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US20120190687A1 - Pyrazinylpyrazoles - Google Patents

Pyrazinylpyrazoles Download PDF

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Publication number
US20120190687A1
US20120190687A1 US13/375,164 US201013375164A US2012190687A1 US 20120190687 A1 US20120190687 A1 US 20120190687A1 US 201013375164 A US201013375164 A US 201013375164A US 2012190687 A1 US2012190687 A1 US 2012190687A1
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Prior art keywords
alkyl
amino
haloalkyl
spp
halogen
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Inventor
Hans-Georg Schwarz
Jens Frackenpohl
Achim Hense
Simon MAECHLING
Stefan Schnatterer
Robert Velten
Stefan Werner
Angela Becker
Olga Malsam
Eva-Maria Franken
Arnd Voerste
Ulrich Görgens
Peter Lümmen
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Bayer CropScience AG
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Bayer CropScience AG
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Assigned to BAYER CROPSCIENCE AG reassignment BAYER CROPSCIENCE AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SCHNATTERER, STEFAN, FRACKENPOHL, JENS, VOERSTE, ARND, FRANKEN, EVA-MARIA, LUMMEN, PETER, SCHWARZ, HANS-GEORG, WERNER, STEFAN, BECKER, ANGELA, MAECHLING, Simon, GORGENS, ULRICH, HENSE, ACHIM, MALSAM, OLGA, VELTEN, ROBERT
Publication of US20120190687A1 publication Critical patent/US20120190687A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • the present invention relates to pyrazin-2-ylpyrazoles, and to the use thereof as insecticides and/or parasiticides.
  • the present invention further provides processes for preparation thereof, and compositions which comprise such pyrazin-2-ylpyrazoles.
  • WO 2007/048733 A describes the use of aminopyrazoles for controlling phytopathogenic harmful fungi, which also encompass pyrazin-2-ylpyrazoles in a generic manner.
  • the pyrazin-2-ylpyrazoles bear only hydrogen as a substituent in the 3 position.
  • phenyl, 2-pyridyl or 3-pyridyl each of which is substituted by one or more substituents selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkenyloxy, alkynyloxy, benzyloxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl, cyano, nitro, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, amino, alkylamino, dialkylamino, alky
  • the compounds of the general formula (I) and the N-oxides and salts thereof possess good insecticidal and parasiticidal properties and can be used in crop protection, in the animal health and materials protection sector, more particularly for protection of industrial materials to control unwanted pests, such as insects, spider mites, endo- or ectoparasites.
  • preferred compounds of the general formula (I) are those in which the R 2 radical is amino and substituted amino, where the substituted amino may be mono- or independently disubstituted by alkyl, haloalkyl, cycloalkylalkyl, optionally halogen- or phenyl-substituted alkenyl, alkynyl, heterocyclylalkyl and/or heteroarylalkyl, where the heteroaromatic ring may optionally be mono- or polysubstituted by one or more substituents selected independently from halogen, alkyl, haloalkyl and alkoxy; benzyl, where the phenyl ring in the benzyl may optionally be mono- or polysubstituted by one or more substituents selected independently from halogen, alkyl, haloalkyl and alkoxy,
  • preferred compounds of the general formula (I) are those in which
  • the X radical is phenyl, 2-pyridyl or 3-pyridyl, each of which is substituted by one or more substituents selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylsulphanyl, haloalkylsulphanyl, alkylsulphinyl, haloalkylsulphinyl, alkylsulphonyl, haloalkylsulphonyl, cyano, nitro and dialkylamino; or phenyl, 2-pyridyl and 3-pyridyl optionally substituted by one or more halogen atoms, cyano, nitro, alkyl, alkoxy or haloalkyl, where vicinal alkyl, haloalkyl and/or alkoxy groups on the phenyl substituent, 2-pyridyl substituent or 3-pyridyl substituent, together with the carbon atom
  • the R 2 radical is amino and substituted amino, where the substituted amino may be mono- or independently disubstituted by alkyl, haloalkyl, cycloalkylalkyl, optionally halogen- or phenyl-substituted alkenyl, alkynyl, heterocyclylalkyl and/or heteroarylalkyl, where the hetcroaromatic ring may optionally be mono- or polysubstituted by one or more substituents selected independently from halogen, alkyl, haloalkyl and alkoxy; benzyl, where the phenyl ring in the benzyl may optionally be mono- or polysubstituted by one or more substituents selected independently from halogen, alkyl, haloalkyl and alkoxy; the R 3 and R 4 radicals are each independently hydrogen, halogen, alkyl, cycloalkyl, haloalkyl, cyano and/or hydroxyl and
  • especially preferred compounds of the general formula (I) are those in which
  • the X radical is phenyl, 2-pyridyl or 3-pyridyl, each of which is substituted by one or more substituents selected from the group consisting of fluorine, chlorine, bromine, iodine, CF 3 , methoxy, ethoxy, propanyloxy, trifluoroethoxy, methylsulphanyl, 2,2,2-trifluoroethylsulphanyl, methylsulphinyl, 2,2,2-trifluoroethylsulphinyl, methylsulphonyl, 2,2,2-trifluoroethylsulphonyl, cyano and dimethylamino; or phenyl optionally substituted by one or more halogen atoms, cyano, nitro, methyl, methoxy or CF 3 , where vicinal alkyl or alkoxy groups on the phenyl substituent, together with the carbon atoms to which they are bonded, may form a five- to seven-membere
  • especially preferred compounds of the general formula (I) are those in which
  • the X radical is phenyl, 2-pyridyl or 3-pyridyl, each of which is substituted by one or more substituents selected from the group consisting of fluorine, chlorine, bromine, iodine, CF 3 , methoxy, ethoxy, propanyloxy, trifluoroethoxy, methylsulphanyl, 2,2,2-trifluoroethylsulphanyl, 2,2,2-trifluoroethylsulphinyl, cyano and dimethylamino; or phenyl optionally substituted by one or more halogen atoms, cyano or CF 3 , where vicinal alkyl or alkoxy groups on the phenyl substituent, together with the carbon atoms to which they are bonded, may form a five- to seven-membered cyclic system which contains 1 or 2 oxygen atoms, where no two oxygen atoms are directly bonded to one another, and the alkyl moiety thereof may be substituted by
  • especially preferred compounds of the general formula (I) are those in which
  • the X radical is phenyl or 2-pyridyl, each of which is substituted by one or more substituents selected from the group consisting of fluorine, chlorine, bromine, iodine, CF 3 , methoxy, ethoxy, propanyloxy, trifluoroethoxy, cyano and dimethylamino; or phenyl optionally substituted by one or more halogen atoms, cyano or CF 3 , where vicinal alkyl or alkoxy groups on the phenyl substituent, together with the carbon atoms to which they are bonded, may form a five- to seven-membered cyclic system which contains 1 or 2 oxygen atoms, where no two oxygen atoms are directly bonded to one another, and the alkyl moiety thereof may be substituted by one or more further alkyl radicals; the R 1 radical is CH 2 CH 3 , CH(CH 3 ) 2 , CH 2 CH 3 CH 3 , C(OCH 3 )HCH
  • the compound of the formula (I) also includes compounds quaternized at a nitrogen atom by a) protonation, b) alkylation or c) oxidation.
  • the compounds of the formula (I) may form salts as a result of addition of a suitable inorganic or organic acid, for example HCl, HBr, H 2 SO 4 or HNO 3 , or else oxalic acid or sulphonic acids, onto a basic group, for example amino or alkylamino.
  • a suitable inorganic or organic acid for example HCl, HBr, H 2 SO 4 or HNO 3
  • oxalic acid or sulphonic acids onto a basic group, for example amino or alkylamino.
  • Suitable substituents present in deprotonated form for example sulphonic acids or carboxylic acids, can form internal salts with groups which are themselves protonatable, such as amino groups. Salts can likewise be formed by replacing the hydrogen in suitable substituents, for example sulphonic acids or carboxylic acids, with a cation suitable in the agrochemical sector.
  • salts are, for example, metal salts, especially alkali metal salts or alkaline earth metal salts, especially sodium salts and potassium salts, or else ammonium salts, salts with organic amines or quaternary ammonium salts having cations of the formula [NRR′R′′R′′′] + in which R to R′′′ are each independently an organic radical, especially alkyl, aryl, aralkyl or alkylaryl.
  • the alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino, alkylsulphinyl and alkylsulphonyl radicals and the corresponding unsaturated and/or substituted radicals may each be straight-chain or branched in the carbon skeleton.
  • the lower carbon skeletons are preferred for these radicals, for example having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms, or in the case of unsaturated groups having 2 to 6 carbon atoms, especially 2 to 4 carbon atoms.
  • Alkyl radicals including in the combined definitions such as alkoxy, haloalkyl, etc., are, for example, methyl; ethyl; propyl such as n- or i-propyl; butyl such as n-, i-, t- or 2-butyl; pentyl such as n-pentyl, isopentyl and neopentyl; hexyl such as n-hexyl, i-hexyl, 3-methylpentyl, 2,2-dimethylbutyl and 2,3-dimethylbutyl; and heptyl such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl; alkenyl and alkynyl radicals are defined as the possible unsaturated radicals corresponding to the alkyl radicals; where at least one double bond or triple bond, preferably one double bond or triple bond, is present.
  • Alkenyl is, for example, vinyl, 1-allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl; alkynyl is, for example, ethynyl, propargyl/propynyl, but-2-yn-1-yl, but-3-yn-1-yl and 1-methylbut-3-yn-1-yl.
  • Cycloalkyl groups are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • the cycloalkyl groups may be in bi- or tricyclic form.
  • the lower carbon skeletons are preferred, for these radicals, for example having 1 to 6 carbon atoms or 2 to 6, especially 1 to 4, carbon atoms or preferably 2 to 4 carbon atoms, and the corresponding unsaturated and/or substituted radicals are each straight-chain or branched in the carbon skeleton.
  • examples are trifluoromethyl, difluoromethyl, 2,2,2-trifluoroethyl, trifluoroallyl, 1-chloroprop-1-yl-3-yl.
  • Alkylene groups in these radicals are the lower carbon skeletons, for example those having 1 to 10 carbon atoms, especially 1 to 6 carbon atoms or preferably 2 to 4 carbon atoms, and the corresponding unsaturated and/or substituted radicals in the carbon skeleton, which may each be straight-chain or branched. Examples are methylene, ethylene, n- and isopropylene and n-, s-, i-, t-butylene.
  • Hydroxyalkyl groups in these radicals are the lower carbon skeletons, for example those having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms, and the corresponding unsaturated and/or substituted radicals in the carbon skeleton, which may each be straight-chain or branched. Examples thereof are 1,2-dihydroxyethyl and 3-hydroxypropyl.
  • Halogen is fluorine, chlorine, bromine or iodine; haloalkyl, haloalkenyl and haloalkynyl are, respectively, alkyl, alkenyl and alkynyl which are partly or fully substituted by halogen, preferably by fluorine, chlorine or bromine, especially by fluorine and/or chlorine, examples being monohaloalkyl, perhaloalkyl, CF 3 , CHF 2 , CH 2 F, CF 3 CF 2 , CH 2 FCHCl, CCl 3 , CHCl 2 , CH 2 CH 2 Cl; haloalkoxy is, for example, OCF 3 , OCHF 2 , OCH 2 F, CF 3 CF 2 O, OCH 2 CF 3 , and OCH 2 CH 2 Cl; this correspondingly applies to haloalkenyl and other halogen-substituted radicals.
  • Aryl is a monocyclic, bicyclic or polycyclic aromatic system, for example phenyl or naphthyl, preferably phenyl.
  • heterocyclyl radical or the heterocyclic ring When the heterocyclyl radical or the heterocyclic ring is optionally substituted, it may be fused to other carbocyclic or heterocyclic rings.
  • heterocyclyl polycyclic systems are also included, for example 8-azabicyclo[3.2.1]octanyl or 1-azabicyclo[2.2.1]heptyl.
  • spirocyclic systems are also included, for example 1-oxa-5-azaspiro[2.3]hexyl.
  • the heterocyclic ring contains preferably 3 to 9 ring atoms, especially 3 to 6 ring atoms, and one or more, preferably 1 to 4, especially 1, 2 or 3, heteroatoms in the heterocyclic ring, preferably from the group consisting of N, O, and S, although no two oxygen atoms should be directly adjacent.
  • heteroaryl in the context of the present invention is understood to mean systems as defined above under “heterocyclyl”, but which are heteroaromatic, i.e. are a fully unsaturated, aromatic heterocyclic compound.
  • substituted by one or more radicals independently means one or more identical or different radicals, where two or more radicals on one cycle as a base skeleton may form one or more rings.
  • Substituted radicals such as a substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl radicals are, for example, a substituted radical derived from the unsubstituted base skeleton, where the substituents are, for example, one or more, preferably 1, 2 or 3, radicals from the group of halogen, alkoxy, alkylthio, hydroxyl, amino, nitro, carboxyl or a group equivalent to the carboxyl group, cyano, isocyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino such as acylamino, mono- and dialkylamino, trialkylsilyl and optionally substituted cycloalkyl, optionally substituted aryl, optionally substitute
  • unsaturated aliphatic and aromatic radicals such as optionally substituted alkenyl, alkylnyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio, alkenyloxycarbonyl, alkynyloxycarbonyl, alkenylcarbonyl, alkynylcarbonyl, mono- and dialkenylaminocarbonyl, mono- and dialkynylaminocarbonyl, mono- and dialkenylamino, mono- and dialkynylamino, trialkenylsilyl, trialkynylsilyl, optionally substituted cycloalkenyl, optionally substituted cycloalkynyl, phenyl, phenoxy.
  • substituted cyclic radicals with aliphatic moieties in the ring also included are cyclic systems with those substituents which are bonded to the ring by a double bond, for example with an alkylidene group such as methylidene or ethylidene or an oxo group, imino group or substituted imino group.
  • radicals When two or more radicals form one or more rings, these may be carbocyclic, heterocyclic, saturated, partly saturated, unsaturated, for example also aromatic and optionally further substituted.
  • the fused rings are preferably 5- or 6-membered rings, particular preference being given to benzofused cycles.
  • first substituent level may, if they contain hydrocarboneous moieties, optionally be further substituted therein (“second substituent level”), for example by one of the substituents as defined for the first substituent level.
  • second substituent level may be further substituted therein, for example by one of the substituents as defined for the first substituent level.
  • substituent levels are possible.
  • substituted radical preferably encompasses just one or two substituent levels.
  • Preferred substituents for the substituent levels are, for example, amino, hydroxyl, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, carboxyl, carbonamide, SF 5 , aminosulphonyl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, monoalkylamino, dialkylamino, N-alkanoylamino, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, alkoxycarbonyl, alkenyloxy-carbonyl, alkynyloxycarbonyl, aryloxycarbonyl, alkanoyl, alkenylcarbonyl, alkynylcarbonyl, aryl-carbonyl, alkylthio, cycloalkylthio, alkenylthio, cycloalkenylthio, al
  • radicals with carbon atoms preference is given to those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, especially 1 or 2 carbon atoms.
  • substituents from the group of halogen for example fluorine, chlorine and bromine, (C 1 -C 4 )-alkyl, preferably methyl or ethyl, (C 1 -C 4 )-haloalkyl, preferably trifluoromethyl, (C 1 -C 4 )-alkoxy, preferably methoxy or ethoxy, (C 1 -C 4 )-haloalkoxy, nitro and cyano.
  • Optionally substituted aryl or heteroaryl is preferably phenyl, or heteroaryl which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical of different radicals from the group of halogen, (C 1 -C 4 )-alkyl, (C 3 -C 6 )-cycloalkyl, (C 1 -C 4 )-alkoxy, (C 1 -C 4 )-haloalkyl, (C 1 -C 4 )-haloalkoxy, (C 1 -C 4 )-alkylthio, cyano and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoromethyl and 2-, 3- and 4-trichloromethylphenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-,
  • inventive compounds may be present as mixtures of different possible isomeric forms, especially of stereoisomers, for example, E and Z isomers, threo and erythro isomers, and optical isomers, but if appropriate also of tautomers. Both the E and Z isomers, and the threo and erythro isomers, and the optical isomers, any desired mixtures of these isomers, and the possible tautomeric forms are claimed.
  • R 1 , R 3 , R 4 and R 5 are each as defined above.
  • keto nitriles or the tautomers or hydrates thereof, of the formulae (IIA), (IIB) and (IIC) are condensed with pyrazinylhydrazines of the general formula (III), which first forms hydrazones of the formula (IV) as an intermediate and, in the course of a prolonged reaction time and at relatively higher temperature, the ring closure proceeds to give the aminopyrazole of the formula (IA).
  • acids as a catalyst, in which case inorganic acids such as hydrochloric acid and organic acids such as sulphonic acids or acetic acid may be suitable.
  • the keto nitriles may be present in the tautomeric forms (IIA) and (IIB) and as the hydrate (IIC).
  • the starting compounds may also be used in the form of their salts; for example, the keto nitriles may be used in the form of their alkali metal salts, and the pyrazinylhydrazines in the form of their hydrochlorides.
  • keto nitriles of the formula (II) can be prepared by known methods, for example W. R. Nes, Alfred Burger, J. Amer. Chem. Soc. 72 (1950), 5409-5413.
  • pyrazinylhydrazines of the formula (III) are commercially available.
  • Pyrazinylhydrazines of the formula (III) are prepared, for example, by the methods described in Methoden der Organischen Chemie [Methods of Organic Chemistry](Houben-Weyl), Organische Stickstoff-Veritatien [Organic Nitrogen Compounds], volume E 16a, part 1, p. 678-775, Georg Thieme Verlag Stuttgart—New York, 1990 and WO 98/32739 A.
  • LG halogen or alkylsulphonyl
  • R 1 , R 3 , R 4 and R 5 are each as defined above.
  • 1H-aminopyrazoles of the formula (V) are reacted with pyrazinyl halides or pyrazinyl alkyl sulphones of the formula (VI) in the presence of a base in organic solvents, preferably forming a particular isomer, the aminopyrazole of the formula (IA).
  • the 1H-aminopyrazoles of the formula (V) can be prepared by known methods (see also DE-A 2643640, C. Chen et al, Bioorg. Med. Chem. Lett., 14 (2004), 14, 3669; Gilligan, Paul J. et al, Bioorg. Med. Chem., 8, (2000), 1, 181-190).
  • pyrazinyl halides or pyrazinyl alkyl sulphones of the formula (VI) are commercially available or can be synthesized by methods known to those skilled in the art. Reactions of pyrazinyl halides with 1H-pyrazoles are described, inter alia, in: Journal of Chemical Research, Synopses, 1989 (7), 189 and Dalton Transactions, 2003 (10), 2053-2060.
  • R 1 , R 3 , R 4 and R 5 are each as defined above.
  • keto nitriles or the tautomers or hydrates thereof, of the formulae (IIA), (IIB) and (IIC) are reacted with chlorinating agents, for example phosphoryl chloride, thionyl chloride, phosgene, chlorine or oxalyl chloride, optionally diluted in an inert organic solvent or promoted by auxiliary bases such as nitrogen bases, to give chloroacrylonitriles (VII), the reaction being performable within the temperature range from ⁇ 20° C. to 120° C.
  • chlorinating agents for example phosphoryl chloride, thionyl chloride, phosgene, chlorine or oxalyl chloride, optionally diluted in an inert organic solvent or promoted by auxiliary bases such as nitrogen bases, to give chloroacrylonitriles (VII), the reaction being performable within the temperature range from ⁇ 20° C. to 120° C.
  • condensation with pyrazinylhydrazines (III) is effected in a suitable organic solvent in the presence of basic auxiliary reagents, for example alkoxides or nitrogen bases, the reaction being performable within the temperature range from ⁇ 20° C. to 120° C.
  • basic auxiliary reagents for example alkoxides or nitrogen bases
  • the keto nitriles may be present in the tautomeric forms (IIA) and (IIB) and as the hydrate (IIC).
  • the starting compounds may also be used in the form of their salts; for example, the keto nitriles may be used in the form of their alkali metal salts, and the pyrazinylhydrazines in the form of their hydrochlorides.
  • keto nitriles of the formula (II) can—as already mentioned with regard to process (A)—be prepared by known methods: W. R. Nes, Alfred Burger, J. Amer. Chem. Soc. 72 (1950), 5409-5413.
  • pyrazinylhydrazines of the formula (III) are commercially available. Pyrazinylhydrazines of the formula (III) are prepared, for example, by the methods described in Methoden der Organischen Chemie (Houben-Weyl), Organische Stickstoff-Veritatien, volume E 16a, part 1, p. 678-775, Georg Thieme Verlag Stuttgart—New York, 1990 and WO 98/32739 A.
  • Inventive compounds of the formula (IB) and (IC) in which at least one radical of R 6 and R 7 is not hydrogen can be synthesized proceeding from the inventive compound (IA) by the process (D) according to the invention:
  • LG halogen or alkylsulphonyl
  • R 1 , R 3 , R 4 and R 5 are each as defined above;
  • LG is halogen or alkylsulphonyl
  • compounds of the formula (IA) are reacted with one or two alkylating agents or acylating agents R 6 -LG or R 7 -LG, monosubstitution and disubstitution forming aminopyrazoles of the formulae (IB) and (IC).
  • Suitable alkylating agents are alkyl bromides, alkyl dibromides, alkyl iodides, alkyl diiodides, dialkyl sulphates and alkyl sulphonates.
  • the acylating agents used are carboxylic anhydrides and carbonyl chlorides.
  • W protecting group, for example DMF-DMA adduct
  • R 1 , R 3 , R 4 and R 5 are each as defined above.
  • bromides or iodides of the formula (VIII) are reacted with boronic acids or boronic esters of the formula (IX) in the presence of suitable palladium catalysts and bases (Suzuki reaction) within the temperature range from ⁇ 20° C. to 120° C. in suitable solvents.
  • the bromides or iodides of the formula (VIII) can be prepared by known methods, described, for example, in: Chemistry of Heterocyclic Compounds (New York, N.Y., United States), 41(1), 105-110; 2005; Bioorganic & Medicinal Chemistry, 12, 2004 (12), 3345-3355; Journal of Medicinal Chemistry, 20, 1977 (12), 1562-1569.
  • boronic acids or boronic esters of the formula (IX) are commercially available, or they are preparable easily by known methods. This is described, for example, in WO 99/64428 A.
  • the NH 2 group of the bromides or iodides of the formula (VIII) can be provided with a protecting group, for example by means of reaction of (VIII) with dimethylformamide dimethyl acetal (DMF-DMA).
  • the resulting imines (XI) can, after successful Suzuki coupling, be converted in the presence of strong acids, for example hydrochloric acid, in suitable solvents, for example methanol, to the end compounds (IA).
  • inventive compounds of the general formula (I) are suitable for protecting plants and plant organs, for increasing harvest yields, for improving the quality of the harvested material and for controlling animal pests, especially insects, arachnids, helminths, nematodes and molluscs, which are encountered in agriculture, in horticulture, in animal husbandry, in forests, in gardens and leisure facilities, in the protection of stored products and of materials, and in the hygiene sector. They can preferably be used as crop protection agents. They are active against normally sensitive and resistant species and against all or some stages of development.
  • the abovementioned pests include:
  • Anoplura for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.
  • Acarus siro Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Biyobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus lat
  • Gastropoda From the class of the Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.
  • helminths from the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Lo
  • Hymenoptera From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.
  • Isopoda for example, Armadillidium vulgare, Oniscus asellus and Porcellio scaber.
  • Orthoptera for example, Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.
  • Symphyla for example, Scutigerella immaculata.
  • Thysanoptera From the order of the Thysanoptera, for example, Basothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni and Thrips spp.
  • Thysanura for example, Lepisma saccharina.
  • the phytoparasitic nematodes include, for example, Anguina spp., Aphelenchoides spp., Belonoaimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Rotylenchus spp., Trichodorus spp., Tylenchorhynchus spp., Tylenchulus spp., Tylenchulus semipenetrans and Xiphineina spp.
  • inventive compounds can optionally, at certain concentrations or application rates, also be used as herbicides, safeners, growth regulators or agents for improving plant properties, or as microbicides, for example as fungicides, antimycotics, bactericides, viricides (including agents against viroids) or as agents against MLO (mycoplasma-like organisms) and RLO (Rickettsia-like organisms). They can optionally also be used as intermediates or precursors for the synthesis of other active ingredients.
  • the active ingredients can be converted to the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural compounds impregnated with active ingredient, synthetic substances impregnated with active ingredient, fertilizers and also microencapsulations in polymeric substances.
  • customary formulations such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspoemulsion concentrates, natural compounds impregnated with active ingredient, synthetic substances impregnated with active ingredient, fertilizers and also microencapsulations in polymeric substances.
  • formulations are produced in a known manner, for example by mixing the active ingredients with extenders, i.e. liquid solvents, and/or solid carriers, optionally with the use of surfactants, i.e. emulsifiers and/or dispersants, and/or foam formers.
  • extenders i.e. liquid solvents, and/or solid carriers
  • surfactants i.e. emulsifiers and/or dispersants, and/or foam formers.
  • foam formers i.e. emulsifiers and/or foam formers.
  • auxiliaries are those which are suitable for imparting particular properties, such as certain technical properties and/or also particular biological properties, to the composition itself and/or to preparations derived therefrom (for example spray liquors, seed dressings).
  • auxiliaries include: extenders, solvents and carriers.
  • Suitable extenders are, for example, water, polar and nonpolar organic chemical liquids, for example from the classes of the aromatic and nonaromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), the alcohols and polyols (which may optionally also be substituted, etherified and/or esterified), the ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly)ethers, the unsubstituted and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, the sulphones and sulphoxides (such as dimethyl sulphoxide).
  • aromatic and nonaromatic hydrocarbons such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes
  • the alcohols and polyols which may optionally also
  • Useful liquid solvents essentially include: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and also their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl sulphoxide, and also water.
  • aromatics such as xylene, toluene or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride
  • aliphatic hydrocarbons such as
  • Useful solid carriers include:
  • useful solid carriers for granules include: for example, crushed fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic flours, and granules of organic material such as paper, sawdust, coconut shells, maize cobs and tobacco stalks;
  • useful emulsifiers and/or foam-formers include: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and also protein hydro
  • oligo- or polymers for example those derived from vinylic monomers, from acrylic acid, from EO and/or PO alone or in combination with, for example, (poly)alcohols or (poly)amines. It is also possible to use lignin and its sulphonic acid derivatives, unmodified and modified celluloses, aromatic and/or aliphatic sulphonic acids and their adducts with formaldehyde.
  • tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids.
  • dyes such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • Further additives may be perfumes, mineral or vegetable, optionally modified oils, waxes and nutrients (including trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • Additional components may be stabilizers, such as low-temperature stabilizers, preservatives, antioxidants, light stabilizers or other agents which improve chemical and/or physical stability.
  • the formulations contain generally from 0.01 to 98% by weight of active ingredient, preferably from 0.5 to 90%.
  • the inventive active ingredient may be present in its commercially available formulations and in the use forms, prepared from these formulations, as a mixture with other active ingredients, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, safeners, fertilizers or semiochemicals.
  • active ingredients such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, herbicides, safeners, fertilizers or semiochemicals.
  • inventive active ingredients When used as insecticides, the inventive active ingredients may also be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with synergists.
  • Synergists are compounds which increase the action of the active ingredients, without any need for the synergist added to be active itself.
  • inventive active ingredients When used as insecticides, the inventive active ingredients may also be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with inhibitors which reduce degradation of the active ingredient after use in the environment of the plant, on the surface of parts of plants or in plant tissues.
  • the active ingredient content of the use forms prepared from the commercially available formulations may vary within wide limits.
  • the active ingredient concentration of the use forms may be from 0.00000001 to 95% by weight of active ingredient, preferably between 0.00001 and 1% by weight.
  • Plants are understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or cannot be protected by plant variety rights.
  • Parts of plants shall be understood to mean all above-ground and below-ground parts and organs of plants, such as shoot, leaf, flower and root, examples including leaves, needles, stems, trunks, flowers, fruit bodies, fruits and seeds, and also roots, tubers and rhizomes.
  • the plant parts also include harvested material, and also vegetative and generative propagation material, for example cuttings, tubers, rhizomes, slips and seed.
  • the inventive treatment of the plants and plant parts with the active ingredients is effected directly or through action on the environment, habitat or storage space thereof by the customary treatment methods, for example by dipping, spraying, evaporation, fogging, scattering, painting on and, in the case of propagation material, especially in the case of seeds, also by applying one or more coats.
  • plants of the plant cultivars which are each commercially available or in use are treated in accordance with the invention.
  • Plant cultivars are understood to mean plants which have new properties (“traits”) and have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They may be cultivars, bio- or genotypes.
  • the inventive treatment may also result in superadditive (“synergistic”) effects.
  • superadditive for example, reduced application rates and/or broadening of the activity spectrum and/or an increase in the efficacy of the compounds and compositions used in accordance with the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or higher nutrient value of the harvested products, increased storability and/or processability of the harvested products, which exceed the effects normally to be expected.
  • transgenic plants or plant cultivars which are treated with preference in accordance with the invention include all plants which, through the genetic modification, received genetic material which imparts particularly advantageous useful properties (“traits”) to these plants.
  • traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, increased storability and/or processability of the harvested products.
  • transgenic plants include the important crop plants, such as cereals (wheat, rice), maize, soya, potatoes, sugar beet, tomatoes, peas and other vegetable types, cotton, tobacco, oilseed rape, and also fruit plants (with the fruits of apples, pears, citrus fruits and grapes), particular emphasis being given to maize, soya, potatoes, cotton, tobacco and oilseed rape.
  • Bt plants Traits that are particularly emphasized are increased defence of the plants against insects, arachnids, nematodes, slugs and snails by toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF, and also combinations thereof) (referred to hereinafter as “Bt plants”).
  • Traits that are also particularly emphasized are the increased defence of the plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes, and correspondingly expressed proteins and toxins. Traits that are additionally particularly emphasized are the increased tolerance of the plants to certain active herbicidal ingredients, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (for example the “PAT” gene). The genes which impart the desired traits in question may also be present in combinations with one another in the transgenic plants.
  • SAR systemic acquired resistance
  • PAT phosphinotricin
  • Bt plants include maize varieties, cotton varieties, soya varieties and potato varieties which are sold under the trade names YIELD GARD® (for example maize, cotton, soya), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato).
  • YIELD GARD® for example maize, cotton, soya
  • KnockOut® for example maize
  • StarLink® for example maize
  • Bollgard® cotton
  • Nucotn® cotton
  • NewLeaf® potato
  • herbicide-tolerant plants include maize varieties, cotton varieties and soya varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize).
  • Herbicide-resistant plants plants bred in a conventional manner for herbicide tolerance
  • the plants listed can be treated in accordance with the invention particularly advantageously with the compounds of the general formula (I).
  • the preferred ranges stated above for the active ingredients also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds or mixtures specifically mentioned in the present text.
  • inventive compounds can be used to control a multitude of different pests, including, for example, harmful sucking insects, biting insects and other pests which are plant parasites, stored material pests, pests which destroy industrial material, and hygiene pests including parasites in the animal health sector, and for the control thereof, for example the elimination and eradication thereof.
  • the present invention thus also includes a method for controlling pests.
  • the active ingredients according to the present invention act against animal parasites, especially ectoparasites or endoparasites.
  • animal parasites especially ectoparasites or endoparasites.
  • endoparasites includes especially helminths such as cestodes, nematodes or trematodes, and protozoa such as coccidia.
  • Ectoparasites are typically and preferably arthropods, especially insects such as flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice, fleas and the like, or acaricides such as ticks, for example hard ticks or soft ticks, or mites such as scab mites, harvest mites, bird mites and the like.
  • insects such as flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice, fleas and the like, or acaricides such as ticks, for example hard ticks or soft ticks, or mites such as scab mites, harvest mites, bird mites and the like.
  • These parasites include:
  • Anoplurida for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.; specific examples are: Linognathus setosus, Linognathus vituli, Linognathus ovillus, Linognathus oviformis, Linognathus pedalis, Linognathus stenopsis, Haematopinus asini macrocephalus, Haematopinus eurysternus, Haematopinus suis, Pediculus liumanus capitis, Pediculus humanus corporis, Phylloera vastatrix, Phthirus pubis, Solenopotes capillatus;
  • Nematocerina and Brachycerina for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Odagmia spp., Willielmia spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calli
  • Pulex spp. Ctenocephalides spp., Tunga spp., Xenopsylla spp., Ceratophyllus spp.
  • specific examples are: Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis;
  • Ornithonyssus spp. Pneumonyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp., Acarapis spp.; specific examples are: Argas persicus, Argas reflexus, Ornithodorus moubata, Otobius megnini, Rhipicephalus ( Boophilus ) microplus, Rhipicephalus ( Boophilus ) decoloratus, Rhipicephalus ( Boophilus ) annulatus, Rhipicephalus ( Boophilus ) calceratus, Hyalomma anatolicum, Hyalomma aegypticum, Hyalomma marginatum, Hyalomma transiens, Rhipicephalus evertsi, Ixodes ricinus, Ixodes hexagonus, Ixodes can
  • Acarapis spp. for example, Acarapis spp., Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp.
  • the inventive active ingredients are also suitable for controlling arthropods, helminths and protozoa which attack animals.
  • the animals include agricultural livestock, for example cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, cultured fish, honeybees.
  • the animals also include domestic animals—also referred to as companion animals—for example dogs, cats, caged birds, aquarium fish, and test animals, for example hamsters, guinea pigs, rats and mice.
  • control of these arthropods, helminths and/or protozoa should reduce cases of death and improve the performance (for meat, milk, wool, hides, eggs, honey etc.) and the health of the host animal, and so the use of the inventive active ingredients enables more economically viable and easier animal husbandry.
  • control of the parasites can also contribute to preventing the transmission of infectious substances.
  • control as used herein with regard to the field of animal health means that the active ingredients act by reducing the occurrence of the parasite in question in an animal infested with such parasites to a harmless level. More specifically, “control” as used herein means that the active ingredient kills the parasite in question, retards its growth or inhibits its proliferation.
  • inventive active ingredients can employed directly when they are used for the treatment of animals. They are preferably employed in the form of pharmaceutical compositions which may comprise the pharmaceutically acceptable excipients and/or auxiliaries known in the prior art.
  • the active ingredients are employed in a known manner, by enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-through process and suppositories, by parenteral administration, for example by injection (intramuscular, subcutaneous, intravenous, intraperitoneal inter alia), implants, by nasal administration, by dermal administration in the form, for example, of dipping or bathing, spraying, pouring on and spotting on, washing and powdering, and also with the aid of moulded articles containing the active ingredient, such as collars, earmarks, tailmarks, limb bands, halters, marking devices, etc.
  • the active ingredients can be formulated as a shampoo or as suitable formulations applicable in aerosols or unpressurized sprays, for example pump sprays and atomizer sprays,
  • the inventive active ingredients can be employed as formulations (for example powders, wettable powders [“WP”], emulsions, emulsifiable concentrates [“EC”], free-flowing compositions, homogeneous solutions and suspension concentrates [“SC”]), which contain the active ingredients in an amount of 1 to 80% by weight, directly or after dilution (e.g. 100- to 10 000-fold dilution), or they can be used as a chemical bath.
  • formulations for example powders, wettable powders [“WP”], emulsions, emulsifiable concentrates [“EC”], free-flowing compositions, homogeneous solutions and suspension concentrates [“SC”]
  • WP wettable powders
  • EC emulsions
  • SC suspension concentrates
  • inventive active ingredients can be used in combination with suitable synergists or other active ingredients, for example acaricides, insecticides, anthelmintics, anti-protozoal agents.
  • inventive compounds are especially suitable for use in material protection, preferably for protection of industrial materials, which is understood to mean inanimate materials, such as preferably plastics, adhesives, sizes, papers and cardboards, leather, wood, wood processing products and paints.
  • industrial materials which is understood to mean inanimate materials, such as preferably plastics, adhesives, sizes, papers and cardboards, leather, wood, wood processing products and paints.
  • the compounds according to the invention can at the same time be used for protection of objects which come into contact with saltwater or brackish water, especially of hulls, screens, nets, buildings, moorings and signalling systems, against fouling.
  • the ready-to-use compositions may optionally comprise further active ingredients for controlling fouling, insects, bacteria or fungi, for example insecticides, herbicides or microbicides (fungicides, antimycotics, bactericides, viricides (including anti-viroidal agents), or anti-MLO (mycoplasma-like organism) and anti-RLO (Rickettsia-like organism) agents.
  • active ingredients for controlling fouling insects, bacteria or fungi, for example insecticides, herbicides or microbicides (fungicides, antimycotics, bactericides, viricides (including anti-viroidal agents), or anti-MLO (mycoplasma-like organism) and anti-RLO (Rickettsia-like organism) agents.
  • inventive compounds can be used alone or in combinations with other active ingredients as antifouling compositions.
  • the active ingredients are also suitable for controlling animal pests in the domestic sector, in hygiene and in the protection of stored products, especially insects, arachnids and mites, which are found in enclosed spaces, for example dwellings, factory halls, offices, vehicle cabins and the like. They can be used to control these pests alone or in combination with other active ingredients and auxiliaries in domestic insecticide products. They are active against sensitive and resistant species and against all developmental stages. These pests include:
  • Scorpionidea for example, Buthus occitanus .
  • Acarina for example, Argas persicus, Argas reflexus, Bryobia spp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dennatophagoides forinae .
  • Araneae for example, Aviculariidae, Araneidae.
  • Opiliones for example, Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium .
  • From the order of the Isopoda for example, Oniscus asellus, Porcellio scaber .
  • Diplopoda for example, Blaniulus guttulatus, Polydesmus spp.
  • From the order of the Chilopoda for example, Geophilus spp.
  • Zygentoma for example, Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.
  • Psocoptera for example, Lepinatus spp., Liposcelis spp.
  • Coleoptera for example, Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum .
  • Aedes aegypti Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa .
  • Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis .
  • Hymenoptera for example, Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum .
  • Anoplura for example, Pediculus humanus capitis, Pediculus humanus corporis, Pemphigus spp., Phylloera vastatrix, Phthirus pubis .
  • Heteroptera for example, Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.
  • the calibration is effected with unbranched alkan-2-ones (having 3 to 16 carbon atoms) with known log P values (log P values determined on the basis of the retention times by linear interpolation between two successive alkanones).
  • the lambda max values were determined in the maxima of the chromatographic signals using the UV spectra from 200 nm to 400 nm.
  • Test animals adult engorged Boophilus microplus females of the SP-resistant Parkhurst strain
  • the active ingredient solution is diluted with water to the concentration desired in each case.
  • This active ingredient preparation is pipetted into tubes. 8-10 ticks are transferred into a further tube with holes. The tube is immersed into the active ingredient formulation, and all ticks are completely wetted. After the liquid has run out, the ticks are transferred onto filter discs in plastic dishes and stored in a climate-controlled room. The activity is assessed after 7 days by laying of fertile eggs. Eggs whose fertility is not outwardly visible are stored in glass tubes in a climate-controlled cabinet until the larvae hatch. Efficacy of 100% means that none of the ticks has laid any fertile eggs.
  • Boophilus microplus Test (BOOPMI Injection)
  • an appropriate active ingredient formulation 10 mg of active ingredient are mixed with 0.5 ml of solvent and the concentrate is diluted with solvent to the desired concentration.
  • the active ingredient solution is injected into the abdomen ( Boophilus microplus ), and the animals are transferred into dishes and stored in a climate-controlled room.
  • the efficacy is assessed by laying of fertile eggs. After 7 days, the efficacy in % is determined. 100% means that none of the ticks has laid any fertile eggs.
  • CTECFE Ctenocephalides felis Test
  • active ingredient formulation 10 mg of active ingredient are mixed with 0.5 ml of dimethyl sulphoxide. A portion of the concentrate is diluted with citrated cow's blood and the desired concentration is established. About 20 unfed adult fleas ( Ctenocephalides felis ) are introduced into a chamber closed at the top and bottom with gauze. A metal cylinder, the bottom of which is closed with Parafilm, is placed onto the chamber. The cylinder contains the blood/active ingredient preparation, which can be imbibed by the fleas through the Parafilm membrane. After 2 days, the kill in % is determined. 100% means that all fleas have been killed; 0% means that none of the fleas have been killed.
  • an appropriate active ingredient formulation 10 mg of active ingredient are mixed with 0.5 ml of dimethyl sulphoxide and the concentrate is diluted with water to the desired concentration. Vessels containing horse meat treated with the active ingredient preparation of the desired concentration are populated with about 20 Lucilia cuprina larvae. After 2 days, the kill in % is determined. 100% means that all of the larvae have been killed; 0% means that none of the larvae have been killed.
  • an appropriate active ingredient formulation 10 mg of active ingredient are mixed with 0.5 ml of dimethyl sulphoxide and the concentrate is diluted with water to the desired concentration. Vessels containing a sponge treated with the active ingredient preparation of the desired concentration are populated with adult Musca domestica . After 2 days, the kill in % is determined. 100% means that all of the flies have been killed; 0% means that none of the flies have been killed.
  • an appropriate active ingredient formulation 10 mg of active ingredient are mixed with 0.5 ml of dimethyl sulphoxide and the concentrate is diluted with water to the desired concentration.
  • Tick nymphs Amblyomma hebraeum
  • the ticks are transferred on filter paper into a Petri dish and stored in a climate-controlled cabinet. After 42 days, the kill in % is determined. 100% means that all of the ticks have been killed; 0% means that none of the ticks have been killed.
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • an appropriate active ingredient preparation 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Discs of Chinese cabbage Brassica pekinensis
  • the green peach aphid Myzus persicae
  • the efficacy in % is determined. 100% means that all of the aphids have been destroyed; 0% means that none of the aphids have been destroyed.
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • an appropriate active ingredient preparation 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Discs of Chinese cabbage Brassica pekinensis
  • the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Discs of Chinese cabbage Brassica pekinensis
  • an active ingredient preparation of the desired concentration and, after drying, populated with larvae of the mustard beetle ( Phaedon cochleariae ).
  • the efficacy in % is determined. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • an appropriate active ingredient preparation 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Discs of maize leaves Zea mays
  • the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Discs of maize leaves Zea mays
  • the efficacy in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.
  • the following compounds of the Preparation Examples show an efficacy of 100% at an application rate of 500 g/ha: Ex. No. 9, 14, 15, 17, 20, 21, 22, 28, 43, 44, 46, 47, 48, 51, 65, 66, 74, 75, 77, 79, 86, 87, 89, 116, 121, 122, 123, 124, 130, 131, 132, 133, 134, 139, 140, 141, 144, 150, 157, 161, 168, 169, 170, 171, 172, 173, 174, 175
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • an appropriate active ingredient preparation 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Discs of bean leaves Phaseolus vulgaris
  • red spider mite Tetranychus urticae
  • the efficacy in % is determined. 100% means that all spider mites have been killed; 0% means that none of the spider mites have been killed.

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WO2016174049A1 (en) * 2015-04-30 2016-11-03 Bayer Animal Health Gmbh Anti-parasitic combinations including halogen-substituted compounds
US10548316B2 (en) 2015-06-18 2020-02-04 Nippon Soda Co., Ltd. Diarylazole compound and harmful organism control agent
US10377737B2 (en) 2015-11-30 2019-08-13 Hokko Chemical Industry Co., Ltd. 1,2,3-triazole derivative and insecticide and acaricide containing said derivative as active ingredient
US11046659B2 (en) 2015-11-30 2021-06-29 Hokko Chemical Industry Co., Ltd. 1,2,3-triazole derivative and insecticide and acaricide containing said derivative as active ingredient
US11180456B2 (en) 2015-12-16 2021-11-23 Nippon Soda Co., Ltd. Arylazole compound and pest control agent
US11884633B2 (en) 2015-12-16 2024-01-30 Nippon Soda Co., Ltd. Arylazole compound and pest control agent
US11078181B2 (en) 2016-12-19 2021-08-03 Nippon Soda Co., Ltd. Diaryl pyrazole compound and formulation for controlling harmful organisms

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WO2010136145A1 (de) 2010-12-02
KR101758935B1 (ko) 2017-07-17
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US20110021539A1 (en) 2011-01-27
EP2435420B1 (de) 2013-04-03
CN102459235A (zh) 2012-05-16
KR20120061779A (ko) 2012-06-13
AR076798A1 (es) 2011-07-06
EP2266973A1 (de) 2010-12-29
AU2010252346A1 (en) 2011-12-22
CA2763498A1 (en) 2010-12-02
ES2409891T3 (es) 2013-06-28
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