WO2002050052A1 - N-acyl aminoacetonitriles aux proprietes pesticides - Google Patents

N-acyl aminoacetonitriles aux proprietes pesticides Download PDF

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Publication number
WO2002050052A1
WO2002050052A1 PCT/EP2001/014922 EP0114922W WO0250052A1 WO 2002050052 A1 WO2002050052 A1 WO 2002050052A1 EP 0114922 W EP0114922 W EP 0114922W WO 0250052 A1 WO0250052 A1 WO 0250052A1
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crc
alkyl
halo
substituents
alkoxy
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PCT/EP2001/014922
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English (en)
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Pierre Ducray
Arthur Steiger
Jacques Bouvier
Werner Zambach
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Syngenta Participations Ag
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Priority to AU2002224942A priority Critical patent/AU2002224942A1/en
Publication of WO2002050052A1 publication Critical patent/WO2002050052A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
    • C07D295/215—Radicals derived from nitrogen analogues of carbonic acid
    • 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
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • A01N39/04—Aryloxy-acetic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
    • C07C255/26—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton containing cyano groups, amino groups and singly-bound oxygen atoms bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
    • C07C255/44—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms at least one of the singly-bound nitrogen atoms being acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/30—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by halogen atoms, or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/32—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms
    • C07C275/34—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms having nitrogen atoms of urea groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring

Definitions

  • the present invention relates to compounds of formula
  • R is aryl unsubstituted or mono- to penta-substituted by R 7 ; or is heteroaryl unsubstituted or mono- to tetra-substituted by R 7 , it being possible for the substituents in each case to be the same or different when they number more than 1 ;
  • R 2 is CrCealkyl, halo-CrCealkyl, NR 8 R 9 , C(R 10 )(Rn)OR ⁇ 2 or, in each case bonded via N, pyrrolidinyl, piperidyl, imidazolidinyl, piperazinyl, pyrazolidinyl, morpholinyl, indolinyl or isoindolinyl;
  • R 4 , R 5 and R 6 are each independently of the others hydrogen, halogen, C ⁇ -C 6 alkyl, halo- C ⁇ -C 6 alkyl, CrC 6 alkoxy, halo-C C 6 alkoxy, CrC 6 alkylthio, halo-C Cealkylthio, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl; unsubstituted or mono- to tri-substituted C 3 -C 8 cycloalkyl, the substituents being selected from the group consisting of halogen and CrCealkyl; or unsubstituted or mono- to tri-substituted phenyl, the substituents being selected from the group consisting of halogen, C C 6 alkyl and phenyl; or R 4 and R 5 together with the carbon atoms to which they are bonded are a five- to seven- membered, saturated or partially unsaturated, heterocyclic ring containing
  • R 7 is halogen, C Cealkyl, halo-C C 6 alkyI, CrC 6 aIkoxy, halo-CrC -alkoxy, C r C 6 alkylthio, halo-CrC 6 alkylthio, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, unsubstituted or mono- to penta-substituted aryl, unsubstituted or mono- to penta-substituted phenylacetylenyl or unsubstituted or mono- to tetra-substituted heteroaryl, the substituents of the aryl, phenylacetylenyl and heteroaryl radicals being selected from the group consisting of halogen, nitro, cyano, C r C 6 alkyl, halo- CrC 6 alkyl, C C 6 alkoxy and halo-C C 6 alkoxy,
  • R 10 and Rn are each independently of the other hydrogen, C C 6 alkyl or halo-CrCealkyl;
  • R 12 is unsubstituted or mono- to penta-substituted aryl, the substituents being selected from the group consisting of halogen, nitro, cyano, C ⁇ -C 6 alkyl, halo-C ⁇ -C 6 alkyl, C ⁇ -C 6 alkoxy, halo- C C 6 alkoxy and R 13 , and it being possible for the substituents to be the same or different when they number more than 1 ;
  • R ⁇ 3 is unsubstituted or mono- to penta-substituted aryl or aryloxy, the substituents of the aryl and aryloxy radicals being selected from the group consisting of halogen, nitro, cyano, C Cealkyl, halo-CrCealkyl, C r C 6 alkoxy and halo-d-Cealkoxy, and it being possible for the substituents to be the same or different when they number more than 1 ;
  • X is O, S, S(O) or S(O 2 ); and n is 0 or 1 ; and, where appropriate, E/Z isomers, mixtures of E/Z isomers and/or tautomers thereof, in each case in free form or in salt form; to a process for the preparation of, and to the use of, such compounds and isomers and tautomers thereof; to starting compounds for the preparation of compounds of formula (I); to pesticidal compositions in which the active ingredient is selected from the compounds of formula (I) and tautomers thereof; and to a method of controlling pests, particularly plant- destructive insects and representatives of the order Acarina, and also endo- and ectoparasites, especially helminths, in and on warm-blooded productive livestock and domestic animals, using such compositions.
  • pests particularly plant- destructive insects and representatives of the order Acarina, and also endo- and ectoparasites, especially helminths, in and on warm-blooded productive livestock
  • the compounds of formula (I) and, where appropriate, tautomers thereof are capable of forming salts, for example acid addition salts.
  • Those acid addition salts are formed, for example, with strong inorganic acids, such as mineral acids, e.g. sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as unsubstituted or substituted, e.g. halo-substituted, CrC 4 alkanecarboxylic acids, e.g. acetic acid, saturated or unsaturated dicarboxylic acids, e.g. oxalic, malonic, maleic, fumaric and phthalic acid, hydroxycarboxylic acids, e.g.
  • strong inorganic acids such as mineral acids, e.g. sulfuric acid, a phosphoric acid or a hydrohalic acid
  • strong organic carboxylic acids such as unsubstituted or substituted, e.g. halo-substi
  • compounds of formula (I) having at least one acid group are capable of forming salts with bases.
  • Suitable salts with bases are, for example, metal salts, such as alkali metal and alkaline earth metal salts, e.g.
  • sodium, potassium and magnesium salts and salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri- lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or tri- hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine.
  • corresponding internal salts may optionally also be formed. Preference is given, firstly, to the free form.
  • preference is given to agrochemically advantageous salts.
  • Aryl is phenyl or naphthyl.
  • Heteroaryl is pyridyl, pyrimidyl, s-triazinyl, 1 ,2,4-triazinyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, triazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, benzothienyl, benzofuranyl, benzothiazolyl, indolyl or indazolyl, preferably pyridyl, pyrimidyl, s-triazinyl or 1 ,2,4-triazinyl, especially pyridyl or pyrimidyl.
  • Alkyl both as a group perse and as a structural element of other groups and compounds, for example haloalkyl, alkoxy and alkylthio, is, in each case taking due account of the particular number of carbon atoms contained in the group or compound in question, either straight-chained, i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, or branched, e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
  • straight-chained i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl
  • branched e.g. isopropyl, isobutyl, sec-
  • Alkenyl both as a group perse and as a structural element of other groups and compounds, is, in each case taking due account of the particular number of carbon atoms and conjugated or isolated double bonds contained in the group or compound in question, either straight- chained, for example allyl, 2-butenyl, 3-pentenyl, 1-hexenyl, 1-heptenyl, 1 ,3-hexadienyl or 1 ,3-octadienyl, or branched, for example isopropenyl, isobutenyl, isoprenyl, tert-pentenyl, isohexenyl, isoheptenyl or isooctenyl.
  • Alkynyl both as a group per se and as a structural element of other groups and compounds, is, in each case taking due account of the particular number of carbon atoms and conjugated or isolated double bonds contained in the group or compound in question, either straight- chained, for example propargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl, 3-hexen-1-ynyl or 1 ,5-heptadien-3-ynyl, or branched, for example 3-methylbut-1-ynyl, 4-ethylpent-1 -ynyl, 4- methylhex-2-ynyl or 2-methylhept-3-ynyl.
  • straight- chained for example propargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl, 3-hexen-1-ynyl or 1 ,5-heptadien-3-y
  • Cycloalkyl both as a group perse and as a structural element of other groups and compounds, for example halocycloalkyl, is, in each case taking due account of the particular number of carbon atoms contained in the group or compound in question, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • Halogen both as a group per se and as a structural element of other groups and compounds, for example haloalkyl, haloalkoxy and haloalkylthio, is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine.
  • Halo-substituted, carbon-containing groups and compounds for example haloalkyl, haloalkoxy and haloalkylthio, may be partially halogenated or perhalogenated, the halogen substituents in the case of multiple halogenation being identical or different.
  • haloalkyl both as a group perse and as a structural element of other groups and compounds, for example haloalkoxy and haloalkylthio, are methyl mono- to tri-substituted by fluorine, chlorine and/or by bromine, for example CHF 2 or CF 3 ; ethyl mono- to penta- substituted by fluorine, chlorine and/or by bromine, for example CH 2 CF 3 , CF 2 CF 3 , CF 2 CCl 3 , CF 2 CHCI 2) CF 2 CHF 2 , CF 2 CFCl 2 , CF 2 CHBr 2 , CF 2 CHClF, CF 2 CHBrF or CCIFCHCIF; propyl or isopropyl each mono- to hepta-substituted by fluorine, chlorine and/or by bromine, for example CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 , CH 2 CF 2 CF 3
  • Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert- butoxy and a pentyloxy or hexyloxy isomer, preferably methoxy and ethoxy.
  • Haloalkoxy groups preferably have a chain length of from 1 to 6 carbon atoms.
  • Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1 ,1 ,2,2- tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difIuoroethoxy and 2,2,2-trichloro- ethoxy, preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
  • Alkylthio groups preferably have a chain length of from 1 to 6 carbon atoms.
  • Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio and ethylthio.
  • RT is aryl unsubstituted or mono- to penta-substituted by R 7 , it being possible for the substituents in each case to be the same or different when they number more than 1 ; especially aryl mono- to tri-substituted by R 7 , it being possible for the substituents in each case to be the same or different when they number more than 1 ;
  • R 2 is C C 6 alkyl, halo-C C 6 alkyl, NR 8 R 9 , C(R ⁇ o)(R ⁇ )OR 12 or, in each case bonded via N, pyrrolidinyl, piperidyl or morpholinyl; especially C r C 6 alkyl, NR 8 R 9 , C(R 10 )(R ⁇ ,)OR 12 or pyrrolidinyl bonded via N; more especially C C 4 alkyl, NR 8 R 9 or C(R 10 )(Rn)OR 12 ;
  • R 3 is hydrogen, CrC 6 alkyl, CrCealkoxy-CrCealkyl or benzyl; especially hydrogen or C C 4 alkyl; more especially hydrogen;
  • R 4 , R 5 and R 6 are each independently of the others hydrogen, C r C 6 alkyl, halo-CrCealkyl, C r C 6 alkoxy, halo-CrC 6 alkoxy, C 2 -C 6 alkenyl, C 2 -C 6 - alkynyl, C 3 -C 6 cycloalkyl; especially hydrogen, C C 4 alkyl, halo-C r C 4 alkyl or C 3 -C 6 cycloalkyl; more especially R 4 is C ⁇ -C 2 alkyl and R 5 and R 6 are each independently of the other hydrogen or d-C 2 alkyl;
  • R 7 is halogen, CrC ⁇ alkyl, halo-CrC 6 alkyl, CrCealkoxy, halo-d-C 6 alkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, unsubstituted or mono- to penta- substituted aryl or unsubstituted or mono- to tetra-substituted heteroaryl, the substituents in each case being selected from the group consisting of halogen, nitro, cyano, d-C 6 alkyl, halo-CrC 6 alkyl, CrC 6 alkoxy and halo-CrC 6 alkoxy, and it being possible for the substituents in each case to be the same or different when they number more than 1 ; especially halogen, C C 4 alkyl, halo-C C alkyl, C C 4 alkoxy, halo-C C 4 alkoxy
  • R 8 and R 9 are each independently of the other hydrogen or mono- to tri-substituted aryl, the substituents being selected from the group consisting of halogen, nitro, cyano, CrC 4 alkyl, halo-CrC alkyl, C C 4 alkoxy and halo-d-C 4 - alkoxy, and it being possible for the substituents in each case to be the same or different when they number more than 1 ; especially hydrogen or unsubstituted or mono- or di- substituted aryl, the substituents being selected from the group consisting of halogen, CrC 2 alkyl and halo-d-C 2 alkyl, and it being possible for the substituents in each case to be the same or different when they number more than 1 ; more especially hydrogen or mono- substituted aryl, the substituents being selected from the group consisting of halogen, d-C 2 alkyl and halo-C C 2 alkyl
  • R 12 is unsubstituted or mono- to tri-substituted aryl, the substituents being selected from the group consisting of halogen, nitro, cyano, C C 4 - alkyl, halo-CrC 4 alkyl, C C alkoxy and halo-d-C 4 alkoxy, and it being possible for the substituents to be the same or different when they number more than 1 ; especially unsubstituted or mono- to tri-substituted aryl, the substituents being selected from the group consisting of halogen, C C 2 alkyl and halo-d-d-alkyl, and it being possible for the substituents to be the same or different when they number more than 1 ; more especially mono- or di-substituted aryl, the substituents being selected from the group consisting of halogen and halo-d-C 2 alkyl, and it being possible for the substituents to
  • R ⁇ is aryl unsubstituted or mono- to penta- substituted by R 7 , it being possible for the substituents in each case to be the same or different when they number more than 1 ;
  • R 2 is CrCealkyl, halo-CrC 6 alkyl, NR 8 R 9 , C(R 10 )(R 1 i)OR 12 or, in each case bonded via N, pyrrolidinyl, piperidyl or morpholinyl;
  • R 3 is hydrogen or d-C 6 alkyl;
  • R 4 , R 5 and R 6 are each independently of the others hydrogen, d-C 4 - alkyl, halo-d-C 4 alkyl, Crdalkoxy, halo-C r C 4 alkoxy, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl or unsubstituted or substituted C 3 -C 6 cycloalkyl, the
  • X is O or S; and n is 1 ;
  • R ⁇ is aryl mono- to tri-substituted by R 7 , it being possible for the substituents in each case to be the same or different when they number more than 1 ;
  • R 2 is d-C 6 alkyl, NR 8 R 9 , C(R 10 )(Rn)OR 12 or pyrrolidinyl bonded via N;
  • R 3 is hydrogen or d-C 4 alkyl;
  • R 4 , R 5 and R 6 are each independently of the others hydrogen, C C 4 - alkyl, halo-C r C 4 alkyl or C 3 -C 6 cycloalkyl;
  • R 7 is halogen, C C 4 alkyl, halo-d-C 4 alkyl, C C 4 - alkoxy, halo-C C 4 alkoxy or unsubstituted or mono- to penta-substituted aryl, the substituents being selected from the group consisting of halogen, nitro
  • R ⁇ is aryl mono- to tri-substituted by R 7 , it being possible for the substituents in each case to be the same or different when they number more than 1 ;
  • R 2 is C r C 4 alkyl, NR 8 R 9 or C(R 10 )(Rn)OR 12 ;
  • R 3 is hydrogen;
  • R 4 is d-C 2 alkyI and R 5 and R 6 are each independently of the other hydrogen or C C 2 alkyl;
  • R 7 is halogen, d-C 2 alkyl, halo-d-C 2 alkyl, C C 2 alkoxy or halo-C C 2 alkoxy;
  • R 8 and R 9 are each independently of the other hydrogen or mono-substituted aryl, the substituents being selected from the group consisting of halogen, CrC 2 alkyl and halo-CrC 2 alkyl;
  • R 10 and Rn are each independently of the other hydrogen or C C 2 alkyl;
  • the invention relates also to the process for the preparation of compounds of formula (I), in each case in free form or in salt form, which process comprises, for example, reacting a compound of formula
  • R Q which is known or which can be prepared analogously to corresponding known compounds and in which R 2 is as defined for formula (1) and Q is a leaving group, optionally in the presence of a basic catalyst, and in each case, if desired, converting a compound of formula (I), in each case in free form or in salt form, obtainable in accordance with the process or by another method into a different compound of formula (I), separating a mixture of isomers obtainable in accordance with the process and isolating the desired isomer and/or converting a free compound of formula (I) obtainable in accordance with the process into a salt or converting a salt of a compound of formula (I) obtainable in accordance with the process into the free compound of formula (I) or into a different salt.
  • the reactants can be reacted with one another as such, that is to say without the addition of a solvent or diluent, for example in the molten state. Generally, however, it is advantageous to add an inert solvent or diluent or a mixture thereof.
  • solvents and diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene, bromo- benzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetra- chloromethane, dichloroethane, trichloroethene and tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran and di
  • Preferred leaving groups are OH, halogens, tosylates, mesylates and triflates, especially halogens, more especially chlorine.
  • Suitable bases for facilitating the reaction are, for example, alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or alkylsilylamides, or alkylamines, alkylenediamines, unsubstituted or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
  • DBU ,5-diazabicyclo[5.4.0]undec-5- ene
  • the reaction is advantageously carried out in a temperature range of from about 0°C to about +150°C, preferably from about 20°C to about +100°C.
  • the invention relates also to the process for the preparation of compounds of formula (II), in each case in free form or in salt form, which process comprises, for example, reacting a compound of formula
  • Suitable cyanides are sodium cyanide, potassium cyanide, trimethylsilyl cyanide and acetone cyanohydrin.
  • Compounds of formula (I) obtainable in accordance with the process or by another method can be converted in a manner known perse into different compounds of formula (I) by replacing one or more substituents of the starting compound of formula (I) by (an)other substituent(s) according to the invention in customary manner.
  • reaction step it is possible in a reaction step to replace only one substituent by another substituent according to the invention or it is possible in the same reaction step to replace a plurality of substituents by other substituents according to the invention.
  • Salts of compounds of formula (I) can be prepared in a manner known perse.
  • acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchange reagent and salts with bases are obtained by treatment with a suitable base or a suitable ion exchange reagent.
  • Salts of compounds of formula (I) can be converted in customary manner into the free compounds of formula (I); acid addition salts can be converted, for example, by treatment with a suitable basic medium or a suitable ion exchange reagent and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchange reagent.
  • Salts of compounds of formula (I) can be converted into different salts of compounds of formula (I) in a manner known per se; for example acid addition salts can be converted into different acid addition salts, for example by treatment of a salt of an inorganic acid, such as a hydrochloride, with a suitable metal salt, such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt being formed, for example silver chloride, is insoluble and is therefore precipitated out from the reaction mixture.
  • a salt of an inorganic acid such as a hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds of formula (I) having salt-forming properties can be obtained in free form or in the form of salts.
  • the compounds of formula (l) can also be obtained in the form of their hydrates and/or can include other solvents, for example any solvent that may have been used for the crystallisation of compounds in solid form.
  • the compounds of formulae (I) and (II) may be in the form of one of the possible isomers or in the form of a mixture thereof, for example depending upon the number of asymmetric carbon atoms and the absolute and relative configuration thereof, in the form of pure isomers, such as antipodes and/or diastereoisomers, or in the form of mixtures of isomers, such as mixtures of enantiomers, for example racemates, mixtures of diastereoisomers or mixtures of racemates; the invention relates both to the pure isomers and to all possible mixtures of isomers and this is to be understood accordingly hereinbefore and hereinafter, even when stereochemical details are not specifically mentioned in each case.
  • Mixtures of enantiomers or racemates so obtainable can be separated into the optical antipodes by known methods, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbents, for example high-pressure liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific immobilised enzymes, or via the formation of inclusion compounds, for example using chiral crown ethers, in which case only one enantiomer is complexed.
  • HPLC high-pressure liquid chromatography
  • Pure diastereoisomers and enantiomers can be obtained not only by separation of corresponding mixtures of isomers but also, according to the invention, by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials that have appropriate stereochemistry.
  • the invention relates especially to the preparation process described in the Example.
  • the invention relates also to the novel starting materials and intermediates that are used according to the invention in the preparation of compounds of formula (I), to their use and to processes for the preparation thereof.
  • the compounds of formula (I) according to the invention are active ingredients exhibiting valuable preventive and/or curative activity with a very advantageous biocidal spectrum, even at low rates of concentration, while being well tolerated by warmblooded organisms, fish and plants.
  • the compounds are especially suitable for use in the area of controlling endo- and ecto-parasites of animals and plant-destructive insects and representatives of the order Acarina.
  • the active ingredients according to the invention are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects and representatives of the order Acarina.
  • the pesticidal activity of the active ingredients according to the invention may manifest itself directly, i.e.
  • the compounds of formula (I) are especially distinguished by an unusually long duration of action.
  • the said animal pests of plants include those mentioned in European Patent Application EP-A-736 252, page 5, line 55 to page 6, line 55.
  • the pests mentioned therein are therefore included by reference in the subject matter of the present invention.
  • the compounds of formula (I) can also be used against pests affecting hygiene, especially of the order Diptera with the families Sarcophagidae, Anophilidae and Culicidae; and of the orders Orthoptera, Dictyoptera (e.g. the family Blattidae) and Hymenoptera (e.g. the family Formicidae).
  • the compounds of formula (I) also have long-lasting activity in the case of mites and insects that are parasites of plants.
  • spider mites of the order Acarina they are effective against eggs, nymphs and adults of Tetranychidae (Tetranychus spp. and Panonychus spp.).
  • insects of the order Homoptera possess a high degree of activity in sucking insects of the order Homoptera, especially against pests of the families Aphididae, Delphacidae, Cicadellidae, Psyllidae, Loccidae, Diaspididae and Eriophydidae (e.g. rust mite on citrus fruit); of the orders Hemiptera, Heteroptera and Thysanoptera, and in phytophagous insects of the orders Lepidoptera, Coleoptera, Diptera and Orthoptera.
  • the compounds according to the invention can be used to control, i.e. to inhibit or destroy, pests of the mentioned type occurring especially on plants, more especially on useful plants and ornamentals in agriculture, in horticulture and in forestry, or on parts of such plants, such as the fruits, blossoms, leaves, stems, tubers or roots, while in some cases parts of plants that grow later are still protected against those pests.
  • the compounds of formula (I) are therefore effective against all development stages of sucking and phytophagous insects on crops such as cereals, e.g. wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, e.g. pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, e.g.
  • crops such as cereals, e.g. wheat, barley, rye, oats, rice, maize and sorghum
  • beet such as sugar beet and fodder beet
  • fruit e.g. pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, e.g.
  • strawberries, raspberries and blackberries leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil, cocoa and groundnuts; cucurbitaceae, such as marrows, cucumbers and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruits, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocado, cinnamon and camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas, natural rubber plants and ornamentals.
  • the compounds of formula (I) are also effective against plant-nematodes of the species Meloidogyne, Heterodera, Pratylenchus, Ditylenchus, Radopholus, Rizoglyphus and others.
  • ectoparasites occurring as parasites on warmblooded organisms are understood to mean especially insects, mites and ticks. Included are insects of the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera.
  • ectoparasites that trouble humans and animals and transmit pathogens
  • pathogens for example flies, such as Musca domestica, Musca vetustissima, Musca autumnalis, Fannia canicularis, Sarcophaga carnaria, Lucilia cuprina, Hypoderma bovis, Hypoderma lineatum, Chrysomyia chloropyga, Dermatobia hominis, Cochliomyia hominivorax, Gasterophilus intestinalis, Oestrus ovis, Stomoxys calcitrans, Haematobia irritans and midges (Nematocera), such as Culicidae, Simuliidae, Psychodidae, and also bloodsucking parasites, for example fleas, such as Ctenocephalides felis and Ctenocephalides canis (cat and dog fleas), Xenopsylla cheopis, Pulex irritans, Dermatophilus
  • ticks are, for example, Boophilus, Amblyomma, Anocentor, Dermacentor, Haemaphysalis, Hyalomma, Ixodes, Rhipicentor, Margaropus, Rhipicephalus, Argas, Otobius and Ornithodoros and the like, which preferentially infest warm-blooded animals, including farm animals, such as cows, pigs, sheep and goats, poultry, such as hens, turkeys and geese, animals bred for their fur, such as mink, fox, chinchillas, rabbits and the like, and domestic animals, such as cats and dogs, but also humans.
  • farm animals such as cows, pigs, sheep and goats
  • poultry such as hens, turkeys and geese
  • animals bred for their fur such as mink, fox, chinchillas, rabbits and the like
  • domestic animals such as cats and dogs, but also humans.
  • the compounds of formula (I) are especially effective against helminths, among which the endoparasitic nematodes and trematodes may be the cause of serious diseases of mammals and poultry, for example of sheep, pigs, goats, cattle, horses, donkeys, dogs, cats, guinea-pigs and ornamental birds.
  • Typical nematodes in that indication are: Haemonchus, Trichostrongylus, Ostertagia, Nematodirus, Cooperia, Ascaris, Bunostonum, Oesophagostonum, Chabertia, Trichuris, Strongylus, Trichonema, Dictyocaulus, Capillaria, Heterakis, Toxocara, Ascaridia, Oxyuris, Ancylostoma, Uncinaria, Toxascaris and Para- scaris.
  • the trematodes special mention should be made of the family of the Fasciolideae, especially Fasciola hepatica.
  • the special advantage of the compounds of formula (I) is their efficacy against such parasites that are resistant to benzimidazole-based active ingredients.
  • Parasites of the families Filariidae and Setariidae are found in the internal cell tissue and the organs, for example the heart, the blood vessels, the lymph vessels and the subcutaneous tissue. In this context special mention should be made of dog heartworm, Dirofilaria immitis.
  • the compounds of formula (I) are highly effective against those parasites.
  • the compounds of formula (I) are suitable for controlling parasites that are pathogens of humans, among which, as typical representatives occurring in the digestive tract, mention should be made of those of the species Ancylostoma, Necator, Ascaris, Strongyloides, Trichinella, Capillaria, Trichuris and Enterobius.
  • the compounds of the present invention are also effective against parasites of the species Wuchereria, Brugia, Onchocerca and Loa from the family of the Filariidae, which occur in the blood, in tissue and various organs, and also against Dracunculus and parasites of the species Strongyloides and Trichinella, which infect especially the gastrointestinal tract.
  • the compounds of formula (I) are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology and can therefore be formulated in known manner e.g. into emulsifiable concentrates, directly dilutable solutions, dilute emulsions, soluble powders, granules, and also encapsulations in polymer substances.
  • the methods of application are selected in accordance with the intended objectives and the prevailing circumstances.
  • the invention relates also to pesticides, such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising at least one of the active ingredients of the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances. They are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, for example with solvents, solid carriers, and optionally surface-active compounds (surfactants).
  • extenders for example with solvents, solid carriers, and optionally surface-active compounds (surfactants).
  • the active ingredient is used in those compositions in pure form: a solid active ingredient, for example, in a specific particle size, or preferably together with at least one of the adjuvants customary in formulation technology, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).
  • a solid active ingredient for example, in a specific particle size, or preferably together with at least one of the adjuvants customary in formulation technology, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).
  • formulation adjuvants there are used, for example, solid carriers, solvents, stabilisers, "slow release” adjuvants, dyes and optionally surface-active substances (surfactants).
  • Suitable carriers and adjuvants include all those substances customarily used in crop protection products, especially in snail and slug control products.
  • Suitable adjuvants, such as solvents, solid carriers, surface-active compounds, non-ionic surfactants, cationic surfactants, anionic surfactants and other adjuvants in the compositions used according to the invention include e.g. those described in EP-A-736 252, page 7, line 51 , to page 8, line 39. They are included by reference in the subject matter of the present invention.
  • compositions for use in crop protection generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of active ingredient and from 1 to 99.9 % by weight, especially from 5 to 99.9 % by weight, of at least one solid or liquid adjuvant, it generally being possible for from 0 to 25 % by weight, especially from 0.1 to 20 %, of the compositions to consist of surfactants.
  • the end user will normally employ dilute formulations, which have much lower active ingredient concentrations.
  • Emulsifiable concentrates active ingredient: 1 to 95 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % solvent: 5 to 98 %, preferably 70 to 85 %
  • Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 1 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surfactant: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 99 %, preferably 15 to 98 %
  • Granules active ingredient: 0.5 to 30 %, preferably 3 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • the anthelmintic compositions according to the invention for the control of animal parasites in and on warm-blooded organisms generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compound of formula (I), from 99.9 to 1 % by weight, especially from 99.8 to 5 % by weight, of a solid or liquid auxiliary, which includes from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant.
  • Preferred forms of administration for use in warm-blooded organisms for controlling helminths include solutions, emulsions, suspensions (drenches), feed additives, powders, tablets including effervescent tablets, boli, capsules, micro-encapsulations and pour-on formulations, it being necessary to ensure that the formulation adjuvants are physiologically tolerable.
  • Suitable solvents in the use of formulations for controlling animal parasites are, for example: alcohols, e.g. ethanol, propanol or butanol, and glycols and ethers and esters thereof, e.g. propylene glycol, dipropylene glycol ether, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones, e.g. cyclohexanone, isophorone or diacetone alcohol, strong polar solvents, e.g. N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide or water, vegetable oils, e.g. rapeseed oil, castor oil, coconut oil or soybean oil, and also, where appropriate, silicone oils.
  • alcohols e.g. ethanol, propanol or butanol
  • glycols and ethers and esters thereof e.g. propylene glycol, dipropylene glycol ether, ethylene glycol, ethylene glyco
  • Suitable binders for tablets and boli are chemically modified natural polymeric substances soluble in water or in alcohol, for example starch, cellulose or protein derivatives (e.g. methylcellulose, carboxymethylcellulose, ethyl hydroxyethylcellulose, proteins such as zein, gelatin and the like) and synthetic polymers, e.g. polyvinyl alcohol, polyvinylpyrrolidone etc.. Tablets also comprise fillers (e.g. starch, microcrystalline cellulose, sugar, lactose etc.), lubricants and disintegrants.
  • fillers e.g. starch, microcrystalline cellulose, sugar, lactose etc.
  • the anthelmintic compositions are in the form of feed concentrates, there are used as carriers, for example, performance feeds, feed grains or protein concentrates.
  • feed concentrates or compositions can also comprise, besides the active ingredients, auxiliaries, vitamins, antibiotics, chemotherapeutic agents or other pesticides, especially bacteriostatics, fungistatics, coccidiostatics and also hormone preparations, substances having an anabolic action or substances that promote growth, that influence the quality of meat of slaughtered animals or that are useful in some other way for the organism.
  • the final feed or drinking troughs contain the active ingredients in a concentration of preferably from 0.0005 to 0.02 % by weight (5-200 ppm).
  • the compounds of formula (I) according to the invention can be used alone or in combination with other biocides.
  • they in order to enhance the effect they can be combined with pesticides having the same direction of action or, in order to broaden the spectrum of activity, they can be combined with substances having a different direction of action. It can also be of advantage to add so-called 'repellents'.
  • the compounds of formula (I) are advantageously combined with substances having endoparasiticidal properties. They can, of course, also be used in combination with anti-bacterial agents. Since the compounds of formula (l) are "adulticides", i.e.
  • Suitable mixing partners for use in crop protection and for use in controlling endo- and ectoparasites on warm-blooded organisms are biocides, for example the insecticides and acaricides mentioned hereinbelow and sufficiently known to the person skilled in the art which have a different mechanism of action, for example chitin synthesis inhibitors, growth regulators; active ingredients that act in the same manner as juvenile hormones; active ingredients that act as adulticides; broad-spectrum insecticides, broad-spectrum acaricides, and nematicides; and also the sufficiently known anthelmintics, and substances repelling insects and/or Acarina, the said repellents and detachers.
  • biocides for example the insecticides and acaricides mentioned hereinbelow and sufficiently known to the person skilled in the art which have a different mechanism of action, for example chitin synthesis inhibitors, growth regulators; active ingredients that act in the same manner as juvenile hormones; active ingredients that act as adulticides; broad-spectrum
  • suitable insecticides and acaricides are azamethiphos; chlorfenvinphos; cypermethrin, cypermethrin high-cis; cyromazine; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; jodfenphos; kinoprene; lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon; profenofos; diofenolan; a substance obtainable from the Bacillus thuringiensis strain GC91 or from the strain NCTC11821 ; pymetrozine; bromopropylate; methoprene; disulfuton; quinalphos; tau- fluva ⁇ nate; thiocyclam; thiometon; aldicarb;
  • anthelmintics that can be added to the compositions are mentioned hereinbelow, a number of the examples thereof having, in addition to anthelmintic activity, also an insecticidal and acaricidal activity, some of them already being mentioned in the list above:
  • praziquantel 2-cyclohexylcarbonyl-4-oxo-1 ,2,3,6,7,11 b-hexahydro-4H-pyrazino[2,1 - ⁇ jisoquinoline
  • A2 closantel 3,5-diiodo-N-[5-chloro-2-methyl-4-(a-cyano-4-chlorobenzyl)phenyl]salicyl- amide
  • triclabendazole 5-chloro-6-(2,3-dichlorophenoxy)-2-methylthio-1 H-benzimidazole
  • omphalotin a macrocyclic fermentation product of the fungus Omphalotus olearius described in WO 97/20857
  • abamectin avermectin B1
  • ivermectin 22,23-dihydroavermectin B1
  • moxidectin 5-O-demethyl-28-deoxy-25-(1 ,3-dimethyl-1-butenyl)-6,28-epoxy-23-
  • Non-limiting examples of suitable repelling substances are:
  • a further substantial aspect of the present invention relates to combination preparations for the control of parasites on warm-blooded organisms, which combination preparations comprise, in addition to a compound of formula (I), at least one further active ingredient having the same direction of action or a different direction of action and at least one physiologically tolerable carrier.
  • the present invention is not limited to two- component combinations.
  • compositions according to the invention can be administered to the animals being treated by topical, peroral, parenteral or subcutaneous means, the compositions being in the form of solutions, emulsions, suspensions (drenches), powders, tablets, boli, capsules and pour-on formulations.
  • the pour-on or spot-on method comprises applying the compound of formula (I) to a locally defined area of the skin or coat, advantageously on the back of the neck or the backbone of the animal. This is carried out, for example, by applying a swab or spray of the pour-on or spot-on formulation to a relatively small area of the coat from where the active ingredient becomes distributed over a wide area of the coat almost automatically as a result of the spreading constituents of the formulation assisted by the movements of the animal.
  • Pour-on and spot-on formulations advantageously comprise carriers that promote rapid distribution over the surface of the skin or in the coat of the host animal and are generally termed spreading oils. There are suitable, for example, oily solutions; alcoholic and iso- propanolic solutions, e.g.
  • solutions of 2-octyl-dodecanol or oleyl alcohol solutions in esters of monocarboxylic acids, such as isopropyl myristate, isopropyl palmitate, lauric acid oxalic ester, oleic acid oleyl ester, oleic acid decyl ester, hexyl laurate, oleyl oleate, decyl oleate, capric acid esters of saturated fatty alcohols of chain length C 12 -C 18 ; solutions of esters of dicarboxyiic acids, such as dibutyl phthalate, diisopropyl isophthalate, adipic acid diisopropyl ester, di-n-butyl adipate or solutions of esters of aliphatic acids, e.g.
  • glycols It may be advantageous for a dispersant known from the pharmaceutical or cosmetic industry also to be present.
  • examples are 2-pyrrolidone, 2-(N-alkyl)pyrrolidone, acetone, polyethylene glycol and its ethers and esters, propylene glycol or synthetic triglycerides.
  • the oily solutions include e.g. vegetable oils, such as olive oil, groundnut oil, sesame oil, pine oil, linseed oil and castor oil.
  • vegetable oils may also be in epoxidised form. It is also possible to use paraffins and silicone oils.
  • a pour-on or spot-on formulation will contain from 1 to 20 % by weight of a compound of formula (I), from 0.1 to 50 % by weight dispersant and from 45 to 98.9 % by weight solvent.
  • the pour-on or spot-on method can be used especially advantageously for herd animals, such as cattle, horses, sheep and pigs, where it is difficult or time-consuming to treat all the animals orally or via injection.
  • this method can of course also be used for all other animals, including individual domestic animals and pets, and is very popular with the keepers of the animals because it can often be carried out without the expert assistance of a veterinary surgeon.
  • Such formulations may also comprise further ingredients, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers as well as other active ingredients for obtaining special effects.
  • further ingredients such as stabilisers, antifoams, viscosity regulators, binders and tackifiers as well as other active ingredients for obtaining special effects.
  • the present invention relates also to such anthelmintic compositions employed by the end user. ln each of the methods according to the invention for controlling pests and in each of the pesticidal compositions according to the invention, the active ingredients of formula (I) can be used in any of their spatial configurations or mixtures thereof.
  • the invention also encompasses a method for the prophylactic protection of warm-blooded organisms, especially of productive livestock, domestic animals and pets, against parasitic helminths, which method comprises administering to the animals the active ingredient of formula (I) or active ingredient formulations prepared therefrom as an additive to the feed or to the drinking troughs or in solid or liquid form orally, by injection or parenterally.
  • the invention also encompasses the compounds of formula (I) according to the invention for use in one of the mentioned methods.
  • Granules a) b) active ingredient from Tables 1 or 2 5 % 10 % kaolin 94 % - highly disperse silicic acid 1 % - attapulgite - 90 %
  • the active ingredient is dissolved in methylene chloride and sprayed onto the carrier, and the solvent is then evaporated off in vacuo. Such granules can be mixed into the animal feed.
  • Granules active ingredient from Tables 1 or 2 3 % polyethylene glycol (MW 200) 3 % kaolin 94 %
  • the finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • I active ingredient from Tables 1 or 2 33.00 % methylcellulose 0.80 % highly disperse silicic acid 0.80 % maize starch 8.40 % crystalline lactose 22.50 % maize starch 17.00 % microcrystalline cellulose 16.50 % magnesium stearate 1.00 %
  • Methylcellulose is stirred into water. After the material has swelled, silicic acid is stirred in and the mixture is homogeneously suspended. The active ingredient and maize starch are mixed. The aqueous suspension is incorporated into the resulting mixture and kneaded to a dough. The mass thereby obtained is granulated through a 12 M sieve and dried.
  • Preparation The active ingredient is dissolved in a portion of the oil with stirring and optionally with gentle heating, and after cooling the solution is made up to the desired volume and sterile-filtered through a suitable 0.22 micron membrane filter.
  • active ingredient from Tables 1 or 2 0.1-1.0 g polyethoxylated castor oil (40 ethylene oxide units) 10 g 1 ,2-propanediol 20 g benzyl alcohol i g aqua ad inject. ad 100 ml
  • active ingredient from Tables 1 or 2 0.1-1.0 g polyethoxylated sorbitan monooleate (20 ethylene oxide units) 8 g 4-hydroxymethyl-1 ,3-dioxolane (glycerol formal) 20 g benzyl alcohol i g aqua ad inject. ad 100 ml
  • Preparation The active ingredient is dissolved in the solvents and the surfactant, and the solution is made up to the desired volume with water. Sterile-filtration is then carried out through a suitable membrane filter of 0.22 micron pore diameter.
  • the aqueous systems may preferably be used also for oral and/or intraruminal administration.
  • compositions may also comprise further ingredients such as stabilisers, e.g. vegetable oils and epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilisers as well as other active ingredients for obtaining special effects.
  • stabilisers e.g. vegetable oils and epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilisers as well as other active ingredients for obtaining special effects.
  • compositions further biologically active substances or additives that have neutral behaviour towards the compounds of formula (I) and have no adverse effect on the host animal to be treated, and also mineral salts or vitamins.
  • compositions according to the invention are prepared in known manner, in the absence of adjuvants, for example by grinding, sieving and/or compressing a solid active ingredient or mixture of active ingredients, for example to a specific particle size, or in the presence of at least one adjuvant, for example by intimately mixing and/or grinding the active ingredient or mixture of active ingredients with the adjuvant(s).
  • the invention relates also to those processes for the preparation of the compositions according to the invention and to the use of the compounds I in the preparation of those compositions.
  • the invention relates also to the methods of application of the compositions, i.e. the methods of controlling pests of the mentioned type, such as spraying, atomising, dusting, coating, dressing, scattering or pouring, which are selected in accordance with the intended objectives and prevailing circumstances, and to the use of the compositions for controlling pests of the mentioned type.
  • Typical rates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, of active ingredient.
  • the rates of application per hectare are generally from 1 to 2000 g of active ingredient per hectare, especially from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.
  • a preferred method of application in the area of crop protection is application to the foliage of the plants (foliar application), the number of applications and the rate of application depending on the risk of infestation by the pest in question.
  • the active ingredient can also penetrate the plants through the roots (systemic action) if the locus of the plants is impregnated with a liquid formulation or if the active ingredient is incorporated in solid form into the locus of the plants, for example into the soil, e.g. in granular form (soil application). In paddy rice crops, such granules may be applied in metered amounts to the flooded rice field.
  • the compositions according to the invention are also suitable for protecting plant propagation material, including genetically modified propagation material, e.g.
  • the propagation material can be treated with the formulation before planting: seed, for example, can be dressed before being sown.
  • the compounds according to the invention can also be applied to grains (coating), either by impregnating the grains with a liquid formulation or by coating them with a solid formulation.
  • the formulation can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing.
  • the invention relates also to those methods of treating plant propagation material and to the plant propagation material thus treated.
  • the crude product is then extracted from the mixture using ethyl acetate; the organic phase is separated off, washed with aqueous sodium hydrogen carbonate and saturated sodium chloride solution, dried using magnesium sulfate and concentrated by evaporation.
  • the residue is purified by high-pressure column chromatography on silica gel using hexane/ethyl acetate (2:1 ). The title compound, having a melting point of 120-122°, is thereby obtained.
  • Example B.1 In vivo test against Trichostrongylus colubriformis and Haemonchus contortus in gerbils (Meriones unguiculatus) on peroral administration
  • Gerbils aged from six to eight weeks are each infested with about 2000 third-stage larvae of T. colubriformis and H. contortus by artificial feeding. 6 days after infestation, the gerbils are lightly anaesthetised using N 2 O and treated, by means of peroral administration, with the test compounds dissolved in a mixture of 2 parts of DMSO and 1 part of polyethylene glycol (PEG 300), in amounts of 100, 32 and 10 - 0.1 mg/kg. On day 9 (3 days after treatment), when most of the H. contortus larvae still present are in the late fourth stage and most of the T. colubriformis are immature adults, the gerbils are sacrificed in order to count the worms.
  • PEG 300 polyethylene glycol
  • the effectiveness is calculated as the % reduction in the number of worms in each gerbil compared with the geometric mean of the number of worms in 8 infested but untreated gerbils. ln this test, a large reduction in the nematode infestation is obtained using compounds of formula (I).
  • Example B.2 Action against Heliothis virescens caterpillars
  • the percentage reduction in population and in feeding damage are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
  • the compounds of the Tables exhibit good activity against Heliothis virescens in this test.
  • Example B.3 Action against Plutella xylostella caterpillars
  • Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising
  • the percentage reduction in population and in feeding damage are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
  • the compounds of the Tables exhibit good activity against Plutella xylostella.
  • Maize seedlings are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient and, after the spray-coating has dried, are populated with 10 larvae of Diabrotica balteata in the second stage and then placed in a plastics container. Evaluation is carried out 6 days later. The percentage reduction in population (% activity) is determined by comparing the number of dead larvae on the treated plants with that on untreated plants. The compounds of the Tables exhibit good activity against Diabrotica balteata in this test.

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Abstract

La présente invention concerne des composés de la formule (1), dans laquelle R1 est un aryle non substitué ou mono à penta-substitué par R7, ou est un hétéroaryle non substitué ou mono à tétra-substitué par R7, les substituants pouvant dans chaque cas être les mêmes ou différents lorsqu'ils représentent plus que 1 ; R2 est, entre autres, un C1-C6 alkyle ou un halo-C1-C6 alkyle; R3 est, par exemple, un hydrogène, un C1-C6 alkyle ou un halo-C1-C6 alkyle; R4, R5 et R6 sont par exemple, un hydrogène, un halogène, un C1-C6 alkyle ou halo-C1-C6 alkyle; R7 est, par exemple, un halogène, un C1-C6 alkyle, un halo-C1-C6 alcoxy; X est O, S, S(O) ou S(O2); et n est 0 ou 1 ; et, le cas échéant, des isomères E/Z, des mélanges d'isomères E/Z et/ou les tautomères de ces derniers, dans chaque cas sous forme libre ou sous forme de sel ; lesquels composés possèdent des propriétés pesticides avantageuses et sont adaptés à la lutte contre les parasites des organismes à sang chaud et contre les parasites des plantes.
PCT/EP2001/014922 2000-12-20 2001-12-18 N-acyl aminoacetonitriles aux proprietes pesticides WO2002050052A1 (fr)

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WO2002060257A1 (fr) * 2001-01-22 2002-08-08 Novartis Ag Composition pharmaceutique contenant des composes d'aminoacetonitrile et utilisation d'une telle composition pour la preparation d'une composition pharmaceutique destinee a lutter contre les endoparasites chez les animaux
WO2002102155A1 (fr) * 2001-06-15 2002-12-27 Novartis Ag Composé d'aminoacétonitrile pour supprimer les endoparasites
US7053088B2 (en) 2002-05-22 2006-05-30 Amgen Inc. Vanilloid receptor ligands and their use in treatments
US7144888B2 (en) 2002-08-08 2006-12-05 Amgen Inc. Vanilloid receptor ligands and their use in treatments
US7301022B2 (en) 2005-02-15 2007-11-27 Amgen Inc. Vanilloid receptor ligands and their use in treatments
WO2008096231A1 (fr) 2007-02-09 2008-08-14 Pfizer Limited Agents antiparasitaires
WO2008102232A1 (fr) * 2007-02-21 2008-08-28 Pfizer Limited Agents antiparasitaires de type benzofurane
US7511044B2 (en) 2004-02-11 2009-03-31 Amgen Inc. Vanilloid receptor ligands and their use in treatments
US7534798B2 (en) 2004-02-11 2009-05-19 Amgen Inc. Vanilloid receptor ligands and their use in treatments
US7964621B2 (en) 2008-10-21 2011-06-21 Merial Limited Thioamide compounds, method of making and method of using thereof
US8088801B2 (en) 2007-05-15 2012-01-03 Merial Limited Aryloazol-2-yl cyanoethylamino compounds, method of making and method of using thereof
CN103030574A (zh) * 2013-01-04 2013-04-10 中国农业大学 一类含氰基酰胺类化合物及其合成方法与应用
US8461176B2 (en) 2008-11-14 2013-06-11 Merial Limited Enantiomerically enriched aryloazol-2-yl cyanoethylamino compounds, method of making and method of using thereof
WO2013122041A1 (fr) * 2012-02-14 2013-08-22 日本曹達株式会社 Composé aryloxyacétamide et pesticide associé
JP2013216626A (ja) * 2012-04-10 2013-10-24 Nippon Soda Co Ltd アリールオキシ酢酸アミド化合物を含有する殺ダニ剤または殺虫剤
US8822689B2 (en) 2012-09-19 2014-09-02 Merial Limited Aryloazol-2-yl cyanoethylamino compounds, method of making and method of using thereof
WO2015163280A1 (fr) * 2014-04-22 2015-10-29 日本曹達株式会社 Agent antiparasitaire ou parasiticide

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WO2002060257A1 (fr) * 2001-01-22 2002-08-08 Novartis Ag Composition pharmaceutique contenant des composes d'aminoacetonitrile et utilisation d'une telle composition pour la preparation d'une composition pharmaceutique destinee a lutter contre les endoparasites chez les animaux
AU2002250841B2 (en) * 2001-01-22 2005-03-03 Novartis Ag Pharmaceutical composition containing aminoacetonitril compounds and the use thereof for the prepartion of a pharmaceutical composition for the treatment of endoparasitic pests in animals
US7052707B2 (en) 2001-01-22 2006-05-30 Novartis Animal Health Us, Inc. Pharmaceutical composition containing aminoacetonitril compounds and the use thereof for the preparation of a pharmaceutical composition for the treatment of endoparasitic pests in animals
US7063856B2 (en) 2001-01-22 2006-06-20 Novartis Animal Health Us, Inc. Pharmaceutical composition containing aminocetonitrile compounds and the use thereof for the preparation of a pharmaceutical composition for the treatment of endoparasitic pests in animals
WO2002102155A1 (fr) * 2001-06-15 2002-12-27 Novartis Ag Composé d'aminoacétonitrile pour supprimer les endoparasites
US7678383B2 (en) 2001-06-15 2010-03-16 Novartis Ag Aminoacetonitrile compounds for controlling endoparasites
US7053088B2 (en) 2002-05-22 2006-05-30 Amgen Inc. Vanilloid receptor ligands and their use in treatments
US7524874B2 (en) 2002-05-22 2009-04-28 Amgen Inc. Vanilloid receptor ligands and their use in treatments
US7396831B2 (en) 2002-05-22 2008-07-08 Amgen Inc. Vanilloid receptor ligands and their use in treatments
US7332511B2 (en) 2002-08-08 2008-02-19 Amgen Inc. Vanilloid receptor ligands and their use in treatments
US7148221B2 (en) 2002-08-08 2006-12-12 Amgen Inc. Vanilloid receptor ligands and their use in treatments
US7144888B2 (en) 2002-08-08 2006-12-05 Amgen Inc. Vanilloid receptor ligands and their use in treatments
US8227469B2 (en) 2004-02-11 2012-07-24 Amgen Inc. Vanilloid receptor ligands and their use in treatments
US7511044B2 (en) 2004-02-11 2009-03-31 Amgen Inc. Vanilloid receptor ligands and their use in treatments
US7534798B2 (en) 2004-02-11 2009-05-19 Amgen Inc. Vanilloid receptor ligands and their use in treatments
US7301022B2 (en) 2005-02-15 2007-11-27 Amgen Inc. Vanilloid receptor ligands and their use in treatments
WO2008096231A1 (fr) 2007-02-09 2008-08-14 Pfizer Limited Agents antiparasitaires
US7608604B2 (en) 2007-02-09 2009-10-27 Pfizer Limited Antiparasitic agents
WO2008102232A1 (fr) * 2007-02-21 2008-08-28 Pfizer Limited Agents antiparasitaires de type benzofurane
US7622500B2 (en) 2007-02-21 2009-11-24 Pfizer Limited Antiparasitic agents
AU2008217028B2 (en) * 2007-02-21 2013-07-25 Zoetis Uk Limited Benzofuran antiparasitic agents
US8283475B2 (en) 2007-05-15 2012-10-09 Merial Limited Aryloazol-2-yl cyanoethylamino compounds, method of making and method of using thereof
US8088801B2 (en) 2007-05-15 2012-01-03 Merial Limited Aryloazol-2-yl cyanoethylamino compounds, method of making and method of using thereof
US7964621B2 (en) 2008-10-21 2011-06-21 Merial Limited Thioamide compounds, method of making and method of using thereof
US8314146B2 (en) 2008-10-21 2012-11-20 Merial Limited Thioamide compounds, method of making and method of using thereof
US8461176B2 (en) 2008-11-14 2013-06-11 Merial Limited Enantiomerically enriched aryloazol-2-yl cyanoethylamino compounds, method of making and method of using thereof
JPWO2013122041A1 (ja) * 2012-02-14 2015-05-11 日本曹達株式会社 アリールオキシ酢酸アミド化合物および有害生物防除剤
WO2013122041A1 (fr) * 2012-02-14 2013-08-22 日本曹達株式会社 Composé aryloxyacétamide et pesticide associé
CN104105688A (zh) * 2012-02-14 2014-10-15 日本曹达株式会社 芳氧基乙酰胺化合物和有害生物防除剂
EP2796449A4 (fr) * 2012-02-14 2015-11-18 Nippon Soda Co Composé aryloxyacétamide et pesticide associé
US9334259B2 (en) 2012-02-14 2016-05-10 Nippon Soda Co., Ltd. Aryloxyacetamide compound and pesticide
AU2013219467B2 (en) * 2012-02-14 2016-07-07 Nippon Soda Co., Ltd. Aryloxyacetamide compound and pesticide
JP2013216626A (ja) * 2012-04-10 2013-10-24 Nippon Soda Co Ltd アリールオキシ酢酸アミド化合物を含有する殺ダニ剤または殺虫剤
US8822689B2 (en) 2012-09-19 2014-09-02 Merial Limited Aryloazol-2-yl cyanoethylamino compounds, method of making and method of using thereof
CN103030574A (zh) * 2013-01-04 2013-04-10 中国农业大学 一类含氰基酰胺类化合物及其合成方法与应用
WO2015163280A1 (fr) * 2014-04-22 2015-10-29 日本曹達株式会社 Agent antiparasitaire ou parasiticide

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