WO2006097279A1 - Composes de type amidrazone de lutte contre les parasites - Google Patents

Composes de type amidrazone de lutte contre les parasites Download PDF

Info

Publication number
WO2006097279A1
WO2006097279A1 PCT/EP2006/002331 EP2006002331W WO2006097279A1 WO 2006097279 A1 WO2006097279 A1 WO 2006097279A1 EP 2006002331 W EP2006002331 W EP 2006002331W WO 2006097279 A1 WO2006097279 A1 WO 2006097279A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
phenyl
compound
crc
cycloalkyl
Prior art date
Application number
PCT/EP2006/002331
Other languages
English (en)
Other versions
WO2006097279A8 (fr
Inventor
Christopher Koradin
Wolfgang Von Deyn
Michael Rack
David G. Kuhn
Deborah L. Culbertson
Douglas Anspaugh
Hassan Oloumi-Sadeghi
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO2006097279A1 publication Critical patent/WO2006097279A1/fr
Publication of WO2006097279A8 publication Critical patent/WO2006097279A8/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
    • C07C259/12—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. N-hydroxyamidines
    • C07C259/20—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. N-hydroxyamidines with at least one nitrogen atom of hydroxamidine groups bound to another nitrogen atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • the present invention relates to new amidrazone compounds which are useful for combating animal pests, in particular insects, arachnids and nematodes.
  • the invention also relates to a method for combating insects, nematodes and arachnids.
  • EP-A 604798 discloses inter alia compounds of the general formula
  • W, B and A are each independently N or C-R a
  • Y and R a independently of each other are inter alia hydrogen, halogen, CN, NO 2 , alkyl, haloalkyl, alkoxy or haloalkoxy
  • R x and R y independently of each other are inter alia hydrogen or a C-bound radical such as optionally substituted alkyl, alkenyl, alkinyl or cycloalkyl
  • R z is inter alia hydrogen, optionally substituted alkyl, cycloalkyl or phenyl.
  • the activity of these compounds against the aforementioned pests is not always satisfactory.
  • X and Y are both hydrogen, R 1 and R 2 are both methyl and Ar is 4-chlorophenyl;
  • X and Y are both hydrogen, R 1 is ethyl or but-2-en-1yl, R 2 is phenyl and Ar is 4- nitrophenyl; - X and Y form a chemical bond, R 1 is methyl, Ar is phenyl, R 2 is methyl, phenyl, 4- methylphenyl, 4-methoxy phenyl, 3-pyridyl or 4 pyridyl;
  • R 1 is tert.-butoxymethyl
  • R 2 is phenyl and Ar is phenyl or 4-methylphenyl
  • X and Y form a chemical bond
  • R 1 and R 2 are identical and selected from phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, 4-bromophenyl, 4- ethoxyphenyl and 4-ethoxycarbonylphenyl, and Ar is phenyl;
  • the present invention relates to amidrazone compounds of the general for- mula I
  • X and Y are hydrogen or together form a chemical bond
  • Ar is an aromatic radical selected from phenyl and a 5- or 6-membered heteroaryl having 1, 2, 3 or 4 heteroatoms as ring members, which are selected, independ- ently of one another, from O, N and S, and where the aromatic radical may have
  • R a is (are) selected, independently of one another, from halogen, cyano, nitro, CrC 10 -alkyl, C r C 10 -haloalkyl, C 3 -C 10 -cylcoalkyl, C 3 -C 10 -halocycloalkyl, C 2 - C 10 -alkenyl, C 2 -C 10 -haloalkenyl, C 2 -C 10 -alkynyl, C 3 -C 10 -haloalkynyl, C 1 -C 10 - alkoxy, CrC ⁇ -haloalkoxy, C 2 -C 10 -alkenyloxy, C 2 -C 10 -haloalkenyloxy, C 2 - do-alkynyloxy, C 3 -C 10 -haloalkynyloxy, CrC ⁇ -alkylthio, CrC ⁇ -haloalkylthio, Ci-Cio-alkylsulf
  • R a is (are) selected, independently of one another, from halogen, cyano, nitro, Ci-Cio-alkyl, CrC ⁇ -haloalkyl, C 3 -C 10 -cylcoalkyl, C 3 -C 10 -halocycloalkyl, C 2 - Cio-alkenyl, C 2 -Ci 0 -haloalkenyl, C 2 -C 10 -alkynyl, C 3 -C 10 -haloalkynyl, C 1 -C 10 - alkoxy, CrC 1Q -haloalkoxy, C 2 -C 10 -alkenyloxy, C 2 -C 10 -hal
  • R 1 is selected from the group consisiting of CrC 10 -alkyl, CrC 4 -alkoxy-CrC 4 -alkyl, cyano-C r C 4 -alkyl, hydroxy-C 1 -C 4 -alkyl, CrC 10 -haloalkyl, W-(C 1 -C 4 -BIkVl)-SiIyI-C 1 - C 4 -alkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -haloalkenyl, C 2 -C 10 -alkynyl, C 2 -C 10 -haloalkynyl, C 3 -C 10 -cycloalkyl, phenyl, heteroaryl, C 3 -C 10 -CyClOaIkVl-C 1 -C 4 -BIkVl, phenyl-CrC 4 - alkyl and heteroaryl-CrC 4 -
  • R 2 is selected from the group consisiting of Ci-C 10 -alkyl, CrC 4 -alkoxy- CrC 4 -alkyl, Crdo-haloalkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -haloalkenyl, C 2 -C 10 -alkynyl, C 2 -C 10 - haloalkynyl, C 3 -C 10 -cycloalkyl, phenyl, heteroaryl, C 3 -C 10 -cycloalkyl-CrC 4 -alkyl, phenyl-C r C 4 -alkyl and heteroaryl-C r C 4 -alkyl, wherein C 3 -C 10 -cycloalkyl, heteroaryl and phenyl in the last six mentioned radicals may be unsubstituted or carry 1, 2, 3, 4 or 5 substituents R b as defined above, wherein one of the subsituent
  • R 3 , R 4 are selected independently of one another from H, C r C 10 -alkyl, d-C ⁇ -haloalkyl,
  • X and Y are both hydrogen, R 1 and R 2 are both methyl and Ar is 4-chlorophenyl; - X and Y are both hydrogen, R 1 is ethyl or but-2-en-1yl, R 2 is phenyl and Ar is A- nitrophenyl;
  • R 1 is methyl
  • Ar is phenyl
  • R 2 is methyl, phenyl, A- methylphenyl, 4-methoxyphenyl, 3-pyridyl or 4 pyridyl;
  • R 1 is tert.-butoxymethyl
  • R 2 is phenyl and Ar is phenyl or 4-methylphenyl
  • R 1 and R 2 form a Chemical bond
  • R 1 and R 2 are identical and selected from phenyl
  • the compounds of the general formula I can be used for controlling pests, selected from harmful insects, arachnids and nematodes.
  • the compounds of the formula I are in particular useful from combating insects.
  • compositions for combating such pests preferably in the form of directly sprayable solutions, emulsions, pastes, oil dispersions, powders, materials for scattering, dusts or in the form of granules, which comprises a pesticidally effective amount of at least one compound of the general formula I or at least a salt thereof and at least one carrier which may be liquid and/or solid and which is prefarably agronomically acceptable, and/or at least one surfactant.
  • the invention provides a method for combating such pests, which comprises contacting said pests, their habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from an attack of or infestation by said pest, with a pesticidally effective amount of a compound of the general formula I as defined herein or a salt thereof.
  • the invention provides in particular a method for protecting crops, including seeds, from attack or infestation by harmful insects, arachnids and/or nematodes, said method comprises contacting a crop with a pesticidally effective amount of at least one compound of formula I as defined herein or with a salt thereof.
  • the invention also provides a method for protecting non-living materials from attack or infestation by the aforementioned pests, which method comprises contacting the nonliving material with a pesticidally effective amount of at least one compound of formula I as defined herein or with a salt thereof.
  • Suitable compounds of the general formula I encompass all possible stereoisomers (cis/trans isomers, enantiomers) which may occur and mixtures thereof.
  • the present invention provides both the pure enantiomes or diastereomers or mixtures thereof, the pure cis- and trans-isomers and the mixtures thereof.
  • the compounds of the general formula I may also exist in the form of different tautomers if Ar carries an amino or an- hydroxy group.
  • the invention comprises the single tautomers, if seperable, as well as the tautomer mixtures.
  • Salts of the compounds of the formula I are preferably agriculturally acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality or by reacting an acidic compound of formula I with a suitable base.
  • Suitable agriculturally useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention.
  • Suit- able cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH 4 + ) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C 4 -alkyl, CrC 4 -hydroxyalkyl, C r C 4 -alkoxy, C r C 4 -alkoxy-C r C 4 -alkyl, hydroxy-C 1 -C 4 -alkoxy-C r C 4 -alkyl, phenyl or benzyl.
  • substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethyl- ammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl- ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl- triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C 4 - alkyl)sulfonium, and sulfoxonium ions, preferably tri(C r C 4 -alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hy- drogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C r C 4 -alkanoic acids, preferably formate, acetate, propionate and bu- tyrate. They can be formed by reacting the compounds of the formulae Ia and Ib with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • the organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
  • the prefix C n -C n indicates in each case the possible number of carbon atoms in the group.
  • Halogen will be taken to mean fluoro, chloro, bromo and iodo.
  • C r C 1( ralkyr as used herein refers to a branched or unbranched saturated hydrocarbon group having 1 to 10 carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1- methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3- methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1 ,2- dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1- dimethylbutyl, 1,2-dimethylbutyi, 1,3-dimethylbuty
  • C r C 4 -alkyl means for example methyl, ethyl, propyl, 1- methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl or 1 ,1-dimethylethyl.
  • CrC ⁇ -haloalkyl refers to a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example C 1 -C 4 - haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoro- methyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chloro- difluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoro
  • C 1 - do-haloalkyl in particular comprises CrC 2 -fluoroalkyl, which is synonym with methyl or ethyl, wherein 1 , 2, 3, 4 or 5 hydrogen atoms are substituted by fluorine atoms, such as fluoromethyl, difluoromethyl trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl and pentafluoromethyl.
  • CrC 10 -alkoxy and “CrCi 0 -alkylthio” refer to straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond in the alkyl group.
  • Examples include C 1 -C 4 - alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy, futher C 1 -C 4 -alkylthio such as methylthio, ethylthio, propylthio, isopro- pylthio, and n-butylthio.
  • C r Ci 0 -haloalkoxy and " C r C 10 -haloalkylthio” refer to straight- chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond in the alkyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example CrC 2 -haloalkoxy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloroethoxy,
  • C 1 -C 2 - fluoroalkoxy and C r C 2 -fluoroalkylthio refer to C r C 2 -fluoroalkyl which is bound to the remainder of the molecule via an oxygen atom or a sulfur atom, respectively.
  • C 2 -C 10 -alkenyr intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any posi- tion, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3- butenyl, 1-methyl-1-propenyl, 2-methyl- 1-propenyl, 1-methyl-2-propenyl, 2 ⁇ methyl-2- propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl- 1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2- butenyl, 1-methyl-3-butenyl, 2-methyl-3-but
  • C 2 -C 10 -haloalkenyr intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
  • C 2 -C 10 -alkenyloxy intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, the alkenyl group being bonded through oxygen linkages, respectively, at any bond in the alkenyl group, for example ethenyloxy, propenyloxy and the like.
  • C 2 -C 10 -haloalkenyloxy intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, the alkenyl group being bonded through oxygen linkages, respectively, at any bond in the alkenyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
  • C 2 -C 10 -alkynyl refers to a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and containing at least one triple bond, such as ethynyl, propynyl, 1-butynyl, 2-butynyl, and the like.
  • C 3 -C 10 -haioalkynyr refers to a branched or unbranched un- saturated hydrocarbon group having 3 to 10 carbon atoms and containing at least one triple bond, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, with the proviso that the halogen atom is not directly bound to the triple bond.
  • C 2 -C 10 -alkynyloxy refers to a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and containing at least one triple bond, the alkynyl group being bonded through oxygen linkages at any bond in the alkynyl group.
  • C 3 -Cio-haloalkynyloxy refers to a branched or unbranched unsaturated hydrocarbon group having 3 to 10 carbon atoms and containing at least one triple bond, the group being bonded through oxygen linkages at any bond in the alkynyl group, where some or all of the hydrogen atoms in these group may be replaced by halogen atoms as mentioned above, with the proviso that the halogen atom is not directly bound to the triple bond.
  • C 3 -C 1( rcycloalkyr refers to a monocyclic 3- to 10-membered saturated carbon atom ring, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo- heptyl, cyclooctyl and cyclodecyl.
  • Ca-do-cycloalkyl-CrC ⁇ alkyl refers to a monocyclic 3- to 10- membered saturated carbon atom ring which is attached to the remainder of the molecule by an C r C 4 -alkylene group, e.g. cyclopropylmethyl, 1-cyclopropyiethan-i-yl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctyl- methyl and cyclodecylmethyl.
  • C r C 4 -alkylene group e.g. cyclopropylmethyl, 1-cyclopropyiethan-i-yl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctyl- methyl and cyclodecylmethyl.
  • C 3 -Ci 0 -halocycloalkyr refers to a monocyclic 3- to 10- membered saturated carbon atom ring, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example chloro-, dichloro- and trichlorocyclopropyl, fluoro-, difluoro- and trifluorocyclopropyl, chloro-, dichloro-, trichloro, tetrachloro-, pentachloro- and hexachlorocyclohexyl and the like.
  • phenyl-CrC 4 -alkyl refers to an optionally substitueted phenyl group which is attached to the remainder of the molecule by an Ci-C 4 -alkylene group, e.g. benzyl, 1-phenylethan-1-yl, 2-phenylethan-1-yl, 2-methyl-2-phenylethan-1-yl and the like.
  • d-Cio-alkylcarbonyl refers to Ci-Ci O -alkyl which is bound to the remainder of the molecule via a carbonyl group.
  • Examples include CO-CH 3 , CO-C 2 H 5 , CO-CH 2 -C 2 H 5 , CO-CH(CH 3 ) 2 , n-butylcarbonyl, CO-CH(CHg)-C 2 H 5 , CO-CH 2 -CH(CHs) 2 , CO-C(CH 3 ) 3 , n-pentylcarbonyl, 1- methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 2,2- dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, n-hexylcarbonyl, 1 ,1- dimethylpropylcarbonyl, 1 ,2-dimethylpropylcarbonyl, 1-methylpentylcarbonyl, 2- methylpent
  • CrCio-haloalkylcarbonyl refers to C r C 10 -haloalkyl which is bound to the remainder of the molecule via a carbonyl group. Examples include chloromethylcarbonyl, dichloromethylcarbonyl, trichloromethylcarbonyl, fluoromethylcarbonyl, difluoromethylcarbonyl, trifluoromethylcarbonyl etc.
  • CrCio-alkoxycarbonyl refers to C r C 10 -alkoxy which is bound to the remainder of the molecule via a carbonyl group.
  • Examples include CO-OCH 3 , CO-OC 2 H 5 , CO-OCH 2 -C 2 H 5 , CO-OCH(CH 3 ) 2 , n-butoxycarbonyl, CO-OCH(CHg)-C 2 H 5 , CO-OCH 2 -CH(CH 3 ).:, CO-OC(CH 3 ) 3 , n-pentoxycarbonyl, 1- methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2,2- dimethylpropoxycarbonyl, 1-ethylpropoxycarbonyl, n-hexoxycarbonyl, 1,1- dimethylpropoxycarbonyl, 1 ,2-dimethylpropoxycarbonyl, 1-methylpentoxycarbonyl, 2- methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4-methylpentoxycarbonyl, 1,1- dimethylbutoxycarbonyl, 1 ,2-dimethylbutoxycarbonyl, 1,3-dimethylbutoxycarbonyl
  • halo-Crdo-alkoxycarbonyl refers to CrC 10 -haloalkoxy which is bound to the remainder of the molecule via a carbonyl group.
  • halo-Crdo-alkoxy-Cr Cio-alkyl refers to C r C 10 -alkyl, as defined herein, in particular to methyl, ethyl, 1 -propyl or 2-propyl, which is substituted by one radical selected from hydroxy, Ci-C 10 -alkoxy, C 1 -C 10 - haloalkoxy, CrC ⁇ -alkoxycarbonyl or CrC 10 -haloalkoxycarbonyl.
  • heterocyclic radical with 1 , 2, 3 or 4 heteroatoms which are selected, independently of one another, from O, N and S " comprises monocyclic 5- or 6-membered heteroaromatic rings (heteroaryl) and nonaromatic saturated or partially unsaturated 5- or 6-membered mono-heterocycles, which carry 1 , 2, 3, or 4 heteroatoms as ring members.
  • the heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
  • non-aromatic rings examples include pyrrolidinyl, pyrazolinyl, imidazolinyl, pyr- rolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3-dioxolanyl, di- oxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperaz- inyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, thiopyranyl, dihy- drothiopyrany
  • Examples for monocyclic 5- to 6-membered heteroaryl include triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, isothiazolyl and isoxazolyl.
  • heteroaryl-CrC 4 -alkyr refers to an optionally substitueted heteroaryl group which is attached to the remainder of the molecule by an C 1 -C 4 - alkylene group, examples including triazinylmethyl, pyrazinylmethyl, pyrimidylmethyl, pyridazinylmethyl, pyridylmethyl, thienylmethyl, furylmethyl, pyrrolylmethyl, pyrazolyl- methyl, imidazolyl, triazolylmethyl, tetrazolylmethyl, thiazolylmethyl, oxazolylmethyl, thiadiazolylmethyl, oxadiazolylmethyl, isothiazolylmethyl and isoxazolylmethyl.
  • the invention relates to compounds of the formula I 1 wherein both X and Y are hydrogen. These compounds are also referred to as compounds Ia. Compounds Ia may also exist in their tautomeric form Ia 1 .
  • the invention relates to compounds of the formula I, wherein both X and Y form a chemical bond. These compounds are also referred to as compounds Ib.
  • Ar in formula I is an option- ally substituted aromatic radical selected from phenyl or pyridyl, such as 2-, 3- or 4- pyridyl.
  • the aromatic radical may be unsubstituted or preferably carries 1 , 2, 3, 4 or 5 substituents R a as defined above.
  • Preferred substuituents R a are selected, independently of one another, from halogen, CN 1 OH 1 NO 2 , C r C 4 -alkyl, CrC 4 -alkoxy, C r C 4 -haloalkoxy and C r C 4 -haloalkyl.
  • fluorine chlorine, NO 2 , CN, methyl, CHF 2 , CF 3 , CF 2 CI, methoxy, OCHF 2 , and OCF 3 .
  • Ar is phenyl, which carries 1 , 2, 3, 4 or 5 substituents R a as defined above. Amongst these compounds those are preferred, wherein at least one substituent R a is located in the ortho- and/or para-position of the phenyl ring, with particular preference given to those, wherein one or two substituents R a are located in the ortho-positions of the phenyl ring and one substituent R a is located in the para-position of the phenyl ring.
  • substuituents R a which are selected, independently of one another, from halogen, CN, OH, NO 2 , C r C 4 -alkyl, C r C 4 -alkoxy, C r C 4 -haloalkoxy and C 1 -C 4 - haloalkyl, in particular fluorine, chlorine, NO 2 , CN, methyl, CHF 2 , CF 3 , CF 2 CI, methoxy, OCHF 2 , and OCF 3 .
  • radical Ar is of the formula A
  • R a1 is selected from the group consisting of hydrogen, halogen, CN, OH, NO 2 , C 1 -C 4 - alkyl, Ci-C 4 -a!koxy, CrC 4 -haloalkoxy and CrC 4 -haloalkyl, in particular hydrogen, methyl, fluorine, chlorine, NO 2 , CN, CHF 2 , CF 3 , CF 2 CI 1 methoxy, OCHF 2 , and OCF 3 ;
  • R a2 is selected from the group consisting of hydrogen or halogen, in particular hydrogen, fluorine or chlorine;
  • R a3 is selected from the group consisting of hydrogen, halogen, CN, OH, NO 2 , C 1 -C 4 - alkyl, C r C 4 -alkoxy, CrC 4 -haloalkoxy and C r C 4 -haloalkyl, in particular hydrogen, halogen, C r haloalkyl or C r haloalkoxy, e.g. fluorine, chlorine, bromine, methyl, methoxy, trichloromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy;
  • R a4 is selected from the group consisting of hydrogen and halogen, in particular hydrogen, fluorine or chlorine;
  • R a5 is selected from the group consisting of hydrogen, halogen, CN, OH, NO 2 , C 1 -C 4 - alkyl, C r C 4 -alkoxy, C r C 4 -haloalkoxy and C r C 4 -haloalkyl, in particular hydrogen, methyl, fluorine, chlorine, NO 2 , CN, CHF 2 , CF 3 , CF 2 CI, methoxy, OCHF 2 , and OCF 3 .
  • radicals Ar of the formula A include 2-fluoro-6-chlorophenyl, 2,6-difluoro- phenyl, 2,6-dichlorophenyl, 2-fluoro-6-methylphenyl, 2,4,6-trifluorophenyl, pentafluoro- phenyl, 2-methyl-4-fluorophenyl, 2-trifluoromethylphenyl, 2-chlorophenyl, 2-fluoro- phenyl, 2,4-difluorophenyl, 2-fluoro-4-chlorophenyl, 2-methoxy-6-fluorophenyl, 2-chloro-4-fl ⁇ orophenyl, 2-methyl-4-chlorophenyl, 2-trifluoromethyl-4-fluorophenyl,
  • R 1 is selected from the group consisting of CrC 6 -alkyl, CrC 6 -halo- alkyl, C 3 -C 6 -cycloalkyl, CrC 4 -alkoxy-C 2 -C 4 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 3 -C 6 - haloalkenyl, C 3 -C 6 -haloalkynyl, Cs-Ce-cycloalkylmethyl, wherein C 3 -C 6 -cycloalkyl in the last two radicals may carry 1 , 2, 3 or 4 radicals R b as defined above and inparticular radicals R b which are selected from halogen and methyl.
  • R 1 is Ci-C ⁇ -alkyl, C 3 -C 6 -alkenyl and C 3 -C 6 -alkynyl, wherein these radicals may carry a halogen atom.
  • Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 2-butyl, tert.-butyl, 2-bromoethyl, 2-chloroethyl, 1-propen-3-yl, 1-chloro-1-propen-3-yl, 2-buten ⁇ 1-yl, 3-methyl-2-buten-1-yl, 1-propin-3-yl, 1-butin-3-yl, cyclohexylmethyl, cyclopropylmethyl, 2-ethoxy-ethyl, 2-trimethylsilyl-ethyl, cyanomethyl, 2-chloro-1- propen-3-yl.
  • R 1 is phenyl-CrC 4 -alkyl, in particular benzyl, 1- phenylethyl, 2-phenylethyl, 1-methyl-1-phenylethyl, wherein the phenyl ring in these radicals may be unsubstituted or substituted by a radical R b as defined above, with R b being particularly selected from methyl, halogen and methoxy.
  • R 2 is a radical, which is attached to the remainder of the molecule by a secondary or tertiary carbon atom.
  • R 2 is selected from secondary or tertiary CrC ⁇ -alkyl, C 3 -C 6 -cycloalkyl and phenyl, wherein C 3 -C 6 -cycloalkyl and phenyl may be unsubstituted or carry 1 , 2, 3, 4 or 5 substituents selected from the radicals R b and wherein one of the subsituents on C 3 -C 6 -cycloaIkyl may also be phenyl that may carry 1 , 2, 3 or 4 substituents selected from the radicals R bb wherein R bb has the one of the meanings of R b as defined above.
  • radicals R b on phenyl are selected from methyl, trifluoromethyl, phenyl and halogen.
  • radicals on cyloalkyl are selected from methyl, trifluoromethyl, phenyl, which may carry 1 , 2 or 3 radicals R bb , and halogen.
  • R bb is preferably selected from halogen, C r C 4 -alkyl, C r C 4 -alkoxy, halo-C r alkoxy and halo-C r alkyl.
  • a particularly preferred embodiment of the invention relates to compounds of the for- mula I (and likewise to compounds Ia, Ia 1 and Ib), wherein R 2 is C 3 -C 6 -cycloalkyl in particular cyclopropyl which may be unsubstituted or carry 1 , 2, 3, 4 or 5 substituents selected from the radicals R b .
  • R 2 is C 3 -C 6 -cycloalkyl in particular cyclopropyl which may be unsubstituted or carry 1 , 2, 3, 4 or 5 substituents selected from the radicals R b .
  • preference is given to compounds wherein the radicals R b on the C 3 -C 6 -cycloalkyl radical are selected from methyl, trifluoromethyl, phenyl which may carry 1 , 2 or 3 halogen atoms and halogen.
  • Exam- pies include 2,2-dichlorocyclopropyl, 2,2-dichloro-1-methylcyclopropyl, 1-trifluoro- methylcyclopropyl, 1-fluorocyclopropyl, 2,2-dichloro-3,3-dimethylcyclopropyl, 1-methyl- cyclopropyl, 2,2-dibromocyclopropyl, 2,2-dibromo-1-methylcyclopropyl, 2-chloro-2- fluoro-1-methylcyclopropyl, 2-chloro-1-methylcyclopropyl, 1-phenylcyclopropyl, 1-(4- methoxyphenyl)cyclopropyl, 1-(4-chlorophenyl)cyclopropyl, 1-((2,4-dichlorophenyl)- cyclopropyl and 2-methylcyclopropyl.
  • Table 1 Compounds of the formulae Ia, Ia 1 and Ib, wherein Ar is 2-fluoro-6-chlorophenyl and the combination of R 1 and R 2 for one compound corresponds in each case to one row of table A.
  • Table 3 Compounds of the formulae Ia 1 Ia 1 and Ib, wherein Ar is 2,6-dichlorophenyl and the combination of R 1 and R 2 for one compound corresponds in each case to one row of table A.
  • Table 4 Compounds of the formulae Ia, Ia 1 and Ib, wherein Ar is 2-fluoro-6-methylphenyi and the combination of R 1 and R 2 for one compound corresponds in each case to one row of table A.
  • Table 7 Compounds of the formulae Ia, Ia' and Ib, wherein Ar is 2-methyl-4-fluorophenyl and the combination of R 1 and R 2 for one compound corresponds in each case to one row of table A.
  • Table 8 Compounds of the formulae Ia, Ia 1 and Ib, wherein Ar is 2-trifluoromethylphenyl and the combination of R 1 and R 2 for one compound corresponds in each case to one row of table A.
  • Table 10 Compounds of the formulae Ia, Ia 1 and Ib, wherein Ar is 2-chlorophenyl and the combination of R 1 and R 2 for one compound corresponds in each case to one row of table A.
  • Ar, R 1 and R 2 have the abovementioned meanings, and Hal and Hal' are independently of each other halogen.
  • Hal and Hal' have preferably the same meaning, especially Hal and Hal' denote chlorine.
  • an N-arylhydrazinoyl halide of the formula IV is prepared by reacting an acyl halide Il with an aryl hydrazine compound III in the presence of thionyl halide such as thionyl chloride.
  • the reaction can be performed according to standard methods of organic chemistry well known in the art and disclosed e.g. in EP 0 604 798.
  • the N-arylhydrazinoyl halide IV is reacted with an hydroxylamine ether hydrohalide V.
  • the reaction can be performed by analogy to the reaction of primary amines with hydrazinoyl halides as disclosed e.g. in EP 0 604 798.
  • the compounds IV and V are reacted in equimolar amounts. It may, however, be advantageous to use compound V in excess, e.g. up to 10 mol per mol of compound IV.
  • the reaction is carried out in the presence of a base.
  • bases are tertiary amines such as trimethylamine, triethylamine, diisoproylethylamine (H ⁇ nig's base) or tripropylamine or pyridine or mixtures thereof; with triethylamine and H ⁇ nig's base being especially preferred.
  • the molar ratio of the base to compound V is generally from 0.6:1 to 5:1.
  • Suitable organic solvents or diluents include ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane or tetrahydrofuran, aromatic solvents, in particular alkylaromatic solvents such as tolu- ene, xylene etc., halogenated hydrocarbons, in particular haloalkanes such as tri- chloromethane, dichloromethane, ethylenchloride, 1 ,2-dichloroethylene and mixtures thereof.
  • Especially preferred solvents include diethyl ether and dichloromethane. Customary reaction temperatures are from 0 0 C to 80 0 C or.
  • hydroxylamin ether hydrohalides V are commericially available or known from the literature or can be prepared by known methods.
  • Acyl halides Il can be prepared from the corresponding carboxylic acids Vl. The latter are commericially available or known from the literature or can be prepared by stan- dard methods. It is not necessary to isolate the acyl halide II, which can be reacted with compound III without purification.
  • arylhydrazines of formula III are known in the art or may be obtained applying methods well known in the art, e.g., by diazotization of an appropiate aniline of the for- mula Ar-NH 2 , wherein Ar has the abovementioned meanings, and reduction of the resulting diazonium salt.
  • step 1 the carboxylic acid Vl is initially reacted with the hydrazine compound III in the presence of triphenylphosphine and a tetrahalomethane, such as tetrachloro- methane, to yield the N-arylhydrazinoyl halide compound Il (step 1), which can then be converted into the corresponding compound Ia by reacting an appropiate O-alkylated hydroxylamine-hydrohalide III (step 2) as described above. Accordingly, step 2 is carried out in the presence of a base. The reactions of steps 1 and 2 are carried out as a one-pot reaction.
  • a polymer-supported triphenylphosphine is used in step 1.
  • Suitable carriers for the polymer-supported triphenylphosphin are poly(ethylene glycol) or cross-linked polystyrene.
  • the use of polymer-supported triphenylphosphine resins allows to easily remove the triphenylphosphine oxide formed seperating the insoluble polymer materials from the reaction mixture.
  • Step 1 and step 2 are preferably carried out in the presence of a solvent.
  • Suitable sol- vents are halogenated hydrocarbons such as trichloromethane, dichloromethane, ethylenchloride or 1 ,2-dichloroethylene, with dichloromethane being preferred.
  • the solvent used in step 1 is usually used in step 2, too.
  • Step 1 can be carried out by mixing the carboxylic acid Vl, the hydrazine compound III, the triphenylphosphine, the tetrahalomethane and optionally the solvent in a reaction vessel.
  • the reaction temperatures are usually in the range of 0 to 80°C.
  • the reaction is usually carried out under atmospheric pressure. However elevated pressure or reduced pressure might also be applied.
  • reaction vessel is charged with the O-alkylated hydroxylamine-hydrohalide III and a base, if desired (step 2).
  • Suitable bases includes those mentioned in scheme 1 , with H ⁇ nig's base being especially preferred.
  • Step 2 is usually carried out at temperatures of from O 0 C to 80 0 C.
  • the stoichiometric ratios are, for example, as follows: 1 to 10 equivalents of triphenylphosphine; 0.2 to 2 equivalents of carboxylic acid; 0.2 to 2 equivalents of arylhydrazine; 3 to 30 equivalents of halomethane; 0.4 to 4 equivalents of hydroxylamine ether hydro- halide; and 1 to 10 equivalents of base.
  • Ia' The dehydrogenation of Ia or Ia 1 , respectively, may be effected by using oxidants having high redox potentials and which are known to dehydrogenate hydrazine compounds.
  • Suitable oxidandts include quinones, such as chloranil (2,3,5,6-tetrachloro-1 ,4- benzoquinone) or DDQ (2,3-dichloro-5,6-dicyano-1 ,4-benzoquinone), Pb(OAc) 4 (lead (IV) acetate) (Uneyama et al, Bull. Chem. Soc. Jpn.
  • the oxidant and compound Ia or Ia' are reacted in at least equimolar amounts. It may be advantageous to employ the oxidant in excess, e.g. the molar ratio of compound Ia to oxidant is in the range from 1 :1 to 1:2.5.
  • Suitable sol- vents include ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether or tetrahydrofuran, haloalkanes such as trichloromethane, dichloromethane or dichloro- ethane, aliphatic or aromatic hydrocarbons such as cyclohexane and petrol ether, benzene, toluene or o-, m- and p-xylene and mixtures thereof.
  • ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether or tetrahydrofuran
  • haloalkanes such as trichloromethane, dichloromethane or dichloro- ethane
  • aliphatic or aromatic hydrocarbons such as cyclohexane and petrol ether, benzene, toluene or o-, m- and
  • the reaction is carried out in the presence of an organic base such as a tertiary amine e.g. a trialkylamine such as triethylamine or pyridine.
  • an organic base such as a tertiary amine e.g. a trialkylamine such as triethylamine or pyridine.
  • the molar ratio of base to oxidant is usually in the range from 1 :0.8 to 1 :5.
  • Customary reaction temperatures are from 0 0 C to 120 0 C.
  • reaction mixture to isolate compound Ib can be performed by conventional processes, including filtration, extraction and solvent removing. Purification can be achieved e.g. by crystallization and/or chromatography.
  • intermediates and end products are obtained in the form of colourless or slightly brownish viscous oils which can be purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and the end products are obtained as solids, purification can also be carried out by recrystillization or digestion.
  • the compounds of the formula I are in particular suitable for efficiently controlling ar- thropodal pests such as arachnids and insects as well as nematodes..
  • Insects from the order of Lepidoptera, for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Den- drolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mel- lonella, Grapholitha funebrana, Grapholitha molesta, Heliothis
  • Thysanoptera e.g. Dichromothrips spp., Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
  • Hymenoptera e.g. Athalia rosae, Alia cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, So- lenopsis geminata and Solenopsis invicta,
  • Heteroptera e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor,
  • Orthoptera e.g. Acheta domestica, Blatta orientalis, Blattella ger- manica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asy- namorus.
  • Orthoptera e.g. Acheta domestica, Blatta orientalis, Blattella ger- manica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rub
  • Nematodes plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rosto- Kunststoffsis and other Globodera species; Heterodera avenae, Heterodera glycines, Het- erodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Cri
  • the compounds of the formula I and their salts are also useful for controlling arachnids (Arachnoidea), such as acarians (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas per- sicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appen- diculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp.
  • arachnoidea such as
  • Tetranychidae spp. such as Tetranychus cinnaba ⁇ nus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis.
  • Compounds of the formula I are particularly useful for controlling insects of the order Lepidoptera.
  • the compounds I can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the use form depends on the particular purpose; it is intended to ensure in each case a fine and uniform distribution of the compound according to the invention.
  • the formulations are prepared in a known manner, e.g. by extending the active ingredient with solvents and/or carriers, if desired using emulsifiers and dispersants.
  • Solvents/auxiliaries which are suitable, are essentially: - water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters.
  • aromatic solvents for example Solvesso products, xylene
  • paraffins for example mineral fractions
  • alcohols for example methanol, butanol, pentanol, benzyl alcohol
  • ketones for example cyclohe
  • solvent mixtures may also be used.
  • carriers such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g. highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose.
  • ground natural minerals e.g. kaolins, clays, talc, chalk
  • ground synthetic minerals e.g. highly disperse silica, silicates
  • emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates)
  • dispersants such as lignin-sulfite waste liquors and methylcellulose
  • Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylpheny
  • Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin
  • Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.
  • solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth
  • the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient.
  • the active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • a compound according to the invention 10 parts by weight of a compound according to the invention are dissolved in water or in a water-soluble solvent.
  • wetters or other auxiliaries are added.
  • the active ingredient dissolves upon dilution with water.
  • DC Dispersible concentrates 20 parts by weight of a compound according to the invention are dissolved in cyclohexanone with addition of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion.
  • a dispersant for example polyvinylpyrrolidone
  • a compound according to the invention 40 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5% strength).
  • This mixture is introduced into water by means of an emulsifier (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.
  • a compound according to the invention in an agitated ball mill, 20 parts by weight of a compound according to the invention are milled with addition of dispersant, wetters and water or an organic solvent to give a fine active ingredient suspension. Dilution with water gives a stable suspension of the active ingredient.
  • Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of a compound according to the invention are ground finely with addition of dispersants and wetters and made into water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active ingredient.
  • 75 parts by weight of a compound according to the invention are ground in a rotor- stator mill with addition of dispersant, wetters and silica gel. Dilution with water gives a stable dispersion or solution with the active ingredient.
  • I Granules 0.5 parts by weight of a compound according to the invention is ground finely and associated with 95.5% carriers. Current methods are extrusion, spray drying or the fluidized bed. This gives granules to be applied undiluted.
  • the active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, eg. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring.
  • the use forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the active ingredients according to the invention.
  • Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
  • emulsions, pastes or oil dispersions the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier.
  • concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil and such concentrates are suitable for dilution with water.
  • the active ingredient concentrations in the ready-to-use products can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%.
  • the active ingredients may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active ingredient, or even to apply the active ingredient without additives.
  • UUV ultra-low-volume process
  • compositions of this invention may also contain other active ingredients, for example other pesticides such as insecticides and herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides.
  • pesticides such as insecticides and herbicides
  • fertilizers such as ammonium nitrate, urea, potash, and superphosphate
  • phytotoxicants and plant growth regulators herbicides
  • plant growth regulators if appropriate also added only immediately prior to use (tank mix).
  • the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
  • These agents usually are admixed with the agents according to the invention in a weight ratio of 1 : 100 to 100: 1.
  • Organophosphates Acephate, Azinphos-methyl, Chlorpyrifos, Chlorfenvinphos, Diazi- non, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, Ethion, Fenitrothion, Fenthion, Isoxathion, Malathion, Methamidophos, Methidathion, Methyl-Parathion, Mevinphos, Monocrotophos, Oxydemeton-methyl, Paraoxon, Parathion, Phenthoate, Phosalone, Phosmet, Phosphamidon, Phorate, Phoxim, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprophos, Tetrachlorvinphos, Terbufos, Triazophos, Trichlorfon;
  • Pyrethroids Bifenthrin, Cyfluthrin, Cypermethrin, alpha-Cypermethrin, Deltamethrin, Esfenvalerate, Ethofenprox, Fenpropathrin, Fenvalerate, Cyhalothrin, Lambda- Cyhalothrin, Permethrin, Silafluofen, Tau-Fiuvalinate, Tefluthrin, Tralomethrin, Zeta- Cypermethrin;
  • Arthropod growth regulators a) chitin synthesis inhibitors: benzoylureas: Chlorflua- zuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novalu- ron, Teflubenzuron, Triflumuron; Buprofezin, Diofenolan, Hexythiazox, Etoxazole, Clofentazine; b) ecdysone antagonists: Halofenozide, Methoxyfenozide, Tebufenozide; c) juvenoids: Pyriproxyfen, Methoprene, Fenoxycarb; d) lipid biosynthesis inhibitors: Spirodiclofen;
  • compositions are particularly useful for protecting plants against infestation of said pests or to combat these pests in infested plants.
  • the compounds of formula I are also suitable for the treatment of seeds. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter.
  • compositions which are useful for seed treatment are e.g.:
  • a Soluble concentrates (SL, LS)
  • Preferred FS formulations of compounds of formula I for seed treatment usually comprise from 0.5 to 80% of the active ingredient, from 0,05 to 5 % of a wetter, from 0.5 to 15 % of a dispersing agent, from 0, 1 to 5 % of a thickener, from 5 to 20 % of an antifreeze agent, from 0,1 to 2 % of an anti-foam agent, from 1 to 20 % of a pigment and/or a dye, from 0 to 15 % of a sticker /adhesion agent, from 0 to 75 % of a filler/vehicle, and from 0,01 to 1 % of a preservative.
  • Suitable pigments or dyes for seed treatment formulations are pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1 , pigment red 57:1, pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
  • Suitable adhesives are block copolymers EO/PO surfac- tants but also polyvinylalcohols, polyvinylpyrrolidones, polyacrylates, polymethacry- lates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyl- eneamides, polyethyleneimines (Lupasol®, Polymin®), polyethers and copolymers derived from these polymers.
  • compounds of formula I are preferably used in a bait composition.
  • the bait can be a liquid, a solid or a semisolid preparation (e.g. a gel).
  • Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks.
  • Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources.
  • Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickyness, moisture retention or aging characteristics.
  • the bait employed in the composition is a product which is sufficiently attractive to in- cite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it.
  • the attractiveness can be manipulated by using feeding stimulants or sex pheromones.
  • Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey.
  • Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant.
  • Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.
  • Formulations of compounds of formula I as aerosols are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches.
  • Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, etha- nol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g.
  • kerosenes having boiling ranges of approximately 50 to 250 0 C, dimethyl- formamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
  • emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of
  • the oil spray formulations differ from the aerosol recipes in that no propellants are used.
  • the compounds of formula I and its respective compositions can also be used in mos- quito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
  • the compounds of formula I and its compositions can be used for protecting non-living material, in particular cellulose-based materials such as wooden materials e.g. trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).
  • cellulose-based materials such as wooden materials e.g. trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).
  • the compounds of formula I are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets, heat insulating material such as styrene foams, etc.
  • the ant controller of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like.
  • the pests are controlled by contacting the target parasite/pest, its food supply, habitat, breeding ground or its locus with a pesti- cidally effective amount of compounds of formula I or with a salt thereof or with a composition, containing a pesticidally effective amount of a compound of formula I or a salt thereof.
  • “Locus” means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is growing or may grow.
  • pesticidally effective amount means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the pesticidally effective amount can vary for the various compounds/compositions used in the invention.
  • a pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
  • the compounds of the invention can also be applied preventively to places at which occurrence of the pests is expected.
  • the compounds of formula I may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of com- pounds of formula I.
  • "contacting” includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).
  • the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.
  • the application rates of the mixture are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 200 g per 100 kg of seed.
  • the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m 2 , preferably from 0.001 to 2O g per 100 m 2 .
  • Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m 2 treated material, desirably from 0.1 g to 50 g per m 2 .
  • lnsecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and / or insecticide.
  • the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound.
  • the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
  • the products were characterized by coupled High Performance Liquid Chromatogra- phy/mass spectrometry (HPLC/MS), by 1 H-NMR or by their melting point.
  • HPLC/MS High Performance Liquid Chromatogra- phy/mass spectrometry
  • HPLC HPLC
  • Chrolith Speed ROD Chrolith Speed ROD, dimensions 50 x 4.6 mm, from Merck KGaA, Germany
  • the mobile phase used was acetonitrile/water with 0.1% trifluoroacetic acid in a ratio of 5:95 to 95:5 in 5 minutes).
  • HPLC was carried out using either method A (high speed overview method; recorded on Agilent 1100 LC/MSD) or method B (slow method; recorded on Agilent 1100 LC/MSD).
  • Mass spectrometry was carried out using a quadrupole mass spectrometer with electrospray ionization at 80V in the positive mode.
  • the following abbreviations are used: m.p. melting point RT retension time HPLC/MS eq. equivalent(s) Ex.
  • Example 2 Mass spectrometry was carried out using a quadrupole mass spectrometer with electrospray ionization at 80V in the positive mode.
  • the following abbreviations are used: m.p. melting point RT retension time HPLC/MS eq. equivalent(s) Ex.
  • Example 1 m.p. melting point RT retension time HPLC/MS eq. equivalent(s)
  • N-oxy-amidrazones were prepared according to route B below.
  • the active compounds were formulated as a 20:80 acetone:water solution.
  • Surfactant Alkamuls EL 620 was added at the rate of 0.1% (vol/vol).
  • Potted rice plants of 3-4 weeks of age are sprayed with 10 ml of the test solution using air driven hand atomizer (Devillbis atomizer) at 1.7 bar.
  • the treated plants are allowed to dry for about 1 hour and covered with Mylar cages.
  • the plants are inoculated with 10 adults of the specie (5 male and 5 females) and kept at 25- 27°C and 50-60% humidity for 3 days. Mortality is assed after 24, 48 and 72 hours after treatment. Dead insects are usually found in the water surface. Each treatment is replicated once.
  • the active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic ® surfactant.
  • Cotton plants at the cotyledon stage were infested by placing a heavily infested leaf from the main colony on top of each cotyledon. The aphids were allowed to transfer to the host plant overnight, and the leaf used to transfer the aphids was removed. The cotyledons were dipped in the test solution and allowed to dry. After 5 days, mortality counts were made.
  • Cowpea Aphid (aphis craccivora)
  • the active compounds were formulated in 50:50 acetone:water and 0.1 % (vol/vol) Alkamuls EL 620 surfactant.
  • Potted cowpea beans of 7-10 days of age are inoculated with aphids 24 h before treatment by clipping a leaf infested with cowpea aphid approximately 30 individuals.
  • the treated beans are sprayed with 5 ml of the test solution using air driven hand atomizer (Devillbis atomizer) at 25 psi, allowed to air dry and kept at 25-27 0 C and 50-60% humidity for 3 days. After 72 h, mortality was assessed.
  • air driven hand atomizer (Devillbis atomizer)
  • the compound of example no. 4 at 300 ppm showed a mortality of at least 80% in comparison with untreated controls.
  • the active compounds were formulated in 50:50 acetone:water and 0.1 % (vol/vol) Alkamuls EL 620 surfactant.
  • a 6 cm leaf disk of cabbage leaves is dipped in the test solution for 3 seconds and allowed to air dry in a Petri plate lined with moist filter paper.
  • the leaf disk is inoculated with 10 third instar larvae and kept at 25-27°C and 50-60% humidity for 3 days. Mortality and feeding rate are assessed after 72 h of treatment.
  • the compounds of example no. 1 and 2 at 500 ppm showed a mortality of at least 80% mortality in comparison with untreated controls.
  • the compounds of example no. 3, 4, 5, 6, and 8 at 300 ppm a mortality of at least 80% in comparison with untreated controls.
  • the active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic ® surfactant.
  • Pepper plants in the 2 nd leaf-pair stage (variety 'California Wonder') were infested with approximately 40 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections were removed after 24 hr. The leaves of the intact plants were dipped into gradient solutions of the test compound and allowed to dry. Test plants were maintained under fluorescent light (24 hour pho- toperiod) at about 25 0 C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on check plants, was determined after 5 days.
  • a Sieva lima bean leaf expanded to 7-8 cm in length is dipped in the test solution with agitation for 3 seconds and allowed to dry in a hood.
  • the leaf is then placed in a 100 x 10 mm petri dish containing a damp filter paper on the bottom and ten 2nd instar caterpillars.
  • observations are made of mortality, reduced feeding, or any interference with normal molting.
  • the active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic® surfactant.
  • Selected cotton plants were grown to the cotyledon state (one plant per pot).
  • the cotyledons were dipped into the test solution to provide complete coverage of the foliage and placed in a well-vented area to dry.
  • Each pot with treated seedling was placed in a plastic cup and 10 to 12 whitefly adults (approximately 3-5 day old) were introduced.
  • the insects were colleted using an aspirator and an 0.6 cm, non-toxic Tygon® tubing (R-3603) connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding.
  • the cups were covered with a re-usable screened Hd (150 micron mesh polyester screen PeCap from Tetko Inc). Test plants were maintained in the holding room at about 25 0 C and 20-40% relative humidity for 3 days avoiding direct exposure to the fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment of the plants.
  • Hd 150 micron mesh polyester screen PeCap from Tetko Inc.
  • Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions.
  • the test compound was diluted to a concentration of 300 ppm (wt compound: vol diluent) in a 1 :1 mixture of acetone:water, plus 0.01% Kinetic ® surfactant.
  • Thrips potency of each compound was evaluated by using a floral-immersion technique.
  • Plastic petri dishes were used as test arenas. All petals of individual, intact orchid flowers were dipped into treatment solution for approximately 3 seconds and allowed to dry for 2 hours. Treated flowers were placed into individual petri dishes along with 10 - 15 adult thrips. The petri dishes were then covered with lids.
  • Examples 6 and 7 according to the present invention and comparative compounds A and B according to EP 0 604 798 were tested in greenhouse-assays for their ability to combat spodoptera eridania (southern armyworm) and plutella xylostella (diamondback moth), respectively, as described above.
  • Comparative compounds A and B were prepared according to the methods given in EP 0 604 798.
  • the compound of the example 6 according to the present invention at 300 ppm showed a mortality of at least 80 %, whereas comparison compound A at 300 ppm showed no mortality.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne de nouveaux composés de type amidrazone qui sont utiles pour lutter contre les parasites, en particulier les insectes, les arachnides et les nématodes. L'invention concerne également un procédé de lutte contre les insectes, les nématodes et les arachnides. Les composés de type amidrazone répondent à la formule générale (I), y compris les tautomères de I et les sels de ceux-ci ; où X et Y représentent un atome d’hydrogène ou forment ensemble une liaison chimique ; Ar représente un radical aromatique choisi parmi le phényle et un radical hétéroaryle à 5 ou 6 chaînons ayant 1, 2, 3 ou 4 hétéroatomes en tant qu’éléments du noyau, qui sont choisis, indépendamment les uns des autres, parmi O, N et S, et où le radical aromatique peut avoir 1, 2, 3, 4 ou 5 substituants Ra ; R1 est choisi dans le groupe constitué par des radicaux alkyle en C1-C10, (alcoxy en C1-C4)(alkyle en C1-C4), cyano(alkyle en C1-C4), hydroxyalkyle en C1-C4, halogénoalkyle en C1-C10, tri-(alkyle en C1-C4)-silyl-(alkyle en C1-C4), alcényle en C2-C10, halogéno(alcényle en C2-C10), alcynyle en C2-C10, halogéno(alcynyle en C2-C10), cycloalkyle en C3-C10, phényle, hétéroaryle, (cycloalkyle en C3-C10)(alkyle en C1-C4), phényle-(alkyle en C1-C4) et hétéroaryle-(alkyle en C1-C4), où les radicaux cycloalkyle en C3-C10, hétéroaryle et phényle dans les six derniers radicaux mentionnés peuvent être non substitués ou substitués par 1, 2, 3, 4 ou 5 substituants Rb tels que définis ci-dessus ; R2 est choisi dans le groupe constitué par des radicaux alkyle en C1-C10, (alcoxy en C1-C4)(alkyle en C1-C4), halogénoalkyle en C1-C10, alcényle en C2-C10, halogéno(alcényle en C2-C10), alcynyle en C2-C10, halogéno(alcynyle en C2-C10), cycloalkyle en C3-C10, phényle, hétéroaryle, (cycloalkyle en C3-C10)(alkyle en C1-C4), phényle-(alkyle en C1-C4) et hétéroaryle-(alkyle en C1-C4), les radicaux cycloalkyle en C3-C10, hétéroaryle et phényle dans les six derniers radicaux mentionnés pouvant être non substitués ou substitués par 1, 2, 3, 4 ou 5 substituants Rb tels que définis ci-dessus.
PCT/EP2006/002331 2005-03-15 2006-03-14 Composes de type amidrazone de lutte contre les parasites WO2006097279A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US66207605P 2005-03-15 2005-03-15
US60/662,076 2005-03-15

Publications (2)

Publication Number Publication Date
WO2006097279A1 true WO2006097279A1 (fr) 2006-09-21
WO2006097279A8 WO2006097279A8 (fr) 2007-05-18

Family

ID=36613405

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/002331 WO2006097279A1 (fr) 2005-03-15 2006-03-14 Composes de type amidrazone de lutte contre les parasites

Country Status (1)

Country Link
WO (1) WO2006097279A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009059607A2 (fr) 2007-11-05 2009-05-14 Vestergaard Frandsen Sa Pièce comportant deux objets insecticides qui permettent de lutter contre les insectes résistants

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4270947A (en) * 1979-07-02 1981-06-02 Stauffer Chemical Company α-(Phenylazo)-2,6-dichlorobenzaldimino esters and their use as herbicides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4270947A (en) * 1979-07-02 1981-06-02 Stauffer Chemical Company α-(Phenylazo)-2,6-dichlorobenzaldimino esters and their use as herbicides

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
CHEM. BER., vol. 35, 1902, pages 753 *
DATABASE BEILSTEIN Beilstein Institut zur Förderung der Chemischen Wissenschaft, Frankfurt am Main, DE; XP002389345, retrieved from XFIRE Database accession no. 3130776, 6098309 *
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; KANG, FU'AN ET AL: "Correlation between structure and stability of nitronic acids and nitronic esters", XP002389344, retrieved from STN Database accession no. 1998:713936 *
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; MISRA, B. N. ET AL: "Reactions of N-acyl-O-alkylhydroxylamines: part V - preparation of hydroxamic ester chlorides and their nucleophilic reactions", XP002389342, retrieved from STN Database accession no. 1985:5857 *
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; NESYNOV, E. P. ET AL: "Aryl esters and amides of substituted carboxylic, carbazinic, and thioimido acids and O-aryl oximes and their effectiveness in controlling plant diseases", XP002389341, retrieved from STN Database accession no. 1975:527289 *
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; NESYNOV, E. P.: "Reaction of aryldiazonium salts with aldoximes", XP002389343, retrieved from STN Database accession no. 1977:55117 *
FIZIOLOGICHESKI AKTIVNYE VESHCHESTVA (1966-1992) , 7, 49-53 CODEN: FAVUAI; ISSN: 0533-1153, 1975 *
INDIAN JOURNAL OF CHEMISTRY, SECTION B: ORGANIC CHEMISTRY INCLUDING MEDICINAL CHEMISTRY , 23B(8), 728-32 CODEN: IJSBDB; ISSN: 0376-4699, 1984 *
SCIENCE IN CHINA, SERIES B: CHEMISTRY , 41(5), 504-509 CODEN: SCBCFQ; ISSN: 1006-9291, 1998 *
ZHURNAL ORGANICHESKOI KHIMII , 12(9), 1995-2001 CODEN: ZORKAE; ISSN: 0514-7492, 1976 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009059607A2 (fr) 2007-11-05 2009-05-14 Vestergaard Frandsen Sa Pièce comportant deux objets insecticides qui permettent de lutter contre les insectes résistants

Also Published As

Publication number Publication date
WO2006097279A8 (fr) 2007-05-18

Similar Documents

Publication Publication Date Title
US20090069317A1 (en) Insecticidal Methods Using 3-Amino-1,2-Benzisothiazole Derivatives
KR20070086639A (ko) 동물 해충 방제를 위한 신규2-시아노-3-(할로)알콕시-벤젠술폰아미드 화합물
JP2008534478A (ja) 種子処理用の２−シアノベンゼンスルホンアミド化合物
EP1956907A2 (fr) Derives de cyanobenzene pour lutter contre des animaux nuisibles
MX2007013917A (es) Compuestos con estructura de 1-(1,2-difenil-etil)-3-(2-hidroxietil )-tiourea para combatir plagas animales.
JP2006510697A (ja) 殺虫性ジベンゾ（ヘテロ）アゼピン誘導体
EP1940849B1 (fr) Composes d'isothiazolopyridine-3-ylenamines pour combattre les parasites d'animaux
JP4520989B2 (ja) 動物害虫を駆除するために用いる６−ハロゲノ−［１，２，４］トリアゾロ［１，５−ａ］ピリミジン類
JP2009531374A (ja) 動物害虫を駆除するための３−アミノ−１，２−ベンゾイソチアゾール化合物
JP2011510033A (ja) 化合物
US20050049146A1 (en) Use of substituted dibenzothiepine derivatives as insecticidal, acaricidal and nematicidal agents
WO2006058730A1 (fr) Composes d'hydrazide pour lutter contre des parasites animaux
WO2004105488A1 (fr) Derives de l'hydrazone combattant les insectes et arachnides nuisibles
WO2006056462A1 (fr) Composes d'azine permettant de combattre les parasites des animaux
JP2011513357A (ja) 化合物
JP2011524859A (ja) ３−アミノ−ベンゾ［ｄ］イソチアゾールジオキシド誘導体類及び殺虫剤としてのそれらの使用
WO2006097279A1 (fr) Composes de type amidrazone de lutte contre les parasites
US20060166984A1 (en) Amino substituted benzo(hetero)cyclic derivatives
US20070066627A1 (en) Hydrazone derivatives for combatting harmful insects and arachnids

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

WWW Wipo information: withdrawn in national office

Country of ref document: RU

122 Ep: pct application non-entry in european phase

Ref document number: 06723410

Country of ref document: EP

Kind code of ref document: A1

WWW Wipo information: withdrawn in national office

Ref document number: 6723410

Country of ref document: EP