixed range of carbon atoms mean a straight-chain or branched hydrocarbon radical with a number of carbon atoms corresponding to this range, which contains at least one multiple bond, which can be located at any position of the unsaturated radical in question.
  • (C 2 -C 4 ) alkenyl thus stands for example for the vinyl, allyl, 2-methyl-2-propene or 2-butenyl group
  • (C 2 -C 6 ) alkenyl stands for the abovementioned radicals and, for example, for the pentenyl, 2-methylpentenyl or the hexenyl group.
  • (C 2 -C 2o) alkenyl includes the radicals mentioned above and, for example, that
  • (C 2 -C 4 ) alkynyl stands for example for the ethynyl, propargyl, 2-methyl-2-propyne or 2-butynyl group.
  • (C 2 -C 6 ) alkynyl are the radicals mentioned above and, for example, the 2-pentynyl or the 2-hexynyl group and under "(C 2 -C 20 ) alkynyl" the abovementioned
  • (C 3 -C 8 ) cycloalkyl stands for monocyclic alkyl radicals, such as the cyclopropyl
  • (-C-C 4 ) alkoxy- (CrC6) alkyloxy means an alkoxy group as defined above which is substituted by a further alkoxy group, such as 1-ethoxyethoxy.
  • (C 3 -C 8 ) cycloalkoxy or "(C 3 -C 8 ) cycloalkylthio” is one of the (C 3 -C 8 ) cycloalkyl radicals mentioned above which is linked via an oxygen or sulfur atom , to understand.
  • (C 3 -C 8 ) cycloalkyl- (C 1 -C 6 ) alkoxy means, for example, cyclopropylmethoxy
  • (C r C 4 ) alkyl (C 3 -C 8 ) cycloalkoxy stands for example for the methylcyclopropyloxy, methylcyclobutyloxy or the butylcyclohexyloxy group.
  • (C 1 -C 6 ) alkylsulfinyl means, for example, methyl, ethyl, propyl, isopropyl
  • (-C-C 6 ) alkylamino represents a nitrogen atom which is substituted by one or two, identical or different alkyl radicals of the above definition.
  • (C C ⁇ J-mono- or dialkylcarbamoyl) means a carbamoyl group with one or two hydrocarbon radicals which have the meaning given under the expression "(dC 6 -alkyl)" and which can be the same or different in the case of two hydrocarbon radicals .
  • (CrC 6 ) -dihaloalkylcarbamoyl means a carbamoyl group which carries two (dC 6 ) -haloalkyl radicals as defined above or one (dC 6 ) -haloalkyl radical and one (-C-C 6 ) alkyl radical as defined above.
  • (-C-C 6 ) alkanoyl stands for example for the acetyl, propionyl, butyryl or 2-M ethyl butyryl group;
  • aryl is to be understood as meaning a carbocyclic aromatic radical, that is to say composed of carbon atoms, having preferably 6 to 14, in particular 6 to 12, carbon atoms, such as phenyl, naphthyl or biphenylyl, preferably phenyl.
  • Aroyl accordingly means an aryl radical as defined above which is bonded via a carbonyl group, such as, for example, the benzoyl group.
  • heterocyclyl stands for a cyclic radical which can be fully saturated, partially unsaturated or fully unsaturated and which is interrupted by one or more identical or different atoms from the group nitrogen, sulfur or oxygen, but not directly adjacent to two oxygen atoms may be and at least one carbon atom must be present in the ring, such as a residue of thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1, 3,4-oxadiazole, 1, 3,4- Thiadiazole, 1, 3,4-triazole, 1, 2,4-oxadiazole, 1, 2,4-thiadiazole, 1, 2,4-triazole, 1, 2,3-triazole, 1, 2,3,4- Tetrazole, benzo [b] thiophene, benzo [b] furan, indole, benzo [c] thiophene, benzo [c] furan, isoind
  • Aryl radical e.g. the benzyloxy, phenylethoxy, phenylbutoxy or naphthylmethoxy radical.
  • Arylthio means an aryl residue linked via a sulfur atom, e.g. the phenylthio or the 1- or 2-naphthylthio radical.
  • aryloxy means e.g. the phenoxy or 1- or 2-naphthyloxy radical.
  • Aryl- (C 1 -C 4 ) alkylthio stands for an aryl radical which is linked via an alkylthio radical, for example the benzylthio, naphthylmethylthio or the phenylethylthio radical.
  • (CrC6) -trialkylsilyl means a silicon atom which bears three identical or different alkyl radicals as defined above.
  • aryl- (C ⁇ -C ⁇ J-dialkylsilyl for a silicon atom which carries an aryl radical and two identical or different alkyl radicals as defined above
  • diaryl- (-C ⁇ -C 6 ) alkylsilyl for a silicon atom which has an alkyl radical and carries two identical or different aryl radicals as defined above
  • triarylsilyl for a silicon atom bearing three identical or different aryl radicals as defined above.
  • Preferred compounds of the general formula (I) are those in which
  • Q is a 5 atom heterocyclic group
  • R 1 , R 2 , R 3 , R 4 and R 6 each independently of one another are hydrogen, halogen,
  • R 5 and R 7 each independently of one another are hydrogen, halogen, CrCi2-alkyl, C 3 -C 8 -cyclo-alkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, the latter four hydrocarbon radicals optionally being or polysubstituted by identical or different radicals containing from a group A2 C ⁇ -C 6 alkylcarbonyl, Ci-Ce-alkylaminocarbonyl, C 1 -C- 6 - alkoxy, C ⁇ -C 6 alkylthio, C ⁇ -C 6 -alkylamino, CrC ⁇ - Alkylcarbonylamino, phenyl, furyl, pyrryl, thienyl, halogen, cyano, phenyloxy, phenylthio and phenylamino, the ten first-mentioned radicals from group A2 optionally being replaced one or more times by identical or different radicals from group B1 and
  • R 10 is hydrogen, benzyl, CC 6 alkyl, CC 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, phenyl, CC 6 alkylcarbonyl or d-Ce-alkylsulfonyl, the eight last-mentioned radicals optionally being substituted one or more times by identical or different halogen atoms.
  • R 1 , R 2 , R 3 , R 4 and R 6 each independently of one another halogen, C Ci 2 alkyl,
  • C2-Ci2-alkenyl the latter two radicals optionally having one or more of the same or different radicals from a group A3 containing C 1 -C 4 -alkycarbonyl, C 1 -C 4 -alkylaminocarbonyl, -C 4 -alkoxy, dC -alkylthio , dd-alkylamino, CC 4 - alkylcarbonylamino, CC -alkylsulfonylamino, phenyl, furyl, pyrryl, thienyl, fluorine, chlorine, bromine, cyano, phenyloxy, phenylthio and phenylamino, the eleven first-mentioned radicals of group A3 optionally one or more times OR 10 , SR 10 or N (R 10 ) 2 are substituted by identical or different radicals from group B1 and the last three radicals from group A3, each optionally one or more times by identical or different radicals from group B2
  • R 5 and R 7 are each, independently of one another, halogen, d-Ci 2 -alkyl, C 2 -C ⁇ 0 -alkenyl, the latter two radicals optionally being replaced one or more times by identical or different radicals from a group A4 containing dC 4 -alkylcarbonyl, C 1 -C 4 alkylaminocarbonyl, dC 4 - alkoxy, C 1 -C 4 alkylthio, dd-alkylamino, dd-alkylcarbonylamino, phenyl, furyl, pyrryl, thienyl, fluorine, chlorine, bromine, cyano, phenyloxy, phenylthio and phenylamino, where the ten first-mentioned radicals of group A4, if appropriate one or more times by identical or different radicals from group B1 and the three last-mentioned radicals of group A4, if appropriate one or more are substituted several times
  • R 10 is hydrogen, dC 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, phenyl, dd-
  • Alkenyl the latter two radicals optionally being substituted one or more times by identical or different radicals from a group A5 containing C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkylaminocarbonyl, dd-alkoxy, C 1 -C 4 -alkylthio, CC 4 - Alkylamino, CC 4 - alkylcarbonylamino, -CC 4 -alkylsulfonylamino, phenyl, fluorine, chlorine, bromine, cyano, phenyloxy, phenylthio and phenylamino, the eight first-mentioned radicals of group A5 optionally being made one or more times by identical or different radicals the group B1 and the last three radicals of the group A5 optionally substituted one or more times by identical or different radicals from the group B2, are substituted; R 5 and R 7 are each independently C ⁇ -C ⁇ o-alkyl, C 2
  • the compounds of the general formula (I) have acidic or basic properties and can form salts. If the compounds of the general formula (I) carry, for example, groups such as hydroxyl, carboxy or other acid-inducing groups, these compounds can be reacted with bases to form salts.
  • bases are, for example, hydroxides, carbonates, hydrogen carbonates of the alkali and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, furthermore ammonia, primary, secondary and tertiary amines with (Ci-d) - alkyl radicals and mono-, di- and Trialkanolamines of (dC 4 ) alkanols.
  • the compounds of the general formula (I) carry, for example, groups such as amino, alkylamino or other groups which induce basic properties, these compounds can be reacted with acids to form salts.
  • suitable acids are, for example, mineral acids, such as hydrochloric, sulfuric and phosphoric acids, organic acids, such as acetic acid and oxalic acid, and acidic salts, such as NaHS04 and KHS04.
  • the salts obtainable in this way also have insecticides, acaricidal and nematicidal properties.
  • the compounds of the general formula (I) can have one or more asymmetric carbon atoms or stereoisomers on double bonds. Enantiomers or diastereomers can therefore occur.
  • the invention encompasses both the pure isomers and their mixtures.
  • the mixtures of diastereomers can be separated into the isomers by customary methods, for example by selective crystallization from suitable solvents or by chromatography. Racemates can be separated into the enantiomers by customary methods.
  • R 1 is as defined in formula (I).
  • an acid halide, an ester or an anhydride can be used as the activated derivative.
  • Suitable bases are amines, such as triethylamine, diisopropylethylamine, pyridine or lutidine, alkali metal hydroxides, alkali metal alcoholates, such as sodium ethanolate or potassium tert-butanolate, or alkyl metal compounds, such as butyllithium.
  • the reaction described can be carried out as a one-step process or as a two-step process, with compounds of the formula (IV) being run through:
  • Compounds of formula (IV) can be cyclized to the 1,2,4-oxadiazoles at temperatures up to 180 ° C. by heating in an inert solvent.
  • Compounds of the formula (IV) are also directly accessible from the acid of the formula (II) and amidoximes of the formula (III) by using a dehydrating reagent such as dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylamino-propyl) carbodiimide or N, N'-carbonyldiimidazole.
  • the compounds of the formula (I) can be obtained in a manner known from the literature from the reaction of a compound of the formula (VII) with an electrophilic aminating reagent, such as hydroxylamine-O-sulfonic acid ( Y. Lin, SA Lang, SR Petty, J. Org. Chem. 1980, 45, 3750).
  • an electrophilic aminating reagent such as hydroxylamine-O-sulfonic acid
  • Amidoximes of the formula (V) can be reacted with activated derivatives of the acids of the formula (VI) or with the acids of the formula (VI) themselves.
  • Acid hydrazides of the formula (XI) can also be reacted with orthoesters of the formula (XII) in which R 1 is as defined above and R 12 is (CrC 4 ) alkyl.
  • the reaction can be carried out with or without a solvent and with or without an activating reagent.
  • a hydrocarbon such as toluene or an ether such as 1, 2-dimethoxyethane can be used as the solvent.
  • Phosphorus oxychloride is an example of an activating reagent.
  • the reaction temperature is generally the reflux temperature of the solvent.
  • Inorganic acid chlorides such as phosphorus oxychloride or thionyl chloride
  • inorganic acids such as sulfuric acid or polyphosphoric acid, or a mixture of phosphoric acid and acetic anhydride (Houben-Weyl, Methods of Organic Chemistry, Volume E8a, pages 935 - 941) can be used as the dehydrating reagent.
  • the reaction can be carried out without or in a solvent. Suitable solvents are inert, such as toluene, benzene, dimethoxyethane, dimethylformamide, dimethylacetamide and chlorobenzene.
  • the reaction temperature is advantageously in a range between 50 ° C and 150 ° C.
  • Compounds of the formula (XIV) can be obtained, for example, by oxidation of the corresponding hydroxy compound of the formula (XV), it being possible to use all the reagents customarily used for this purpose in organic chemistry (see, for example, Milos Hudlicky, "Oxidations in Organic Chemistry", ACS Monograph 186, American Chemical Society, Washington, DC, 1990)
  • the compounds of the formula (I) can be obtained by condensing thioamides of the formula (XVII) with carbonyl derivatives of the formula (XVIII), where Z is halogen, in particular chlorine or bromine, acyloxy or Sulfonyloxy, especially methanesulfonyloxy or tolylsulfonyloxy means.
  • Compounds of the formula (XV) can be obtained by reacting activated derivatives of the acid in the formula (II) with ⁇ -amino alcohols of the formula (XVI), if appropriate with the participation of a base, e.g. Triethylamine, in an inert solvent, e.g. Dichloromethane, accessible.
  • a base e.g. Triethylamine
  • an inert solvent e.g. Dichloromethane
  • An acid halide or an anhydride can be used as the activated derivative of the acid.
  • the compounds of the formula (I) can be prepared by reacting thioamides of the formula (XVII) with compounds of the formula (XIX), the two substituents Z being as defined above and can either be the same or different (AR Katritzky "Comprehensive Heterocyclic Chemistry", Volume 6, page 306 312, Pergamon Press, Oxford).
  • Thioamides of the formula (XVII) are either commercially available or can be obtained by adding hydrogen sulfide to the corresponding carbonitriles in the presence of a base (A.E.S. Fairfull, J.L. Löwe, D.A. Peak, J. Chem. Soc. 1952, 742).
  • This reaction can be carried out with or without the use of a solvent, alcohols such as ethanol and propanol or aromatic hydrocarbons such as toluene and xylene being used as solvents. If the reaction is carried out in a solvent, the reflux temperature of the solvent is expediently chosen as the reaction temperature. If, on the other hand, the reaction is carried out without a solvent, it can optionally be heated up to 200.degree.
  • radicals R 1 to R 9 can, if desired, be further derivatized, the wide range of methods of organic chemical synthesis being able to be used.
  • compounds of formula (I) in which m is 0 can be reacted with an oxidation reagent, e.g. meta-chloroperbenzoic acid.
  • an oxidation reagent e.g. meta-chloroperbenzoic acid.
  • Repellent in the sense of the connection is a substance or mixture of substances that has a defensive or expelling effect on other living beings, in particular pests and nuisances.
  • the term also includes effects such as the antifeeding effect, in which food intake is disturbed or prevented (antagonistic effect), suppression of egg laying or influencing population development.
  • the invention therefore also relates to the use of compounds of the formula (I) in order to achieve the effects mentioned, in particular in the pests mentioned in the biological examples.
  • the invention also relates to a method for repelling or expelling harmful organisms, one or more compounds of the formula (I) being applied at the location from which the harmful organisms are to be kept or sold.
  • spreading can mean, for example, treatment of the plant or of the seed.
  • the compounds of the formula (I) are notable for the fact that, if one wishes to take advantage of the effects mentioned above, the agent is applied at an earlier point in time than is customary in the case of direct control. The effect often lasts for a very long time, so that a duration of action of often more than 2 months is achieved.
  • insects in particular insects, arachnids (Acarina), helminths and molluscs, very particularly preferred over insects and arachnids, which occur in agriculture, animal husbandry, in forests, in the protection of stored goods and materials as well as in the hygiene sector. They are against normally sensitive and resistant species as well as all or individual stages of development effective.
  • the pests mentioned above include:
  • Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp.
  • Rhipicephalus spp. Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,
  • Chorioptes spp. Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Eotetranychus spp., Oligonychus spp., Eutetranychus spp ..
  • Thysanura e.g. Lepisma saccharina.
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
  • Trialeurodes vaporariorum Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis,
  • Aspidiotus hederae, Pseudococcus spp., Psylla spp .. From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Agristella sppber, Bucculisellappl ., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nu
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp.
  • Dacus oleae Tipula paludosa.
  • Arachnida for example Scorpio maurus, Latrodectus mactans.
  • helminths for example Haemonchus, Trichostrongulus, Ostertagia, Cooperia, Chabertia, Strongyloides, Oesophagostomum, Hyostrongulus, Ancylostoma, Ascaris and Heterakis as well as Fasciola.
  • Gastropoda e.g. Deroceras spp., Arion spp., Lymnaea spp., Galba spp., Succinea spp., Biomphalaria spp., Bulinus spp., Oncomelania spp ..
  • Bivalva e.g. Dreissena spp ..
  • Plant parasitic nematodes which can be controlled according to the invention include, for example, the root parasitic soil nematodes, such as those of the genera Meloidogyne (root-knot nematodes such as Meloidogyne incognita, Meloidogyne hapla and Meloidogyne javanica), Heterodera and Globodera (cyst-forming nematodes, such as Globodera rostochiensis, Globodera pallida, Heterodera trifolii) and of the genera Radopholus, such as Radopholus similis, Pratylenchus such as Pratyglenchus neglectus, Pratylenchus penetrans and Pratylenchus curvitatus;
  • the root parasitic soil nematodes such as those of the genera Meloidogyne (root-knot nematodes such as Meloidogyne incognita, Meloidogyne
  • Tylenchulus such as Tylenchulus semipenetrans, Tylenchorhynchus, such as Tylenchorhynchus dubius and Tylenchorhynchus claytoni, Rotylenchus such as Rotylenchus robustus, Heliocotylenchus such as Haliocotylenchus multicinctus, Belonoaimus such as Belonoaimus Trachusususus longusus x longus.
  • the compounds of the invention can also be used to combat the nematode genera Ditylenchus (stem parasites such as Ditylenchus dipsaci and Ditylenchus destructor), Aphelenchoides (leaf nematodes such as Aphelenchoides ritzemabosi) and Anguina (flower nematodes such as Anguina tritici).
  • Ditylenchus stem parasites such as Ditylenchus dipsaci and Ditylenchus destructor
  • Aphelenchoides leaf nematodes such as Aphelenchoides ritzemabosi
  • Anguina flower nematodes such as Anguina tritici
  • the invention also relates to an agent for repelling harmful organisms (repellants) containing one or more compounds of the formula (I) in addition to one or more suitable formulation auxiliaries.
  • the agents according to the invention generally contain from 0.1 to 95% by weight of the active compounds of the formulas (I). They can be formulated in different ways, depending on how it is specified by the biological and / or chemical-physical parameters. Possible formulation options include:
  • WP Wettable powder
  • EC emulsifiable concentrates
  • SL aqueous solutions
  • SC oil or water-based dispersions
  • SE suspoemulsions
  • SE suspoemulsions
  • DP dusts
  • mordants granules in the form of , Spray, elevator and adsorption granules
  • WG water-dispersible granules
  • ULV formulations waxes or microcapsules.
  • the necessary formulation aids i.e. Carrier and / or surface-active substances, such as inert materials, surfactants, solvents and other additives, are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J .; H. v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N.Y .; Marsden, “Solvent Guide,” 2nd Ed., Interscience, N.Y. 1950; McCutcheon's, “Detergents and Emulsifiers Annual", MC Publ.
  • Carrier and / or surface-active substances such as inert materials, surfactants, solvents and other additives
  • Spray powders are preparations which are uniformly dispersible in water, in addition to the active ingredient a diluent or inert substance also contain wetting agents, for example polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenol sulfonates and dispersants, for example sodium lignosulfonate, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium.
  • wetting agents for example polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenol sulfonates and dispersants, for example sodium lignosulfonate, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium.
  • Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers.
  • organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons.
  • alkylarylsulfonic acid calcium salts such as cadodecylbenzene sulfonate
  • nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide / ethylene oxide condensation products, alkyl polyethers, sorbitan fatty acid or fatty acid sorboxyl ester, polyoxyethylene esters or fatty acid sorbitan polyethylsorboxy or fatty acid sorbitates or polyoxyethylene sorbitates.
  • Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. Talc, natural clays such as kaolin, bentonite, pyrophillite or diatomaceous earth.
  • Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. Polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material.
  • Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules — if desired in a mixture with fertilizers.
  • the active substance concentration in wettable powders is usually about 10 to 90% by weight, the remainder to 100% by weight consists of customary formulation components. In the case of emulsifiable concentrates, the active substance concentration can be approximately 5 to 80% by weight. Dust-like formulations usually contain 5 to 20% by weight of active ingredient, sprayable solutions about 2 to 20% by weight. In the case of granules, the active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulation aids, fillers, etc. are used. In addition, the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers or carriers.
  • the concentrates present in the commercial form are optionally diluted in a customary manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and sometimes also for microgranules using water. Dust-like and granulated preparations as well as sprayable solutions are usually no longer diluted with other inert substances before use.
  • the required application rate varies. It can fluctuate within wide limits, e.g. between 0.0005 and 10.0 kg / ha or more of active substance, but is preferably between 0.001 and 5 kg / ha.
  • the active compounds according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations in mixtures with other active compounds, such as sterilants, growth-regulating substances, acaricides, insecticides, nematicides, fungicides or herbicides.
  • the insecticides and acaricides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, formamidines, tin compounds, substances produced by microorganisms and others.
  • Preferred mixing partners are 1. from the group of phosphorus compounds
  • Alanycarb (OK-135), Aldicarb, 2-sec-butylphenylmethylcarbamate (BPMC), Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Benfuracarb, Ethiofencarb, Furathiocarb, HCN-801, Isoprocarb, Methomyl, 5-Methyl-m-cumenylbutyryl ( carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, 1-methylthio (ethylideneamino) -N-methyl-N- (morpholinothio) carbamate (UC 51717), triazamate;
  • the active substance content of the use forms prepared from the commercially available formulations can be from 0.00000001 to 95% by weight of active substance, preferably between 0.00001 and 1% by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • the repellents according to the invention are also suitable against endoparasites and ectoparasites in the veterinary field or in the field of animal husbandry.
  • the active compounds according to the invention are used here in a known manner, such as by oral use in the form of, for example, tablets, capsules, drinkers, granules, by dermal use in the form of, for example, dipping (dipping), spraying (spraying), pouring on (pour-on and spot) -on) and powdering and by parenteral use in the form of, for example, injection.
  • the compounds of the formula (I) can accordingly also be particularly advantageous in animal husbandry (for example cattle, sheep, pigs and poultry such as chickens and geese) etc.) can be used.
  • animal husbandry for example cattle, sheep, pigs and poultry such as chickens and geese
  • the compounds if appropriate in suitable formulations and if appropriate with the drinking water or feed, are administered to the animals orally. Since excretion in the faeces is effective, the development of insects in the faeces of the animals can be prevented very easily in this way.
  • the appropriate dosages and formulations depend in particular on the type and stage of development of the livestock and also on the infestation pressure and can be easily determined and determined using the usual methods.
  • the new compounds can be used in cattle, for example, in doses of 0.01 to 1 mg / kg body weight.
  • the repellents of the formula (I) according to the invention have an outstanding systemic action.
  • the active substances can therefore also be introduced into the plants via parts of plants, both underground and above ground (roots, stems, leaves), if the repellents are applied in liquid or solid form to the immediate vicinity of the plant (e.g. granules in the soil application, application in flooded rice fields).
  • the repellents according to the invention can be used in a special way for the treatment of vegetative and generative propagation material, such as, for example, seeds from, for example, cereals, vegetables, cotton, rice, sugar beet and other crops and ornamental plants, onions, cuttings and tubers of other vegetatively propagated crops. and ornamental plants.
  • the treatment for this can take place before the sowing or planting process (e.g. by special techniques of seed coating, by dressing in liquid or solid form or seed box treatment), during the sowing process or planting or after the sowing or planting process by special application techniques (eg seed row treatment).
  • the amount of active ingredient used can vary over a wide range depending on the application. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil.
  • the compounds of the formula (I) are also outstandingly suitable as repellents in the home and garden, in particular for repelling / expelling flies, mosquitoes and cockroaches, in particular Blatella germanica and Periplanta american
  • connection therefore also relates to the use of an agent according to the invention as a repellent in the home and garden.
  • the compound of the formula (I) according to the invention can also be combined as a mixture with other pesticides, preferably from the group of the abovementioned.
  • Corresponding agents are used in this area, for example, as solutions, aerosols, combustible solids (so-called combustible coils), as solids / powders, from which the active substance is then released thermally, for example by electrical heating.
  • the repellents are advantageously used in the home as an incense mixture and in the form of aerosols based on water or solvents.
  • the repellent can contain a combustible or non-combustible material, for example in the form of the known spirals.
  • the active ingredient is released, for example, by electrical heating.
  • Suitable carriers are pyrethrum mar ⁇ , taboo powder, pyrethrum stem powder, sawdust, starch and coconut flour.
  • the dose of the active ingredient is, for example, 0.005-1% by weight. If a non-combustible carrier is selected, the active substance dose is, for example, 0.05-95
  • the repellent according to the invention can also be used as a combustible oil (lamp oil) and then soaks, for example, a wick, which is then ignited can.
  • a combustible oil lamp oil
  • Such an oil preferably contains the active ingredient in a concentration of 0.05-95% by weight.
  • the use of the repellents according to the invention includes any other application in which compounds of the formula (I) act.
  • Such indirect applications can be, for example, the use of compounds which, for example in the soil or in the plant, decompose or degrade to form compounds of the formula (I).
  • a dusting agent is obtained by mixing 10 parts by weight of active ingredient and 90 parts by weight of talc as an inert substance and comminuting them in a hammer mill.
  • a wettable powder which is readily dispersible in water is obtained by adding 25 parts by weight of active ingredient, 65 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyl taurine as a wetting agent. and dispersant mixes and grinds in a pin mill.
  • a dispersion concentrate which is readily dispersible in water is prepared by mixing 40 parts by weight of active compound with 7 parts by weight of a sulfosuccinic acid half-ester, 2 parts by weight of a lignosulfonic acid sodium salt and 51 parts by weight of water and in a attritor ground to a fineness of less than 5 microns.
  • An emulsifiable concentrate can be prepared from 15 parts by weight of active ingredient, 75 parts by weight of cyclohexane as solvent and 10 parts by weight of oxyethylated nonylphenol (10 EO) as emulsifier.
  • Granules can be produced from 2 to 15 parts by weight of active ingredient and an inert granule carrier material such as attapulgite, pumice granules and / or quartz sand.
  • a suspension of the wettable powder from example b) having a solids content of 30% is expediently used and sprayed onto the surface of an attapulgite granulate, dried and mixed intimately.
  • the proportion by weight of the wettable powder is approximately 5% and that of the inert carrier material approximately 95% of the finished granulate.
  • Ph phenyl THP: 2-tetrahydropyranyl
  • the compounds show "antifeeding" properties, which e.g. can be demonstrated in beetles (Lepidoptera).
  • Freeze-dried feed cubes for Anthonomus grandis (cotton boll weevil), with a size of approx. 2x2x2 cm, were immersed in a spray mixture which consisted of an aqueous emulsion of an EC 20 formulation and the concentration of which, based on the active substance, was 1000 ppm in the compounds according to the invention.
  • a spray mixture which consisted of an aqueous emulsion of an EC 20 formulation and the concentration of which, based on the active substance, was 1000 ppm in the compounds according to the invention.
  • the cubes were dried on a sheet of filter paper.
  • a treated cube and an untreated cube (dipped in clear water) were placed next to each other at a small distance into a container (approx. 20 x 20 cm) and 10 adults (3 days old) from Anthonomus grandis were added to each.
  • the container was closed with a lid and stored in the laboratory at about 22 ° C. and observed for 14 days.
  • each plant bowl was placed in a wire gauze cage next to an untreated plant bowl and 20 individuals, three to four days old, of Colorado potato beetles were entered per cage.
  • the cages were then placed in a climatic chamber at 25 ° C. with a light / dark rhythm of 16/8 hours and after 4 days the potato beetle had eaten on the potato plants.
  • Plant protection could also be achieved with the thrips species Frankliniella occidentalis, e.g. the connections were brought to the roots of the plants.
  • Cotton plants were sown and treated as described in Example 6. Compounds according to the invention were added to the individual seeds as granule formulations in dosages of 30, 10 and 3 mg ai. After growing up and reaching the four-leaf stage, each plant was individually infected with a mixed population of the thrips species Frankliniella occidentalis. This was achieved by holding plants populated with thrips over those to be infected and brushing the animals over with a brush. With this action, an average of 20 - 40 animals were transferred and brought to the treated plants. Thereafter, hoods made of transparent plastic tubes, which contained an upper opening made of fine gauze, were placed over each plant and kept in the greenhouse at about 23 to 26 ° C. for 14 days. The feeding damage was then assessed.
  • Example 4 Example 4
  • An antifeeding effect could be determined when cotton plants had been sprayed with the compounds and the larvae of the butterfly Spodoptera litoralis could eat on the leaves.
  • Cotton plants (four-leaf stage) were sprayed from above with the aid of a track sprayer with an aqueous emulsion of an EC 20 formulation of two compounds according to the invention until the draining stage.
  • the aqueous emulsions were adjusted to ai concentrations of 300, 100, 30 and 10 ppm.
  • individual sheets were removed from the Plants removed and inserted with the petioles into small pipette tips filled with water.
  • the leaves After sealing the pipette neck with a little cotton, the leaves were placed individually next to a similar but untreated leaf in boxes (20X20 cm) and these were each loaded with 10 larvae (L1) of the butterfly species Spodoptera litoralis. The feed was regularly rated up to 10 days after the start of the experiment.
  • the tested compounds showed a decrease in the oviposition in the females of the cabbage moth Plutella xylostella on cabbage plants.
  • Example 6 In a manner similar to that in Example 6, the egg-laying behavior of the cotton capsule beetle Anthonomus grandis was disturbed and the number of egg-laying was reduced as soon as the beetle carried out its ripening action on cotton plants treated with compounds according to the invention.
  • Cotton seed was placed on the bottom of 4 cm deep holes in the soil of a plant pot (1 seed per hole) and granules were given a formulation of two compounds according to the invention in the holes, so that 10 mg (a.i.) of the granules was added to each seed.
  • the holes were then closed and the pots were placed in the greenhouse at about 27 ° C. After reaching a height of approx. 30 cm (2-4 leaf stages), 20 newly hatched adults of Anthonomus grandis were added to the plants and these were kept together in cages for 3 days so that the animals could carry out their ripening feed on the treated cotton plants.
  • the beetles were then brought together in a box (20 x 20 cm) with a cube (2 x 2 x 2 cm) of freshly prepared egg laying diet, where they could lay eggs.
  • the cube was removed at intervals and exchanged for a fresh one.
  • the egg-coated was washed out under water and the laid eggs obtained and counted using a fine sieve.
  • Whitefly Plants of the Phaseolus vulgaris broad bean were produced by the same method as described in Example 6 and a granulate formulation (FG02) was added to each seed hole, so that a dosage of 10 resp. 1 mg ai per plant was reached. After 3 weeks in the greenhouse at temperatures between 24 and 28 ° C the plants in the two-leaf stage so that two of them together with two untreated plants could be placed in a cage with a base area of 70 x 70 cm. The plants were compared in pairs so that one treated and one untreated plant alternated clockwise.
  • FG02 granulate formulation
  • a repellent effect could also be demonstrated when the plants were sprayed with an aqueous emulsion of an EC 20 formulation of the test preparations and Trialeurodes vaporariorum also served as test animals.
  • Example 10 The plants for this experiment were prepared in the same manner as for Example 8. After reaching the two-leaf stage, the plants were treated with an aqueous emulsion of an EC 20 formulation in a concentration of 100 ppm (ai). After the spray coating had dried, the plants were caged in the same way as in Example 8, and 100 white fly adults were also placed in the cages. After 24 and 96 hours, the number of whiteflies on the underside of the leaves was counted.
  • ai aqueous emulsion of an EC 20 formulation in a concentration of 100 ppm
  • the population development of the black bean louse Aphis fabae was observed in Vicia faba.
  • the seeds were placed individually on the bottom of holes about 4 cm deep, which were pressed into the soil by plant pots, and then granulate formulation (FG02) of compounds according to the invention was applied in the respective dosage given in the table.
  • FG02 granulate formulation
  • each plant was infected with a piece of leaf containing 50 to 70 lice as the starting population. After this leaf piece dried out, the aphids spread over the plant and formed a new population.
  • a transparent plastic tube was placed over each plant pot, which contained a ventilation opening closed with fine gauze at the upper end.
  • Seed of the bean Phaseolus vulgaris was sown and treated as in Example 10 and after reaching the two-leaf stage, each leaf of a plant was populated with 10 females of the mite by means of a brush hair. After translating the animals, the plants were also covered with transparent plastic hoods, as in the previous example. After 35 days in the greenhouse and after growing the plants to the 6-8 leaf stage, after careful The population strengths were determined under the stereomicroscope (aliquot areas).
  • the compounds according to the invention can also be used to ward off pests in the hygiene field and in the vicinity of people.
  • Flies / Repellent test The inside of the lid and the lower part of a glass petri dish were divided into 4 radial segments. Both on the lid and on the lower part, two opposite radial segments remained untreated, the other opposite segments were treated with a 1% solution of the active ingredient in acetone. After the acetone evaporated and the spray coating dried on, 20 adults of Anopheles spec or Musca spec. placed in the Petri dish and closed with the lid treated in the same way. The number of insects that are on the treated or untreated segments of the lid. of the soil were determined every 5 minutes within a period of 30 minutes, then again after 45 and after 60 minutes.
  • Termite repellent test Compounds according to the invention were dissolved in acetone in the stated concentrations and dropped evenly onto filter paper disks, after which the acetone was allowed to evaporate.
  • One untreated and one treated filter paper disk was placed on earth in containers which, after moistening with deionized water, contained 80 individuals from Reticulotermes workers and a soldier. These containers were set up at 27 ° C and the paper feed noted after 1, 2, 3, 4 and 7 days.
  • a special test set-up was chosen to demonstrate the indirect repellent properties of the compounds according to the invention.
  • a population of 25 male and 25 female adults was given a choice of 4 "shelters" (roof-shaped folded cardboard strips), two of which were treated (immersion in a 1% solution of carboxamide active ingredient in acetone) and two were not treated.
  • the number of cockroaches under a respective cardboard strip was counted every day.

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Abstract

Des 4-haloalkyl-3-hétérocyclylpyridines et des 4-haloalkyl-5-hétérocyclylpyrimidinese la formule générale (I) conviennent comme répulsifs contre des parasites animaux, notamment des insectes, des tétranyques, des ectoparasites et des helminthes. Dans la formule (I), Q représente un groupe hétérocyclique à 5 atomes éventuellement substitué par halogène ou des radicaux organiques, Y représente halogénoalkyle C1-C6, X représente CH ou N et m vaut 0 ou 1.
PCT/EP1999/009949 1998-12-17 1999-12-15 4-haloalkyl-3-heterocyclylpyridines et 4-haloalkyl-5-heterocyclylpyrimidines et leur utilisation comme repulsifs WO2000035285A1 (fr)

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DE1998158191 DE19858191A1 (de) 1998-12-17 1998-12-17 4-Haloalkyl-3-heterocyclylpyridine und 4-Haloalkyl-5-heterocyclyl-pyrimidine und ihre Verwendung als Repellentien
DE19858191.2 1998-12-17

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WO2013014204A3 (fr) * 2011-07-26 2013-04-04 Sanofi Dérivés d'acide 3-hétéroaroylaminopropionique et leur utilisation comme produits pharmaceutiques
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US8815924B2 (en) 2004-10-21 2014-08-26 Merck Patent Gmbh Heterocyclic carbonyl compounds
US9420788B2 (en) 2007-08-13 2016-08-23 Monsanto Technology Llc Compositions and methods for controlling nematodes
US9578881B2 (en) 2011-05-06 2017-02-28 Vanderbilt University Compositions for inhibition of insect sensing
US10611734B2 (en) 2015-02-24 2020-04-07 Bayer Cropscience Aktiengesellschaft Process for the preparation of triazoles
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CN114933573B (zh) * 2022-05-06 2023-10-20 贵州大学 3-取代-1,2,4-噁二唑-5-羧酸类衍生物、其制备方法及应用

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WO2004014902A3 (fr) * 2002-08-09 2004-07-08 Astrazeneca Ab Nouveaux composes
WO2004014902A2 (fr) * 2002-08-09 2004-02-19 Astrazeneca Ab Nouveaux composes
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JP2011524349A (ja) * 2008-06-13 2011-09-01 バイエル・クロツプサイエンス・アクチエンゲゼルシヤフト 殺有害生物剤としての新規ヘテロ芳香族アミド及びチオアミド
EP2345328A4 (fr) * 2008-09-19 2014-06-25 Sumitomo Chemical Co Composition utilisée en milieu agricole
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EP2432780A1 (fr) * 2009-05-18 2012-03-28 Sumitomo Chemical Company, Limited Composé pyrimidine et son utilisation dans la lutte antiparasitaire
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WO2010134478A1 (fr) * 2009-05-18 2010-11-25 Sumitomo Chemical Company, Limited Composé pyrimidine et son utilisation dans la lutte antiparasitaire
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WO2013010947A2 (fr) 2011-07-15 2013-01-24 Basf Se Méthodes pesticides utilisant des composés 3-pyridyl thiazole substitués et dérivés pour combattre les parasites animaux de type ii
WO2013010946A2 (fr) 2011-07-15 2013-01-24 Basf Se Méthodes pesticides utilisant des composés 3-pyridyl thiazole substitués et dérivés pour combattre les parasites animaux de type i
US9751858B2 (en) 2011-07-26 2017-09-05 Sanofi 3-heteroaroylamino-propionic acid derivatives and their use as pharmaceuticals
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EP3037417A3 (fr) * 2011-07-26 2016-10-12 Sanofi Dérivés de l'acide 3-hétéroaroylamino-propionique et leur utilisation en tant que produits pharmaceutiques
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CN104640442A (zh) * 2012-06-14 2015-05-20 巴斯夫欧洲公司 使用取代3-吡啶基噻唑化合物和衍生物防除动物有害物的灭害方法
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