WO2009156090A2 - Insecticidal sulfur-derivatized 1-azinylpyrazoles - Google Patents

Insecticidal sulfur-derivatized 1-azinylpyrazoles Download PDF

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WO2009156090A2
WO2009156090A2 PCT/EP2009/004391 EP2009004391W WO2009156090A2 WO 2009156090 A2 WO2009156090 A2 WO 2009156090A2 EP 2009004391 W EP2009004391 W EP 2009004391W WO 2009156090 A2 WO2009156090 A2 WO 2009156090A2
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Prior art keywords
alkyl
haloalkyl
spp
alkoxy
general formula
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PCT/EP2009/004391
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German (de)
French (fr)
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WO2009156090A3 (en
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Hans-Georg Schwarz
Thomas Schenke
Achim Hense
Robert Velten
Simon MAECHLING
Stefan Werner
Eva-Maria Franken
Ulrich Görgens
Peter Lümmen
Ulrich Ebbinghaus-Kintscher
Arnd Voerste
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Bayer Cropscience Aktiengesellschaft
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Publication of WO2009156090A2 publication Critical patent/WO2009156090A2/en
Publication of WO2009156090A3 publication Critical patent/WO2009156090A3/en

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    • 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
    • C07D401/02—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 two hetero rings
    • C07D401/04—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 two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring

Definitions

  • the present invention relates to sulfur-derivatized 1-azinylpyrazoles, their use as insecticides and / or parasiticides, and processes for their preparation.
  • Another object of the present invention are various intermediates which are passed through in the preparation of the sulfur-derivatized 1-azinylpyrazoles invention.
  • Another object of the present invention are finally agents which contain such Azinylpyrazole.
  • DE 197 51 943 A1 relates to 1-methyl-5-alkylsulfonyl, 1-methyl-5-alkylsulfinyl and 1-methyl-5-alkylthio-substituted pyrazolylpyrazoles, processes for their preparation and their use as herbicides.
  • 5-amino-1-methyl-3- (methylsulfanyl) -1H-pyrazole-4-carbonitrile is passed through as an intermediate.
  • no insecticidal activity of this intermediate is disclosed.
  • EP 1 829 867 A1 generically discloses pharmaceutically active sulfur derivatized 1-azinylpyrazoles.
  • the object of the present invention is therefore to provide alternative insecticides and / or parasiticides which show an improved action or a broadened spectrum of action in comparison with the active compounds known from the prior art.
  • the problem is solved by special sulfur-derivatized 1-azinylpyrazoles.
  • the present invention therefore provides sulfur-derivatized 1-azinylpyrazoles of the general formula (I) or their N-oxides,
  • a 1 and A 2 are nitrogen or CR 3 ;
  • B is alkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, haloalkyl, alkoxyalkyl, cyanoalkyl,
  • R 1 and R 2 are each independently hydrogen, alkyl, haloalkyl, cyanoalkyl, alkoxyalkyl, alkylcarbonyl, haloalkylcarbonyl, cycloalkyl, cycloalkylalkyl, alkylsulfonyl, alkenyl, alkynyl, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, alkoxycarbonylalkyl; Phenalkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the aromatic group by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; Heterocyclylalkyl which may optionally be mono- or polysubstituted by identical or different substituents on the heterocycle by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; Heteroaryl
  • R 4 and R 5 are each independently alkyl or together bridging alkylidene
  • R 6 is hydrogen or alkyl
  • X is phenyl, 2-pyridyl or 3-pyridyl, each substituted by one or more identical or different substituents selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkenoxy, alkynyloxy, Cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, haloalkylsulfanyl, alkylsulfmyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkyl kylsilyl, nitro, amino, alkylamino, dialkylamino
  • Y is -S-, -S (O) -, -SO 2 -, or one of the following groupings
  • the compounds of the general formula (I) according to the invention have very good insecticidal and parasiticidal properties and can be used in crop protection, veterinary hygiene and material protection for controlling undesired pests, such as insects, endo- or ectoparasites.
  • the invention also relates to all stereoisomers which are encompassed by formula (I) and mixtures thereof.
  • stereoisomers such as enantiomers, diastereomers, Z and E isomers are all of the formula (I) and can be obtained by conventional methods from mixtures of stereoisomers or by stereoselective reactions in combination with the use of stereochemically pure starting materials are produced.
  • Compounds of the general formula (I) optionally consist of a mixture of the respective enantiomers which are chiral on the sulfur function,
  • Racemic mixtures for example of optically active sulfoxides of the general formula (I), can be separated by known processes. Such racemate resolution methods are in
  • Eligible e.g. Adduct formation with an optically active auxiliary reagent, separation of the diastereomeric adducts into the corresponding diastereomers, e.g. by crystallization, chromatography, especially column chromatography and
  • optically active acid is e.g. Camphorsulfonic acid, camphoric acid, bromocamphorsulfonic acid, quinic acid, tartaric acid, dibenzoyltartaric acid and other analogous acids
  • optically active bases are e.g. Quinine, cinchonine, quinidine, brucine, 1-phenylethylamine and other analogous bases in question.
  • the crystallizations are then usually carried out in aqueous or aqueous-organic solvents, wherein the diastereomer with the lower solubility, if appropriate after inoculation, first fails.
  • the one enantiomer of the compound of formula (I) is then released from the precipitated salt or the other from the crystals by acidification or with base.
  • racemates can be separated chromatographically with chiral stationary phases. Enantiomer separations of this type can be carried out from mg to the 100 kg range with preparative HPLC systems in single or continuous operation.
  • the compounds of the invention are generally defined by the formula (I).
  • Preferred, particularly preferred and very particularly preferred radical definitions of the above and below-mentioned formulas are given below. These definitions apply equally to the end products of general formula (I) as well as to all intermediates.
  • a 1 is preferably nitrogen and A 2 is preferably CH or CR 3 .
  • a 1 is preferably CH or CR 3 and A 2 is CH or CR 3 , where in the case of several radicals R 3, the radicals R 3 may each be identical or different.
  • a 1 is preferably C-R 3 and A 2 is preferably nitrogen.
  • the invention further relates in a fourth embodiment to compounds of the formula (I) or to compounds according to one of the first to third embodiments in which the radical B is
  • C, -C 6 alkyl Haio-C 1 -C 6 alkyl, C r C 6 alkoxy-C 6 alkyl, Ci-C6 - alkoxycarbonyl-C, -C 6 alkyl , C 2 -C 6 alkenyl; C 2 -C 6 alkynyl, tri (C 1 -C 4 alkyl) silyl C 1 -C 6 alkyl; Phenyl-Ci-C ö alkyl which on the aromatic ring may optionally be singly or multiply substituted identically or differently by fluorine, chlorine, bromine, iodine, methyl, trifluoromethyl or methodological xy; and 2-pyridyl-C, -C 6 -alkyl;
  • the invention relates to compounds of the formula (I) or to compounds according to one of the first to fourth embodiments in which the radicals R 1 and R 2 are each independently of one another
  • halogen particularly preferably represents halogen, C) -C 6 -alkyl, C r C 6 -haloalkyl, QC 6 -alkoxy and C 1 -C 6 -haloalkoxy;
  • Ci-C 6 alkyl very particularly preferably represents halogen, Ci-C 6 alkyl, C 1 -C 6 -HaIOaIlCyI and C 1 -C 6 -alkoxy group;
  • the invention in a seventh embodiment relates to compounds of the formula (I) or to compounds according to one of the first to sixth embodiments in which the radical X is preferably phenyl, 2-pyridyl or 3-pyridyl, which in each case may optionally be mono- or polysubstituted by identical or different substituents, by one or more substituents selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy , COOH, nitro, amino, alkylamino, dialkylamino, wherein vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system containing from 0 to 2 oxygen atoms contains, and whose alkyl moiety may optionally be substituted by one or more fluorine atoms, is;
  • phenyl which may optionally be mono- or polysubstituted or differently substituted by one or more substituents selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, COOH, nitro, amino, alkylamino , Dialkylamino, wherein vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy together with the carbon atoms to which they are attached, can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms, and its alkyl moiety optionally with a or more than one fluorine atom may be substituted;
  • phenyl which is monosubstituted or polysubstituted by at least one substituent selected from the group consisting of halogen, C 1 -C 6 haloalkyl and C 1 -C 6 alkoxy, vicinal alkyl, haloalkyl, alkoxy and or haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system which contains 0 to 2 oxygen atoms and whose alkyl moiety may optionally be substituted by one or more fluorine atoms;
  • the invention relates to compounds of the formula (I) or to compounds according to one of the first to eighth embodiments of the radical n
  • the radical B is alkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, haloalkyl, alkoxyalkyl, cyanoalkyl, alkylthioalkyl Alkylsulfinylalkyl, alkylsulfonylalkyl, aminoalkyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkenyl and alkynyl, each of which may optionally be mono- or polysubstituted by identical or different substituents by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; Phenalkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the aromatic group by halogen, alkyl, haloal
  • radical B This excludes from the definition of the compounds of the general formula (I) in particular the compounds which, as radical B, have a carbonylalkylamino radical and an alkylamino radical.
  • radical B Preferred, particularly preferred, very particularly preferred and special meanings for the radical B correspond to the above definitions.
  • the meanings of the remaining radicals or substituents of the general formula (I) can correspond to the general, preferred, particularly preferred, very particularly preferred and special meanings.
  • substituents may be halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkenoxy, alkynoxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, haloalkyl sulfanyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, nitro, amino
  • halogens in particular fluorine, chlorine, bromine or iodine
  • Haloalkyl such as CF 3
  • Alkoxy such as OCH 3
  • compounds in which vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached form a five- to six-membered cyclic system containing from 0 to 2 oxygen atoms and its alkyl moiety, if appropriate may be substituted with one or more fluorine atoms.
  • the meanings of the other radicals or substituents of the general formula (I) may correspond to the general, preferred, particularly preferred, very particularly preferred and special meanings.
  • compounds of the general formula (I), in particular compounds according to the abovementioned embodiments, in which the radical A 1 is CR 3 and the radical A 2 is N is included.
  • the meanings of the remaining radicals or substituents of the general formula (I) may correspond to the general, preferred, particularly preferred, very particularly preferred and special meanings.
  • Preferred, particularly preferred, very particularly preferred and especially are compounds which in each case carry the substituents mentioned under preferred, particularly preferred, very particularly preferred and particularly preferred.
  • halogen means fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine.
  • halogen means, for example, a fluorine, chlorine, bromine or iodine atom.
  • Halogen substituted radicals e.g. Haloalkyl
  • Halogen substituted radicals are halogenated once or several times up to the maximum possible number of substituents.
  • the halogen atoms may be the same or different.
  • Saturated or unsaturated hydrocarbon radicals such as alkyl, alkenyl or alkynyl may also be used in conjunction with heteroatoms, e.g. in alkoxy, as far as possible, in each case straight-chain or branched.
  • Alkyl means a straight-chain or branched open-chain hydrocarbon radical.
  • alkyl (Ci-Ci 2) -alkyl, particularly preferably (Ci-Cg) -alkyl, in particular (Ci-Ce) -alkyl, in particular (C r C 4) alkyl, comprising.
  • alkyl radicals in assembled radicals, for example, alkoxy, haloalkyl, and are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, Hexyl and 1,3-dimethylbutyl, heptyls such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl.
  • monohaloalkyl such as CH 2 CH 2 Cl, CH 2 CH 2 F, CHClCH 3 , CHFCH 3 , CH 2 Cl, CH 2 F
  • Perhaloalkyl such as CC
  • Alkenyl furthermore denotes a straight-chain or branched open-chain hydrocarbon radical having at least one double bond.
  • alkenyl (C 2 -Ci 2 ) -
  • Alkenyl particularly preferably (C 2 -C 8 ) -alkenyl, in particular (C 2 -C 6 ) -alkenyl, especially (C 2 -C 4 ) -
  • Alkenyl includes.
  • suitable alkenyl radicals are 1,3-butadienyl and 1,4-pentadienyl, but also allenyl or cumulenyl radicals having one or more cumulated double bonds, such as, for example, allenyl (1,2-propadienyl), 1,2-butadienyl and 1,2 , 3-Pentatrienyl.
  • radical alkenyl are vinyl, which may optionally be substituted by further alkyl radicals, for example prop-1-en-1-yl, but-1-en-1-yl; Allyl, 1-methyl-prop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, 1-methyl-but-3-ene 1-yl and 1-methylbut-2-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, butyric 3-en-1-yl, 1-methylbut-3-en-1-yl or 1-methylbut-2-en-1-yl, pentenyl, 2-methylpentenyl and hexenyl.
  • alkyl radicals for example prop-1-en-1-yl, but-1-en-1-yl; Allyl, 1-methyl-prop-2-en-1-yl, 2-methyl-
  • Alkynyl furthermore denotes a straight-chain or branched open-chain hydrocarbon radical having at least one triple bond. Optionally, one or more double bonds may be present.
  • Corresponding examples are ethynyl, propargyl, 1-methylprop-2-yn-1-yl, 2-butynyl, 2-pentynyl, 1,3-butatrienyl or 3-penten-1-yn-1-yl or 2-yl Hexynyl, preferably propargyl, but-2-yn-1-yl, but-3-yn-1-yl or 1-methyl-but-3-yn-1-yl.
  • Alkylidene e.g. B. in the form (Ci-C 10 ) alkylidene, means the radical of a straight-chain or branched open-chain hydrocarbon radical which is bonded via a double bond.
  • Cycloalkyl means a carbocyclic saturated ring system preferably having 3 to 8 ring C atoms, e.g. Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • substituents wherein substituents having a double bond on the cycloalkyl, z.
  • alkylidene group such as methyl iden, are included.
  • polycyclic aliphatic systems are also included, such as, for example, bicyclo [1.1.0] butan-1-yl, bicyclo [1.1.0] butan-2-yl, bicyclo [2.1.0] pentane-1 -yl, bicyclo [2.1.0] pentan-2-yl, bicyclo [2.1.0] pentan-5-yl, bicyclo [2.2. l] hept-2-yl (norbornyl), adamantan-1-yl and adamantan-2-yl.
  • spirocyclic aliphatic systems are also included, for example spiro [2.2] pent-1-yl, spiro [2.3] hex-1-yl, spiro [2.3] hex-4-yl, 3-spiro [ 2.3] hex-5-yl.
  • Cycloalkenyl means a carbocyclic, non-aromatic, partially unsaturated ring system having preferably 4 to 8 C atoms, for example 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, or 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, 1,3-cyclohexadienyl or 1, 4-cyclohexadienyl, wherein also substituents having a double bond on the cycloalkenyl, z.
  • an alkylidene group such as methylidene, are included.
  • Aryl is a mono-, bi- or polycyclic aromatic system having preferably 6 to 14, in particular 6 to 10 ring C atoms, for example phenyl, naphthyl, anthryl, phenanthrenyl, and the like, preferably phenyl.
  • aryl In the case of substituted or unsubstituted aryl, there are also more cyclic systems, such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenylyl, where the binding site is on the aromatic system.
  • aryl is also encompassed by the term "optionally substituted phenyl”.
  • heterocyclyl or heterocyclic ring When the heterocyclyl or heterocyclic ring is optionally substituted, it may be fused with other carbocyclic or heterocyclic rings.
  • heterocyclyl In the case of optionally substituted heterocyclyl, more cyclic systems are also included, such as, for example, 8-azabicyclo [3.2.1] octanyl or 1-azabicyclo [2.2.1] heptyl.
  • spirocyclic systems are also included, such as, for example, 1-oxa-5-azaspiro [2.3] hexyl.
  • the heterocyclic ring preferably contains 3 to 9 ring atoms, in particular 3 to 6 ring atoms, and one or more, preferably 1 to 4, in particular 1, 2 or 3 heteroatoms in the heterocyclic ring, preferably from the group consisting of N , O, and S, but not two oxygen atoms should be directly adjacent.
  • heteroaryl is understood to mean systems as defined above under “heterocyclyl” but which are heteroaromatic, ie. H. represent a fully unsaturated aromatic heterocyclic compound.
  • substituted by one or more radicals means, independently of one another, one or more identical or different radicals, it being possible for two or more radicals to form one or more rings on one cycle as main body.
  • Substituted radicals such as a substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl radical, are, for example, a substituted radical derived from the unsubstituted radical, where the substituents for example one or more, preferably 1, 2 or 3, radicals from the group consisting of halogen, alkoxy, alkylthio, hydroxyl, amino, nitro, carboxy or a group equivalent to the carboxy group, cyano, isocyanato, 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 substituted heterocycly
  • substituents in addition to the said saturated hydrocarbon-containing radicals corresponding unsaturated aliphatic and aromatic radicals such as optionally substituted alkenyl, alkynyl, 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, etc., included.
  • substituted cyclic radicals having a-liphatischen portions in the ring and cyclic systems are also having such substituents which are bonded to a double bond on the ring, z. B. with an alkylidene group such as methyl iden or ethylidene or an oxo group, imino group or substituted imino group are substituted.
  • radicals form one or more rings
  • these may be carbocyclic, heterocyclic, saturated, partially saturated, unsaturated, for example also aromatic and, where appropriate, further substituted.
  • the annelated rings are preferably 5- or 6-membered rings, particularly preferred are benzo-fused rings.
  • first substituent level may, if they contain carbon-containing moieties, optionally further substituted there (“second substituent level”), for example by one of the substituents as defined for the first substituent , Corresponding further substituent levels are possible.
  • substituted radical includes only one or two substituent levels.
  • Preferred substituents for the substituent levels are, for example, amino, hydroxyl, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, carboxy, carbonamide, SF 5 , aminosulfonyl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, monoalkylamino, dialkyl amino, N- Alkanoylamino, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryloxycarbonyl, alkanoyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, alkylthio, cycloalkylthio, alkenylthio, cycloalkene nylthio, al
  • the compounds of the general formula (I) can be obtained, if appropriate, by addition of a suitable inorganic or organic acid, for example mineral acids, in particular HCl, HBr, H 2 SO 4 , H 3 PO 4 or HNO 3 , or, for example, organic acids, in particular carboxylic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, lactic acid or salicylic acid or, for example, sulfonic acids, in particular p-toluenesulfonic acid, to a basic group, such as amino, alkylamino, dialkylamino, piperidino, morpholino or pyridino, salts.
  • a suitable inorganic or organic acid for example mineral acids, in particular HCl, HBr, H 2 SO 4 , H 3 PO 4 or HNO 3
  • organic acids in particular carboxylic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, lactic acid or
  • Suitable substituents which are in deprotonated form e.g. Sulfonic acids or carboxylic acids, may form internal salts with their turn protonatable groups, such as amino groups.
  • the present compounds of the general formula (I) can be prepared by the following processes, the compounds of the general formula (I)
  • ⁇ BB aryl, hetaryl
  • a 1 , A 2 , B, X, R 3 and n have the meanings given above and LG stands for any leaving group.
  • the present invention therefore also relates to a process for the preparation of the compounds of general formula (I) by the following reaction
  • R 1 and R 2 are hydrogen, R 3 , X, Y, B and n are as defined above.
  • the educt used for this reaction is recovered according to the reaction scheme shown above.
  • the leaving group LG is not particularly limited and may be, for example, a halogen, an alkylsulfonyl, an alkylsulfinyl, an alkylsulfanyl or nitro.
  • ketene S, S-dithioacetals of the general formula (IV), (IV-A) or (IV-B) are first reacted with hydrazine hydrate in a suitable solvent.
  • the resulting aminopyrazoles of general formula (V) are then reacted with azinyl derivatives of general formula (VI) containing a suitable leaving group "LG" such as halogens, alkylsulfonates, arylsulfonates, alkylsulfonyls, alkylsulfinyls, alkylsulfanyls or nitro.
  • LG suitable leaving group
  • a further subject of the present invention are the intermediates of the general formula (IV) in this synthesis.
  • G 1 , G 2 and G 3 are selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkenoxy, alkynoxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, haloalkylsulfanyl, Alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, nitro, amino, alkylamino, dialkylamino, alkylsulfonylamino, dialkylsulf
  • G 1 , G 2 and G 3 are each independently selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, COOH nitro, amino, alkylamino, dialkylamino, vicinal alkyl, Haloalkyl, alkoxy and / or Haloalko- xy phenomenon together with the carbon atoms to which they are attached, can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms, and the alkyl moiety may be optionally substituted with one or more fluorine atoms ,
  • G 1, G 2 and G 3 are each independently selected from the group consisting of halogen, Ci.C ö -haloalkyl and Ci-C 6 -alkoxy, where vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system which contains 0 to 2 oxygen atoms, and whose alkyl moiety may optionally be substituted by one or more fluorine atoms.
  • G 1 , G 2 and G 3 each independently of one another, selected from the group consisting of fluorine, chlorine, bromine, iodine, CF 3 , CH 3 O, OCH 2 O, OCH 2 CH 2 and OCF 2 O.
  • X has one of the following meanings:
  • the present invention furthermore relates to the intermediates of the general formula (IV-A) in this synthesis.
  • G 1 , G 2 and G 3 are selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkenoxy, alkynoxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, haloalkylsulfanyl, Alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, nitro, amino, alkylamino, dialkylamino, alkylsulfonylamino, dialkylsulf
  • G 1 , G 2 and G 3 are each independently selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, COOH nitro, amino, alkylamino, dialkylamino, vicinal alkyl, Haloalkyl, alkoxy and / or Haloalko- xy phenomenon together with the carbon atoms to which they are attached, can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms, and the alkyl moiety may be optionally substituted with one or more fluorine atoms ,
  • G 1 , G 2 and G 3 each independently of one another, selected from the group consisting of halogen, C 1 -C 6 -haloalkyl and C 1 -C 6 -alkoxy, where vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms, and whose alkyl moiety may be optionally substituted with one or more fluorine atoms.
  • G 1 , G 2 and G 3 each independently of one another, selected from the group consisting of fluorine, chlorine, bromine, iodine, CF 3 , CH 3 O, OCH 2 O, OCH 2 CH 2 and OCF 2 O.
  • X has one of the following meanings:
  • G 1 , G 2 and G 3 are selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkenoxy, alkynoxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, haloalkylsulfanyl, Alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, nitro, amino, alkylamino, dialkylamino, alkylsulfonylamino, dialkylsulf
  • G 1 , G 2 and G 3 are each independently selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, COOH, nitro, amino, alkylamino, dialkylamino, vicinal alkyl , Haloalkyl, alkoxy and / or Haloalko- xy phenomenon together with the carbon atoms to which they are attached, can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms, and its alkyl moiety optionally substituted with one or more fluorine atoms can.
  • G 1 , G 2 and G 3 each independently, selected from the group consisting of halogen, Ci.C ⁇ -haloalkyl and Ci-C 6 alkoxy, wherein vicinal alkyl, haloalkyl, alkoxy and / or Haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms. contains atoms, and whose alkyl moiety may optionally be substituted with one or more fluorine atoms.
  • G 1 , G 2 and G 3 each independently of one another, selected from the group consisting of fluorine, chlorine, bromine, iodine, CF 3 , CH 3 O, OCH 2 O, OCH 2 CH 2 and OCF 2 O.
  • X has one of the following meanings:
  • R, R, A, A, B, X, R and n have the meanings given above.
  • corresponding thioethers of the general formula (IA) are reacted with one mole of a suitable oxidizing agent, for example with H 2 O 2 , sodium periodate, tert-butyl hypochlorite, calcium hypochlorite Ca (OCl) 2 , sodium chlorite NaClO 2 , sodium hypochlorite NaOCl, peracids or O 2 and catalytic cerium ammonium nitrate.
  • a suitable oxidizing agent for example with H 2 O 2 , sodium periodate, tert-butyl hypochlorite, calcium hypochlorite Ca (OCl) 2 , sodium chlorite NaClO 2 , sodium hypochlorite NaOCl, peracids or O 2 and catalytic cerium ammonium nitrate.
  • a suitable oxidizing agent for example with H 2 O 2 , sodium periodate, tert-butyl hypochlorite, calcium hypochlorite Ca (OCl) 2 ,
  • a 1 , A 2 , B, X, R 3 , R 6 and n have the meanings given above.
  • A, A, B, X, Y, R, R, R and n have the meanings given above.
  • the free NH 2 group of the compounds (IA) - (IF) is prepared by the generally known processes for basic alkylation or acylation with the corresponding alkylation. or acylating reagents (XI) and (Xu) reacted.
  • A, A, B, X, Y, R, R, R and n have the meanings given above.
  • the present invention therefore also relates to a process for the preparation of the compounds of general formula (I) by the following reaction:
  • A, A, B, X, Y, R, R, R and n have the meanings given above.
  • a 1 , A 2 , B, X, R 3 and n have the meanings given above and LG stands for any leaving group.
  • G 1 , G 2 and G 3 are selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkenoxy, alkynoxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, haloalkylsulfanyl, Alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, nitro, amino, alkylamino, dialkylamino, alkylsulfonylamino, dialkylsulf
  • G 1 , G 2 and G 3 are each independently selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, COOH, nitro, amino, alkylamino, dialkylamino, vicinal alkyl , Haloalkyl, alkoxy and / or Haloalko- xy phenomenon together with the carbon atoms to which they are attached, can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms, and its alkyl moiety optionally with one or more fluorine atoms may be substituted.
  • G 1 , G 2 and G 3 each independently, selected from the group consisting of halogen, Ci.C 6 -haloalkyl and C 1 -C 6 -Akoxy, where vicinal alkyl, haloalkyl, alkoxy and or haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system which contains 0 to 2 oxygen atoms, and whose alkyl moiety may optionally be substituted by one or more fluorine atoms.
  • G 1 , G 2 and G 3 each independently of one another, selected from the group consisting of fluorine, chlorine, bromine, iodine, CF 3 , CH 3 O, OCH 2 O, OCH 2 CH 2 and OCF 2 O.
  • X has one of the following meanings:
  • the active compounds according to the invention are suitable for plant tolerance, favorable warm-blood toxicity and good environmental compatibility for the protection of plants and plant organs, for increasing crop yields, improving the quality of the crop and for controlling animal pests, in particular insects, arachnids, helminths, nematodes and molluscs which are found in agriculture, horticulture, livestock, forests, gardens and recreational facilities, in the protection of materials and materials and in the hygiene sector. They can preferably be used as crop protection agents. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • the above mentioned pests include:
  • Anoplura e.g. Damalinia spp., Haematopinus spp., Ligognathus spp., Pediculus spp., Trichodectes spp.
  • arachnids e.g. Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia 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, Polyphago- tarsonemus latus, Psoroptes spp., Rhipicephalus spp , Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici.
  • Naupactus xanthographus Naptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Otiorrhynchus sulcatus, Oxycetonia jucunda, Phaedon cochleareae, Phyllophaga spp., Popillia japonica, Premnotrypes spp.
  • Gastropoda e.g. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.
  • helminths e.g. 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., Loa Loa, Nemat
  • protozoa such as Eimeria
  • Eimeria protozoa
  • Doralis spp. Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Geococcus coffeae, Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp ., Laodelph ax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari, Metcalfella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Lepidoptera From the order of Lepidoptera, for example Acronicta major, Aedia leucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Caceacia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp.
  • Orthoptera e.g. Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.
  • siphonaptera e.g. Ceratophyllus spp., Xenopsylla cheopis.
  • Symphyla e.g. Scutigerella immaculata.
  • Thysanoptera e.g. Basothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirothrips spp., Taeniothrips cardamoni, Thrips spp.
  • Thysanura e.g. Lepisma saccharina.
  • the plant parasitic nematodes include e.g. Anguina spp., Aphelenchoides spp., Belonoclampus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Rotary Lenchus spp., Trichodorus spp., Tylenchorhynchus spp., Tylenchulus spp., Tylenchulus semipetnetrans, Xiphinema spp.
  • Anguina spp. Aphelenchoides spp., Belonoclampus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera
  • the compounds according to the invention may also be used in certain concentrations or application rates 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-organism) and RLO (Rickettsia-like-organism) can be used. If appropriate, they can also be used as intermediates or precursors for the synthesis of further active ingredients.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, scattering granules, suspension-emulsion concentrates, active substance-impregnated natural products, active ingredient impregnated synthetic materials, fertilizers and micro-encapsulants in polymeric materials.
  • These formulations are prepared in a known manner, for example by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents. The preparation of the formulations is carried out either in suitable systems or before or during use.
  • Excipients which can be used are those which are suitable for imparting special properties to the composition itself and / or preparations derived therefrom (for example spray liquor, seed dressing), such as certain technical properties and / or specific biological properties.
  • Typical auxiliaries are: extenders, solvents and carriers.
  • polar and non-polar organic chemical liquids e.g. from the classes of aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (which may also be substituted, etherified and / or esterified), ketones (such as acetone, cyclohexanone), Esters (including fats and oils) and (poly) ethers, simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide).
  • aromatic and non-aromatic hydrocarbons such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes
  • alcohols and polyols which may also be substituted, etherified and / or esterified
  • ketones such
  • Suitable liquid solvents are essentially: 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, e.g.
  • Petroleum fractions mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl sulfoxide, and water.
  • Suitable solid carriers are:
  • ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals, such as finely divided silica, alumina and silicates, as solid carriers for granules in question: eg broken and fractionated natural rocks such Calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as paper, sawdust, coconut shells, corn cobs and tobacco stalks;
  • suitable emulsifiers and / or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol Ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable
  • oligo- or polymers for example starting 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 liginine and its sulfonic acid derivatives, simple and modified celluloses, aromatic and / or aliphatic sulfonic acids and also adducts thereof with formaldehyde.
  • Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-type polymers can be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins and synthetic phospholipids.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • inorganic pigments e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • additives may be fragrances, mineral or vegetable optionally modified oils, waxes and nutrients (also trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • Stabilizers such as low-temperature stabilizers, preservatives, antioxidants, light stabilizers or other agents which improve the chemical and / or physical stability, may furthermore be present.
  • the formulations generally contain between 0.01 and 98% by weight of active ingredient, preferably between 0.5 and 90%.
  • the active ingredient according to the invention can be present in its commercial formulations as well as in the formulations prepared from these formulations in admixture with other active ingredients such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners, fertilizers or semiochemicals.
  • active ingredients such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners, fertilizers or semiochemicals.
  • Particularly favorable mixing partners are, for example, the following: fungicides:
  • inhibitors of nucleic acid synthesis such as benalaxyl, benalaxyl-M, bupirimate, clozylacon, dimethirimol, ethirimol, furalaxyl, hymexazole, metalaxyl, metalaxyl-M, ofurace, oxadixyl and oxolic acid.
  • Mitosis and cell division inhibitors such as benomyl, carbendazim, chlorfenazole, diethofencarb, ethaboxam, fuberidazole, pencycuron, thiabendazole, thiophanate, thiophanate-methyl and zoxamide.
  • inhibitors of respiration such as diflumetorim as an inhibitor at complex I of the respiratory chain; Bixafen, boscalid, carboxin, fenfuram, flutolanil, fluopyram, furametpyr, furmecyclox, isopyrazam (mixture of the syn-epimeric racemate 1RS, 4SR, 9RS and the anti-epimeric racemate 1RS, 4SR, 9SR), isopyrazam (syn epimeric racemate 1RS, 4SR, 9RS), isopyrazam (syn-epimeric enantiomer 1R, 4S, 9R), isopyrazam (syn-epimeric enantiomer 1S, 4R, 9S), isopyrazam (anti-epimeric racemate 1RS, 4SR, 9SR), isopyrazam (anti-epimeric racemate 1RS, 4SR, 9SR), isopyrazam (anti-epimeric racemate 1RS, 4SR,
  • decouplers such as binapacryl, dinocap, fluazinam and meptyldinocap.
  • inhibitors of ATP production such as, for example, fentin acetate, fentin chloride, fentin hydroxide and silthiofam.
  • inhibitors of amino acid and protein biosynthesis such as andoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim and pyrimethanil.
  • signal transduction inhibitors such as fenpiclonil, fludioxonil and quinoxyfen.
  • Inhibitors of lipid and membrane synthesis such as biphenyl, chlozolinate, edifenphos, etridiazole, iodocarb, Iprobenfos, iprodione, isoprothiolane, procymidone, propamocarb, propamocarb hydrochloride, pyrazophos, tolclofos-methyl and vinclozolin.
  • inhibitors of ergosterol biosynthesis such as aldimorph, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, Dodemorph, Dodemo ⁇ h Acetate, Epoxiconazole, Etaconazole, Fenarimol, Fenbuconazole, Fenhexamid, Fenpropidin, Fenpropimo ⁇ h, Fluquinconazole, Flurprimidol, Flusilazole, Flutriafol, Furconazole, Furconazole Cis, Hexaconazole, Imazalil, Imazalil Sulfate, Imibenconazole, Ipconazole, Metconazole, Myclobutanil, Naftifine, Nuarimol, Oxpoconazole, Paclobutrazol, Pefurazoate, Penconazole, Pipera
  • inhibitors of cell wall synthesis such as Benthiavalicarb, Dimethomo ⁇ h, Flumo ⁇ h, Iprovalicarb, Mandipropamid, Polyoxins, Polyoxorim, Prothiocarb, Validamycin A and valefenalate.
  • inhibitors of melanin biosynthesis such as, for example, caryropamide, diclocymet, fenoxanil, fthalide, pyroquilone and tricyclazole.
  • resistance inducers such as acibenzolar-S-methyl, probenazole and tiadinil.
  • Acetylcholinesterase (AChE) inhibitors such as carbamates, e.g. Alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxime, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamates, Trimethacarb, XMC and xylylcarb; or
  • AChE Acetylcholinesterase
  • Organophosphates eg acephates, azamethiphos, azinphos (-methyl, -ethyl), cadusafos, chiorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos (-methyl), coumaphos, cyanophos, demeton-s-methyl, diazinon, dichlorvos / DDVP, Dicrotophos, Dimethoate, Dimethylvinphos, Disulphon, EPN, Ethion, Ethoprophos, Famphur, Fenamiphos, Fenitrothion, Fenthion, Fosthiazate, Heptenophos, Isofenphos, Isopropyl O- (methoxyaminothio-phosphoryl) salicylate, Isoxathion, Malathion, Mecarbam, Methamidophos, Methidathion, Mevinphos, Monocrotophos, Naled, Ometho
  • GABA-regulated chloride channel antagonists such as organochlorines, eg, chlordane and endosulfan (alpha); or fiproles (phenylpyrazoles), for example ethiprole, fipronil, pyrroliprole and pyriprole.
  • sodium channel modulators / voltage-dependent sodium channel blockers such as, for example, pyrethroids, eg acrinathrin, allethrin (d-cis-trans, d-trans), bifenthrin, bioallethrin, bioalbhrine-S-cyclopentenyl, Bioresmethrin, cycloprothrin, cyfluthrin (beta), cyhalothrin (gamma, lambda), cypermethrin (alpha, beta, theta, zeta), cyphenothrin [(IR) trans-lsome], deltamethrin, dimefluthrin , Empenthrin [(5 1 Z) - (IA) -IsOmCrC], esfenvalerates, etofenprox, fenpropathrin, fenvalerates, flucythrinates, flumethrin,
  • nicotinergic acetylcholine receptor agonists such as neonicotinoids, e.g. Acetamidipride, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; or nicotine.
  • Allosteric acetylcholine receptor modulators such as spinosyns, e.g. Spinetoram and spinosad.
  • chloride channel activators such as avermectins / milbemycins, e.g. Abamectin, Emamectin benzoate, Lepimectin and Milbemectin.
  • Juvenile hormone analogs e.g. Hydroprene, kinoprene, methoprene; or fenoxycarb; Pyritexyfen.
  • agents with unknown or non-specific mechanisms of action such as
  • Fumigant e.g. Methyl bromide and other alkyl halides; or chloropicrin; Sulfuryl fluoride; Borax; Tartar emetic.
  • mite growth inhibitors e.g. Clofentezine, diflovidazine, hexythiazox, etoxazole.
  • Microbial disruptors of insect intestinal membrane such as Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis, and BT plant proteins, eg Cryl Ab, Cry 1 Ac, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Abl.
  • insect intestinal membrane such as Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis, and BT plant proteins, eg Cryl Ab, Cry
  • inhibitors of oxidative phosphorylation, ATP disruptors such as diafenthiourone; or organotin compounds, eg azocyclotine, cyhexatin, fenbutatin oxide; or propriety; Tetradifon.
  • Nicotinergic acetylcholine receptor antagonists such as Bensultap, Cartap (hydrochloride), thiocylam, and thiosultap (sodium).
  • inhibitors of chitin biosynthesis type 0, such as benzoylureas, e.g. Bistrifluron, chlorofluorazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron.
  • benzoylureas e.g. Bistrifluron, chlorofluorazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron.
  • inhibitors of chitin biosynthesis type 1, such as buprofezin.
  • Moulting agents such as Cyromazine.
  • Diacylhydrazines e.g. Chromafenozide, Halofenozide, Methoxyfenozide and Tebufenozide.
  • Octopaminergic agonists such as amitraz.
  • side-III electron transport inhibitors / side II electron transport inhibitors such as, for example, hydramethylnone; acequinocyl; fluacrypyrim; or Cyflumetofen and Cyenopyrafen.
  • Electron transport inhibitors such as side-I electron transport inhibitors, from the group of METI acaricides, e.g. Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebfenpyrad, Tolfenpyrad; or Rotenone (Denis).
  • METI acaricides e.g. Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebfenpyrad, Tolfenpyrad; or Rotenone (Denis).
  • (23) inhibitors of acetyl-CoA carboxylase such as tetronic acid derivatives, e.g. Spidrodiclofen and spiromesifen; or tetramic acid derivatives, e.g. Spirotetramat.
  • side FV electron transport inhibitors such as phosphenes, e.g. Aluminum phosphide, calcium phosphide, phosphine, zinc phosphide; or cyanide.
  • Ryanodine receptor effectors such as diamides, eg chlorantraniliprole (rynaxypyr), cyantraniliprole (cyazypyr) and flubendiamide.
  • Other drugs with unknown mechanism of action such as Azadirachtin, Amidofiumet, Benzoximate, Bifenazate, Chinomethionat, Cryolite, Dicofol, Flufenerim, Pyridalyl and Pyrifluquinazone; or the following known effective compounds
  • the active compounds according to the invention can furthermore be present when used as insecticides in their commercial formulations as well as in the formulations prepared from these formulations in admixture with synergists.
  • Synergists are compounds which increase the effect of the active ingredients without the added synergist itself having to be active.
  • the active compounds according to the invention may furthermore, when used as insecticides in their commercial formulations and in the forms of use prepared from these formulations, be present in mixtures with inhibitors which reduce degradation of the active ingredient after application in the environment of the plant, on the surface of plant parts or in plant tissues ,
  • the active substance content of the application forms prepared from the commercial formulations can vary within wide ranges.
  • the active ingredient concentration of the use forms may be from 0.00000001 up to 95% by weight of active compound, preferably between 0.00001 and 1% by weight.
  • the application is done in a custom forms adapted to the application.
  • plants are understood as meaning 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 plant varieties that are protectable or unprotectable by plant variety rights.
  • Plant parts are to be understood as meaning all aboveground and underground parts and organs of the plants, such as shoot, leaf, flower and root, by way of example leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds and roots, tubers and rhizomes.
  • the plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.
  • Treatment methods eg by dipping, spraying, evaporating, misting, spreading, spreading painting, injecting and propagating material, in particular seed, by single or multi-layer coating.
  • plants and their parts can be treated.
  • wild species or plant species obtained by conventional biological breeding methods such as crossing or protoplast fusion
  • plant varieties and their parts are treated.
  • transgenic plants and plant cultivars obtained by genetic engineering if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated.
  • the terms "parts” or “parts of plants” or “plant parts” have been explained above.
  • Plant varieties are understood as meaning plants having new traits which have been bred by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, biotypes and genotypes.
  • the treatment according to the invention may also result in superadditive (“synergistic”) effects.
  • superadditive for example, reduced application rates and / or extensions of the spectrum of action and / or an increase in the effect of the substances and agents usable in 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 power , facilitated harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or machinability of the harvested products, which go beyond the actual expected effects.
  • the preferred plants or plant varieties to be treated according to the invention to be treated include all plants which, as a result of the genetic engineering modification, obtained genetic material which gives these plants particularly advantageous valuable properties ("traits").
  • traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to bottoms salt, increased flowering, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products , higher shelf life and / or workability of the harvested products.
  • Further and particularly emphasized examples of such properties are an increased defense of the plant against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as increased tolerance of the plants to certain herbicidal active substances.
  • transgenic plants are the important crops, such as cereals (wheat, rice), maize, soya, potatoes, sugar beets, tomatoes, peas and other vegetables, cotton, tobacco, rapeseed, and fruit plants (with the fruits apples, pears, Citrus fruits and grapes), with special emphasis on maize, soya, potato, cotton, tobacco and oilseed rape.
  • Traits which are particularly emphasized are the increased defense of the plants against insects, arachnids, nematodes and snails by toxins which are formed in the plants, in particular those which are produced by the genetic material from Bacillus thuringiensis (for example by the genes Cry ⁇ A (cf.
  • Bt plants are produced in the plants (hereinafter "Bt plants”. Traits also highlight the increased resistance of plants to fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (eg "PAT" gene).
  • SAR systemic acquired resistance
  • PAT phosphinotricin
  • genes which confer the desired properties can also occur in combinations with one another in the transgenic plants.
  • “Bt plants” are maize varieties, cotton varieties, soybean varieties and potato varieties which are sold under the trade names YIELD GARD® (eg corn, cotton, soya), KnockOut® (eg maize), StarLink® (eg maize), Bollgard® ( Cotton), Nucotn® (cotton) and NewLeaf® (potato).
  • herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties, which are sold under the trade names Roundup Ready® (tolerance to glyphosate eg corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, eg rapeseed), IMI® (tolerance against imidazolinone) and STS® (tolerance to sulfonylureas eg corn).
  • Roundup Ready® tolerance to glyphosate eg corn, cotton, soy
  • Liberty Link® tolerance to phosphinotricin, eg rapeseed
  • IMI® tolerance against imidazolinone
  • STS® tolerance to sulfonylureas eg corn
  • Clearfield® varieties eg corn
  • the listed plants can be treated particularly advantageously according to the invention with the compounds of the general formula I or the active substance mixtures according to the invention.
  • the preferred ranges given above for the active compounds or mixtures also apply to the Treatment of these plants. Particularly emphasized is the plant treatment with the compounds or mixtures specifically mentioned in the present text.
  • the compounds of the present invention can be used to control a variety of pests including, for example, noxious sucking insects, biting insects and other plant parasitic pests, storage pests, pests that destroy industrial materials and use and control pests including parasites in the animal health field for example their extinction and eradication.
  • the present invention thus also includes a method of controlling pests.
  • the active substances according to the present invention act against animal parasites, in particular ectoparasites or endoparasites.
  • the term endoparasites includes in particular helminths such as cestodes, nematodes or trematodes, and protozoa such as kozzidia.
  • Ectoparasites are typically and preferably arthropods, especially insects such as flies (stinging and licking), parasitic fly larvae, lice, hair-pieces, feathers, fleas and the like; or acarids such as ticks, for example ticks or leather ticks, or mites such as mange mites, mites, feather mites and the like.
  • These parasites include:
  • Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phytus spp., 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 humanus capitis, Pediculus humanus corporis, Phylloera vastatrix, Phthirus pubis, Solenopotes capillatus;
  • Trimenopon spp. Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp .; specific examples are: Bovicola bovis, Bovicola ovis, Bovicola limbata, Damalina bovis, Trichodectes canis, Felicola subrostratus, Bovicola caprae, Lepikentron ovis, Werneckiella equi;
  • Nematocerina and Brachycerina eg Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Odagmia spp , Wilhelmia spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp.
  • rophilus spp. Hippobosca spp., Lipoptena spp., Melophagus spp., Rhinoestrus spp., Tipula spp .; specific examples are: Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles gambiae, Anopheles maculipennis, Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Fannia canicularis, Sarcophaga carnaria, Stomoxys calcitrans, Tipula paludosa, Lucilia cuprina, Lucilia sericata, Simulium reptans, Phlebotomus papatasi, Phlebotomus longipalpis, Odagmia omata
  • siphonaptrida e.g. Pulex spp., Ctenocephalides spp., Tunga spp., Xenopsyl Ia spp., Ceratophyllus spp .; specific examples are: Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis;
  • heteropterid e.g. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
  • Omithonyssus spp. the original genus of the multiple ticks
  • Omithonyssus 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 (Boophillus annulatus), Rhipicephalus (Boophilus) calceratus, Hyalomma anatolicum, Hyalomma aegypti cumulus, Hyalomma marginatum, Hyalomma transiens, Rhipicephalus evertsi, Ixodes ricin
  • Actinedida Prostigmata
  • Acaridida e.g. Acarapis spp., Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pteroli- spp.
  • the active compounds according to the invention are also suitable for controlling arthropods, helminths and protozoa which infest animals.
  • the animals include farm animals such as e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, farmed fish, honey bees.
  • farm animals such as e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, farmed fish, honey bees.
  • the animals also include domestic animals - also referred to as pets - such as pets. Dogs, cats, caged birds, aquarium fish and so-called experimental animals such. Hamsters, guinea pigs, rats and mice.
  • control of the parasites can also help to prevent the transmission of infectious substances.
  • control means that the active substances act by controlling the occurrence of the parasite reduce the animal infected with such parasites to harmless levels. More specifically, as used herein, “control” means that the agent kills the subject parasite, inhibits its growth, or inhibits its proliferation.
  • the active compounds according to the invention when used for the treatment of animals, can be used directly.
  • they are used as pharmaceutical compositions which may contain pharmaceutically acceptable excipients and / or adjuvants known in the art.
  • the active ingredients may be shampoo or suitable, in aerosols or pressureless sprays , eg Pump sprays and atomizer sprays, applicable, formulated formulations.
  • the active compounds according to the invention can be used as formulations (for example powders, wettable powders, WPs), emulsions, emulsifiable concentrates (EC), flowable agents, homogeneous Solutions and suspension concentrates [suspension concentrates, "SC"]) containing the active ingredients in an amount of 1 to 80 wt .-%, directly or after dilution (eg 100- to 10,000facher dilution) apply or use them as a chemical bath.
  • formulations for example powders, wettable powders, WPs), emulsions, emulsifiable concentrates (EC), flowable agents, homogeneous Solutions and suspension concentrates [suspension concentrates, "SC”]
  • the active compounds according to the invention can be used in combination with suitable synergists or other active substances such as, for example, acaricides, insecticides, anthelmintics, antiprotozoal agents.
  • the compounds according to the invention show a high insecticidal activity against insects which destroy industrial materials.
  • insects By way of example and preferably without limiting however, the following insects are mentioned:
  • Hymenoptera such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur;
  • Termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zooter- mopsis nevadensis, Coptotermes formosanus;
  • Non-living materials such as preferably plastics, adhesives, glues, papers and cardboard, leather, wood, wood processing products and paints.
  • the ready-to-use agents may optionally contain further insecticides and optionally one or more fungicides.
  • the compounds according to the invention can be used to protect against fouling of objects, in particular hulls, sieves, nets, structures, quay systems and signal systems, which come into contact with seawater or brackish water.
  • the compounds according to the invention can be used alone or in combinations with other active substances as antifouling agents.
  • the active compounds are also suitable for controlling animal pests in household, hygiene and storage protection, in particular of insects, arachnids and mites, which are used in closed rooms, such as apartments, factory buildings, offices, vehicle cabins u.a. occurrence. They can be used to control these pests, alone or in combination with other active ingredients and adjuvants in household insecticide products. They are effective against sensitive and resistant species and against all stages of development. These pests include:
  • Scorpionidea eg Buthus occitanus.
  • Acarina for example, Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus galinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.
  • Zygentoma e.g. Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.
  • Ctenocephalides canis Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
  • Hymenoptera e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
  • Heteroptera e.g. Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.
  • Application is in aerosols, non-pressurized sprays, e.g. Pump and atomizer sprays, misting machines, foggers, foams, gels, evaporator products with cellulose or plastic evaporator plates, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-less or passive evaporation systems, moth papers, moth cakes and moth gels, as granules or dusts, in scattered edema or bait stations.
  • Pump and atomizer sprays misting machines, foggers, foams, gels, evaporator products with cellulose or plastic evaporator plates, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-less or passive evaporation systems, moth papers, moth cakes and moth gels, as granules or dusts, in scattered edema or bait stations.
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Chinese cabbage leaf discs (Brassica pekinensis) are sprayed with a preparation of active compound of the desired concentration and, after drying, are populated with larvae of the horseradish leaf beetle (Phaedon cochleariae).
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Maize leaf discs (Zea mays) are sprayed with an active compound preparation of the desired concentration and, after drying, are infested with caterpillars of the armyworm (Spodoptera frugiperd®).
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Bean leaf discs Phaseolus vulgaris infected by all stages of the common spider mite (Tetranychus urticae) are sprayed with an active compound preparation of the desired concentration.
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Chinese cabbage leaf discs (Brassica pekinensis), which are infested by all stages of the green pepper aphid (Myzus persicae), are sprayed with an active compound preparation of the desired concentration.
  • Vessels are filled with sand, drug solution, Meloidogyne j / icogM / ta-egg larvae suspension and lettuce seeds.
  • the lettuce seeds germinate and the plantlets develop.
  • the galls develop at the roots.
  • the nematicidal activity is determined by means of bile formation in%. 100% means that no bile was found; 0% means that the number of bile on the treated plants corresponds to that of the untreated control.
  • Boophilus microplus test (BOOPMI injection)
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with water to the desired concentration.
  • the drug solution is injected into the abdomen (Boophilus microplus), the animals are transferred into trays and stored in an air-conditioned room. The effect control takes place on storage of fertile eggs.
  • active compound For the preparation of a suitable preparation of active compound, 2 parts by weight of active compound are mixed with the stated amount of solvent. Part of the concentrate is diluted with citrated bovine blood and the desired concentration is produced.
  • fasting adult fleas (Ctenocephalides felis) are placed in a chamber sealed with gauze at the top and bottom.
  • a metal cylinder is placed on the chamber, the underside of which is sealed with parafilm.
  • the cylinder contains the blood-drug preparation that can be absorbed by the fleas through the parafilm membrane.
  • Vessels containing horsemeat treated with the preparation of active compound of the desired concentration are infested with Lucilia cuprina larvae.
  • Vessels containing a sponge treated with the preparation of active compound of the desired concentration are mated with Musca domestica adults.

Abstract

The present invention relates to sulfur-derivatized 1-azinylpyrazoles, the use thereof as insecticides and / or parasiticides and processes for the preparation thereof.  Further objects of the present invention are various intermediates of the production of the sulfur-derivatized 1-azinylpyrazoles of the invention.  Further objects of the present invention finally are materials, which contain such azinylpyrazoles.

Description

Insektizide Schwefel-derivatϊsierte 1-Azinylpyrazole Insecticidal sulfur derivatized 1-azinylpyrazoles
Die vorliegende Erfindung betrifft Schwefel-derivatisierte 1 -Azinylpyrazole, ihre Verwendung als Insektizide und/oder Parasitizide und Verfahren zu ihrer Herstellung.The present invention relates to sulfur-derivatized 1-azinylpyrazoles, their use as insecticides and / or parasiticides, and processes for their preparation.
Weiterer Gegenstand der vorliegenden Erfindung sind diverse Zwischenprodukte, welche bei der Herstellung der erfindungsgemäßen Schwefel-derivatisierten 1 -Azinylpyrazole durchlaufen werden.Another object of the present invention are various intermediates which are passed through in the preparation of the sulfur-derivatized 1-azinylpyrazoles invention.
Weiterer Gegenstand der vorliegenden Erfindung sind schließlich Mittel, die solche Azinylpyrazole enthalten.Another object of the present invention are finally agents which contain such Azinylpyrazole.
DE 197 51 943 Al betrifft l-Methyl-5-alkylsulfonyl-, l-Methyl-5-alkylsulfinyl- und l-Methyl-5- alkylthio-substituierte Pyrazolylpyrazole, Verfahren zu ihrer Herstellung und ihre Verwendung als Herbizide. In der entsprechenden Synthese der Herbizide wird unter anderem 5-Amino-l-methyl-3- (methylsulfanyl)-lH-pyrazol-4-carbonitril als Zwischenprodukt durchlaufen. Allerdings wird in der DE 197 51 943 Al keine insektizide Wirkung dieses Zwischenproduktes offenbart.DE 197 51 943 A1 relates to 1-methyl-5-alkylsulfonyl, 1-methyl-5-alkylsulfinyl and 1-methyl-5-alkylthio-substituted pyrazolylpyrazoles, processes for their preparation and their use as herbicides. In the corresponding synthesis of the herbicides, inter alia, 5-amino-1-methyl-3- (methylsulfanyl) -1H-pyrazole-4-carbonitrile is passed through as an intermediate. However, in DE 197 51 943 Al no insecticidal activity of this intermediate is disclosed.
Liu et al., Youji Huaxue (2006), 26(11), 1600-1605, beschreiben 5-Amino-l-(pyrimidin-4-yl)-3- (methylsulfanyl)-lH-pyrazol-4-carbonitrile auch als Zwischenprodukte in der Synthese von Herbiziden.Liu et al., Youji Huaxue (2006), 26 (11), 1600-1605, also discloses 5-amino-1- (pyrimidin-4-yl) -3- (methylsulfanyl) -1H-pyrazole-4-carbonitrile Intermediates in the synthesis of herbicides.
Meegalla et al. beschreiben die Synthese und insektizide Aktivität von 3-Thiomethyl-4- (hetero)aryl-5-amino-l-phenylpyrazolen als GABA-Kanal-Blocker (Bioorganic & Medicinal Che- mistry Letters (2004), 14, 4949-4953; WO 2001 07413).Meegalla et al. describe the synthesis and insecticidal activity of 3-thiomethyl-4- (hetero) aryl-5-amino-1-phenylpyrazoles as GABA channel blockers (Bioorganic & Medicinal Chemistry Letters (2004), 14, 4949-4953; 2001 07413).
Die EP 1 829 867 Al offenbart generisch pharmazeutisch wirksame Schwefel-derivatisierte 1- Azinylpyrazole .EP 1 829 867 A1 generically discloses pharmaceutically active sulfur derivatized 1-azinylpyrazoles.
Grundsätzlich besteht Bedarf nach weiteren insektiziden und/oder parasitären Wirkstoffen, da die aus dem Stand der Technik bekannten Wirkstoffe häufig keine ausreichende Wirkung bzw. ein ausreichend breites Wirkspektrum zeigen.In principle, there is a need for further insecticidal and / or parasitic active ingredients, since the active compounds known from the prior art frequently do not have a sufficient effect or a sufficiently broad spectrum of activity.
Aufgabe der vorliegenden Erfindung ist daher die Bereitstellung von alternativen Insektiziden und/oder Parasitiziden, die gegenüber den aus dem Stand der Technik bekannten Wirkstoffen eine verbesserte Wirkung bzw. ein verbreitertes Wirkspektrum zeigen.The object of the present invention is therefore to provide alternative insecticides and / or parasiticides which show an improved action or a broadened spectrum of action in comparison with the active compounds known from the prior art.
Gelöst wird die Aufgabe durch spezielle Schwefel-derivatisierte 1 -Azinylpyrazole. Gegenstand der vorliegenden Erfindung sind daher Schwefel -derivatisierte 1-Azinylpyrazole der allgemeinen Formel (I) oder deren N-Oxide,The problem is solved by special sulfur-derivatized 1-azinylpyrazoles. The present invention therefore provides sulfur-derivatized 1-azinylpyrazoles of the general formula (I) or their N-oxides,
Figure imgf000003_0001
Figure imgf000003_0001
in welcherin which
A1 und A2, jeweils unabhängig voneinander, für Stickstoff oder C-R3 stehen;A 1 and A 2 , each independently, are nitrogen or CR 3 ;
B für Alkyl, Cycloalkyl, Cycloalkenyl, Cycloalkylalkyl, Haloalkyl, Alkoxyalkyl, Cyanoalkyl,B is alkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, haloalkyl, alkoxyalkyl, cyanoalkyl,
Alkylthioalkyl, Alkylsulfinylalkyl, Alkylsulfonylalkyl, Aminoalkyl, Monoalkylaminoalkyl, Dialkylaminoalkyl, Alkylcarbonylalkyl, Alkoxycarbonylalkyl, Monoalkylaminocarbony- lalkyl, Diaminoalkylcarbonylalkyl, Alkenyl und Alkinyl, welche jeweils gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein können durch Halogen, Alkyl, Haloalkyl, Alkoxy, Trialkylsilyl, Nitro oder Cyano; Phenalkyl, welches am Aromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano; Heterocyclylalkyl, welches am He- terocyclus gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH / =O, -SH / =S, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl,Alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, aminoalkyl, monoalkylaminoalkyl, dialkylaminoalkyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, monoalkylaminocarbony- lalkyl, diaminoalkylcarbonylalkyl, alkenyl and alkynyl, which may each be optionally mono- or polysubstituted by or differently substituted by halogen, alkyl, haloalkyl, alkoxy, trialkylsilyl, nitro or cyano; Phenalkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the aromatic group by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; Heterocyclylalkyl which may optionally be mono- or polysubstituted by identical or different substituents on the heterocycle by -OH / OO, -SH / SS, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl,
Alkylsulfϊnyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; Heteroa- rylalkyl, welches am Heteraromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH, -SH, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfϊnyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; Phenyl, welches gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH, -SH, -NH2 Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfϊnyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; Heteroaryl, welches gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH, -SH, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; oder He- terocyclyl, welches gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH / =O, -SH / =S, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfϊnyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano;Alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; Heteroarylalkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the heteroaromatic radical by -OH, -SH, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; Phenyl, which may optionally be mono- or polysubstituted by identical or different substituents, by -OH, -SH, -NH 2 halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; Heteroaryl, which may optionally be mono- or polysubstituted by identical or different substituents by -OH, -SH, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; or heterocyclyl which may optionally be monosubstituted or polysubstituted by identical or different substituents by -OH / OO, -SH / SS, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino , Nitro or cyano;
steht; R1 und R2, jeweils unabhängig voneinander, für Wasserstoff, Alkyl, Haloalkyl, Cyanoalkyl, Alko- xyalkyl, Alkylcarbonyl, Haloalkylcarbonyl, Cycloalkyl, Cycloalkylalkyl, Alkylsulfonyl, Alkenyl, Alkinyl, Alkoxycarbonyl, Alkenyloxycarbonyl, Alkinyloxycarbonyl, Alkoxycar- bonylalkyl; Phenalkyl, welches am Aromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano; Heterocyclylalkyl, welches am Heterocyclus gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano; Heteroarylalkyl, welches am Heteraromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Al- kyl, Haloalkyl, Alkoxy, Nitro oder Cyano; oder Phenylcarbonyl, welches am Aromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano;stands; R 1 and R 2 are each independently hydrogen, alkyl, haloalkyl, cyanoalkyl, alkoxyalkyl, alkylcarbonyl, haloalkylcarbonyl, cycloalkyl, cycloalkylalkyl, alkylsulfonyl, alkenyl, alkynyl, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, alkoxycarbonylalkyl; Phenalkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the aromatic group by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; Heterocyclylalkyl which may optionally be mono- or polysubstituted by identical or different substituents on the heterocycle by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; Heteroarylalkyl which may optionally be mono- or polysubstituted by identical or different substituents on the heteroaromatic radical by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; or phenylcarbonyl which optionally substituted one or more times identically or differently on the aromatic by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano;
stehen; oderstand; or
R1 und R2 gemeinsam für =CH-NR4R5 R 1 and R 2 together for = CH-NR 4 R 5
stehen;stand;
R3 für Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfmyl, Alkylsulfonyl, HaIo- alkoxy, Haloalkylsulfanyl, Haloalkylsulfmyl, Haloalkylsulfonyl, Alkylcarbonyl, Formyl, - CR6=NO-R6, Alkoxycarbonyl, Hydroxy, -SH, Nitro, Cyano, NH2, Monoalkylamino oder DialkylaminoR 3 is halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfmyl, alkylsulfonyl, haloalkoxy, haloalkylsulfanyl, haloalkylsulfmyl, haloalkylsulfonyl, alkylcarbonyl, formyl, --CR 6 = NO-R 6 , alkoxycarbonyl, hydroxy, -SH, nitro, cyano , NH 2 , monoalkylamino or dialkylamino
steht;stands;
R4 und R5 jeweils unabhängig voneinander für Alkyl oder gemeinsam für verbrückendes AlkylidenR 4 and R 5 are each independently alkyl or together bridging alkylidene
stehen;stand;
R6 für Wasserstoff oder für AlkylR 6 is hydrogen or alkyl
steht;stands;
X für Phenyl, 2-Pyridyl oder 3-Pyridyl steht, jeweils substituiert durch einen oder mehrere gleiche oder verschiedene Substituenten ausgewählt aus der Gruppe, bestehend aus Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alkoxyalkoxy, Cycloalkyl, Alkenoxy, Alki- noxy, Cycloalkylalkoxy, Haloalkoxy, Haloalkoxyalkyl, Alkylsulfanyl, Haloalkylsulfanyl, Alkylsulfmyl, Haloalkylsulfinyl, Alkylsulfonyl, Haloalkylsulfonyl, Cyano, Alkylcarbonyl, Alkoxycarbonyl, Alkoxycarbonylalkyl, Carboxyl, Carboxamid, Dialkylcarboxamid, Trial- kylsilyl, Nitro, Amino, Alkylamino, Dialkylamino, Alkylsulfonylamino, Dialkylsulfony- lamino, -CR6=NO-R6, -CR6=NO-Haloalkyl, oder Formyl steht, wobei vicinale Alkyl-, Ha- loalkyl, Alkoxy- und/oder Haloalkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann;X is phenyl, 2-pyridyl or 3-pyridyl, each substituted by one or more identical or different substituents selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkenoxy, alkynyloxy, Cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, haloalkylsulfanyl, alkylsulfmyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkyl kylsilyl, nitro, amino, alkylamino, dialkylamino, alkylsulfonylamino, dialkylsulfonylamino, -CR 6 = NO-R 6 , -CR 6 = NO-haloalkyl, or formyl, where vicinal alkyl, haloalkyl, alkoxy and / or or haloalkoxy groups together with the carbon atoms to which they are attached may form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms, and whose alkyl portion may be optionally substituted with one or more fluorine atoms;
Y für -S-, -S(O)-, -SO2-, oder eine der folgenden GruppierungenY is -S-, -S (O) -, -SO 2 -, or one of the following groupings
Figure imgf000005_0001
Figure imgf000005_0001
steht;stands;
n für 0 bis 3n for 0 to 3
steht;stands;
und die Verbindungen der allgemeinen Formel (I) - insofern chemisch möglich - Salze, Tautome- re, Diastereomere und optische Isomere (z.B. falls Y für -S(O)- , -S(=N-CN)- oder -S(O)-(=N-CN / =N-R6)- steht) umfassen.and the compounds of the general formula (I) - insofar chemically possible - salts, tautomers, diastereomers and optical isomers (for example, if Y is -S (O) -, -S (= N-CN) - or -S (O ) - (= N-CN / = NR 6 ) -).
Erfindungsgemäß wurde herausgefunden, dass die erfϊndungsgemäßen Verbindungen der allgemeinen Formel (I) sehr gute insektizide und parasitizide Eigenschaften besitzen und sich im Pflanzenschutz, in der Veterinärhygiene und im Materialschutz zur Bekämpfung unerwünschter Schädlinge, wie Insekten, Endo- oder Ektoparasiten, verwenden lassen.According to the invention, it has been found that the compounds of the general formula (I) according to the invention have very good insecticidal and parasiticidal properties and can be used in crop protection, veterinary hygiene and material protection for controlling undesired pests, such as insects, endo- or ectoparasites.
Gegenstand der Erfindung sind auch alle Stereoisomeren, die von Formel (I) umfaßt sind, und deren Gemische. Solche Verbindungen der Formel (I) enthalten ein oder mehrere asymmetrische C-Atome (= asymmetrisch substituierte C-Atome), oder/und asymmetrische Schwefelatome in Form von Sulfoxiden, Sulfoximinen bzw. Sulfiminen, die in zwei enantiomeren Formen existieren können, oder auch Doppelbindungen, die in den allgemeinen Formeln (I) nicht gesondert angegeben sind. Die durch ihre spezifische Raumform definierten möglichen Stereoisomeren, wie Enantiomere, Diastereomere, Z- und E-Isomere sind alle von der Formel (I) umfaßt und können nach üblichen Methoden aus Gemischen der Stereoisomeren erhalten oder auch durch stereoselektive Reaktionen in Kombination mit dem Einsatz von stereochemisch reinen Ausgangsstoffen hergestellt werden. Verbindungen der allgemeinen Formel (I) bestehen gegebenenfalls aus einem Gemisch der jeweiligen, an der Schwefel-Funktion chiralen Enantiomere,The invention also relates to all stereoisomers which are encompassed by formula (I) and mixtures thereof. Such compounds of formula (I) contain one or more asymmetric C atoms (= asymmetrically substituted C atoms), or / and asymmetric sulfur atoms in the form of sulfoxides, sulfoximines or sulfimines, which may exist in two enantiomeric forms, or double bonds , which are not specified separately in the general formulas (I). The possible defined by their specific spatial form possible stereoisomers, such as enantiomers, diastereomers, Z and E isomers are all of the formula (I) and can be obtained by conventional methods from mixtures of stereoisomers or by stereoselective reactions in combination with the use of stereochemically pure starting materials are produced. Compounds of the general formula (I) optionally consist of a mixture of the respective enantiomers which are chiral on the sulfur function,
Figure imgf000006_0001
Figure imgf000006_0002
Figure imgf000006_0003
Figure imgf000006_0001
Figure imgf000006_0002
Figure imgf000006_0003
wobei die Reste R1, R2, R3, B, X, A1, A2 und n die gemäß Formel (I) zuvor angegebene Bedeutung haben.where the radicals R 1 , R 2 , R 3 , B, X, A 1 , A 2 and n have the meaning given above according to formula (I).
Für die Herstellung von Enantiomeren der allgemeinen Formel (I) kommen neben enantioselekti- ven Synthesen (z.B. Okrasa et al., Tetrahedron: Asymmetry (2002), 13(5), 519-522) auch übliche Racemattrennungsmethoden in Frage (vgl. Handbücher der Stereochemie).For the preparation of enantiomers of the general formula (I), in addition to enantioselective syntheses (eg Okrasa et al., Tetrahedron: Asymmetry (2002), 13 (5), 519-522), customary racemate resolution methods are also suitable (cf. stereochemistry).
Racemische Gemische, beispielsweise von optisch aktiven Sulfoxiden der allgemeinen Formel (I), lassen sich nach bekannten Verfahren trennen. Derartige Racemattrennungsmethoden sind inRacemic mixtures, for example of optically active sulfoxides of the general formula (I), can be separated by known processes. Such racemate resolution methods are in
Handbüchern der Stereochemie beschrieben, beispielsweise in „Basic Organic Stereochemistry"Handbooks of stereochemistry described, for example, in "Basic Organic Stereochemistry"
(Eds.: Eliel, Ernest L.; Wilen, Samuel H.; Doyle, Michael P.; 2001; John Wiley & Sons) und(Eds .: Eliel, Ernest L., Wilen, Samuel H., Doyle, Michael P., 2001, John Wiley & Sons) and
„Stereochemisty of Organic Compounds (Eds.: Eliel, Ernest L.; Wilen, Samuel H.; Mander, Lewis"Stereochemistry of Organic Compounds" (Eds .: Eliel, Ernest L .; Wilen, Samuel H .; Mander, Lewis
N.; 1994; John Wiley & Sons). In Frage kommen hierbei, z.B. Adduktbildung mit einem optisch aktiven Hilfsreagens, Trennung der diastereomeren Addukte in die entsprechenden Diastereomere, z.B. durch Kristallisation, Chromatographieverfahren, vor allem Säulenchromatographie undN .; 1994; John Wiley & Sons). Eligible, e.g. Adduct formation with an optically active auxiliary reagent, separation of the diastereomeric adducts into the corresponding diastereomers, e.g. by crystallization, chromatography, especially column chromatography and
Hochdruckflüssigchromatographie, Destillation, gegebenenfalls unter reduziertem Druck,High pressure liquid chromatography, distillation, optionally under reduced pressure,
Extraktion und andere Verfahren und anschließende Rückspaltung der Diastereomeren in dieExtraction and other methods and subsequent cleavage of the diastereomers in the
Enantiomeren. Für präparative Mengen oder im industriellen Maßstab kommen Verfahren wie die Kristallisation diastereomerer Salze, die aus den Verbindungen (I) mit optisch aktiven Säuren und gegebenenfalls bei vorhandenen sauren Gruppen mit optisch aktiven Basen erhalten werden können, in Frage.Enantiomers. For preparative quantities or on an industrial scale are processes such as the crystallization of diastereomeric salts, the compounds of (I) with optically active acids and optionally be obtained with existing acidic groups with optically active bases, in question.
Zur Racemattrennung durch Kristallisation diastereomerer Salze kommen als optisch aktive Säure z.B. Camphersulfonsäure, Camphersäure, Bromcamphersulfonsäure, Chinasäure, Weinsäure, Di- benzoylweinsäure und andere analoge Säuren in Betracht; als optisch aktive Basen kommen z.B. Chinin, Cinchonin, Chinidin, Brucin, 1 -Phenylethylamin und andere analoge Basen in Frage.For racemate separation by crystallization of diastereomeric salts, optically active acid is e.g. Camphorsulfonic acid, camphoric acid, bromocamphorsulfonic acid, quinic acid, tartaric acid, dibenzoyltartaric acid and other analogous acids; as optically active bases are e.g. Quinine, cinchonine, quinidine, brucine, 1-phenylethylamine and other analogous bases in question.
Die Kristallisationen werden dann meist in wässrigen oder wässrig-organischen Lösemitteln durchgeführt, wobei das Diastereomer mit der geringeren Löslichkeit gegebenenfalls nach Animpfen zunächst ausfällt. Das eine Enantiomer der Verbindung der Formel (I) wird danach aus dem ausgefällten Salz oder das andere aus dem Kristallisat durch Ansäuern bzw. mit Base freigesetzt.The crystallizations are then usually carried out in aqueous or aqueous-organic solvents, wherein the diastereomer with the lower solubility, if appropriate after inoculation, first fails. The one enantiomer of the compound of formula (I) is then released from the precipitated salt or the other from the crystals by acidification or with base.
Desweiteren können Racemate chromatographisch mit chiralen Stationärphasen getrennt werden. Derartige Enantiomerentrennungen lassen sich vom mg bis in den 100 kg Bereich mit präparativen HPLC Anlagen im Einzel- oder kontinuierlichen Betrieb durchführen.Furthermore, racemates can be separated chromatographically with chiral stationary phases. Enantiomer separations of this type can be carried out from mg to the 100 kg range with preparative HPLC systems in single or continuous operation.
Die erfindungsgemäßen Verbindungen sind durch die Formel (I) allgemein definiert. Bevorzugte, besonders bevorzugte und ganz besonders bevorzugte Restedefinitionen der vorstehenden und nachfolgend genannten Formeln sind im Folgenden angegeben. Diese Definitionen gelten für die Endprodukte der allgemeinen Formel (I) wie für alle Zwischenprodukte gleichermaßen.The compounds of the invention are generally defined by the formula (I). Preferred, particularly preferred and very particularly preferred radical definitions of the above and below-mentioned formulas are given below. These definitions apply equally to the end products of general formula (I) as well as to all intermediates.
Im Rahmen der vorliegenden Erfindung ist es möglich, die einzelnen allgemeinen, bevorzugten, besonders bevorzugten, ganz besonders bevorzugten und speziellen Bedeutungen für dieIn the context of the present invention, it is possible to use the individual general, preferred, particularly preferred, very particularly preferred and special meanings for the
Substituenten wie in den folgenden Ausgestaltungen und Ausführungsformen definiert beliebig miteinander zu kombinieren. Das heißt, dass Verbindungen der allgemeinen Formel (I) von der vorliegenden Erfindung umfasst sind, in welchen beispielsweise der Substituent X eine bevorzugteSubstituents as defined in the following embodiments and embodiments defined to combine with each other. That is, compounds of the general formula (I) are encompassed by the present invention in which, for example, the substituent X is a preferred one
Bedeutung aufweist und die Substituenten R1, R2, R3 und B die allgemeine Bedeutung aufweisen oder aber der Substituent B eine bevorzugte Bedeutung aufweist, der Substituent X eine besonders bevorzugte Bedeutung aufweist und die Substituenten R1 bis R3 eine ganz besondere Bedeutung aufweisen.Meaning and the substituents R 1 , R 2 , R 3 and B have the general meaning or the substituent B has a preferred meaning, the substituent X has a particularly preferred meaning and the substituents R 1 to R 3 have a very special meaning ,
In einer ersten Ausgestaltung der vorliegenden Erfindung stehen gemeinsam A1 bevorzugt für Stickstoff und A2 bevorzugt für CH oder C-R3.In a first embodiment of the present invention, A 1 is preferably nitrogen and A 2 is preferably CH or CR 3 .
In einer zweiten Ausgestaltung der vorliegenden Erfindung stehen gemeinsam A1 bevorzugt für CH oder C-R3 und A2 für CH oder C-R3, wobei bei mehreren Resten R3 die Reste R3 jeweils gleich oder verschieden sein können. In einer dritten Ausgestaltung der vorliegenden Erfindung stehen gemeinsam A1 bevorzugt für C- R3 und A2 bevorzugt für Stickstoff.In a second embodiment of the present invention, together A 1 is preferably CH or CR 3 and A 2 is CH or CR 3 , where in the case of several radicals R 3, the radicals R 3 may each be identical or different. In a third embodiment of the present invention, A 1 is preferably C-R 3 and A 2 is preferably nitrogen.
Die Erfindung bezieht sich ferner in einer vierten Ausgestaltung auf Verbindungen der Formel (I) oder auf Verbindungen nach einer der ersten bis dritten Ausgestaltung in denen der Rest BThe invention further relates in a fourth embodiment to compounds of the formula (I) or to compounds according to one of the first to third embodiments in which the radical B is
bevorzugt für C,-C6-Alkyl, C3-C8-Cycloalkyl, C3-C8-Cycloalkenyl, C3-C8-Cycloalkyl-Ci-C6-alkyl, Halo-Ci-C6-alkyl, C1 -C6-AIkOXy-C1 -C6-alkyl, Cyano-C^Cs-alkyl, d-Cβ-Alkylthio-Q-Cö-alkyl, C1- Q-Alkylsulfinyl-CrCβ-alkyl, Q-Cβ-Alkylsulfonyl-d-Cβ-alkyl, Q-Ce-Alkylcarbonyl-Q-Ce-alkyl, C^Cö-Alkoxycarbonyl-CrCö-alkyl, C2-C6-Alkenyl und C2-C6-Alkinyl, welche jeweils gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein können durch Halogen, Alkyl, Haloalkyl, Alkoxy, Tri-(CrC4-alkyl)-silyl, Nitro oder Cyano; Phenyl-Ci-C6-alkyl, welches am A- romaten gegebenenfalls einfach oder mehrfach gleich oder verschieden sein kann durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano; C3-C8-Heterocyc IyI-C1 -C6-alkyl, welches am He- terocyclus gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH / =0, -SH / =S, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; Q-Cα-Heteroaryl-Q-Ce-alkyl, welches am Heteraromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH, -SH, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; Phenyl, welches gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH, -SH, - NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; C6-C12-Heteroaryl, welches gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH, -SH, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; oder C3-C8-Heterocyclyl, welches gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH / =0, -SH / =S, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano steht;preferably C 1 -C 6 -alkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkenyl, C 3 -C 8 -cycloalkyl-C 1 -C 6 -alkyl, halo-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 6 alkyl, cyano-C ^ Cs-alkyl, d-Cβ alkylthio QC ö alkyl, C 1 - Q-alkylsulfinyl-CrCβ-alkyl, Q-Cβ- alkylsulfonyl-d-Cβ-alkyl, Q-Ce-alkylcarbonyl-Q-Ce-alkyl, C ^ C alkoxycarbonyl-CrC ö ö alkyl, C 2 -C 6 -alkenyl and C 2 -C 6 -alkynyl, each of which optionally mono- or polysubstituted by identical or different substituents by halogen, alkyl, haloalkyl, alkoxy, tri (CrC 4 alkyl) silyl, nitro or cyano; Phenyl-C 1 -C 6 -alkyl which may be mono- or polysubstituted by identical or different substituents on the aromatic ring by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; C 3 -C 8 -Heterocyc IyI-C 1 -C 6 -alkyl, which may optionally be mono- or polysubstituted by identical or different substituents on the heterocycle by -OH / = 0, -SH / = S, -NH 2 , halogen Alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; Q-Cα-heteroaryl-Q-ce-alkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the heteroaromatic radical by -OH, -SH, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, Monoalkylamino, dialkylamino, nitro or cyano; Phenyl, which may optionally be mono- or polysubstituted by identical or different substituents by -OH, -SH, - NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; C 6 -C 12 -Heteroaryl, which may optionally be mono- or polysubstituted by identical or different substituents by -OH, -SH, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; or C 3 -C 8 -heterocyclyl, which may optionally be monosubstituted or polysubstituted by identical or different substituents by -OH / = O, -SH / SS, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl , Monoalkylamino, dialkylamino, nitro or cyano;
besonders bevorzugt für Ci-C6-Alkyl, C3-C8-Cycloalkyl, C3-C8-Cycloalkenyl, HaIo-C1 -C6-alkyl, C1 -C6-AIkOXy-C1 -Cβ-alkyl, Q-Q-Alkylcarbonyl-C, -C6-alkyl, C1 -C6-Alkoxycarbonyl-C, -C6-alkyl, C2-C6-Alkenyl und C2-C6-Alkinyl, welche jeweils gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein können durch Halogen, Alkyl, Haloalkyl, Alkoxy, Tn-(C1-C4- alkyl)-silyl, Nitro oder Cyano; Phenyl-Q-C6-alkyl, welches am Aromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano; Ce-Cu-Heteroaryl-d-Cβ-alkyl, welches am Heteraromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH, -SH, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Monoalkylamino, Di- alkylamino, Nitro oder Cyano; C6-Ci2-Heteroaryl, welches gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH, -SH, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; C3-C8-Heterocyclyl-Ci-C6-alkyl, welches am Heterocyclus gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH / =O, -SH / =S, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano steht;especially preferred for C 1 -C 6 -alkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkenyl, halo-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl , QQ-alkylcarbonyl-C, -C 6 -alkyl, C 1 -C 6 -alkoxycarbonyl-C, -C 6 -alkyl, C 2 -C 6 -alkenyl and C 2 -C 6 -alkynyl, each of which is optionally mono- or may be the same or different substituted by halogen, alkyl, haloalkyl, alkoxy, Tn- (C 1 -C 4 - alkyl) silyl, nitro or cyano; Phenyl-QC 6 -alkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the aromatic group by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; Ce-Cu-heteroaryl-d-Cβ-alkyl, which may be present on the heteroaromatic mono- or polysubstituted by identical or different substituents by -OH, -SH, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; C 6 -C 2 -heteroaryl, which may optionally be monosubstituted or polysubstituted by identical or different substituents, by -OH, -SH, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; C 3 -C 8 -heterocyclyl-C 1 -C 6 -alkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the heterocycle by -OH / OO, -SH / SS, -NH 2 , halogen, alkyl, haloalkyl Alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano;
ganz besonders bevorzugt für C,-C6-Alkyl, HaIo-C1 -C6-alkyl, CrC6-Alkoxy-Ci-C6-alkyl, Ci-C6- Alkoxycarbonyl-C,-C6-alkyl, C2-C6-Alkenyl; C2-C6-Alkinyl, Tri-(Ci-C4-alkyl)-silyl-Ci-C6-alkyl; Phenyl-Ci-Cö-alkyl welches am Aromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Fluor, Chlor, Brom, Iod, Methyl, Trifluormethyl oder Metho- xy; und 2-Pyridyl-C,-C6-alkyl steht;very particularly preferably C, -C 6 alkyl, Haio-C 1 -C 6 alkyl, C r C 6 alkoxy-C 6 alkyl, Ci-C6 - alkoxycarbonyl-C, -C 6 alkyl , C 2 -C 6 alkenyl; C 2 -C 6 alkynyl, tri (C 1 -C 4 alkyl) silyl C 1 -C 6 alkyl; Phenyl-Ci-C ö alkyl which on the aromatic ring may optionally be singly or multiply substituted identically or differently by fluorine, chlorine, bromine, iodine, methyl, trifluoromethyl or methodological xy; and 2-pyridyl-C, -C 6 -alkyl;
speziell für CH3, CH2CH3, CH(CH3)2, CH2CH2CH3, CH2CH2CH2CH3, CH(CH3)CH2CH3, -CH2CF3, CH2CHF2, CH2CH2CF3, CF3, CH2-Phenyl, CH2-4-Chlorphenyl, CH2-4-Methoxyphenyl, CH2-2- Pyridyl, CH2CH=CH2, CH2CH=CCl2, CH2CCH, CH2CH2OCH3, CH2CH2CF3, CH2CH2Si(CH3)3 und CH2CO2CH3 steht.especially for CH 3 , CH 2 CH 3 , CH (CH 3 ) 2 , CH 2 CH 2 CH 3 , CH 2 CH 2 CH 2 CH 3 , CH (CH 3 ) CH 2 CH 3 , -CH 2 CF 3 , CH 2 CHF 2 , CH 2 CH 2 CF 3 , CF 3 , CH 2 -phenyl, CH 2 -4-chlorophenyl, CH 2 -4-methoxyphenyl, CH 2 -2-pyridyl, CH 2 CH = CH 2 , CH 2 CH = CCl 2 , CH 2 CCH, CH 2 CH 2 OCH 3 , CH 2 CH 2 CF 3 , CH 2 CH 2 Si (CH 3 ) 3 and CH 2 CO 2 CH 3 .
Weiterhin bezieht sich die Erfindung in einer fünften Ausgestaltung auf Verbindungen der Formel (I) oder auf Verbindungen nach einer der ersten bis vierten Ausgestaltung in der die Reste R1 und R2, jeweils unabhängig voneinanderFurthermore, in a fifth embodiment, the invention relates to compounds of the formula (I) or to compounds according to one of the first to fourth embodiments in which the radicals R 1 and R 2 are each independently of one another
bevorzugt für Wasserstoff; C1-C6-AIlCyI, C,-C6-Haloalkyl, Cyano-Q-Ce-alkyl, Ci-C6-Alkoxy- Cx- C6-alkyl, C,-C6-Alkylcarbonyl, C,-C6-Haloalkylcarbonyl, C3-C8-Cycloalkyl, QrCg-Cycloalkyl-d- C6-alkyl, C,-C6-Alkylsulfonyl, C2-C6- Alkenyl, C2-C6-Alkinyl, CrC6-Alkoxycarbonyl, C2-C6- Alkenyloxycarbonyl, C2-C6-Alkinyloxycarbonyl, Ci-C6-Alkoxycarbonyl-C]-C6-alkyl; Phenyl- Ci- C6-alkyl, welches am Aromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano; C3-C8- Heterocyclylalkyl, welches am Heterocyclus gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano; C6- Cπ-Heteroaryl-Ci-Cö-alkyl, welches am Heteroaromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano; oder Phenylcarbonyl, welches am Aromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cya- no; oder R1 und R2 gemeinsam für =CH-NR4R5 mit R4 und R5 jeweils für Ci-C6-Alkyl oder gemeinsam für verbrückendes C2-C4-Alkyliden stehend, stehen;preferred for hydrogen; C 1 -C 6 -alkyl, C, -C6 haloalkyl, cyano-Q-Ce-alkyl, Ci-C 6 alkoxy C x - C 6 alkyl, C, -C 6 alkylcarbonyl, C, - C 6 haloalkylcarbonyl, C 3 -C 8 cycloalkyl, QrCg-cycloalkyl-d- C 6 alkyl, C, -C 6 alkylsulfonyl, C 2 -C 6 - alkenyl, C 2 -C 6 alkynyl, C r C 6 alkoxycarbonyl, C 2 -C 6 - alkenyloxycarbonyl, C 2 -C 6 -alkynyloxycarbonyl, Ci-C 6 alkoxycarbonyl-C] -C6 alkyl; Phenyl-C 1 -C 6 -alkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the aromatic group by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; C 3 -C 8 - heterocyclylalkyl which may optionally be mono- or polysubstituted by identical or different substituents on the heterocycle by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; C 6 - Cπ-heteroaryl-C 1 -C 6 -alkyl which may optionally be mono- or polysubstituted by identical or different substituents on the heteroaromatic radical by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; or phenylcarbonyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the aromatic group by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano no; or R 1 and R 2 together for = CH-NR 4 R 5 with R 4 and R 5 are each Ci-C 6 alkyl or together for bridging C 2 -C 4 alkylidene, are;
besonders bevorzugt für Wasserstoff, C,-C6-Alkyl, C,-C6-Haloalkyl, C-Cβ-Alkoxy-CrQ-alkyl, C,-C6-Alkylcarbonyl, C,-C6-Haloalkylcarbonyl, C3-C8-Cycloalkyl, C3-C8-Cycloalkyl-Ci-C6-alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Ci-C6-Alkoxycarbonyl, C2-C6- Alkenyloxycarbonyl, C2-C6- Alkinyloxycarbonyl, Ci-Cö-Alkoxycarbonyl-CrQ-alkyl; Phenyl-C]-C6-alkyl, welches am Aroma- ten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano; C3-C8-Heterocyclyl-Ci-C6-alkyl, welches am Heterocyclus gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano; oder Phenylcarbonyl, welches am Aromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano) oder R1 und R2 gemeinsam für =CH- NR4R5 mit R4 und R5 jeweils für CrC6-Alkyl oder gemeinsam für verbrückendes C2-C4-Alkyliden stehend, stehen;particularly preferably represents hydrogen, C, -C6 alkyl, C, -C 6 haloalkyl, C-Cβ-alkoxy-CRQ-alkyl, C, -C 6 alkylcarbonyl, C, -C 6 haloalkylcarbonyl, C 3 - C 8 cycloalkyl, C 3 -C 8 cycloalkyl-Ci-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Ci-C 6 alkoxycarbonyl, C 2 -C 6 - alkenyloxycarbonyl , C 2 -C 6 - alkynyloxycarbonyl, C ö alkoxycarbonyl CRQ-alkyl; Phenyl-C] -C 6 -alkyl which may optionally be mono- or polysubstituted by identical or different substituents on the aromatic radical by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; C 3 -C 8 -heterocyclyl-C 1 -C 6 -alkyl which may optionally be mono- or polysubstituted by identical or different substituents on the heterocycle by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; or phenylcarbonyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the aromatic ring by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano) or R 1 and R 2 together represent = CH-NR 4 R 5 with R 4 and R 5 each represent C r C 6 alkyl or together represent bridging C 2 -C 4 alkylidene;
ganz besonders bevorzugt für Wasserstoff, C1-C6-AIlCyI, Ci-C6-Haloalkyl und =CH-NR4R5 stehen;very particularly preferably represents hydrogen, C 1 -C 6 -alkyl, Ci-C 6 haloalkyl and = CH-NR 4 R 5;
speziell für Wasserstoff und =CH-N(CH3)2 stehen.especially for hydrogen and = CH-N (CH 3 ) 2 stand.
Weiterhin bezieht sich die Erfindung in einer sechsten Ausgestaltung auf Verbindungen der Formel (I) oder auf Verbindungen nach einer der ersten bis fünften Ausgestaltung, in der der Rest R3, jeweils unabhängig voneinander, wenn der Rest R3 mehrfach zugegen ist (n = 2 oder 3)Furthermore, in a sixth embodiment, the invention relates to compounds of the formula (I) or to compounds according to one of the first to fifth embodiments, in which the radical R 3 , in each case independently of one another, if the radical R 3 is present more than once (n = 2 Or 3)
bevorzugt für Halogen, Ci-C6-Alkyl, C,-C6-Haloalkyl, Ci-C6-Alkoxy, CrC6-Alkylsulfanyl, C1-C6- Alkylsulfinyl, CrC6-Alkylsulfonyl, C,-C6-Haloalkoxy, Q-Ce-Haloalkylsulfanyl, C1-C6- Haloalkylsulfinyl, Ci-C6-Haloalkylsulfonyl, Ci-C6-Alkylcarbonyl und Formyl steht;preferably represents halogen, Ci-C 6 alkyl, C, -C 6 -haloalkyl, Ci-C 6 alkoxy, C r C 6 alkylsulfanyl, C 1 -C 6 - alkylsulphinyl, C r C 6 alkylsulfonyl, C, C6 haloalkoxy, Q-Ce-haloalkylsulfanyl, C 1 -C 6 - haloalkylsulfinyl, Ci-C 6 haloalkylsulfonyl, Ci-C is 6 alkylcarbonyl and formyl;
besonders bevorzugt für Halogen, C)-C6-AIlCyI, CrC6-Haloalkyl, Q-C6-AIkOXy und C1-C6- Haloalkoxy steht;particularly preferably represents halogen, C) -C 6 -alkyl, C r C 6 -haloalkyl, QC 6 -alkoxy and C 1 -C 6 -haloalkoxy;
ganz besonders bevorzugt für Halogen, Ci-C6-Alkyl, C1-C6-HaIOaIlCyI und C1-C6-AIkOXy steht;very particularly preferably represents halogen, Ci-C 6 alkyl, C 1 -C 6 -HaIOaIlCyI and C 1 -C 6 -alkoxy group;
speziell für Fluor, Chor, Brom, Iod, Trifluormethyl, Methyl, Ethyl, iso-Propyl, Methoxy und Etho- xy steht;is especially fluorine, chlorine, bromine, iodine, trifluoromethyl, methyl, ethyl, iso-propyl, methoxy and ethoxy;
Weiterhin bezieht sich die Erfindung in einer siebten Ausgestaltung auf Verbindungen der Formel (I) oder auf Verbindungen nach einer der ersten bis sechsten Ausgestaltung in der der Rest X bevorzugt für Phenyl, 2-Pyridyl oder 3-Pyridyl, welche jeweils gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein können durch einen oder mehreren Substituenten, ausgewählt aus der Gruppe, bestehend aus Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alko- xyalkoxy, COOH, Nitro, Amino, Alkylamino, Dialkylamino, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder Haloalkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann, steht;Furthermore, the invention in a seventh embodiment relates to compounds of the formula (I) or to compounds according to one of the first to sixth embodiments in which the radical X is preferably phenyl, 2-pyridyl or 3-pyridyl, which in each case may optionally be mono- or polysubstituted by identical or different substituents, by one or more substituents selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy , COOH, nitro, amino, alkylamino, dialkylamino, wherein vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system containing from 0 to 2 oxygen atoms contains, and whose alkyl moiety may optionally be substituted by one or more fluorine atoms, is;
besonders bevorzugt für Phenyl, welches gegebenenfalls einfach oder mehrfach gleich oder ver- schieden substituiert sein können durch einen oder mehreren Substituenten, ausgewählt aus der Gruppe, bestehend aus Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alkoxyalkoxy, COOH, Nitro, Amino, Alkylamino, Dialkylamino, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder Haloalkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann steht;particularly preferably phenyl, which may optionally be mono- or polysubstituted or differently substituted by one or more substituents selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, COOH, nitro, amino, alkylamino , Dialkylamino, wherein vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy together with the carbon atoms to which they are attached, can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms, and its alkyl moiety optionally with a or more than one fluorine atom may be substituted;
ganz besonders bevorzugt für Phenyl, welches einfach oder mehrfach substituiert ist durch mindestens einen Substituenten, ausgewählt aus der Gruppe, bestehend aus Halogen, C1-C6-HaIOaIlCyI und Ci-Cβ-Alkoxy, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder Haloalkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches Sys- tem bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann steht;with very particular preference for phenyl which is monosubstituted or polysubstituted by at least one substituent selected from the group consisting of halogen, C 1 -C 6 haloalkyl and C 1 -C 6 alkoxy, vicinal alkyl, haloalkyl, alkoxy and or haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system which contains 0 to 2 oxygen atoms and whose alkyl moiety may optionally be substituted by one or more fluorine atoms;
speziell für 2-Cl-Phenyl; 2-F-6-F-Phenyl; 3-Cl-Phenyl; 3-CF3-Phenyl; 4-Cl-Phenyl; 4-Br-Phenyl; 4-I-Phenyl; 3-Cl,4-Cl-Phenyl; 3-CF3,4-Cl-Phenyl; 3-Cl,5-Cl-Phenyl; 3-CF3,5-F-Phenyl;, 3-CF3,5- Cl-Phenyl; 3-CF3,5-CF3-Phenyl; 3-Cl,4-Cl,5-Cl-Phenyl; 3-F, 3-Cl,4-OCH3,5-Cl-Phenyl; 3-Cl,(4)- OCH2O-(5)-Phenyl; 3-Cl,(4)-OCF2O-(5)-Phenyl; 3-Cl,(4)-OCH2CH2-(5)-Phenyl; 3-Cl,4-OCH3,5- OCH3-Phenyl; und 3-OCH3,5-CF3-Phenyl steht.especially for 2-Cl-phenyl; 2-F-6-F-phenyl; 3-Cl-phenyl; 3-CF 3 -phenyl; 4-Cl-phenyl; 4-Br-phenyl; 4-I-phenyl; 3-Cl, 4-Cl-phenyl; 3-CF 3 , 4-Cl-phenyl; 3-Cl, 5-Cl-phenyl; 3-CF 3 , 5-F-phenyl ;, 3-CF 3 , 5-Cl-phenyl; 3-CF 3 , 5-CF 3 -phenyl; 3-Cl, 4-Cl, 5-Cl-phenyl; 3-F, 3-Cl, 4-OCH 3 , 5-Cl-phenyl; 3-Cl, (4) - OCH 2 O- (5) -phenyl; 3-Cl, (4) -OCF 2 O- (5) -phenyl; 3-Cl, (4) -OCH 2 CH 2 - (5) -phenyl; 3-Cl, 4-OCH 3 , 5-OCH 3 -phenyl; and 3-OCH 3 , 5-CF 3 -phenyl.
Weiterhin bezieht sich die Erfindung in einer achten Ausgestaltung auf Verbindungen der Formel (I) oder auf Verbindungen nach einer der ersten bis siebten Ausgestaltung der Rest Y bevorzugt für -S-, -S(O)-, -SO2- oder -S(=N-CN)- steht.Furthermore, in an eighth embodiment, the invention relates to compounds of the formula (I) or to compounds according to one of the first to seventh embodiments, the radical Y is preferably -S-, -S (O) -, -SO 2 - or -S ( = N-CN) - stands.
Weiterhin bezieht sich die Erfindung in einer neunten Ausgestaltung auf Verbindungen der Formel (I) oder auf Verbindungen nach einer der ersten bis achten Ausgestaltung der Rest nFurthermore, in a ninth embodiment, the invention relates to compounds of the formula (I) or to compounds according to one of the first to eighth embodiments of the radical n
bevorzugt für 0, 1 oder 2 steht; ganz besonders bevorzugt für 0 oder 1 steht.preferably represents 0, 1 or 2; most preferably 0 or 1 stands.
In einer ganz besonders bevorzugten Ausführungsform der vorliegenden Erfindung sind Verbindungen der allgemeinen Formel (I), insbesondere Verbindungen gemäß oben genannter Ausgestaltungen umfasst, in welchen der Rest B für Alkyl, Cycloalkyl, Cycloalkenyl, Cycloalkylalkyl, HaIo- alkyl, Alkoxyalkyl, Cyanoalkyl, Alkyl thioalkyl, Alkylsulfinylalkyl, Alkylsulfonylalkyl, Aminoal- kyl, Alkylcarbonylalkyl, Alkoxycarbonylalkyl, Alkenyl und Alkinyl, welche jeweils gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein können durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano; Phenalkyl, welches am Aromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl, Haloalkyl, Al- koxy, Nitro oder Cyano; Heterocyclylalkyl, welches am Heterocyclus gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH / =0, -SH / =S, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Monoalkylamino, Dialky- lamino, Nitro oder Cyano; Heteroarylalkyl, welches am Heteraromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH, -SH, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; Phenyl, welches gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH, -SH, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; Heteroaryl, welches gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch - OH, -SH, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; oder Heterocyclyl, welches gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH / =O, -SH / =S, - NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; steht. Damit sind von der Definition der Verbindungen der allgemeinen Formel (I) insbesondere die Verbindungen ausgeschlossen, welche als Rest B einen Carbonylalkylamino-Rest sowie einen Alkylamino-Rest aufweisen. Bevorzugte, besonders bevorzugte, ganz besonders bevorzugte und spezielle Bedeutungen für den Rest B entsprechen den obigen Definitionen. Die Bedeutungen der übrigen Reste bzw. Substitueten der allgemeinen Formel (I) können den allgemeinen, bevorzugten, besonders bevorzugten, ganz besonders bevorzug- ten und speziellen Bedeutungen entsprechen.In a very particularly preferred embodiment of the present invention are compounds of the general formula (I), in particular compounds according to the aforementioned embodiments, in which the radical B is alkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, haloalkyl, alkoxyalkyl, cyanoalkyl, alkylthioalkyl Alkylsulfinylalkyl, alkylsulfonylalkyl, aminoalkyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkenyl and alkynyl, each of which may optionally be mono- or polysubstituted by identical or different substituents by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; Phenalkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the aromatic group by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; Heterocyclylalkyl which may optionally be mono- or polysubstituted by identical or different substituents on the heterocycle by -OH / = O, -SH / SS, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkyl- lamino, nitro or cyano; Heteroarylalkyl which may optionally be mono- or polysubstituted by identical or different substituents on the heteroaromatic radical by -OH, -SH, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; Phenyl, which may optionally be mono- or polysubstituted by identical or different substituents, by -OH, -SH, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; Heteroaryl, which may optionally be mono- or polysubstituted by identical or different substituents by - OH, -SH, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; or heterocyclyl, which may optionally be mono- or polysubstituted by identical or different substituents by -OH / = O, -SH / = S, - NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; stands. This excludes from the definition of the compounds of the general formula (I) in particular the compounds which, as radical B, have a carbonylalkylamino radical and an alkylamino radical. Preferred, particularly preferred, very particularly preferred and special meanings for the radical B correspond to the above definitions. The meanings of the remaining radicals or substituents of the general formula (I) can correspond to the general, preferred, particularly preferred, very particularly preferred and special meanings.
In einer weiteren ganz besonders bevorzugte Ausführungsform der vorliegenden Erfindung sind Verbindungen der allgemeinen Formel (I), insbesondere Verbindungen gemäß oben genannter Ausgestaltungen umfasst, in welchen der Substituent X für substituiertes Phenyl steht. Als Substi- tuenten können dabei Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alkoxyalkoxy, Cycloalkyl, Alkenoxy, Alkinoxy, Cycloalkylalkoxy, Haloalkoxy, Haloalkoxyalkyl, Alkylsulfanyl, Haloalkyl- sulfanyl, Alkylsulfinyl, Haloalkylsulfinyl, Alkylsulfonyl, Haloalkylsulfonyl, Cyano, Alkylcarbo- nyl, Alkoxycarbonyl, Alkoxycarbonylalkyl, Carboxyl, Carboxamid, Dialkylcarboxamid, Trialkylsi- IyI, Nitro, Amino, Alkylamino, Dialkylamino, Alkylsulfonylamino, Dialkylsulfonylamino, - CR6=NO-R6, -CR6=NO-Haloalkyl, oder Formyl in Frage kommen, wobei vicinale Alkyl-, Haloal- kyl, Alkoxy- und/oder Haloalkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann. Besonders bevorzugt sind Halogene, insbesondere Fluor, Chlor, Brom oder Iod; Haloalkyl, wie CF3; Alkoxy, wie OCH3; sowie Verbindungen, in welchen vicinale Alkyl-, Haloal- kyl, Alkoxy- und/oder Haloalkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann. Die Bedeutungen der übrigen Reste bzw. Substituenten der allgemeinen Formel (I) können den allgemeinen, bevorzugten, besonders bevorzugten, ganz besonders bevorzugten und spe- ziellen Bedeutungen entsprechen.In a further very particularly preferred embodiment of the present invention are compounds of the general formula (I), in particular compounds according to the above-mentioned embodiments, in which the substituent X is substituted phenyl. As substituents may be halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkenoxy, alkynoxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, haloalkyl sulfanyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, nitro, amino, alkylamino, dialkylamino, alkylsulfonylamino, dialkylsulfonylamino, --CR 6 = NO-R 6 , -CR 6 = NO-haloalkyl, or formyl are possible, wherein vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached, can form a five- to six-membered cyclic system which contains 0 to 2 oxygen atoms, and whose alkyl moiety may optionally be substituted by one or more fluorine atoms. Particular preference is given to halogens, in particular fluorine, chlorine, bromine or iodine; Haloalkyl, such as CF 3 ; Alkoxy, such as OCH 3 ; and compounds in which vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached form a five- to six-membered cyclic system containing from 0 to 2 oxygen atoms and its alkyl moiety, if appropriate may be substituted with one or more fluorine atoms. The meanings of the other radicals or substituents of the general formula (I) may correspond to the general, preferred, particularly preferred, very particularly preferred and special meanings.
In einer weiteren ganz besonders bevorzugten Ausführungsform der vorliegenden Erfindung sind Verbindungen der allgemeinen Formel (I), insbesondere Verbindungen gemäß oben genannter Ausgestaltungen umfasst, in welchen die Substituenten R1 und R2 für Wasserstoff stehen. Die Bedeutungen der übrigen Reste bzw. Substituenten der allgemeinen Formel (I) können den allgemei- nen, bevorzugten, besonders bevorzugten, ganz besonders bevorzugten und speziellen Bedeutungen entsprechen.In a further very particularly preferred embodiment of the present invention are compounds of the general formula (I), in particular compounds according to the abovementioned embodiments, in which the substituents R 1 and R 2 are hydrogen. The meanings of the remaining radicals or substituents of the general formula (I) may correspond to the general, preferred, particularly preferred, very particularly preferred and special meanings.
In einer weiteren ganz besonders bevorzugten Ausführungsform der vorliegenden Erfindung sind Verbindungen der allgemeinen Formel (I), insbesondere Verbindungen gemäß oben genannter Ausgestaltungen umfasst, in welchen der Rest A1 für N und der Rest A2 für CH steht. Die Bedeu- tungen der übrigen Reste bzw. Substituenten der allgemeinen Formel (I) können den allgemeinen, bevorzugten, besonders bevorzugten, ganz besonders bevorzugten und speziellen Bedeutungen entsprechen.In a further very particularly preferred embodiment of the present invention, compounds of the general formula (I), in particular compounds according to the abovementioned embodiments, in which the radical A 1 is N and the radical A 2 is CH. The meanings of the remaining radicals or substituents of the general formula (I) can correspond to the general, preferred, particularly preferred, very particularly preferred and special meanings.
In einer weiteren ganz besonders bevorzugten Ausführungsform der vorliegenden Erfindung sind Verbindungen der allgemeinen Formel (I), insbesondere Verbindungen gemäß oben genannter Ausgestaltungen umfasst, in welchen der Rest A1 für C-R3 und der Rest A2 für N steht. Die Bedeutungen der übrigen Reste bzw. Substitueten der allgemeinen Formel (I) können den allgemeinen, bevorzugten, besonders bevorzugten, ganz besonders bevorzugten und speziellen Bedeutungen entsprechen. Bevorzugt, besonders bevorzugt, ganz besonders bevorzugt und speziell sind Verbindungen, welche jeweils die unter bevorzugt, besonders bevorzugt, ganz besonders bevorzugt und insbesondere bevorzugt genannten Substituenten tragen.In a further very particularly preferred embodiment of the present invention, compounds of the general formula (I), in particular compounds according to the abovementioned embodiments, in which the radical A 1 is CR 3 and the radical A 2 is N is included. The meanings of the remaining radicals or substituents of the general formula (I) may correspond to the general, preferred, particularly preferred, very particularly preferred and special meanings. Preferred, particularly preferred, very particularly preferred and especially are compounds which in each case carry the substituents mentioned under preferred, particularly preferred, very particularly preferred and particularly preferred.
Die Bezeichnung "Halogen" bedeutet Fluor, Chlor, Brom oder Iod insbesondere Fluor, Chlor oder Brom. Wird die Bezeichnung für einen Rest verwendet, dann bedeutet "Halogen" beispielsweise ein Fluor-, Chlor-, Brom- oder Iodatom.The term "halogen" means fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine. When the term for a group is used, "halogen" means, for example, a fluorine, chlorine, bromine or iodine atom.
Durch Halogen substituierte Reste, z.B. Haloalkyl, sind einfach oder mehrfach bis zur maximal möglichen Substituentenzahl halogeniert. Bei mehrfacher Halogenierung können die Halogenatome gleich oder verschieden sein.Halogen substituted radicals, e.g. Haloalkyl, are halogenated once or several times up to the maximum possible number of substituents. For multiple halogenation, the halogen atoms may be the same or different.
Gesättigte oder ungesättigte Kohlenwasserstoffreste wie Alkyl, Alkenyl oder Alkinyl können, auch in Verbindung mit Heteroatomen, wie z.B. in Alkoxy, soweit möglich, jeweils geradkettig oder verzweigt sein.Saturated or unsaturated hydrocarbon radicals such as alkyl, alkenyl or alkynyl may also be used in conjunction with heteroatoms, e.g. in alkoxy, as far as possible, in each case straight-chain or branched.
Alkyl bedeutet dabei einen geradkettigen oder verzweigten offenkettigen Kohlenwasserstoffrest. Insbesondere werden von dem Begriff „Alkyl" (Ci-Ci2)-Alkyl, besonders bevorzugt (Ci-Cg)-Alkyl, insbesondere (Ci-Ce)-AIkVl, speziell (CrC4)-Alkyl, umfasst. Das gilt insbesondere für Alkylreste, in zusammengesetzten Resten z.B. Alkoxy, Haloalkyl, und bedeuten z.B. Methyl, Ethyl, n- oder i-Propyl, n-, i-, t- oder 2-Butyl, Pentyle, Hexyle, wie n-Hexyl, i-Hexyl und 1,3-Dimethylbutyl, Heptyle, wie n-Heptyl, 1-Methylhexyl und 1,4-Dimethylpentyl.Alkyl means a straight-chain or branched open-chain hydrocarbon radical. In particular, the term "alkyl" (Ci-Ci 2) -alkyl, particularly preferably (Ci-Cg) -alkyl, in particular (Ci-Ce) -alkyl, in particular (C r C 4) alkyl, comprising. This applies in particular for alkyl radicals, in assembled radicals, for example, alkoxy, haloalkyl, and are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, Hexyl and 1,3-dimethylbutyl, heptyls such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl.
Haloalkyl, und -alkenyl bedeuten durch gleiche oder verschiedene Halogenatome, teilweise oder vollständig substituiertes Alkyl oder Alkenyl, z.B. Monohaloalkyl (= Monohalogenalkyl) wie CH2CH2Cl, CH2CH2F, CHClCH3, CHFCH3, CH2Cl, CH2F; Perhaloalkyl wie CCl3 oder CF3 oder CF2CF3; Polyhaloalkyl wie CHF2, CH2F, CH2CHFCl, CHCl2, CF2CF2H, CH2CH2CF3, CH2CHF2, CH2CF3. Entsprechendes gilt für Haloalkenyl und andere durch Halogen substituierten Reste.Haloalkyl, and alkenyl denote by identical or different halogen atoms, partially or fully substituted alkyl or alkenyl, for example monohaloalkyl (= monohaloalkyl) such as CH 2 CH 2 Cl, CH 2 CH 2 F, CHClCH 3 , CHFCH 3 , CH 2 Cl, CH 2 F; Perhaloalkyl such as CCl 3 or CF 3 or CF 2 CF 3 ; Polyhaloalkyl such as CHF 2 , CH 2 F, CH 2 CHFCl, CHCl 2 , CF 2 CF 2 H, CH 2 CH 2 CF 3 , CH 2 CHF 2 , CH 2 CF 3 . The same applies to haloalkenyl and other halogen-substituted radicals.
Alkenyl bedeutet ferner einen geradkettigen oder verzweigten offenkettigen Kohlenwasserstoffrest mit mindestens einer Doppelbindung. Insbesondere werden von dem Begriff „Alkenyl" (C2-Ci2)-Alkenyl furthermore denotes a straight-chain or branched open-chain hydrocarbon radical having at least one double bond. In particular, the term "alkenyl" (C 2 -Ci 2 ) -
Alkenyl, besonders bevorzugt (C2-C8)-Alkenyl, insbesondere (C2-C6)-Alkenyl, speziell (C2-C4)-Alkenyl, particularly preferably (C 2 -C 8 ) -alkenyl, in particular (C 2 -C 6 ) -alkenyl, especially (C 2 -C 4 ) -
Alkenyl, umfasst. Beispiele geeigneter Alkenylreste sind 1,3-Butadienyl und 1 ,4-Pentadienyl, aber auch Allenyl- oder Kumulenylreste mit einer bzw. mehreren kumulierten Doppelbindungen, wie beispielsweise Allenyl (1,2-Propadienyl), 1 ,2-Butadienyl und 1,2,3-Pentatrienyl. Weitere Beispiele für den Rest Alkenyl sind Vinyl, welches gegebenenfalls durch weitere Alkylreste substituiert sein kann, z.B. Prop-1-en-l-yl, But-1-en-l-yl; Allyl, l-Methyl-prop-2-en-l-yl, 2-Methyl-prop-2-en-l- yl, But-2-en-l-yl, l-Methyl-but-3-en-l-yl und l-Methyl-but-2-en-l-yl, 2-Methylprop-l-en-l-yl, 1-Methylprop-l-en-l-yl, l-Methylprop-2-en-l-yl, 2-Methyl-prop-2-en-l-yl, But-2-en-l-yl, But-3-en-l-yl, l-Methyl-but-3-en-l-yl oder l-Methyl-but-2-en-l-yl, Pentenyl, 2-Methylpentenyl und Hexenyl.Alkenyl, includes. Examples of suitable alkenyl radicals are 1,3-butadienyl and 1,4-pentadienyl, but also allenyl or cumulenyl radicals having one or more cumulated double bonds, such as, for example, allenyl (1,2-propadienyl), 1,2-butadienyl and 1,2 , 3-Pentatrienyl. Further examples of the radical alkenyl are vinyl, which may optionally be substituted by further alkyl radicals, for example prop-1-en-1-yl, but-1-en-1-yl; Allyl, 1-methyl-prop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, 1-methyl-but-3-ene 1-yl and 1-methylbut-2-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, butyric 3-en-1-yl, 1-methylbut-3-en-1-yl or 1-methylbut-2-en-1-yl, pentenyl, 2-methylpentenyl and hexenyl.
Alkinyl bedeutet ferner einen geradkettigen oder verzweigten offenkettigen Kohlenwasserstoffrest mit mindestens einer Dreifachbindung. Gegebenenfalls können eine oder mehrere Doppelbindungen vorliegen. Entsrechende Beispiele sind Ethinyl, Propargyl, 1 -Methyl-prop-2-in- 1-yl, 2-Butinyl, 2-Pentinyl, 1,3-Butatrienyl bzw. 3-Penten-l-in-l-yl oder 2-Hexinyl, vorzugsweise Propargyl, But-2-in-l-yl, But-3-in-l-yl oder l-Methyl-but-3-in-l-yl.Alkynyl furthermore denotes a straight-chain or branched open-chain hydrocarbon radical having at least one triple bond. Optionally, one or more double bonds may be present. Corresponding examples are ethynyl, propargyl, 1-methylprop-2-yn-1-yl, 2-butynyl, 2-pentynyl, 1,3-butatrienyl or 3-penten-1-yn-1-yl or 2-yl Hexynyl, preferably propargyl, but-2-yn-1-yl, but-3-yn-1-yl or 1-methyl-but-3-yn-1-yl.
Alkyliden, z. B. auch in der Form (Ci-C10)-Alkyliden, bedeutet den Rest eines geradkettigen oder verzweigten offenkettigen Kohlenwasserstoffrests, der über eine Zweifachbindung gebunden ist. Als Bindungsstelle für Alkyliden kommen naturgemäß nur Positionen am Grundkörper in Frage, an denen zwei H- Atome durch die Doppelbindung ersetzt werden können; Reste sind z. B. =CH2, =CH-CH3, =C(CH3)-CH3, =C(CH3)-C2H5 oder =C(C2H5)-C2H5.Alkylidene, e.g. B. in the form (Ci-C 10 ) alkylidene, means the radical of a straight-chain or branched open-chain hydrocarbon radical which is bonded via a double bond. As a binding site for alkylidene naturally only positions on the body in question, in which two H atoms can be replaced by the double bond; Remains are z. B. = CH 2 , = CH-CH 3 , = C (CH 3 ) -CH 3 , = C (CH 3 ) -C 2 H 5 or = C (C 2 H 5 ) -C 2 H 5 .
Cycloalkyl bedeutet ein carbocyclisches, gesättigtes Ringsystem mit vorzugsweise 3 bis 8 Ring- C-Atomen, z.B. Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl. Im Falle von gegebenenfalls substituiertem Cycloalkyl werden cyclische Systeme mit Substituenten umfasst, wobei auch Substituenten mit einer Doppelbindung am Cycloalkylrest, z. B. eine Alkylidengruppe wie Methyl- iden, umfasst sind.Cycloalkyl means a carbocyclic saturated ring system preferably having 3 to 8 ring C atoms, e.g. Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. In the case of optionally substituted cycloalkyl cyclic systems are included with substituents, wherein substituents having a double bond on the cycloalkyl, z. As an alkylidene group such as methyl iden, are included.
Im Falle von gegebenenfalls substituiertem Cycloalkyl werden auch mehrcyclische aliphatische Systeme umfaßt, wie beispielsweise Bicyclo[1.1.0]butan-l-yl, Bicyclo[1.1.0]butan-2-yl, Bicyc- lo[2.1.0]pentan-l -yl, Bicyclo[2.1.0]pentan-2-yl, Bicyclo[2.1.0]pentan-5-yl, Bicyclo[2.2. l]hept-2-yl (Norbornyl), Adamantan-1-yl und Adamantan-2-yl. Im Falle von substituiertem Cycloalkyl werden auch spirocyclische aliphatische Systeme umfaßt, wie beispielsweise Spiro[2.2]pent-l-yl, Spi- ro[2.3]hex-l-yl, Spiro[2.3]hex-4-yl, 3-Spiro[2.3]hex-5-yl.In the case of optionally substituted cycloalkyl, polycyclic aliphatic systems are also included, such as, for example, bicyclo [1.1.0] butan-1-yl, bicyclo [1.1.0] butan-2-yl, bicyclo [2.1.0] pentane-1 -yl, bicyclo [2.1.0] pentan-2-yl, bicyclo [2.1.0] pentan-5-yl, bicyclo [2.2. l] hept-2-yl (norbornyl), adamantan-1-yl and adamantan-2-yl. In the case of substituted cycloalkyl, spirocyclic aliphatic systems are also included, for example spiro [2.2] pent-1-yl, spiro [2.3] hex-1-yl, spiro [2.3] hex-4-yl, 3-spiro [ 2.3] hex-5-yl.
Cycloalkenyl bedeutet ein carbocyclisches, nicht aromatisches, partiell ungesättigtes Ringsystem mit vorzugsweise 4 bis 8 C-Atomen, z.B. 1 -Cyclobutenyl, 2-Cyclobutenyl, 1-Cyclopentenyl, 2- Cyclopentenyl, 3-Cyclopentenyl, oder 1 -Cyclohexenyl, 2-Cyclohexenyl, 3-Cyclohexenyl, 1,3- Cyclohexadienyl oder 1 ,4-Cyclohexadienyl, wobei auch Substituenten mit einer Doppelbindung am Cycloalkenylrest, z. B. eine Alkylidengruppe wie Methyliden, umfasst sind. Im Falle von gege- benenfalls substituiertem Cycloalkenyl gelten die Erläuterungen für substituiertes Cycloalkyl entsprechend. Aryl bedeutet ein mono-, bi- oder polycyclisches aromatisches System mit vorzugsweise 6 bis 14, insbesondere 6 bis 10 Ring-C-Atomen, beispielsweise Phenyl, Naphthyl, Anthryl, Phenanthrenyl, und ähnliches, vorzugsweise Phenyl.Cycloalkenyl means a carbocyclic, non-aromatic, partially unsaturated ring system having preferably 4 to 8 C atoms, for example 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, or 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, 1,3-cyclohexadienyl or 1, 4-cyclohexadienyl, wherein also substituents having a double bond on the cycloalkenyl, z. As an alkylidene group such as methylidene, are included. In the case of optionally substituted cycloalkenyl, the explanations for substituted cycloalkyl apply correspondingly. Aryl is a mono-, bi- or polycyclic aromatic system having preferably 6 to 14, in particular 6 to 10 ring C atoms, for example phenyl, naphthyl, anthryl, phenanthrenyl, and the like, preferably phenyl.
Im Falle gegebenenfalls substituiertes Aryl sind auch mehrcyclische Systeme, wie Tetrahydronaph- tyl, Indenyl, Indanyl, Fluorenyl, Biphenylyl, umfasst, wobei die Bindungsstelle am aromatischen System ist. Von der Systematik her ist Aryl in der Regel auch von dem Begriff „gegebenenfalls substituiertes Phenyl" umfasst.In the case of substituted or unsubstituted aryl, there are also more cyclic systems, such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenylyl, where the binding site is on the aromatic system. As a rule, aryl is also encompassed by the term "optionally substituted phenyl".
Ein heterocyclischer Rest (Heterocyclyl) enthält mindestens einen heterocyclischen Ring (= carbo- cyclischer Ring, in dem mindestens ein C-Atom durch ein Heteroatom ersetzt ist, vorzugsweise durch ein Heteroatom aus der Gruppe, bestehend aus N, O, S, P, B, Si, Se) der gesättigt, ungesättigt oder heteroaromatisch ist und dabei unsubstituiert oder substituiert sein kann, wobei die Bindungsstelle an einem Ringatom lokalisiert ist.A heterocyclic radical (heterocyclyl) contains at least one heterocyclic ring (= carbocyclic ring in which at least one C atom is replaced by a heteroatom, preferably by a heteroatom from the group consisting of N, O, S, P, B , Si, Se) which is saturated, unsaturated or heteroaromatic and may be unsubstituted or substituted, wherein the binding site is located on a ring atom.
Ist der Heterocyclylrest oder der heterocyclische Ring gegebenenfalls substituiert, kann er mit anderen carbocyclischen oder heterocyclischen Ringen annelliert sein. Im Falle von gegebenenfalls substituiertem Heterocyclyl werden auch mehrcyclische Systeme umfaßt, wie beispielsweise 8- Aza-bicyclo[3.2.1]octanyl oder l-Aza-bicyclo[2.2.1]heptyl. Im Falle von gegebenenfalls substituiertem Heterocyclyl werden auch spirocyclische Systeme umfaßt, wie beispielsweise l-Oxa-5-aza- spiro[2.3]hexyl.When the heterocyclyl or heterocyclic ring is optionally substituted, it may be fused with other carbocyclic or heterocyclic rings. In the case of optionally substituted heterocyclyl, more cyclic systems are also included, such as, for example, 8-azabicyclo [3.2.1] octanyl or 1-azabicyclo [2.2.1] heptyl. In the case of optionally substituted heterocyclyl, spirocyclic systems are also included, such as, for example, 1-oxa-5-azaspiro [2.3] hexyl.
Wenn nicht anders definiert, enthält der heterocyclische Ring vorzugsweise 3 bis 9 Ringatome, insbesondere 3 bis 6 Ringatome, und ein oder mehrere, vorzugsweise 1 bis 4, insbesondere 1, 2 oder 3 Heteroatome im heterocyclischen Ring, vorzugsweise aus der Gruppe, bestehend aus N, O, und S, wobei jedoch nicht zwei Sauerstoffatome direkt benachbart sein sollen.Unless defined otherwise, the heterocyclic ring preferably contains 3 to 9 ring atoms, in particular 3 to 6 ring atoms, and one or more, preferably 1 to 4, in particular 1, 2 or 3 heteroatoms in the heterocyclic ring, preferably from the group consisting of N , O, and S, but not two oxygen atoms should be directly adjacent.
Unter dem Begriff Heteroaryl versteht man im Rahmen der vorliegenden Erfindung wie vorstehend unter "Heterocyclyl" definierte Systeme, die jedoch heteroaromatisch sind, d. h. eine vollständig ungesättigte aromatische heterocyclische Verbindung darstellen.For the purposes of the present invention, the term heteroaryl is understood to mean systems as defined above under "heterocyclyl" but which are heteroaromatic, ie. H. represent a fully unsaturated aromatic heterocyclic compound.
Mit der Definition „mit einem oder mehreren Resten substituiert ist" sind, wenn nicht anders definiert, unabhängig voneinander ein oder mehrere gleiche oder verschiedene Reste gemeint, wobei zwei oder mehrere Reste an einem Cyclus als Grundkörper einen oder mehrere Ringe bilden können.Unless defined otherwise, the definition "substituted by one or more radicals" means, independently of one another, one or more identical or different radicals, it being possible for two or more radicals to form one or more rings on one cycle as main body.
Substituierte Reste, wie ein substituierter Alkyl-, Alkenyl-, Alkinyl-, Cycloalkyl-, Cycloalkenyl-, Aryl-, Phenyl-, Benzyl-, Heterocyclyl- und Heteroarylrest, bedeuten beispielsweise einen vom un- substituierten Grundkörper abgeleiteten substituierten Rest, wobei die Substituenten beispielsweise einen oder mehrere, vorzugsweise 1, 2 oder 3 Reste aus der Gruppe Halogen, Alkoxy, Alkylthio, Hydroxy, Amino, Nitro, Carboxy oder eine der Carboxygruppe äquivalente Gruppe, Cyano, Isocy- ano, Azido, Alkoxycarbonyl, Alkylcarbonyl, Formyl, Carbamoyl, Mono- und Dialkylaminocarbo- nyl, substituiertes Amino, wie Acylamino, Mono- und Dialkylamino, Trialkylsilyl und gegebenen- falls substituiertes Cycloalkyl, gegebenenfalls substituiertes Aryl, gegebenenfalls substituiertes He- terocyclyl, wobei jeder der letztgenannten cyclischen Gruppen auch über Heteroatome oder diva- lente funktionelle Gruppen wie bei den genannten Alkylresten gebunden sein kann, und Alkylsulfi- nyl, wobei beide Enantiomere der Alkylsulfinylgruppe umfasst sind, Alkylsulfonyl, Alkylphosphi- nyl, Alkylphosphonyl und, im Falle cyclischer Reste (= "cyclischer Grundkörper"), auch Alkyl, Haloalkyl, Alkylthio-alkyl, Alkoxy-alkyl, gegebenfalls substituiertes Mono- und Dialkylaminoal- kyl und Hydroxyalkyl bedeuten; im Begriff "substituierte Reste" wie substituiertes Alkyl etc. sind als Substituenten zusätzlich zu den genannten gesättigten kohlenwasserstoffhaltigen Resten entsprechende ungesättigte aliphatische und aromatische Reste, wie gegebenenfalls substituiertes Al- kenyl, Alkinyl, Alkenyloxy, Alkinyloxy, Alkenylthio, Alkinylthio, Alkenyloxycarbonyl, Alkinylo- xycarbonyl, Alkenylcarbonyl, Alkinylcarbonyl, Mono- und Dialkenylaminocarbonyl, Mono- und Dialkinylaminocarbonyl, Mono- und Dialkenylamino, Mono- und Dialkinylamino, Trialkenylsilyl, Trialkinylsilyl, gegebenenfalls substituiertes Cycloalkenyl, gegebenenfalls substituiertes Cycloal- kinyl, Phenyl, Phenoxy etc. eingeschlossen. Im Falle von substituierten cyclischen Resten mit a- liphatischen Anteilen im Ring werden auch cyclische Systeme mit solchen Substituenten umfaßt, die mit einer Doppelbindung am Ring gebunden sind, z. B. mit einer Alkylidengruppe wie Methyl- iden oder Ethyliden oder einer Oxogruppe, Iminogruppe oder substituierten Iminogruppe substituiert sind.Substituted radicals, such as a substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl radical, are, for example, a substituted radical derived from the unsubstituted radical, where the substituents for example one or more, preferably 1, 2 or 3, radicals from the group consisting of halogen, alkoxy, alkylthio, hydroxyl, amino, nitro, carboxy or a group equivalent to the carboxy group, cyano, isocyanato, 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 substituted heterocyclyl, where each of the last-mentioned cyclic groups also has hetero atoms or divalent functional groups Groups may be bonded as in the abovementioned alkyl radicals, and alkylsulfinyl, wherein both enantiomers of the alkylsulfinyl are included, alkylsulfonyl, alkylphosphinyl, alkylphosphonyl and, in the case of cyclic radicals (= "cyclic body"), also alkyl, haloalkyl, alkylthio alkyl, alkoxyalkyl, optionally substituted mono- and dialkylaminoalkyl and hydroxyalkyl; in the term "substituted radicals" such as substituted alkyl etc. are substituents in addition to the said saturated hydrocarbon-containing radicals corresponding unsaturated aliphatic and aromatic radicals such as optionally substituted alkenyl, alkynyl, 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, etc., included. In the case of substituted cyclic radicals having a-liphatischen portions in the ring and cyclic systems are also having such substituents which are bonded to a double bond on the ring, z. B. with an alkylidene group such as methyl iden or ethylidene or an oxo group, imino group or substituted imino group are substituted.
Wenn zwei oder mehrere Reste einen oder mehrere Ringe bilden, so können diese carbocyclisch, heterocyclisch, gesättigt, teilgesättigt, ungesättigt, beispielsweise auch aromatisch und gegebenen- falls weiter substituiert sein. Die anneliierten Ringe sind vorzugsweise 5- oder 6-Ringe, besonders bevorzugt sind benzokondensierte Cyclen.If two or more radicals form one or more rings, these may be carbocyclic, heterocyclic, saturated, partially saturated, unsaturated, for example also aromatic and, where appropriate, further substituted. The annelated rings are preferably 5- or 6-membered rings, particularly preferred are benzo-fused rings.
Die beispielhaft genannten Substituenten ("erste Substituentenebene") können, sofem sie kohlen- wasserstoffhaltige Anteile enthalten, dort gegebenenfalls weiter substituiert sein ("zweite Substitu- tentenebene"), beispielsweise durch einen der Substituenten, wie er für die erste Substituentenebe- ne definiert ist. Entsprechende weitere Substituentenebenen sind möglich. Vorzugsweise werden vom Begriff "substituierter Rest" nur ein oder zwei Substitutentenebenen umfasst.The substituents exemplified ("first substituent level") may, if they contain carbon-containing moieties, optionally further substituted there ("second substituent level"), for example by one of the substituents as defined for the first substituent , Corresponding further substituent levels are possible. Preferably, the term "substituted radical" includes only one or two substituent levels.
Bevorzugte Substituenten für die Substituentenebenen sind beispielsweise Amino, Hydroxy, Halogen, Nitro, Cyano, Isocyano, Mercapto, Isothiocyanato, Carboxy, Carbonamid, SF5, Aminosulfo- nyl, Alkyl, Cycloalkyl, Alkenyl, Cycloalkenyl, Alkinyl, Monoalkyl-amino, Dialkyl-amino, N- Alkanoyl-amino, Alkoxy, Alkenyloxy, Alkinyloxy, Cycloalkoxy, Cycloalkenyloxy, Alkoxy- carbonyl, Alkenyloxy-carbonyl, Alkinyloxy-carbonyl, Aryloxycarbonyl, Alkanoyl, Alkenyl- carbonyl, Alkinyl-carbonyl, Aryl-carbonyl, Alkylthio, Cycloalkylthio, Alkenylthio, Cycloalke- nylthio, Alkinylthio, Alkylsulfenyl, Alkylsulfinyl, wobei beide Enantiomere der Alkylsulfinylgrup- pe umfasst sind, Alkylsulfonyl, Monoalkyl-aminosulfonyl, Dialkyl-aminosulfonyl, Alkylphosphi- nyl, Alkylphosphonyl, wobei für Alkylphosphinyl bzw. Alkylphosphonyl beide Enantiomere umfasst sind, N-Alkyl-aminocarbonyl, N,N-Dialkyl-aminocarbonyl, N-Alkanoyl-amino-carbonyl, N- Alkanoyl-N-alkyl-aminocarbonyl, Aryl, Aryloxy, Benzyl, Benzyloxy, Benzylthio, Arylthio, Ary- lamino, Benzylamino, Heterocyclyl und Trialkylsilyl.Preferred substituents for the substituent levels are, for example, amino, hydroxyl, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, carboxy, carbonamide, SF 5 , aminosulfonyl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, monoalkylamino, dialkyl amino, N- Alkanoylamino, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryloxycarbonyl, alkanoyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, alkylthio, cycloalkylthio, alkenylthio, cycloalkene nylthio, alkynylthio, alkylsulfenyl, alkylsulfinyl, where both enantiomers of the alkylsulfinyl group are included, alkylsulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylphosphinyl, alkylphosphonyl, where for alkylphosphinyl or alkylphosphonyl both enantiomers are included, N-alkylaminocarbonyl , N, N-dialkylaminocarbonyl, N-alkanoylamino-carbonyl, N-alkanoyl-N-alkylaminocarbonyl, aryl, aryloxy, benzyl, benzyloxy, benzylthio, arylthio, arylamino, benzylamino, heterocyclyl and trialkylsilyl.
Die Verbindungen der allgemeinen Formel (I) können je nach Wahl der Substituenten gegebenenfalls durch Anlagerung einer geeigneten anorganischen oder organischen Säure, beispielsweise Mineralsäuren, insbesondere HCl, HBr, H2SO4, H3PO4 oder HNO3, oder beispielsweise organische Säuren, insbesondere Carbonsäuren, wie Ameisensäure, Essigsäure, Propionsäure, Oxalsäure, Milchsäure oder Salicylsäure oder beispielsweise Sulfonsäuren, insbesondere p-Toluolsulfonsäure, an eine basische Gruppe, wie z.B. Amino, Alkylamino, Dialkylamino, Piperidino, Morpholino oder Pyridino, Salze bilden. Diese Salze enthalten dann die konjugierte Base der Säure als AnionDepending on the choice of the substituents, the compounds of the general formula (I) can be obtained, if appropriate, by addition of a suitable inorganic or organic acid, for example mineral acids, in particular HCl, HBr, H 2 SO 4 , H 3 PO 4 or HNO 3 , or, for example, organic acids, in particular carboxylic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, lactic acid or salicylic acid or, for example, sulfonic acids, in particular p-toluenesulfonic acid, to a basic group, such as amino, alkylamino, dialkylamino, piperidino, morpholino or pyridino, salts. These salts then contain the conjugate base of the acid as an anion
Geeignete Substituenten, die in deprotonierter Form, wie z.B. Sulfonsäuren oder Carbonsäuren, vorliegen, können innere Salze mit ihrerseits protonierbaren Gruppen, wie Aminogruppen bilden.Suitable substituents which are in deprotonated form, e.g. Sulfonic acids or carboxylic acids, may form internal salts with their turn protonatable groups, such as amino groups.
Im Folgenden werden die Verbindungen der allgemeinen Formel (I) und ihre Salze auch kurz als erfindungsgemäß verwendete oder erfϊndungsgemäße "Verbindungen der allgemeinen Formel (I)" bezeichnet.In the following, the compounds of the general formula (I) and their salts are also referred to briefly as "compounds of the general formula (I)" used according to the invention or according to the invention.
Die vorliegenden Verbindungen der allgemeinen Formel (I) können nach folgenden Verfahren hergestellt werden, wobei die Verbindungen der allgemeinen Formel (I)The present compounds of the general formula (I) can be prepared by the following processes, the compounds of the general formula (I)
(1) als Verbindungen der allgemeinen Formel (I- A) bezeichnet werden, wenn Y = S ist,(1) as compounds of the general formula (I-A), when Y = S,
(2) als Verbindungen der allgemeinen Formel (I-B) bezeichnet werden, wenn Y = S(=O) ist,(2) as compounds of the general formula (I-B) when Y = S (= O),
(3) als Verbindungen der allgemeinen Formel (I-C) bezeichnet werden, wenn Y = S(O)2 ist,(3) be referred to as compounds of general formula (IC) when Y = S (O) 2 ,
(4) als Verbindungen der allgemeinen Formel (I-D) bezeichnet werden, wenn Y = -S(=N-CN)- ist,(4) are referred to as compounds of general formula (I-D) when Y = -S (= N-CN) -,
(5) als Verbindungen der allgemeinen Formel (I-E) bezeichnet werden, wenn Y = -S(O)(=N- CN)- ist, (6) als Verbindungen der allgemeinen Formel (I-F) bezeichnet werden, wenn Y = -S(O)(=N- R6)- ist;(5) are referred to as compounds of the general formula (IE) when Y is -S (O) (= N-CN) -, (6) as compounds of general formula (IF) when Y = -S (O) (= N-R 6 ) -;
(7) als Verbindungen der allgemeinen Formel (I-G) bezeichnet werden, wenn R1 ≠ Wasserstoff ist;(7) are referred to as compounds of general formula (IG) when R 1 ≠ is hydrogen;
(8) als Verbindungen der allgemeinen Formel (I-H) bezeichnet werden, wenn R1 und R2 ≠ Wasserstoff sind; und(8) are referred to as compounds of general formula (IH) when R 1 and R 2 ≠ are hydrogen; and
(9) als Verbindungen der allgemeinen Formel (I-J), wenn R1 und R2 zusammen eine Imino- Doppelbindung bilden.(9) as compounds of the general formula (IJ) when R 1 and R 2 together form an imino double bond.
Zunächst wird ein Verfahren - Verfahren A - zur Herstellung von Verbindungen der allgemeinen Formel (I- A) beschrieben.First, a process - Process A - for the preparation of compounds of the general formula (I-A) will be described.
Verfahren (A)Procedure (A)
Verbindungen der Formel (I-A) werden z.B. nach folgendem Verfahren (A) synthetisiert:Compounds of formula (I-A) are e.g. synthesized according to the following procedure (A):
Figure imgf000019_0001
Figure imgf000019_0001
/ Hydrazinhydrat Lösungsmittel/ Hydrazine hydrate solvent
CS2, BaseCS 2 , Base
T 2 Äquiv. B-COCI (VIII) CN LG = AbgangsgruppeT 2 equiv. B-COCI (VIII) CN LG = leaving group
(H) S (IV-B)(H) S (IV-B)
^B B = aryl, hetaryl ^ BB = aryl, hetaryl
wobei A1, A2, B, X, R3 und n die oben angegebenen Bedeutungen haben und LG für eine beliebige Abgangsgruppe steht. Die vorliegende Erfindung betrifft daher auch ein Verfahren zur Herstellung der Verbindungen der allgemeinen Formel (I) durch folgende Umsetzungwhere A 1 , A 2 , B, X, R 3 and n have the meanings given above and LG stands for any leaving group. The present invention therefore also relates to a process for the preparation of the compounds of general formula (I) by the following reaction
Figure imgf000020_0001
Figure imgf000020_0001
wobei die Reste R1 und R2 gleich Wasserstoff sind, R3, X, Y, B und n die vorstehende Bedutung aufweisen. Das für diese Umsetzung verwendete Edukt wird gemäß dem oben dargestellten Reak- tiosschema gewonnen.wherein R 1 and R 2 are hydrogen, R 3 , X, Y, B and n are as defined above. The educt used for this reaction is recovered according to the reaction scheme shown above.
Die Abgangsgruppe LG unterliegt keiner besonderen Beschränkung und sie kann beispielsweise ein Halogen, ein Alkylsulfonyl, ein Alkylsulfϊnyl, ein Alkylsulfanyl oder Nitro sein.The leaving group LG is not particularly limited and may be, for example, a halogen, an alkylsulfonyl, an alkylsulfinyl, an alkylsulfanyl or nitro.
Beim erfindungsgemäßen Verfahren (A) zur Herstellung der Verbindungen der Formel (I-A) werden Keten-S,S-dithioacetale der allgemeinen Formel (IV), (IV-A) oder (IV-B) zunächst mit Hydrazinhydrat in einem geeigneten Lösungsmittel umgesetzt. Die resultierenden Aminopyra- zole der allgemeinen Formel (V) werden dann mit Azinylderivaten der allgemeinen Formel (VI) umgesetzt, die eine geeignete Abgangsgruppe „LG" wie z.B. Halogene, Alkylsulfonate, Arylsulfo- nate, Alkylsulfonyle, Alkylsulfϊnyle, Alkylsulfanyle oder Nitro, enthalten.In the process (A) according to the invention for preparing the compounds of the formula (I-A), ketene S, S-dithioacetals of the general formula (IV), (IV-A) or (IV-B) are first reacted with hydrazine hydrate in a suitable solvent. The resulting aminopyrazoles of general formula (V) are then reacted with azinyl derivatives of general formula (VI) containing a suitable leaving group "LG" such as halogens, alkylsulfonates, arylsulfonates, alkylsulfonyls, alkylsulfinyls, alkylsulfanyls or nitro.
Die Synthese von strukturverwandten Keten-S,S-dithioacetalen wird unter anderem beschrieben in:The synthesis of structurally related ketene S, S-dithioacetals is described, inter alia, in:
1. Science of Synthesis (2006), Volume Date 2005, 24, 461-5161. Science of Synthesis (2006), Volume Date 2005, 24, 461-516
2. Chemische Berichte (1962), 95, 2861-28702. Chemical Reports (1962), 95, 2861-2870
3. Journal of Organic Chemistry (1971), 36(22), 3386-33913. Journal of Organic Chemistry (1971), 36 (22), 3386-3391
4. Tetrahedron (1976), 32(14), 1779-17874. Tetrahedron (1976), 32 (14), 1779-1787
5. Journal für Praktische Chemie (Leipzig) (1979), 321(6), 1021-10285. Journal of Practical Chemistry (Leipzig) (1979), 321 (6), 1021-1028
6. US 4,389,4006. US 4,389,400
7. JP 60/0041647. JP 60/004164
8. Synthesis (1991), (4), 301-3038. Synthesis (1991), (4), 301-303
9. Bulletin of the Korean Chemical Society (1998), 19(11), 1262-1265 10. Yakugaku Zasshi (1969), 89(2), 203-2089. Bulletin of the Korean Chemical Society (1998), 19 (11), 1262-1265 10. Yakugaku Zasshi (1969), 89 (2), 203-208
11. Tetrahedron (1989), 45(6), 1801-181411. Tetrahedron (1989), 45 (6), 1801-1814
Die Synthese von strukturverwandten Aminopyrazolen wird beschrieben in:The synthesis of structurally related aminopyrazoles is described in:
1. DD 1133631st DD 113363
2. WO 20010074132. WO 2001007413
3. EP 0 846 687 A3. EP 0 846 687 A
4. Synthetic Communications (2003), 33(4), 555-5624. Synthetic Communications (2003), 33 (4), 555-562
5. Bioorganic & Medicinal Chemistry Letters (2004), 14(19), 4949-49535. Bioorganic & Medicinal Chemistry Letters (2004), 14 (19), 4949-4953
6. Tetrahedron (1990), 46(2), 577-5866. Tetrahedron (1990), 46 (2), 577-586
7. Sulfur Letters (1993), 16(4), 165-1707. Sulfur Letters (1993), 16 (4), 165-170
8. Heterocycles (1996), 43(8), 1597-16008. Heterocycles (1996), 43 (8), 1597-1600
Weiterer Gegenstand der vorliegenden Erfindung sind die in dieser Synthese durchlaufenen Zwischenprodukte der allgemeinen Formel (IV)A further subject of the present invention are the intermediates of the general formula (IV) in this synthesis.
Figure imgf000021_0001
Figure imgf000021_0001
mit X gleichequal to X
Figure imgf000021_0002
Figure imgf000021_0002
wobei G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt werden aus der Gruppe, bestehend aus Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alkoxyalkoxy, Cycloalkyl, Alkenoxy, Alkinoxy, Cycloalkylalkoxy, Haloalkoxy, Haloalkoxyalkyl, Alkylsulfanyl, Haloalkylsulfanyl, Al- kylsulfinyl, Haloalkylsulfinyl, Alkylsulfonyl, Haloalkylsulfonyl, Cyano, Alkylcarbonyl, Alkoxy- carbonyl, Alkoxycarbonylalkyl, Carboxyl, Carboxamid, Dialkylcarboxamid, Trialkylsilyl, Nitro, Amino, Alkylamino, Dialkylamino, Alkylsulfonylamino, Dialkylsulfonylamino, -CR6=NO-R6, - CR6=NO-Haloalkyl, oder Formyl steht, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder HaIo- alkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann.wherein G 1 , G 2 and G 3 , each independently of one another, are selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkenoxy, alkynoxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, haloalkylsulfanyl, Alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, nitro, amino, alkylamino, dialkylamino, alkylsulfonylamino, dialkylsulfonylamino, -CR 6 = NO-R 6 , - CR 6 = NO-haloalkyl, or formyl, where vicinal alkyl, haloalkyl, alkoxy and / or halo alkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms, and whose alkyl moiety may be optionally substituted with one or more fluorine atoms.
Bevorzugt werden G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt aus der Gruppe, bestehend aus Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alkoxyalkoxy, COOH Nitro, A- mino, Alkylamino, Dialkylamino, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder Haloalko- xygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann.G 1 , G 2 and G 3 are each independently selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, COOH nitro, amino, alkylamino, dialkylamino, vicinal alkyl, Haloalkyl, alkoxy and / or Haloalko- xygruppen together with the carbon atoms to which they are attached, can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms, and the alkyl moiety may be optionally substituted with one or more fluorine atoms ,
Besonders bevorzugt werden G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt aus der Gruppe, bestehend aus Halogen, Ci.Cö-Haloalkyl und Ci-C6-Alkoxy, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder Haloalkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substi- tuiert sein kann.Particularly preferred are G 1, G 2 and G 3 are each independently selected from the group consisting of halogen, Ci.C ö -haloalkyl and Ci-C 6 -alkoxy, where vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system which contains 0 to 2 oxygen atoms, and whose alkyl moiety may optionally be substituted by one or more fluorine atoms.
Ganz besonders bevorzugt werden G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt aus der Gruppe, bestehend aus Fluor, Chlor, Brom, Iod, CF3, CH3O, OCH2O, OCH2CH2 und OCF2O.Very particular preference is given to G 1 , G 2 and G 3 , each independently of one another, selected from the group consisting of fluorine, chlorine, bromine, iodine, CF 3 , CH 3 O, OCH 2 O, OCH 2 CH 2 and OCF 2 O.
Speziell weist X eine der folgenden Bedeutungen auf:Specifically, X has one of the following meanings:
2-Cl-Phenyl; 2-F-6-F-Phenyl; 3-Cl-Phenyl; 3-CF3-Phenyl; 4-Cl-Phenyl; 4-Br-Phenyl; 4-I-Phenyl; 3-Cl,4-Cl-Phenyl; 3-CF3,4-Cl-Phenyl; 3-Cl,5-Cl-Phenyl; 3-CF3,5-F-Phenyl; 3-CF3,5-Cl-Phenyl;3- CF3,5-Cl-Phenyl; 3-Cl,4-Cl,5-Cl-Phenyl; 3-F, 4-F,5-F-Phenyl; 3-Cl,4-OCH3,5-Cl-Phenyl; 3-Cl,4- OCH3,5- OCH3-Phenyl; 3-Cl,(4)-OCH2O-(5)-Phenyl; 3-Cl,(4)-OCH2CH2-(5)-Phenyl; 3-Cl,(4)- OCF2O-(5)-Phenyl; und 3-OCH3,5-CF3-Phenyl.2-Cl-phenyl; 2-F-6-F-phenyl; 3-Cl-phenyl; 3-CF 3 -phenyl; 4-Cl-phenyl; 4-Br-phenyl; 4-I-phenyl; 3-Cl, 4-Cl-phenyl; 3-CF 3 , 4-Cl-phenyl; 3-Cl, 5-Cl-phenyl; 3-CF 3 , 5-F-phenyl; 3-CF 3 , 5-Cl-phenyl; 3-CF 3 , 5-Cl-phenyl; 3-Cl, 4-Cl, 5-Cl-phenyl; 3-F, 4-F, 5-F-phenyl; 3-Cl, 4-OCH 3 , 5-Cl-phenyl; 3-Cl, 4-OCH 3 , 5-OCH 3 -phenyl; 3-Cl, (4) -OCH 2 O- (5) -phenyl; 3-Cl, (4) -OCH 2 CH 2 - (5) -phenyl; 3-Cl, (4) - OCF 2 O- (5) -phenyl; and 3-OCH 3 , 5-CF 3 -phenyl.
Weiterer Gegenstand der vorliegenden Erfindung sind die in dieser Synthese durchlaufenen Zwi- schenprodukte der allgemeinen Formel (IV-A)The present invention furthermore relates to the intermediates of the general formula (IV-A) in this synthesis.
Figure imgf000022_0001
Figure imgf000022_0001
mit X gleich
Figure imgf000023_0001
equal to X
Figure imgf000023_0001
wobei G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt werden aus der Gruppe, bestehend aus Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alkoxyalkoxy, Cycloalkyl, Alkenoxy, Alkinoxy, Cycloalkylalkoxy, Haloalkoxy, Haloalkoxyalkyl, Alkylsulfanyl, Haloalkylsulfanyl, Al- kylsulfinyl, Haloalkylsulfinyl, Alkylsulfonyl, Haloalkylsulfonyl, Cyano, Alkylcarbonyl, Alkoxy- carbonyl, Alkoxycarbonylalkyl, Carboxyl, Carboxamid, Dialkylcarboxamid, Trialkylsilyl, Nitro, Amino, Alkylamino, Dialkylamino, Alkylsulfonylamino, Dialkylsulfonylamino, -CR6=NO-R6, - CR6=NO-Haloalkyl, oder Formyl steht, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder HaIo- alkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann.wherein G 1 , G 2 and G 3 , each independently of one another, are selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkenoxy, alkynoxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, haloalkylsulfanyl, Alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, nitro, amino, alkylamino, dialkylamino, alkylsulfonylamino, dialkylsulfonylamino, -CR 6 = NO-R 6 , - CR 6 = NO-haloalkyl, or formyl, wherein vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system, the 0 to Contains 2 oxygen atoms, and its alkyl portion may optionally be substituted with one or more fluorine atoms.
Bevorzugt werden G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt aus der Gruppe, bestehend aus Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alkoxyalkoxy, COOH Nitro, A- mino, Alkylamino, Dialkylamino, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder Haloalko- xygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann.G 1 , G 2 and G 3 are each independently selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, COOH nitro, amino, alkylamino, dialkylamino, vicinal alkyl, Haloalkyl, alkoxy and / or Haloalko- xygruppen together with the carbon atoms to which they are attached, can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms, and the alkyl moiety may be optionally substituted with one or more fluorine atoms ,
Besonders bevorzugt werden G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt aus der Gruppe, bestehend aus Halogen, Ci.C6.Haloalkyl und Ci-C6-Alkoxy, wobei vicinale Alkyl-, HaIo- alkyl, Alkoxy- und/oder Haloalkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann.Particular preference is given to G 1 , G 2 and G 3 , each independently of one another, selected from the group consisting of halogen, C 1 -C 6 -haloalkyl and C 1 -C 6 -alkoxy, where vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms, and whose alkyl moiety may be optionally substituted with one or more fluorine atoms.
Ganz besonders bevorzugt werden G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt aus der Gruppe, bestehend aus Fluor, Chlor, Brom, Iod, CF3, CH3O, OCH2O, OCH2CH2 und OCF2O.Very particular preference is given to G 1 , G 2 and G 3 , each independently of one another, selected from the group consisting of fluorine, chlorine, bromine, iodine, CF 3 , CH 3 O, OCH 2 O, OCH 2 CH 2 and OCF 2 O.
Speziell weist X eine der folgenden Bedeutungen auf:Specifically, X has one of the following meanings:
2-Cl-Phenyl; 2-F-6-F-Phenyl; 3-Cl-Phenyl; 3-CF3-Phenyl; 4-Cl-Phenyl; 4-Br-Phenyl; 4-I-Phenyl; 3-Cl,4-Cl-Phenyl; 3-CF3,4-Cl-Phenyl; 3-Cl,5-Cl-Phenyl; 3-CF3,5-F-Phenyl; 3-CF3,5-Cl-Phenyl;3- CF3)5-Cl-Phenyl; 3-Cl,4-Cl,5-Cl-Phenyl; 3-F, 4-F,5-F-Phenyl; 3-Cl,4-OCH3,5-Cl-Phenyl; 3-Cl,4- OCH3,5- OCH3-Phenyl; 3-Cl,(4)-OCH2O-(5)-Phenyl; 3-Cl,(4)-OCF2O-(5)-Phenyl; 3-Cl,(4)- OCH2CH2-(5)-Phenyl; und 3-OCH3,5-CF3-Phenyl.2-Cl-phenyl; 2-F-6-F-phenyl; 3-Cl-phenyl; 3-CF 3 -phenyl; 4-Cl-phenyl; 4-Br-phenyl; 4-I-phenyl; 3-Cl, 4-Cl-phenyl; 3-CF 3 , 4-Cl-phenyl; 3-Cl, 5-Cl-phenyl; 3-CF 3 , 5-F-phenyl; 3-CF 3 , 5-Cl-phenyl; 3-CF 3) 5-Cl-phenyl; 3-Cl, 4-Cl, 5-Cl-phenyl; 3-F, 4-F, 5-F-phenyl; 3-Cl, 4-OCH 3 , 5-Cl-phenyl; 3-Cl, 4- OCH 3 , 5-OCH 3 -phenyl; 3-Cl, (4) -OCH 2 O- (5) -phenyl; 3-Cl, (4) -OCF 2 O- (5) -phenyl; 3-Cl, (4) - OCH 2 CH 2 - (5) -phenyl; and 3-OCH 3 , 5-CF 3 -phenyl.
Weiterer Gegenstand der vorliegenden Erfindung sind die in dieser Synthese durchlaufenen Zwischenprodukte der allgemeinen Formel (V)Another subject of the present invention are the intermediates of the general formula (V) in this synthesis.
Figure imgf000024_0001
Figure imgf000024_0001
mit X gleichequal to X
Figure imgf000024_0002
Figure imgf000024_0002
wobei G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt werden aus der Gruppe, bestehend aus Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alkoxyalkoxy, Cycloalkyl, Alkenoxy, Alkinoxy, Cycloalkylalkoxy, Haloalkoxy, Haloalkoxyalkyl, Alkylsulfanyl, Haloalkylsulfanyl, Al- kylsulfinyl, Haloalkylsulfinyl, Alkylsulfonyl, Haloalkylsulfonyl, Cyano, Alkylcarbonyl, Alkoxy- carbonyl, Alkoxycarbonylalkyl, Carboxyl, Carboxamid, Dialkylcarboxamid, Trialkylsilyl, Nitro, Amino, Alkylamino, Dialkylamino, Alkylsulfonylamino, Dialkylsulfonylamino, -CR6=NO-R6, - CR6=NO-Haloalkyl, oder Formyl steht, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder HaIo- alkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann.wherein G 1 , G 2 and G 3 , each independently of one another, are selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkenoxy, alkynoxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, haloalkylsulfanyl, Alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, nitro, amino, alkylamino, dialkylamino, alkylsulfonylamino, dialkylsulfonylamino, -CR 6 = NO-R 6 , - CR 6 = NO-haloalkyl, or formyl, wherein vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system, the 0 to Contains 2 oxygen atoms, and its alkyl portion may optionally be substituted with one or more fluorine atoms.
Bevorzugt werden G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt aus der Gruppe, bestehend aus Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alkoxyalkoxy, COOH, Nitro, A- mino, Alkylamino, Dialkylamino, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder Haloalko- xygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann.G 1 , G 2 and G 3 are each independently selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, COOH, nitro, amino, alkylamino, dialkylamino, vicinal alkyl , Haloalkyl, alkoxy and / or Haloalko- xygruppen together with the carbon atoms to which they are attached, can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms, and its alkyl moiety optionally substituted with one or more fluorine atoms can.
Besonders bevorzugt werden G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt aus der Gruppe, bestehend aus Halogen, Ci.Cβ-Haloalkyl und Ci-C6-Alkoxy, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder Haloalkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoff- atome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann.Particularly preferred are G 1 , G 2 and G 3 , each independently, selected from the group consisting of halogen, Ci.Cβ-haloalkyl and Ci-C 6 alkoxy, wherein vicinal alkyl, haloalkyl, alkoxy and / or Haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms. contains atoms, and whose alkyl moiety may optionally be substituted with one or more fluorine atoms.
Ganz besonders bevorzugt werden G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt aus der Gruppe, bestehend aus Fluor, Chlor, Brom, Iod, CF3, CH3O, OCH2O, OCH2CH2 und OCF2O.Very particular preference is given to G 1 , G 2 and G 3 , each independently of one another, selected from the group consisting of fluorine, chlorine, bromine, iodine, CF 3 , CH 3 O, OCH 2 O, OCH 2 CH 2 and OCF 2 O.
Speziell weist X eine der folgenden Bedeutungen auf:Specifically, X has one of the following meanings:
2-Cl-Phenyl; 2-F-6-F-Phenyl; 3-Cl-Phenyl; 3-CF3-Phenyl; 4-Cl-Phenyl; 4-Br-Phenyl; 4-I-Phenyl; 3-Cl,4-Cl-Phenyl; 3-CF3,4-Cl-Phenyl; 3-Cl,5-Cl-Phenyl; 3-CF3,5-F-Phenyl;, 3-CF3,5-Cl-Phenyl; 3- CF3,5-CF3-Phenyl; 3-Cl,4-Cl,5-Cl-Phenyl; 3-F, 3-Cl,4-OCH3,5-Cl-Phenyl; 3-Cl,(4)-OCH2O-(5)- Phenyl; 3-Cl,(4)-OCF2O-(5)-Phenyl; 3-Cl„4-OCH3,5-OCH3-Phenyl; 3-Cl,(4)-OCH2CH2-(5)- Phenyl; und 3-OCH3,5-CF3-Phenyl.2-Cl-phenyl; 2-F-6-F-phenyl; 3-Cl-phenyl; 3-CF 3 -phenyl; 4-Cl-phenyl; 4-Br-phenyl; 4-I-phenyl; 3-Cl, 4-Cl-phenyl; 3-CF 3 , 4-Cl-phenyl; 3-Cl, 5-Cl-phenyl; 3-CF 3 , 5-F-phenyl ;, 3-CF 3 , 5-Cl-phenyl; 3-CF 3 , 5-CF 3 -phenyl; 3-Cl, 4-Cl, 5-Cl-phenyl; 3-F, 3-Cl, 4-OCH 3 , 5-Cl-phenyl; 3-Cl, (4) -OCH 2 O- (5) -phenyl; 3-Cl, (4) -OCF 2 O- (5) -phenyl; 3-Cl "4-OCH3, 5-OCH 3 -phenyl; 3-Cl, (4) -OCH 2 CH 2 - (5) -phenyl; and 3-OCH 3 , 5-CF 3 -phenyl.
Verfahren CB)Method CB)
Verbindungen der Formel (I-B) und (I-C) können z.B. nach folgendem Verfahren (B) synthetisiert werden:Compounds of formula (I-B) and (I-C) may e.g. be synthesized according to the following procedure (B):
Figure imgf000025_0001
Figure imgf000025_0001
2 Oxidations- Äquivalente2 oxidation equivalents
wobei R , R , A , A , B, X, R und n die oben angegebenen Bedeutungen haben.wherein R, R, A, A, B, X, R and n have the meanings given above.
Beim erfϊndungsgemäßen Verfahren (B) zur Herstellung der Verbindungen der allgemeinen Formel (I-B) werden entsprechende Thioether der allgemeinen Formel (I-A) mit einem Mol eines geeigneten Oxydationsmittels umgesetzt, z.B. mit H2O2, Natriumperiodat, /ert.-Butylhypochlorit, Calcium- hypochlorit Ca(OCl)2, Natriumchlorit NaClO2, Natriumhypochlorit NaOCl, Persäuren oder O2 und katalytischem Cerammoniumnitrat. Die resultierenden Sulfoxide der allgemeinen Formel (I-B) können mit einem weiteren Mol Oxidationsmittel zu den Sulfonen der allgemeinen Formel (I-C) umgesetzt werden. Verbindungen der Formel allgemeinen Formel (I-A) können auch direkt zu den Sulfonen der allgemeinen Formel (I-C) in Gegenwart von zwei oder mehr Äquivalenten Oxidationsmittel oxidiert werden. Diese Oxidationsreaktionen sind dem Fachmann an sich geläufig und in zahlreichen Lehrbüchern der organischen präparativen Chemie beschrieben. Ein Überblick zu Oxidationsmethoden für Umsetzungen von Thioethern ist zum Beispiel in J. March „Advanced Organic Chemistry" 4. Auflage, John Wiley & Sons, 1992, S. 1202 und die dort zitierte Literatur dargestellt.In the process (B) according to the invention for preparing the compounds of the general formula (IB), corresponding thioethers of the general formula (IA) are reacted with one mole of a suitable oxidizing agent, for example with H 2 O 2 , sodium periodate, tert-butyl hypochlorite, calcium hypochlorite Ca (OCl) 2 , sodium chlorite NaClO 2 , sodium hypochlorite NaOCl, peracids or O 2 and catalytic cerium ammonium nitrate. The resulting sulfoxides of the general formula (IB) can be reacted with a further mole of oxidizing agent to give the sulfones of the general formula (IC). Compounds of formula general formula (IA) can also be oxidized directly to the sulfones of general formula (IC) in the presence of two or more equivalents of oxidizing agent. These oxidation reactions are familiar to the person skilled in the art and are described in numerous textbooks of organic preparative chemistry. For an overview of oxidation methods for thioether reactions, see, for example, J. March "Advanced Organic Chemistry" 4th Edition, John Wiley & Sons, 1992, p. 1202 and the references cited therein.
Die vorliegende Erfindung betrifft daher auch ein Verfahren zur Herstellung der Verbindungen der allgemeinen Formel (I-B) mit Y = -S(O)- (Verbindung der allgemeinen Formel I-B) durch folgende Umsetzung:The present invention therefore also relates to a process for the preparation of the compounds of general formula (I-B) with Y = -S (O) - (compound of general formula I-B) by the following reaction:
1 Oxidations- Äquivalent
Figure imgf000026_0001
Figure imgf000026_0002
1 oxidation equivalent
Figure imgf000026_0001
Figure imgf000026_0002
wobei die Reste R1, R2, R3, X, B und n die vorstehende Bedurung aufweisen. Das für diese Urnset- zung verwendete Edukt wird beispielsweise gemäß dem oben dargestellten Reaktionsschema gewonnen.wherein the radicals R 1 , R 2 , R 3 , X, B and n have the above Bedurung. The educt used for this initial reaction is obtained, for example, according to the reaction scheme shown above.
Die vorliegende Erfindung betrifft daher auch ein Verfahren zur Herstellung der Verbindungen der allgemeinen Formel (I-C) mit Y = -S(O)2- (Verbindung der allgemeinen Formel I-C) durch folgende Umsetzung:The present invention therefore also relates to a process for the preparation of the compounds of general formula (IC) with Y = -S (O) 2 - (compound of general formula IC) by the following reaction:
Figure imgf000026_0003
Figure imgf000026_0003
2 Oxidations- Äquivalente2 oxidation equivalents
wobei die Reste R1, R2, R3, X, B und n die vorstehende Bedurung aufweisen. Das für diese Umsetzung verwendete Edukt wird beispielsweise gemäß dem oben dargestellten Reaktionsschema gewonnen.wherein the radicals R 1 , R 2 , R 3 , X, B and n have the above Bedurung. The starting material used for this reaction is obtained, for example, according to the reaction scheme shown above.
Verfahren (OProcedure (O
Verbindungen der allgemeinen Formeln (I-D), (I-E) und (I-F) können z.B. nach folgendem Verfahren (C) synthetisiert werden:
Figure imgf000027_0001
Compounds of the general formulas (ID), (IE) and (IF) can be synthesized, for example, by the following process (C):
Figure imgf000027_0001
Hydrolyse Base, R6-LG (X)Hydrolysis Base, R 6 -LG (X)
Figure imgf000027_0002
Figure imgf000027_0002
wobei A1, A2, B, X, R3, R6 und n die oben angegebenen Bedeutungen haben.where A 1 , A 2 , B, X, R 3 , R 6 and n have the meanings given above.
Beim erfindungsgemäßen Verfahren (C) zur Herstellung der Verbindungen der allgemeinen Formel (I-D) werden entsprechende Thioether der allgemeinen Formel (I-A) mit einem Mol eines geeigneten Oxidationsmittels, z.B. NBS oder Iod, und Cyanamid (IX) umgesetzt. Die resultierenden N- Cyano-sulfilimine der allgemeinen Formel (I-D) werden mit einem weiteren Mol-Äquivalent eines geeigneten Oxidationsmittels zu Ν-Cyano-sulfoximinen der allgemeinen Formel (I-E) umgesetzt, z.B. mit H2O2, Νatriumperiodat, tert.-Butylhypochlorit, Calciumhypochlorit Ca(OCl)2, Νatrium- chlorit NaClO2, Natriumhypochlorit NaOCl, Persäuren oder O2 und katalytischem Cerammonium- nitrat. Nach Hydrolyse erhält man NH-Sulfoximine (I-F: R6 = H), die wiederum zu N- Alkylsulfoximinen (I-F: R6 = Alkyl) alkyliert werden können.In the process (C) according to the invention for the preparation of the compounds of the general formula (ID), corresponding thioethers of the general formula (IA) are reacted with one mole of a suitable oxidizing agent, for example NBS or iodine, and cyanamide (IX). The resulting N-cyano-sulfilimines of the general formula (ID) are reacted with a further molar equivalent of a suitable oxidizing agent to give ano-cyano-sulfoximines of the general formula (IE), for example with H 2 O 2 , Νatriumperiodate, tert-butyl hypochlorite , Calcium hypochlorite Ca (OCl) 2 , sodium chlorite NaClO 2 , sodium hypochlorite NaOCl, peracids or O 2 and catalytic cerium ammonium nitrate. Hydrolysis gives NH-sulfoximines (IF: R 6 = H), which in turn can be alkylated to N-alkylsulfoximines (IF: R 6 = alkyl).
Die vorliegende Erfindung betrifft daher auch ein Verfahren zur Herstellung der Verbindungen der allgemeinen Formel (I) mit Y = -S(O)(=N-CN)- durch folgende Umsetzung:The present invention therefore also relates to a process for preparing the compounds of general formula (I) with Y = -S (O) (= N-CN) - by the following reaction:
Figure imgf000027_0003
Figure imgf000027_0003
wobei A , A , B, X, R , R und n die oben angegebenen Bedeutungen haben.where A, A, B, X, R, R and n have the meanings given above.
Das für diese Umsetzung verwendete Edukt der allgemeinen Formel (I) mit Y = -S(=N-CN)- (Verbindung der allgemeinen Formel I-D) bzw. -S(O)(=N-CN)- (Verbindung der allgemeinen Formel I- E) wird vorzugsweise durch folgende Umsetzung gewonnen, welche ebenfalls Gegenstand der vorliegenden Erfindung ist:The educt of the general formula (I) used for this reaction with Y = -S (= N-CN) - (compound of the general formula ID) or -S (O) (= N-CN) - (compound of the general formula I- E) is preferably obtained by the following reaction, which is also the subject of the present invention:
Figure imgf000028_0001
Figure imgf000028_0001
Beispielhaft ist die Synthese von N-Cyano-sulfiliminen, N-Cyano-sulfoximinen und NH- Sulfoximinen beschrieben in:Exemplary is the synthesis of N-cyano-sulfilimines, N-cyano-sulfoximines and NH-sulfoximines described in:
1. Organic Letters (2007), 9(19), 3809-3811.1. Organic Letters (2007), 9 (19), 3809-3811.
2. Organic Letters (2007), 9(15), 2951-29542. Organic Letters (2007), 9 (15), 2951-2954
3. WO 96/39389 A3. WO 96/39389 A
4. US 2005/228027 A4. US 2005/228027 A
Verfahren (D)Method (D)
Verbindungen der Formel (I-G) und (I-H) werden z.B. nach folgendem Verfahren (D) synthetisiert, wenn als Ausgangsverbindungen Verbindungen der allgemeinen Formel (I-A) bis (I-F) verwendet werden, in welchen die Aminfunktion nur Wasserstoffsubstituenten oder zumindest einen Was- serstoffsubstituenten trägt. Auch dieses Verfahren ist Gegenstand der vorliegenden Erfindung. Compounds of the formula (IG) and (IH) are synthesized, for example, by the following process (D) if starting compounds of the general formula (IA) to (IF) are used in which the amine function carries only hydrogen substituents or at least one hydrogen substituent , This method is also the subject of the present invention.
G (XII)G (XII)
Figure imgf000029_0001
Figure imgf000029_0001
wobei A , A , B, X, Y, R , R , R und n die oben angegebenen Bedeutungen haben.where A, A, B, X, Y, R, R, R and n have the meanings given above.
Beim erfindungsgemäßen Verfahren (D) zur Herstellung der Verbindungen der Formel (I-G) und (I-H) wird die freie NH2-Gruppe der Verbindungen (I-A) - (I-F) nach den allgemein bekannten Verfahren zur basischen Alkylierung oder Acylierung mit den entsprechenden Alkylie- rungs- oder Acylierungsreagenzien (XI) und (Xu) umgesetzt.In the process (D) according to the invention for the preparation of the compounds of the formula (IG) and (III), the free NH 2 group of the compounds (IA) - (IF) is prepared by the generally known processes for basic alkylation or acylation with the corresponding alkylation. or acylating reagents (XI) and (Xu) reacted.
Beispielhaft ist die Umsetzung von 5-Aminopyrazolen in WO 2002/008196 A beschrieben. The reaction of 5-aminopyrazoles in WO 2002/008196 A is described by way of example.
Verfahren (E)Procedure (E)
Verbindungen der Formel (I- J) werden z.B. nach folgendem Verfahren (E) synthetisiert:Compounds of formula (I-J) are e.g. synthesized by the following procedure (E):
Figure imgf000030_0001
Figure imgf000030_0001
wobei A , A , B, X, Y, R , R , R und n die oben angegebenen Bedeutungen haben.where A, A, B, X, Y, R, R, R and n have the meanings given above.
Auch diese Umsetzung ist Gegenstand der vorliegenden Erfindung.This implementation is also the subject of the present invention.
Die Umsetzung von heterocyclischen NH2-Gruppen zu Iminen ist literaturbekannt und beispielsweise in Combinatorical Chemistry & High Throughput Screening 2005, 8, 617-622 beschrieben.The reaction of heterocyclic NH 2 groups to form imines is known from the literature and described, for example, in Combinatorical Chemistry & High Throughput Screening 2005, 8, 617-622.
Die vorliegende Erfindung betrifft daher auch ein Verfahren zur Herstellung der Verbindungen der allgemeinen Formel (I) durch folgende Umsetzung: The present invention therefore also relates to a process for the preparation of the compounds of general formula (I) by the following reaction:
Figure imgf000031_0001
Figure imgf000031_0001
wobei A , A , B, X, Y, R , R , R und n die oben angegebenen Bedeutungen haben. where A, A, B, X, Y, R, R, R and n have the meanings given above.
Verfahren (F)Procedure (F)
Verbindungen der Formel (I-A) werden z.B. nach folgendem Verfahren (F) synthetisiert:Compounds of formula (I-A) are e.g. synthesized according to the following procedure (F):
Figure imgf000032_0001
Figure imgf000032_0001
H2N AtA2 H 2 N AtA 2
(XVII)(XVII)
H N-?SH N -? S
Halogemerung
Figure imgf000032_0002
Figure imgf000032_0003
Halogemerung
Figure imgf000032_0002
Figure imgf000032_0003
X-BoronsäureX-boronic acid
LG = Abgangsgruppe HaI = Br oder I
Figure imgf000032_0004
LG = leaving group HaI = Br or I
Figure imgf000032_0004
Bei dem erfϊndungsgemäßen Verfahren (F) zur Herstellung der Verbindungen der allgemeinen Formel (I-A) können auch Carbonester der allgemeinen Formel (XVILT) bzw. deren Carbonsäuren als Zwischenprodukte nach an sich literaturbekannten Verfahren hergestellt werden, die nach De- carboxylierung die Aminopyrazole der allgemeinen Formel (XIX) als Zwischenprodukte liefern. Die Halogenierung von den Verbindungen der allgemeinen Formel (XIX) erfolgt in geeigneten Lösungsmitteln, z.B. in Chlorbenzol, Chloroform, Tetrachlorkohlenstoff oder Eisessig mit geeigne- ten Halogenierungsmitteln, z.B. Brom, Iod, NBS oder NIS. In einer letzten Stufe werden die so erzeugten Halogenide der allgemeinen Formel (XX) in Gegenwart geeigneter Pd-Katalysatoren mit Boronsäuren oder Boronsäureestern zu den erfindungsgemäßen Produkten der allgemeinen Formel (I-A) umgesetzt.In the erfϊndungsgemäßen method (F) for the preparation of the compounds of general formula (IA) and carboxylic esters of the general formula (XVILT) or their carboxylic acids can be prepared as intermediates by processes known per se literature, which after decarboxylation, the aminopyrazoles of the general formula (XIX) as intermediates. The halogenation of the compounds of general formula (XIX) is carried out in suitable solvents, e.g. in chlorobenzene, chloroform, carbon tetrachloride or glacial acetic acid with suitable halogenating agents, e.g. Bromine, iodine, NBS or NIS. In a last step, the halides of the general formula (XX) thus produced are reacted in the presence of suitable Pd catalysts with boronic acids or boronic acid esters to give the products of the general formula (I-A) according to the invention.
In Analogie wird diese Synthese-Sequenz für die Darstellung von l-Aryl-3-thioalkyl-pyrazolen in der WO 2001 /07413 beschrieben. Verfahren (G)By analogy, this synthesis sequence is described for the preparation of 1-aryl-3-thioalkyl-pyrazoles in WO 2001/07414. Method (G)
Verbindungen der Formel (I- A) werden z.B. nach folgendem Verfahren (G) synthetisiert:Compounds of formula (I-A) are e.g. synthesized according to the following procedure (G):
(XXIII)(XXIII)
Figure imgf000033_0001
Figure imgf000033_0001
wobei A1, A2, B, X, R3 und n die oben angegebenen Bedeutungen haben und LG für eine beliebige Abgangsgruppe steht.where A 1 , A 2 , B, X, R 3 and n have the meanings given above and LG stands for any leaving group.
Diese Synthesesequenz zur Darstellung von VII-A aus Tπthiocarbonat (XXII) ist in Analogie beschrieben in: Journal of the Chemical Society, Perkin Transactions 1 : Organic and Bio-Organic Chemistry (1972-1999) (1984), (1), 85-90; eine Umsetzung zu SH-Pyrazol (XXm) ist vergleichbar in Synthetic Communications, 33(4), 555-562; 2003 aufgeführt.This synthesis sequence for the preparation of VII-A from thiocarbonate (XXII) is described in analogy in: Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999) (1984), (1), 85- 90; a reaction to SH-pyrazole (XXm) is comparable to Synthetic Communications, 33 (4), 555-562; 2003 listed.
Weiterer Gegenstand der vorliegenden Erfindung sind die in dieser Synthese durchlaufenen Zwischenprodukte der allgemeinen Formel (XXIII)Another subject of the present invention are the intermediates of the general formula (XXIII) in this synthesis.
Figure imgf000033_0002
Figure imgf000033_0002
mit X gleichequal to X
Figure imgf000033_0003
wobei G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt werden aus der Gruppe, bestehend aus Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alkoxyalkoxy, Cycloalkyl, Alkenoxy, Alkinoxy, Cycloalkylalkoxy, Haloalkoxy, Haloalkoxyalkyl, Alkylsulfanyl, Haloalkylsulfanyl, Al- kylsulfinyl, Haloalkylsulfinyl, Alkylsulfonyl, Haloalkylsulfonyl, Cyano, Alkylcarbonyl, Alkoxy- carbonyl, Alkoxycarbonylalkyl, Carboxyl, Carboxamid, Dialkylcarboxamid, Trialkylsilyl, Nitro, Amino, Alkylamino, Dialkylamino, Alkylsulfonylamino, Dialkylsulfonylamino, -CR6=NO-R6, - CR6=NO-Haloalkyl, oder Formyl steht, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder HaIo- alkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann.
Figure imgf000033_0003
wherein G 1 , G 2 and G 3 , each independently of one another, are selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkenoxy, alkynoxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, haloalkylsulfanyl, Alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, nitro, amino, alkylamino, dialkylamino, alkylsulfonylamino, dialkylsulfonylamino, -CR 6 = NO-R 6 , - CR 6 = NO-haloalkyl, or formyl, wherein vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system, the 0 to Contains 2 oxygen atoms, and its alkyl portion may optionally be substituted with one or more fluorine atoms.
Bevorzugt werden G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt aus der Gruppe, bestehend aus Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alkoxyalkoxy, COOH, Nitro, A- mino, Alkylamino, Dialkylamino, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder Haloalko- xygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechs- gliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann.G 1 , G 2 and G 3 are each independently selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, COOH, nitro, amino, alkylamino, dialkylamino, vicinal alkyl , Haloalkyl, alkoxy and / or Haloalko- xygruppen together with the carbon atoms to which they are attached, can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms, and its alkyl moiety optionally with one or more fluorine atoms may be substituted.
Besonders bevorzugt werden G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt aus der Gruppe, bestehend aus Halogen, Ci.C6-Haloalkyl und C1-C6-AIkOXy, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder Haloalkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie ge- bunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann.Particularly preferred are G 1 , G 2 and G 3 , each independently, selected from the group consisting of halogen, Ci.C 6 -haloalkyl and C 1 -C 6 -Akoxy, where vicinal alkyl, haloalkyl, alkoxy and or haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system which contains 0 to 2 oxygen atoms, and whose alkyl moiety may optionally be substituted by one or more fluorine atoms.
Ganz besonders bevorzugt werden G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt aus der Gruppe, bestehend aus Fluor, Chlor, Brom, Iod, CF3, CH3O, OCH2O, OCH2CH2 und OCF2O.Very particular preference is given to G 1 , G 2 and G 3 , each independently of one another, selected from the group consisting of fluorine, chlorine, bromine, iodine, CF 3 , CH 3 O, OCH 2 O, OCH 2 CH 2 and OCF 2 O.
Speziell weist X eine der folgenden Bedeutungen auf:Specifically, X has one of the following meanings:
2-Cl-Phenyl; 2-F-6-F-Phenyl; 3-Cl-Phenyl; 3-CF3-Phenyl; 4-Cl-Phenyl; 4-Br-Phenyl; 4-I-Phenyl; 3-Cl,4-Cl-Phenyl; 3-CF3,4-Cl-Phenyl; 3-Cl,5-Cl-Phenyl; 3-CF3,5-F-Phenyl;, 3-CF3,5-Cl-Phenyl; 3- CF3,5-CF3-Phenyl; 3-Cl,4-Cl,5-Cl-Phenyl; 3-F, 3-Cl,4-OCH3,5-Cl-Phenyl; 3-Cl,(4)-OCH2O-(5)- Phenyl; 3-Cl,(4)-OCF2O-(5)-Phenyl; 3-Cl„4-OCH3,5-OCH3-Phenyl; 3-Cl,(4)-OCH2CH2-(5)- Phenyl; und 3-OCH3,5-CF3-Phenyl. Die erfindungsgemäßen Wirkstoffe eignen sich bei guter Pflanzenverträglichkeit, günstiger Warm- blütertoxizität und guter Umweltverträglichkeit zum Schutz von Pflanzen und Pflanzenorganen, zur Steigerung der Ernteerträge, Verbesserung der Qualität des Erntegutes und zur Bekämpfung von tierischen Schädlingen, insbesondere Insekten, Spinnentieren, Helminthen, Nematoden und Mollusken, die in der Landwirtschaft, im Gartenbau, bei der Tierzucht, in Forsten, in Gärten und Freizeiteinrichtungen, im Vorrats- und Materialschutz sowie auf dem Hygienesektor vorkommen. Sie können vorzugsweise als Pflanzenschutzmittel eingesetzt werden. Sie sind gegen normal sensible und resistente Arten sowie gegen alle oder einzelne Entwicklungsstadien wirksam. Zu den oben erwähnten Schädlingen gehören:2-Cl-phenyl; 2-F-6-F-phenyl; 3-Cl-phenyl; 3-CF 3 -phenyl; 4-Cl-phenyl; 4-Br-phenyl; 4-I-phenyl; 3-Cl, 4-Cl-phenyl; 3-CF 3 , 4-Cl-phenyl; 3-Cl, 5-Cl-phenyl; 3-CF 3 , 5-F-phenyl ;, 3-CF 3 , 5-Cl-phenyl; 3-CF 3 , 5-CF 3 -phenyl; 3-Cl, 4-Cl, 5-Cl-phenyl; 3-F, 3-Cl, 4-OCH 3 , 5-Cl-phenyl; 3-Cl, (4) -OCH 2 O- (5) -phenyl; 3-Cl, (4) -OCF 2 O- (5) -phenyl; 3-Cl "4-OCH3, 5-OCH 3 -phenyl; 3-Cl, (4) -OCH 2 CH 2 - (5) -phenyl; and 3-OCH 3 , 5-CF 3 -phenyl. The active compounds according to the invention are suitable for plant tolerance, favorable warm-blood toxicity and good environmental compatibility for the protection of plants and plant organs, for increasing crop yields, improving the quality of the crop and for controlling animal pests, in particular insects, arachnids, helminths, nematodes and molluscs which are found in agriculture, horticulture, livestock, forests, gardens and recreational facilities, in the protection of materials and materials and in the hygiene sector. They can preferably be used as crop protection agents. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The above mentioned pests include:
Aus der Ordnung der Anoplura (Phthiraptera) z.B. Damalinia spp., Haematopinus spp., Li- nognathus spp., Pediculus spp., Trichodectes spp..From the order of the Anoplura (Phthiraptera) e.g. Damalinia spp., Haematopinus spp., Ligognathus spp., Pediculus spp., Trichodectes spp.
Aus der Klasse der Arachnida z.B. Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia 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, Polyphago- tarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici.From the class of arachnids, e.g. Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia 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, Polyphago- tarsonemus latus, Psoroptes spp., Rhipicephalus spp , Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici.
Aus der Klasse der Bivalva z.B. Dreissena spp..From the class of bivalva, e.g. Dreissena spp ..
Aus der Ordnung der Chilopoda z.B. Geophilus spp., Scutigera spp..From the order of Chilopoda e.g. Geophilus spp., Scutigera spp.
Aus der Ordnung der Coleoptera z.B. Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zea- landica, Curculio spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica spp., Epilachna spp., Faustinus cubae, Gibbium psylloides, Heteronychus arator, Hylamorpha elegans, Hylotrupes baju- lus, Hypera postica, Hypothenemus spp., Lachnosterna consanguinea, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp., Meligethes aeneus, Melolontha melolontha, Migdolus spp., Monochamus spp., Naupactus xanthographus, Niptus hololeucus, Oryctes rhino- ceros, Oryzaephilus surinamensis, Otiorrhynchus sulcatus, Oxycetonia jucunda, Phaedon cochlea- riae, Phyllophaga spp., Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Sternechus spp., Symphyletes spp., Tenebrio molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp..From the order Coleoptera eg Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apogonia spp., Atomaria spp., Attagenus spp. Bruchidius obtectus, Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Curculio spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica spp., Epilachna spp., Faustinus cubae, Gibbium psylloides, Heteronychus arator, Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnosterna consanguinea, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp., Meligethes aeneus, Melolontha melolontha, Migdolus spp., Monochamus spp. , Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Otiorrhynchus sulcatus, Oxycetonia jucunda, Phaedon cochleareae, Phyllophaga spp., Popillia japonica, Premnotrypes spp. , Psylliodes chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Starchus spp., Symphyletes spp., Tenebrio molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp.
Aus der Ordnung der Collembola z.B. Onychiurus armatus.From the order of Collembola e.g. Onychiurus armatus.
Aus der Ordnung der Dermaptera z.B. Forficula auricularia.From the order of the Dermaptera e.g. Forficula auricularia.
Aus der Ordnung der Diplopoda z.B. Blaniulus guttulatus.From the order of diplopoda e.g. Blaniulus guttulatus.
Aus der Ordnung der Diptera z.B. Aedes spp., Anopheles spp., Bibio hortulanus, Calliphora e- rythrocephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dermatobia hominis, Drosophila spp., Fannia spp., Gastrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp.. Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Sto- moxys spp., Tabanus spp., Tannia spp., Tipula paludosa, Wohlfahrtia spp.From the order of Diptera e.g. Aedes spp., Anopheles spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dermatobia hominis, Drosophila spp., Fannia spp , Gastrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp. Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp. moxys spp., Tabanus spp., Tannia spp., Tipula paludosa, Wohlfahrtia spp.
Aus der Klasse der Gastropoda z.B. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp..From the class Gastropoda, e.g. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.
Aus der Klasse der Helminthen z.B. Ancylostoma duodenale, Ancylostoma ceylanicum, Acylosto- ma 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., Hymeno- lepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp, Strongyloides fuellebomi, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinel- Ia spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.From the class of helminths e.g. 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., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp. , Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosome spp, Strongyloides fuellebomi, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp ., Trichuris trichuria, Wuchereria bancrofti.
Weiterhin lassen sich Protozoen, wie Eimeria, bekämpfen.Furthermore, protozoa, such as Eimeria, can be combated.
Aus der Ordnung der Heteroptera z.B. Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus seria- tus, Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp. Aus der Ordnung der Homoptera z.B. Acyrthosipon spp., Aeneolamia spp., Agonoscena spp., A- leurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui, Aoni- diella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus spp., A- tanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevi- coryne brassicae, Calligypona marginata, Cameocephala fulgida, Ceratovacuna lanigera, Cercopi- dae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chro- maphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., Doralis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Geococcus coffeae, Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari, Metcalfϊella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Parabemi- sia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pte- romalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopa- losiphum spp., Saissetia spp., Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes vaporariorum, Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii.From the order of the Heteroptera eg Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp , Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus seriatetus , Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp. From the order of Homoptera eg Acyrthosipon spp., Aeneolamia spp., Agonoscena spp., A- leurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui, Aodialella spp., Aphanostigma piri, Aphis spp. , Arboridia apicalis, Aspidiella spp., Aspidiotus spp., A tanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Cameocephala fulgida, Ceratovacuna lanigera, Cercopida, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp. Doralis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Geococcus coffeae, Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp ., Laodelph ax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari, Metcalfella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens , Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria Pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhapasophum spp., Saissetia spp., Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes vaporariorum, Trioz a spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii.
Aus der Ordnung der Hymenoptera z.B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp..From the order of Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
Aus der Ordnung der Isopoda z.B. Armadillidium vulgäre, Oniscus asellus, Porcellio scaber.From the order of isopods e.g. Armadillidium vulgaris, Oniscus asellus, Porcellio scaber.
Aus der Ordnung der Isoptera z.B. Reticulitermes spp., Odontotermes spp..From the order of Isoptera e.g. Reticulitermes spp., Odontotermes spp.
Aus der Ordnung der Lepidoptera z.B. Acronicta major, Aedia leucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoe- cia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp., Choristo- neura fumiferana, CIy sia ambiguella, Cnaphalocerus spp., Earias insulana, Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp., FeI tia spp., Galleria mellonella, Helicoverpa spp., Heliothis spp., Hofmannophila pseudospretella, Homona magnanima, Hyponomeuta padella, Laphygma spp., Lithocolletis blancardella, Lithophane antennata, Loxagrotis albicosta, Lymantria spp., MaIa- cosoma neustria, Mamestra brassicae, Mocis repanda, Mythimna separata, Oria spp., Oulema ory- zae, Panolis flammea, Pectinophora gossypiella, Phyllocnistis citrella, Pieris spp., Plutella xylo- stella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp..From the order of Lepidoptera, for example Acronicta major, Aedia leucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Caceacia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp. Choristoneura fumiferana, CIyia ambiguella, Cnaphalocerus spp., Earias insulana, Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp., FeI tia spp., Galleria mellonella, Helicoverpa spp., Heliothis spp., Hofmannophila pseudospretella, Homona magnanima, Hyponomeuta padella , Laphygma spp., Lithocolletis blancardella, Lithophane antennata, Loxagrotis albicosta, Lymantria spp., Malacosoma neustria, Mamestra brassicae, Mocis rep., Mythimna separata, Oria spp., Oulema ory- zae, Panolis flammea, Pectinophora gossypiella, Phyllocnistis citrella, Pieris spp., Plutella xylostella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp ..
Aus der Ordnung der Orthoptera z.B. Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.From the order of Orthoptera e.g. Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.
Aus der Ordnung der Siphonaptera z.B. Ceratophyllus spp., Xenopsylla cheopis.From the order of siphonaptera e.g. Ceratophyllus spp., Xenopsylla cheopis.
Aus der Ordnung der Symphyla z.B. Scutigerella immaculata.From the order of Symphyla e.g. Scutigerella immaculata.
Aus der Ordnung der Thysanoptera z.B. Baliothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scir- tothrips spp., Taeniothrips cardamoni, Thrips spp..From the order of Thysanoptera e.g. Baliothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirothrips spp., Taeniothrips cardamoni, Thrips spp.
Aus der Ordnung der Thysanura z.B. Lepisma saccharina.From the order of Thysanura e.g. Lepisma saccharina.
Zu den pflanzenparasitären Nematoden gehören z.B. Anguina spp., Aphelenchoides spp., Belono- aimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Roty- lenchus spp., Trichodorus spp., Tylenchorhynchus spp., Tylenchulus spp., Tylenchulus semipe- netrans, Xiphinema spp..The plant parasitic nematodes include e.g. Anguina spp., Aphelenchoides spp., Belonoclampus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Rotary Lenchus spp., Trichodorus spp., Tylenchorhynchus spp., Tylenchulus spp., Tylenchulus semipetnetrans, Xiphinema spp.
Die erfϊndungsgemäßen Verbindungen können gegebenenfalls in bestimmten Konzentrationen bzw. Aufwandmengen auch als Herbizide, Safener, Wachstumsregulatoren oder Mittel zur Verbes- serung der Pflanzeneigenschaften, oder als Mikrobizide, beispielsweise als Fungizide, Antimykoti- ka, Bakterizide, Virizide (einschließlich Mittel gegen Viroide) oder als Mittel gegen MLO (My- coplasma-like-organism) und RLO (Rickettsia-like-organism) verwendet werden. Sie lassen sich gegebenenfalls auch als Zwischen- oder Vorprodukte für die Synthese weiterer Wirkstoffe einsetzen.If appropriate, the compounds according to the invention may also be used in certain concentrations or application rates 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-organism) and RLO (Rickettsia-like-organism) can be used. If appropriate, they can also be used as intermediates or precursors for the synthesis of further active ingredients.
Die Wirkstoffe können in die üblichen Formulierungen überführt werden, wie Lösungen, Emulsionen, Spritzpulver, wasser- und ölbasierte Suspensionen, Pulver, Stäubemittel, Pasten, lösliche Pulver, lösliche Granulate, Streugranulate, Suspensions-Emulsions-Konzentrate, Wirkstoff-imprägnierte Naturstoffe, Wirkstoff-imprägnierte synthetische Stoffe, Düngemittel sowie Feinst- verkapselungen in polymeren Stoffen. Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Die Herstellung der Formulierungen erfolgt entweder in geeigneten Anlagen oder auch vor oder während der Anwendung.The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, scattering granules, suspension-emulsion concentrates, active substance-impregnated natural products, active ingredient impregnated synthetic materials, fertilizers and micro-encapsulants in polymeric materials. These formulations are prepared in a known manner, for example by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents. The preparation of the formulations is carried out either in suitable systems or before or during use.
Als Hilfsstoffe können solche Stoffe Verwendung finden, die geeignet sind, dem Mittel selbst oder und/oder davon abgeleitete Zubereitungen (z.B. Spritzbrühen, Saatgutbeizen) besondere Eigenschaften zu verleihen, wie bestimmte technische Eigenschaften und/oder auch besondere biologische Eigenschaften. Als typische Hilfsmittel kommen in Frage: Streckmittel, Lösemittel und Trä- gerstoffe.Excipients which can be used are those which are suitable for imparting special properties to the composition itself and / or preparations derived therefrom (for example spray liquor, seed dressing), such as certain technical properties and / or specific biological properties. Typical auxiliaries are: extenders, solvents and carriers.
Als Streckmittel eignen sich z.B. Wasser, polare und unpolare organische chemische Flüssigkeiten z.B. aus den Klassen der aromatischen und nicht-aromatischen Kohlenwasserstoffe (wie Paraffine, Alkylbenzole, Alkylnaphthaline, Chlorbenzole), der Alkohole und Polyole (die ggf. auch substituiert, verethert und/oder verestert sein können), der Ketone (wie Aceton, Cyclohexanon), Ester (auch Fette und Öle) und (poly-)Ether, der einfachen und substituierten Amine, Amide, Lactame (wie N-Alkylpyrrolidone) und Lactone, der Sulfone und Sulfoxide (wie Dimethylsysulfoxid).As extender, e.g. Water, polar and non-polar organic chemical liquids e.g. from the classes of aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (which may also be substituted, etherified and / or esterified), ketones (such as acetone, cyclohexanone), Esters (including fats and oils) and (poly) ethers, simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide).
Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösemittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösemittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, oder Alkylnaphthaline, chlorierte Aromaten und chlorierte aliphati- sehe Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, mineralische und pflanzliche Öle, Alkohole, wie Butanol oder Glykol sowie deren Ether und Ester, Ketone wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylsulfoxid, sowie Wasser.In the case of using water as an extender, e.g. also organic solvents can be used as auxiliary solvent. Suitable liquid solvents are essentially: 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, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl sulfoxide, and water.
Als feste Trägerstoffe kommen in Frage:Suitable solid carriers are:
z.B. Ammoniumsalze und natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate, als feste Trägerstoffe für Granulate kommen in Frage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Papier, Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengeln; als Emulgier- und/oder schaumerzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsäure-Ester, Polyoxyethylen-Fettalkohol- Ether, z.B. Alkylaryl-polyglykolether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweiß- hydrolysate; als Dispergiermittel kommen in Frage nicht-ionische und/oder ionische Stoffe, z.B. aus den Klassen der Alkohol-POE- und/oder POP-Ether, Säure- und/oder POP- POE-Ester, Alkyl- Aryl- und/oder POP- POE-Ether, Fett- und/oder POP- POE-Addukte, POE- und/oder POP-Polyol Derivate, POE- und/oder POP-Sorbitan- oder-Zucker-Addukte, Alky- oder Aryl-Sulfate, Sulfonate und Phosphate oder die entsprechenden PO-Ether-Addukte. Ferner geeignete Oligo- oder Polymere, z.B. ausgehend von vinylischen Monomeren, von Acrylsäure, aus EO und/oder PO allein oder in Verbindung mit z.B. (poly-) Alkoholen oder (poly-) Aminen. Ferner können Einsatz finden Lig- nin und seine Sulfonsäure-Derivate, einfache und modifizierte Cellulosen, aromatische und/oder aliphatische Sulfonsäuren sowie deren Addukte mit Formaldehyd.For example, ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals, such as finely divided silica, alumina and silicates, as solid carriers for granules in question: eg broken and fractionated natural rocks such Calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as paper, sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol Ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are nonionic and / or ionic substances, for example from the classes of alcohol POE and / or POP ethers, acid and / or POPPOE esters, alkylaryl and / or POP POE ethers, fatty and / or POP-POE adducts, POE and / or POP polyol derivatives, POE and / or POP sorbitol or sugar adducts, alkyl or aryl sulfates, sulfonates and phosphates or the corresponding PO-ether adducts. Further suitable oligo- or polymers, for example starting 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 liginine and its sulfonic acid derivatives, simple and modified celluloses, aromatic and / or aliphatic sulfonic acids and also adducts thereof with formaldehyde.
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulvrige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, PoIy- vinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine und synthetische Phospholipide.Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-type polymers can be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins and synthetic phospholipids.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und Metallphthalocyaninfarbstoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Weitere Additive können Duftstoffe, mineralische oder vegetabile gegebenenfalls modifizierte Öle, Wachse und Nährstoffe (auch Spurennährstoffe), wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink sein.Other additives may be fragrances, mineral or vegetable optionally modified oils, waxes and nutrients (also trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Weiterhin enthalten sein können Stabilisatoren wie Kältestabilisatoren, Konservierungsmittel, Oxi- dationsschutzmittel, Lichtschutzmittel oder andere die chemische und / oder physikalische Stabilität verbessernde Mittel.Stabilizers, such as low-temperature stabilizers, preservatives, antioxidants, light stabilizers or other agents which improve the chemical and / or physical stability, may furthermore be present.
Die Formulierungen enthalten im allgemeinen zwischen 0,01 und 98 Gew.-% Wirkstoff, vorzugsweise zwischen 0,5 und 90 %.The formulations generally contain between 0.01 and 98% by weight of active ingredient, preferably between 0.5 and 90%.
Der erfindungsgemäße Wirkstoff kann in seinen handelsüblichen Formulierungen sowie in den aus diesen Formulierungen bereiteten Anwendungsformen in Mischung mit anderen Wirkstoffen wie Insektiziden, Lockstoffen, Sterilantien, Bakteriziden, Akariziden, Nematiziden, Fungiziden, wachs- tumsregulierenden Stoffen, Herbiziden, Safenern, Düngemitteln oder Semiochemicals vorliegen.The active ingredient according to the invention can be present in its commercial formulations as well as in the formulations prepared from these formulations in admixture with other active ingredients such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners, fertilizers or semiochemicals.
Besonders günstige Mischpartner sind z.B. die folgenden: Fungizide:Particularly favorable mixing partners are, for example, the following: fungicides:
(1) Inhibitoren der Nukleinsäuresynthese, wie beispielsweise Benalaxyl, Benalaxyl-M, Bupirimat, Clozylacon, Dimethirimol, Ethirimol, Furalaxyl, Hymexazol, Metalaxyl, Metalaxyl-M, Ofurace, Oxadixyl und Oxolinsäure.(1) inhibitors of nucleic acid synthesis such as benalaxyl, benalaxyl-M, bupirimate, clozylacon, dimethirimol, ethirimol, furalaxyl, hymexazole, metalaxyl, metalaxyl-M, ofurace, oxadixyl and oxolic acid.
(2) Inhibitoren der Mitose und Zellteilung, wie beispielsweise Benomyl, Carbendazim, Chlorfenazol, Diethofencarb, Ethaboxam, Fuberidazol, Pencycuron, Thiabendazol, Thiophanat, Thiophanat-Methyl und Zoxamid.(2) Mitosis and cell division inhibitors such as benomyl, carbendazim, chlorfenazole, diethofencarb, ethaboxam, fuberidazole, pencycuron, thiabendazole, thiophanate, thiophanate-methyl and zoxamide.
(3) Inhibitoren der Respiration (Atmungsketten-Inhibitoren), wie beispielsweise Diflumetorim als Inhibitor am Komplex I der Atmungskette; Bixafen, Boscalid, Carboxin, Fenfuram, Flutolanil, Fluopyram, Furametpyr, Furmecyclox, Isopyrazam (Mischung aus dem syn-epimeren Razemat 1RS,4SR,9RS und dem anti-epimeren Razemat 1RS,4SR,9SR), Isopyrazam (syn epimeres Razemat 1RS,4SR,9RS), Isopyrazam (syn-epimeres Enantiomer 1R,4S,9R), Isopyrazam (syn-epimeres Enantiomer 1S,4R,9S), Isopyrazam (anti-epimeres Razemat 1RS,4SR,9SR), Isopyrazam (anti- epimeres Enantiomer 1R,4S,9S), Isopyrazam (anti-epimeres Enantiomer 1S,4R,9R),(3) inhibitors of respiration (respiratory chain inhibitors), such as diflumetorim as an inhibitor at complex I of the respiratory chain; Bixafen, boscalid, carboxin, fenfuram, flutolanil, fluopyram, furametpyr, furmecyclox, isopyrazam (mixture of the syn-epimeric racemate 1RS, 4SR, 9RS and the anti-epimeric racemate 1RS, 4SR, 9SR), isopyrazam (syn epimeric racemate 1RS, 4SR, 9RS), isopyrazam (syn-epimeric enantiomer 1R, 4S, 9R), isopyrazam (syn-epimeric enantiomer 1S, 4R, 9S), isopyrazam (anti-epimeric racemate 1RS, 4SR, 9SR), isopyrazam (anti-epimeric enantiomer 1R, 4S, 9S), isopyrazam (anti-epimeric enantiomer 1S, 4R, 9R),
Mepronil, Oxycarboxin, Penflufen, Penthiopyrad, Sedaxane, Thifluzamid als Inhibitoren am Komplex π der Atmungskette; Amisulbrom, Azoxystrobin, Cyazofamid, Dimoxystrobin, Enestroburin, Famoxadon, Fenamidon, Fluoxastrobin, Kresoxim-Methyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin, Pyraoxystrobin, Pyrametostrobin, Pyribencarb, Trifloxystrobin als Inhibitoren am Komplex IE der Atmungskette.Mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, thifluzamide as inhibitors of the complex π of the respiratory chain; Amisulbrom, azoxystrobin, cyazofamide, dimoxystrobin, enestroburin, famoxadone, fenamidone, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyraoxystrobin, pyrametostrobin, pyribencarb, trifloxystrobin as inhibitors of complex IE in the respiratory chain.
(4) Entkoppler, wie beispielsweise Binapacryl, Dinocap, Fluazinam und Meptyldinocap.(4) decouplers such as binapacryl, dinocap, fluazinam and meptyldinocap.
(5) Inhibitoren der ATP Produktion, wie beispielsweise Fentin Acetat, Fentin Chlorid, Fentin Hydroxid und Silthiofam.(5) inhibitors of ATP production, such as, for example, fentin acetate, fentin chloride, fentin hydroxide and silthiofam.
(6) Inhibitoren der Aminosäure- und Protein-Biosynthese, wie beispielsweise Andoprim, Blasticidin-S, Cyprodinil, Kasugamycin, Kasugamycin Hydrochlorid Hydrat, Mepanipyrim und Pyrimethanil.(6) inhibitors of amino acid and protein biosynthesis, such as andoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim and pyrimethanil.
(7) Inhibitoren der Signaltransduktion, wie beispielsweise Fenpiclonil, Fludioxonil und Quinoxyfen.(7) signal transduction inhibitors such as fenpiclonil, fludioxonil and quinoxyfen.
(8) Inhibitoren der Lipid- und Membran-Synthese, wie beispielsweise Biphenyl, Chlozolinat, Edifenphos, Etridiazol, Iodocarb, Iprobenfos, Iprodion, Isoprothiolan, Procymidon, Propamocarb, Propamocarb Hydrochlorid, Pyrazophos, Tolclofos-Methyl und Vinclozolin.(8) Inhibitors of lipid and membrane synthesis, such as biphenyl, chlozolinate, edifenphos, etridiazole, iodocarb, Iprobenfos, iprodione, isoprothiolane, procymidone, propamocarb, propamocarb hydrochloride, pyrazophos, tolclofos-methyl and vinclozolin.
(9) Inhibitoren der Ergosterol-Biosynthese, wie beispielsweise Aldimorph, Azaconazol, Bitertanol, Bromuconazol, Cyproconazol, Diclobutrazol, Difenoconazol, Diniconazol, Diniconazol-M, Dodemorph, Dodemoφh Acetat, Epoxiconazol, Etaconazol, Fenarimol, Fenbuconazol, Fenhexamid, Fenpropidin, Fenpropimoφh, Fluquinconazol, Flurprimidol, Flusilazol, Flutriafol, Furconazol, Furconazol-Cis, Hexaconazol, Imazalil, Imazalil Sulfat, Imibenconazol, Ipconazol, Metconazol, Myclobutanil, Naftifin, Nuarimol, Oxpoconazol, Paclobutrazol, Pefurazoat, Penconazol, Piperalin, Prochloraz, Propiconazol, Prothioconazol, Pyributicarb, Pyrifenox, Quinconazol, Simeconazol, Spiroxamin, Tebuconazol, Terbinafin, Tetraconazol, Triadimefon, Triadimenol, Tridemoφh, Triflumizol, Triforin, Triticonazol, Uniconazol, Viniconazol und Voriconazol.(9) inhibitors of ergosterol biosynthesis, such as aldimorph, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, Dodemorph, Dodemoφh Acetate, Epoxiconazole, Etaconazole, Fenarimol, Fenbuconazole, Fenhexamid, Fenpropidin, Fenpropimoφh, Fluquinconazole, Flurprimidol, Flusilazole, Flutriafol, Furconazole, Furconazole Cis, Hexaconazole, Imazalil, Imazalil Sulfate, Imibenconazole, Ipconazole, Metconazole, Myclobutanil, Naftifine, Nuarimol, Oxpoconazole, Paclobutrazol, Pefurazoate, Penconazole, Piperaline, Prochloraz, Propiconazole, Prothioconazole, Pyributicarb, Pyrifenox, Quinconazole, Simeconazole, Spiroxamine, Tebuconazole, Terbinafine, Tetraconazole, Triadimefon, Triadimenol, Tridemoφh, Triflumizol, Triforin, Triticonazole, Uniconazole, Viniconazole and voriconazole.
(10) Inhibitoren der Zellwandsynthese, wie beispielsweise Benthiavalicarb, Dimethomoφh, Flumoφh, Iprovalicarb, Mandipropamid, Polyoxins, Polyoxorim, Prothiocarb, Validamycin A und Valefenalat.(10) inhibitors of cell wall synthesis, such as Benthiavalicarb, Dimethomoφh, Flumoφh, Iprovalicarb, Mandipropamid, Polyoxins, Polyoxorim, Prothiocarb, Validamycin A and valefenalate.
(11) Inhibitoren der Melanin-Biosynthese, wie beispielsweise Caφropamid, Diclocymet, Fenoxanil, Fthalid, Pyroquilon und Tricyclazol.(11) inhibitors of melanin biosynthesis, such as, for example, caryropamide, diclocymet, fenoxanil, fthalide, pyroquilone and tricyclazole.
(12) Resistenzinduktoren, wie beispielsweise Acibenzolar-S-Methyl, Probenazol und Tiadinil.(12) resistance inducers such as acibenzolar-S-methyl, probenazole and tiadinil.
(13) Verbindungen mit Multisite-Aktivität, wie beispielsweise Bordeauxmischung, Captafol, Captan, Chlorothalonil, Kupfernaphthenat, Kupferoxid, Kupferoxychlorid, Kupferzubereitungen, wie(13) Compounds with multisite activity, such as Bordeaux mixture, captafol, captan, chlorothalonil, copper naphthenate, copper oxide, copper oxychloride, copper preparations, such as
Kupferhydroxid, Kupfersulfat, Dichlofluanid, Dithianon, Dodine und dessen freie Base, Ferbam, Fluorofolpet, Folpet, Guazatin, Guazatinacetat, Iminoctadin, Iminoctadinalbesilat, Iminoctadintriacetat, Mankupfer, Mancozeb, Maneb, Metiram, Zinkmetiram, Kupfer-Oxin, Propamidin, Propineb, Schwefel und Schwefelzubereitungen wie beispielsweise Calciumpolysulfid, Thiram, Tolylfluanid, Zineb und Ziram.Copper hydroxide, copper sulfate, dichlofluanid, dithianon, dodine and its free base, ferbam, fluorofolpet, folpet, guazatine, guazatine acetate, iminoctadine, iminoctadinalesilate, iminoctadine triacetate, mancopper, mancozeb, maneb, metiram, zinc metiram, copper oxine, propamidine, propineb, sulfur and Sulfur preparations such as calcium polysulfide, thiram, tolylfluanid, zineb and zircon.
(14) Weitere Verbindungen, wie beispielsweise 2,3-Dibutyl-6-chlorthieno[2,3-d]pyrimidin-4(3H)-on, (2Z)-3-Amino-2-cyano-3-phenylprop-2-ensäureethylester, N-[2-(l,3-Dimethylbutyl)phenyl]-5-fluor- 1 ,3 -dimethyl- 1 H-pyrazol-4-carboxamid, 3 -(Difluormethyl)- 1 -methyl-N-(3 ',4',5 '-trifluorbiphenyl-2-yl)- lH-pyrazol-4-carboxamid, 3-(Difluormethyl)-N-[4-fluor-2-(l,l,2,3,3,3-hexafluoφropoxy)phenyl]-l- methyl- 1 H-pyrazol-4-carboxamid, (2E)-2-(2- { [6-(3 -Chlor-2-methylphenoxy)-5-fluoφyrirnidin-4- yl]oxy}phenyl)-2-(methoxyimino)-N-methylethanamid) (2E)-2-{2-[({[(2E,3E)-4-(2,6-(14) Other compounds such as 2,3-dibutyl-6-chlorothieno [2,3-d] pyrimidin-4 (3H) -one, (2Z) -3-amino-2-cyano-3-phenylprop-2 ethylenoic acid, N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide, 3- (difluoromethyl) -1-methyl-N- ( 3 ', 4', 5'-trifluorobiphenyl-2-yl) - lH-pyrazole-4-carboxamide, 3- (difluoromethyl) -N- [4-fluoro-2- (1, l, 2,3,3, 3-hexafluoropropoxy) phenyl] -1-methyl-1H-pyrazole-4-carboxamide, (2E) -2- (2- {[6- (3-chloro-2-methylphenoxy) -5-fluoro-pyrirnidin-4-yl ] oxy} phenyl) -2- (methoxyimino) -N-methylethanamide ) (2E) -2- {2 - [({[(2E, 3E) -4- (2,6-
Dichloφhenyl)but-3-en-2-yliden]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylethanamid, 2-Chlor-N-(l,l,3-trimethyl-2,3-dihydro-lH-inden-4-yl)pyridin-3-carboxamid, N-(3-Ethyl-3,5,5- trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamid, 5-Methoxy-2-methyl-4-(2-{[({(lE)-l-[3- (trifluormethyl)phenyl]ethyliden}amino)oxy]methyl}phenyl)-2,4-dihydro-3H-l ,2,4-triazol-3-on, (2E)- 2-(Methoxyimino)-N-methyl-2-(2- { [( {( 1 E)- 1 -[3 -Dichloro-phenyl) -but-3-en-2-ylidene] -amino} oxy) -methyl] -phenyl} -2- (methoxyimino) -N-methylethaneamide, 2-chloro-N- (1,1,3-trimethyl-2,3- dihydro-1H-inden-4-yl) pyridine-3-carboxamide, N- (3-ethyl-3,5,5-trimethylcyclohexyl) -3- (formylamino) -2-hydroxybenzamide, 5-methoxy-2-methyl- 4- (2 - {[({(ILE) -1- [3- (trifluoromethyl) phenyl] ethylidene} amino) oxy] methyl} phenyl) -2,4-dihydro-3H-1,2,4-triazole 3-one, (2E) - 2- (methoxyimino) -N-methyl-2- (2- {[({(1 E) - 1 - [3 -
(trifluormethyl)phenyl]ethyliden}amino)oxy]methyl}phenyl)ethanamid, (2E)-2-(Methoxyimino)-N- methyl-2- {2-[(E)-( { 1 -[3-(trifluormethyl)phenyl]ethoxy}imino)methyl]phenyl}ethanamid, (2E)-2- {2- [( { [( 1 E)- 1 -(3- { [(E)- 1 -Fluor-2-phenylethenyl]oxy}phenyl)ethyliden]amino} oxy)methyl]phenyl} -2- (methoxyimino)-N-methylethanamid, 1 -(4-Chlorphenyl)-2-( IH-1 ,2,4-triazol- 1 -yl)cycloheptanol, 1 - (2,2-Dimethyl-2,3-dihydro-lH-inden-l-yl)-lH-imidazol-5-carbonsaeuremethylester, N-Ethyl-N- methyl-N'-{2-methyl-5-(trifluormethyl)-4-[3-(trimethylsilyl)propoxy]phenyl}imidoformaniid, N'-{5- (Difluorme1hyl)-2-methyl-4-[3-(1rimethylsilyl)propoxy]phenyl}-N-ethyl-N-methylimidoforrnamid, O- { 1 -[(4-Methoxyphenoxy)methyl]-2,2-dimethylpropyl } 1 H-imidazol- 1 -carbothioat, N-[2-(4- { [3 -(4- Chloφhenyl)prop-2-yn- 1 -yl] oxy } -3 -methoxyphenyl)ethyl] -N2-(methylsulfonyl)valinamid, 5-Chlor-7- (4-methylpiperidin-l-yl)-6-(2,4,6-trifluoφhenyl)[l,2,4]triazolo[l,5-a]pyrimidin, 5-Amino-l,3,4- thiadiazol-2-thiol, Propamocarb-Fosetyl, l-[(4-Methoxyphenoxy)methyl]-2,2-dimethylpropyl IH- imidazol- 1 -carboxylat, 1 -Methyl-N-[2-( 1 , 1 ,2,2-tetrafluorethoxy)phenyl]-3-(trifluormethyl)- 1 H- pyrazol-4-carboxamid, 2,3,5,6-TetracMor-4-(methylsulfonyl)pyridin, 2-Butoxy-6-iod-3-propyl-4H- chromen-4-on, 2-Phenylphenol und dessen Salze, 3-(Difluormethyl)-l-methyl-N-[2-(l, 1,2,2- tetrafluorethoxy)phenyl]-lH-pyrazol-4-carboxamid, 3,4,5-Trichlorpyridin-2,6-dicarbonitril, 3-[5-(4- Chloφhenyl)-2,3-dimethylisoxazolidin-3-yl]pyridin, 3-Chlor-5-(4-chloφhenyl)-4-(2,6-difluoφhenyl)- 6-methylpyridazin, 4-(4-Chlθφhenyl)-5-(2,6-difluoφhenyl)-3,6-dimethylpyridazin, 8-(trifluoromethyl) phenyl] ethylidene} amino) oxy] methyl} phenyl) ethanamide, (2E) -2- (methoxyimino) -N-methyl-2- {2 - [(E) - ({1- [3- (trifluoromethyl ) phenyl] ethoxy} imino) methyl] phenyl} ethanamide, (2E) -2- {2- [({[(1E) -1- (3- {[(E) -1-Fluoro-2-phenylethenyl] oxy} phenyl) ethylidene] amino} oxy) methyl] phenyl} -2- (methoxyimino) -N -methylethanamide, 1- (4-chlorophenyl) -2- (IH-1, 2,4-triazol-1-yl) cycloheptanol, 1- (2,2-dimethyl-2,3-dihydro-1H-indene-1 -yl) -1H-imidazole-5-carboxylic acid methyl ester, N-ethyl-N-methyl-N '- {2-methyl-5- (trifluoromethyl) -4- [3- (trimethylsilyl) propoxy] phenyl} imidoformanide, N' - {5- (Difluoromethyl) -2-methyl-4- [3- (1-trimethylsilyl) propoxy] phenyl} -N-ethyl-N-methylimidoforrnamide, O- {1 - [(4-methoxyphenoxy) methyl] -2,2 -dimethylpropyl} 1H-imidazole-1-carbothioate, N- [2- (4- {[3- (4-chlorophenyl) -prop-2-yn-1-yl] oxy} -3-methoxyphenyl) -ethyl] -N 2 - (methylsulfonyl) valinamide, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) [l, 2,4] triazolo [l, 5-a] pyrimidine , 5-amino-l, 3,4-thiadiazole-2-thiol, propamocarb-fosetyl, 1- [(4-methoxyphenoxy) methyl] -2,2-dimethylpropyl-IH-imidazole-1-carboxylate, 1-methyl-N [2- (1,1,2,2-tetrafluoroethoxy) phenyl] -3- (trifluoromethyl) -1H-pyrazole 4-carboxamide, 2,3,5,6-tetracorm-4- (methylsulfonyl) pyridine, 2-butoxy-6-iodo-3-propyl-4H-chromen-4-one, 2-phenylphenol and its salts, (Difluoromethyl) -1-methyl-N- [2- (1,2,2-tetrafluoroethoxy) phenyl] -1H-pyrazole-4-carboxamide, 3,4,5-trichloropyridine-2,6-dicarbonitrile, 3 - [5- (4-chloro-phenyl) -2,3-dimethyl-isoxazolidin-3-yl] pyridine, 3-chloro-5- (4-chloro-phenyl) -4- (2,6-difluoro-phenyl) -6-methyl-pyridazine, 4- (4-chloro-phenyl) -5- (2,6-difluoro-phenyl) -3,6-dimethyl-pyridazine, 8-
Hydroxychinolin, 8-Hydroxychinolinsulfat, Tebufloquin, 5-Methyl-6-octyl-3,7- dihydro[ 1 ,2,4]triazolo[ 1 ,5-a]pyrimidin-7-amin, 5-Ethyl-6-octyl-3 ,7-dihydro[ 1 ,2,4]triazolo[ 1 ,5- a]pyrimidin-7-amin, Ametoctradin, Benthiazol, Bethoxazin, Capsimycin, Carvon, Chinomethionat, Chloroneb, Cufraneb, Cyflufenamid, Cymoxanil, Cyprosulfamide, Dazomet, Debacarb, Dichlorophen, Diclomezin, Dicloran, Difenzoquat, Difenzoquat Methylsulphat, Diphenylamin, Ecomat, Ferimzon, Flumetover, Fluopicolid, Fluoromid, Flusulfamid, Flutianil, Fosetyl-Aluminium, Fosetyl-Calcium, Fosetyl-Natrium, Hexachlorbenzol, Irumamycin, Isotianil, Methasulfocarb, (2E)-2-{2- [({Cyclopropyl[(4-methoxyphenyl)imino]methyl}thio)methyl]phenyl}-3- methoxyacrylsaeuremethylester, Methylisothiocyanat, Metrafenon, (5-Chlor-2-methoxy-4- methylpyridin-3-yl)(2,3,4-trimethoxy-6-methylphenyl)methanon, Mildiomycin, Tolnifanid, N-(4- Chlorbenzyl)-3-[3-methoxy-4-(prop-2-yn-l-yloxy)phenyl]propanamid, N-[(4-Hydroxyquinoline, 8-hydroxyquinoline sulfate, tebufloquine, 5-methyl-6-octyl-3,7-dihydro [1,2,4] triazolo [1,5-a] pyrimidin-7-amine, 5-ethyl-6-octyl 3, 7-dihydro [1,2,4] triazolo [1,5-a] pyrimidin-7-amine, ametoctradin, benthiazole, bethoxazine, capsimycin, carvone, quinomethionate, chloroneb, cufraneb, cyflufenamid, cymoxanil, cyprosulfamide, dazomet, Debacarb, dichlorophen, diclomethine, dicloran, difenzoquat, difenzoquat methylsulphate, diphenylamine, ecomat, ferimzone, flumetover, fluopicolide, fluoromide, flusulfamide, flutianil, fosetyl-aluminum, fosetyl-calcium, fosetyl-sodium, hexachlorobenzene, irumamycin, isotianil, methasulfocarb, ( 2E) -2- {2- [({cyclopropyl [(4-methoxyphenyl) imino] methyl} thio) methyl] phenyl} -3-methoxyacrylic acid methyl ester, methyl isothiocyanate, metrafenone, (5-chloro-2-methoxy-4-methylpyridine) 3-yl) (2,3,4-trimethoxy-6-methylphenyl) methanone, mildiomycin, tolnifanide, N- (4-chlorobenzyl) -3- [3-methoxy-4- (prop-2-yn-1-yloxy ) phenyl] propanamide, N - [(4-
Chloφhenyl)(cyano)methyl]-3-[3-methoxy-4-(prop-2-yn-l-yloxy)phenyl]propanamid, N-[(5-Brom-3- chloφyridin-2-yl)methyl]-2,4-dichlθφyridin-3-carboxamid, N-[l-(5-Brom-3-chloφyridin-2-yl)ethyl]- 2,4-dichloφyridin-3-carboxamid, N-[ 1 -(5-Brom-3-chlθφyridin-2-yl)ethyl]-2-fluor-4-iodpyridin-3- carboxamid, N-{(Z)-[(Cyclopropylmethoxy)imino][6-(difluormethoxy)-2,3-difluoφhenyl]methyl}-2- phenylacetamid, N-{(E)-[(Cyclopropylmethoxy)imino][6-(difluormethoxy)-2,3- difluoφhenyl]methyl}-2-phenylacetamid, Natamycin, Nickel Dimethyldithiocarbamat, Nitrothal- Isopropyl, Octhilinone, Oxamocarb, Oxyfenthiin, Pentachloφhenol und dessen Salze, Phenazin-1- carbonsäure, Phenothrin, Phosphorsäure und deren Salze, Propamocarb Fosetylat, Propanosin- Natrium, Proquinazid, Pyrrolnitrin, Quintozen, S-Prop-2-en-l-yl 5-amino-2-(l-methylethyl)-4-(2- methylphenyl)-3-oxo-2,3-dihydro-lH-pyrazol-l-carbothioat, Tecloftalam, Tecnazene, Triazoxid, TricMamid, 5-Chlor-N'-phenyl-N'-prop-2-yn-l-ylthiophen-2-sulfonohydrazid, Zarilamid, N-Methyl-2- (l-{[5-methyl-3-(trifluormethyl)-lH-pyrazol-l-yl]acetyl}piperidin^-yl)-N-[(lR)-l,2,3,4- tetrahydronaphthalen- 1 -yl] - 1 ,3 -thiazol-4-carboxamid, N-Methyl-2-( 1 - { [5 -methyl-3 -(trifluormethyl)- 1 H-pyrazol- 1 -yl] acetyl}piperidin-4-yl)-N-( 1 ,2,3 ,4-tetrahydronaphthalen- 1 -yl)- 1 ,3 -thiazol-4- carboxamid, 3-(Difluormethyl)-N-[4-fluor-2-( 1,1,2,3,3,3 -hexafluorpropoxy)phenyl] - 1 -methyl- 1 H- pyrazol-4-carboxamid und Pentyl-{6-[({[(l-methyl-lH-tetrazol-5- yl)(phenyl)methyliden]amino}oxy)methyl]pyridin-2-yl}carbamat.Chlorophenyl) (cyano) methyl] -3- [3-methoxy-4- (prop-2-yn-1-yloxy) phenyl] propanamide, N - [(5-bromo-3-chloropyridin-2-yl) methyl] -2,4-dichloro-pyridine-3-carboxamide, N- [1- (5-bromo-3-chloro-pyridin-2-yl) -ethyl] -2,4-dichloro-pyridine-3-carboxamide, N- [1- (5- Bromo-3-chloro-pyridin-2-yl) -ethyl] -2-fluoro-4-iodo-pyridine-3-carboxamide, N - {(Z) - [(cyclopropylmethoxy) -imino] [6- (difluoromethoxy) -2,3-difluoro-phenyl ] methyl} -2-phenylacetamide, N - {(E) - [(cyclopropylmethoxy) imino] [6- (difluoromethoxy) -2,3-difluorophenyl] methyl} -2-phenylacetamide, natamycin, nickel dimethyldithiocarbamate, nitrothal isopropyl, Octhilinone, oxamocarb, oxyfenthiine, pentachlorophenol and its salts, phenazine-1-carboxylic acid, phenothrin, phosphoric acid and its salts, propamocarb fosetylate, propanosine sodium, proquinazide, pyrrolnitrin, quintozene, S-prop-2-en-l-yl amino-2- (1-methylethyl) -4- (2-methylphenyl) -3-oxo-2,3-dihydro-1H-pyrazole-1-carbothioate, Tecloftalam, Tecnazene, triazoxide, Tricamido, 5-chloro-N'-phenyl-N'-prop-2-yn-1-ylthiophene-2-sulfonohydrazide, zarilamide, N-methyl-2- (1 - {[5-methyl-3- (trifluoromethyl) -LH-pyrazol-1-yl] -acetyl} -piperidin ^ -yl) -N - [(1R) -l, 2,3,4-tetrahydronaphthalen-1-yl] -1,3-thiazole-4-carboxamide, N -Methyl 2- (1 - {[5-methyl-3 - (trifluoromethyl) -1 H -pyrazol-1-yl] -acetyl} -piperidin-4-yl) -N- (1,3,3,4-tetrahydronaphthalene - 1 -yl) - 1, 3 -thiazole-4-carboxamide, 3- (difluoromethyl) -N- [4-fluoro-2- (1,1,2,3,3,3-hexafluoropropoxy) phenyl] -. 1 -methyl-1H-pyrazole-4-carboxamide and pentyl {6 - [({[(1-methyl-1H-tetrazol-5-yl) (phenyl) methylidene] amino} oxy) methyl] pyridin-2-yl } carbamate.
Bakterizide:bactericides:
Bronopol, Dichlorophen, Nitrapyrin, Nickel-Dimethyldithiocarbamat, Kasugamycin, Octhilinon, Furancarbonsäure, Oxytetracyclin, Probenazol, Streptomycin, Tecloftalam, Kupfersulfat und andere Kupfer-Zubereitungen.Bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.
Insektizide / Akarizide / Nematizide:Insecticides / acaricides / nematicides:
Die in dieser Beschreibung mit ihrem „common name" genannten Wirkstoffe sind beispielsweise aus „The Pesticide Manual" 14th Ed., British Crop Protection Council 2006, und der Webseite http://www.alanwood.net/pesticides bekannt.The active ingredients mentioned in this specification with their "common name" are known, for example, from "The Pesticide Manual" 14th Ed., British Crop Protection Council 2006, and the website http://www.alanwood.net/pesticides.
(1) Acetylcholinesterase (AChE) Inhibitoren, wie beispielsweise Carbamate, z.B. Alanycarb, Aldi- carb, Bendiocarb, Benfuracarb, Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosul- fan, Ethiofencarb, Fenobucarb, Formetanate, Furathiocarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Thiofanox, Triazamate, Trimethacarb, XMC und Xylylcarb; oder(1) Acetylcholinesterase (AChE) inhibitors such as carbamates, e.g. Alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxime, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamates, Trimethacarb, XMC and xylylcarb; or
Organophosphate, z.B. Acephate, Azamethiphos, Azinphos (-methyl, -ethyl), Cadusafos, ChIo- rethoxyfos, Chlorfenvinphos, Chlormephos, Chlorpyrifos (-methyl), Coumaphos, Cyanophos, De- meton-S-methyl, Diazinon, Dichlorvos/DDVP, Dicrotophos, Dimethoate, Dimethylvinphos, Disul- foton, EPN, Ethion, Ethoprophos, Famphur, Fenamiphos, Fenitrothion, Fenthion, Fosthiazate, Hep- tenophos, Isofenphos, Isopropyl O-(methoxyaminothio-phosphoryl) salicylate, Isoxathion, Ma- lathion, Mecarbam, Methamidophos, Methidathion, Mevinphos, Monocrotophos, Naled, Omethoa- te, Oxydemeton-methyl, Parathion (-methyl), Phenthoate, Phorate, Phosalone, Phosmet, Phospha- midon, Phoxim, Pirimiphos (-methyl), Profenofos, Propetamphos, Prothiofos, Pyraclofos, Pyri- daphenthion, Quinalphos, Sulfotep, Tebupirimfos, Temephos, Terbufos, Tetrachlorvinphos, Thio- meton, Triazophos, Triazamate, Triclorfon und Vamidothion. (2) GABA-gesteuerte Chlorid-Kanal -Antagonisten, wie beispielsweise Organochlorine, z.B. Chlordane und Endosulfan (alpha-); oder Fiprole (Phenylpyrazole), z.B. Ethiprole, Fipronil, Py- rafluprole und Pyriprole.Organophosphates, eg acephates, azamethiphos, azinphos (-methyl, -ethyl), cadusafos, chiorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos (-methyl), coumaphos, cyanophos, demeton-s-methyl, diazinon, dichlorvos / DDVP, Dicrotophos, Dimethoate, Dimethylvinphos, Disulphon, EPN, Ethion, Ethoprophos, Famphur, Fenamiphos, Fenitrothion, Fenthion, Fosthiazate, Heptenophos, Isofenphos, Isopropyl O- (methoxyaminothio-phosphoryl) salicylate, Isoxathion, Malathion, Mecarbam, Methamidophos, Methidathion, Mevinphos, Monocrotophos, Naled, Omethoat, Oxydemeton-methyl, Parathion (-methyl), Phenthoate, Phorate, Phosalone, Phosmet, Phosphoramide, Phoxim, Pirimiphos (-methyl), Profenofos, Propetamphos, Prothiofos, Pyraclofos, Pyridaphenthion, Quinalphos, Sulfotep, Tebupirimfos, Temephos, Terbufos, Tetrachlorvinphos, Thiometone, Triazophos, Triazamate, Triclorfon, and Vamidothion. (2) GABA-regulated chloride channel antagonists such as organochlorines, eg, chlordane and endosulfan (alpha); or fiproles (phenylpyrazoles), for example ethiprole, fipronil, pyrroliprole and pyriprole.
(3) Natrium-Kanal-Modulatoren / Spannungsabhängige Natrium-Kanal-Blocker, wie beispielswei- se Pyrethroide, z.B. Acrinathrin, Allethrin (d-cis-trans, d-trans), Bifenthrin, Bioallethrin, Bioal- lethrin-S-cyclopentenyl, Bioresmethrin, Cycloprothrin, Cyfluthrin (beta-), Cyhalothrin (gamma-, lambda-), Cypermethrin (alpha-, beta-, theta-, zeta-), Cyphenothrin [(lR)-trans-lsomeτe], Delta- methrin, Dimefluthrin, Empenthrin [(51Z)-(IA)-IsOmCrC], Esfenvalerate, Etofenprox, Fenpropathrin, Fenvalerate, Flucythrinate, Flumethrin, Fluvalinate (tau-), Halfenprox, Imiprothrin, Metofluthrin, Permethrin, Phenothrin [(l/?)-trans-Isomer], Prallethrin, Profluthrin, Pyrethrine (pyrethrum), Res- methrin, RU 15525, Silafluofen, Tefluthrin, Tetramethrin [(IR)- Isomere], Tralomethrin, Transfluthrin und ZXI 8901; oder DDT; oder Methoxychlor.(3) sodium channel modulators / voltage-dependent sodium channel blockers such as, for example, pyrethroids, eg acrinathrin, allethrin (d-cis-trans, d-trans), bifenthrin, bioallethrin, bioalbhrine-S-cyclopentenyl, Bioresmethrin, cycloprothrin, cyfluthrin (beta), cyhalothrin (gamma, lambda), cypermethrin (alpha, beta, theta, zeta), cyphenothrin [(IR) trans-lsome], deltamethrin, dimefluthrin , Empenthrin [(5 1 Z) - (IA) -IsOmCrC], esfenvalerates, etofenprox, fenpropathrin, fenvalerates, flucythrinates, flumethrin, fluvalinate (tau-), halfenprox, imiprothrin, metofluthrin, permethrin, phenothrin [(l /?) - trans isomer], prallethrin, profuthrin, pyrethrin (pyrethrum), resmethrin, RU 15525, silafluofen, tefluthrin, tetramethrin [(IR) isomers], tralomethrin, transfluthrin and ZXI 8901; or DDT; or methoxychlor.
(4) Nikotinerge Acetylcholin-Rezeptor-Agonisten, wie beispielsweise Neonikotinoide, z.B. Aceta- miprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid, Thiamethoxam; oder Nikotin.(4) nicotinergic acetylcholine receptor agonists, such as neonicotinoids, e.g. Acetamidipride, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; or nicotine.
(5) Allosterische Acetylcholin-Rezeptor-Modulatoren (Agonisten), wie beispielsweise Spinosyne, z.B. Spinetoram und Spinosad.(5) Allosteric acetylcholine receptor modulators (agonists), such as spinosyns, e.g. Spinetoram and spinosad.
(6) Chlorid-Kanal -Aktivatoren, wie beispielsweise Avermectine/Milbemycine, z.B. Abamectin, Emamectin-benzoate, Lepimectin und Milbemectin.(6) chloride channel activators, such as avermectins / milbemycins, e.g. Abamectin, Emamectin benzoate, Lepimectin and Milbemectin.
(7) Juvenilhormon-Analoge, z.B. Hydroprene, Kinoprene, Methoprene; oder Fenoxycarb; Pyri- proxyfen.(7) Juvenile hormone analogs, e.g. Hydroprene, kinoprene, methoprene; or fenoxycarb; Pyritexyfen.
(8) Wirkstoffe mit unbekannten oder nicht spezifischen Wirkmechanismen, wie beispielsweise(8) agents with unknown or non-specific mechanisms of action, such as
Begasungsmittel, z.B. Methylbromid und andere Alkylhalogenide; oder Chloropicrin; Sulfurylfluo- rid; Borax; Brechweinstein.Fumigant, e.g. Methyl bromide and other alkyl halides; or chloropicrin; Sulfuryl fluoride; Borax; Tartar emetic.
(9) Selektive Fraßhemmer, z.B. Pymetrozine; oder Flonicamid.(9) Selective feeding inhibitors, e.g. pymetrozine; or flonicamide.
(10) Milbenwachstumsinhibitoren, z.B. Clofentezine, Diflovidazin, Hexythiazox, Etoxazole.(10) mite growth inhibitors, e.g. Clofentezine, diflovidazine, hexythiazox, etoxazole.
(11) Mikrobielle Disruptoren der Insektendarmmembran, wie beispielsweise Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis, und BT-Pfianzen-Proteine, z.B. Cryl Ab, Cry 1 Ac, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Abl . (12) Inhibitoren der oxidativen Phosphorylierung, ATP-Disruptoren, wie beispielsweise Diafenthi- uron; oder Organozinnverbindungen, z.B. Azocyclotin, Cyhexatin, Fenbutatin oxide; oder Propar- gite; Tetradifon.(11) Microbial disruptors of insect intestinal membrane, such as Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis, and BT plant proteins, eg Cryl Ab, Cry 1 Ac, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Abl. (12) inhibitors of oxidative phosphorylation, ATP disruptors, such as diafenthiourone; or organotin compounds, eg azocyclotine, cyhexatin, fenbutatin oxide; or propriety; Tetradifon.
(13) Entkoppler der oxidativen Phoshorylierung durch Unterbrechung des H-Protongradienten, wie beispielsweise Chlorfenapyr und DNOC.(13) Decoupling of oxidative phosphorylation by interruption of the H proton gradient, such as chlorfenapyr and DNOC.
(14) Nikotinerge Acetylcholin-Rezeptor- Antagonisten, wie beispielsweise Bensultap, Cartap (- Hydrochlorid), Thiocylam, und Thiosultap (-Natrium).(14) Nicotinergic acetylcholine receptor antagonists, such as Bensultap, Cartap (hydrochloride), thiocylam, and thiosultap (sodium).
(15) Inhibitoren der Chitinbiosynthese, Typ 0, wie beispielsweise Benzoylharnstoffe, z.B. Bistrifluron, Chlorfluazuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenu- ron, Novaluron, Noviflumuron, Teflubenzuron und Triflumuron.(15) inhibitors of chitin biosynthesis, type 0, such as benzoylureas, e.g. Bistrifluron, chlorofluorazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron.
(16) Inhibitoren der Chitinbiosynthese, Typ 1, wie beispielsweise Buprofezin.(16) inhibitors of chitin biosynthesis, type 1, such as buprofezin.
(17) Häutungsstörende Wirkstoffe, wie beispielsweise Cyromazine.(17) Moulting agents, such as Cyromazine.
(18) Ecdysonagonisten/-disruptoren, wie beispielsweise(18) ecdysone agonists / disruptors such as
Diacylhydrazine, z.B. Chromafenozide, Halofenozide, Methoxyfenozide und Tebufenozide.Diacylhydrazines, e.g. Chromafenozide, Halofenozide, Methoxyfenozide and Tebufenozide.
(19) Oktopaminerge Agonisten, wie beispielsweise Amitraz.(19) Octopaminergic agonists, such as amitraz.
(20) Seite-III-Elektronentransportinhibitoren/Seite-II-Elektronentransportinhibitoren, wie beispielsweise Hydramethylnon; Acequinocyl; Fluacrypyrim; oder Cyflumetofen und Cyenopyrafen.(20) side-III electron transport inhibitors / side II electron transport inhibitors such as, for example, hydramethylnone; acequinocyl; fluacrypyrim; or Cyflumetofen and Cyenopyrafen.
(21) Elektronentransportinhibitoren, wie beispielsweise Seite-I-Elektronentransportinhibitoren, aus der Gruppe der METI-Akarizide, z.B. Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebu- fenpyrad, Tolfenpyrad; oder Rotenone (Denis).(21) Electron transport inhibitors, such as side-I electron transport inhibitors, from the group of METI acaricides, e.g. Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebfenpyrad, Tolfenpyrad; or Rotenone (Denis).
(22) Spannungsabhängige Natriumkanal -Blocker, z.B. Indoxacarb; Metaflumizone.(22) voltage dependent sodium channel blockers, e.g. indoxacarb; Metaflumizone.
(23) Inhibitoren der Acetyl-CoA-Carboxylase, wie beispielsweise Tetronsäure-Derivate, z.B. Spi- rodiclofen und Spiromesifen; oder Tetramsäure-Derivate, z.B. Spirotetramat.(23) inhibitors of acetyl-CoA carboxylase, such as tetronic acid derivatives, e.g. Spidrodiclofen and spiromesifen; or tetramic acid derivatives, e.g. Spirotetramat.
(24) Seite-FV-Elektronentransportinhibitoren, wie beispielsweise Phosphene, z.B. Aluminiumphosphid, Kalziumphosphid, Phosphin, Zinkphosphid; oder Cyanid.(24) side FV electron transport inhibitors such as phosphenes, e.g. Aluminum phosphide, calcium phosphide, phosphine, zinc phosphide; or cyanide.
(28) Ryanodinrezeptor-Effektoren, wie beispielsweise Diamide, z.B. Chlorantraniliprole (Rynaxypyr), Cyantraniliprole (Cyazypyr) und Flubendiamide. Weitere Wirkstoffe mit unbekanntem Wirkmechanismus, wie beispielsweise Azadirachtin, Amidofiumet, Benzoximate, Bifenazate, Chinomethionat, Cryolite, Dicofol, Flufenerim, Pyridalyl und Pyrifluquinazon; oder folgende bekannte wirksame Verbindungen(28) Ryanodine receptor effectors such as diamides, eg chlorantraniliprole (rynaxypyr), cyantraniliprole (cyazypyr) and flubendiamide. Other drugs with unknown mechanism of action, such as Azadirachtin, Amidofiumet, Benzoximate, Bifenazate, Chinomethionat, Cryolite, Dicofol, Flufenerim, Pyridalyl and Pyrifluquinazone; or the following known effective compounds
4-{[(6-Brompyrid-3-yl)methyl](2-fluorethyl)amino}furan-2(5H)-on (bekannt aus WO 2007/115644), 4-{[(6-Fluorpyrid-3-yl)methyl](2,2-difluorethyl)amino}furan-2(5H)-on (bekannt aus WO 2007/115644), 4-{[(2-Chlor-l,3-thiazol-5-yl)methyl](2-fluorethyl)amino}furan-2(5H)-on (bekannt aus WO 2007/115644), 4-{[(6-Chlorpyrid-3-yl)methyl](2-fluorethyl)amino}furan-2(5H)- on (bekannt aus WO 2007/ 115644), 4-{[(6-Chlorpyrid-3-yl)methyl](2,2- difluorethyl)amino}furan-2(5H)-on (bekannt aus WO 2007/115644), 4-{[(6-Chlor-5-fluorpyrid-3- yl)methyl](methyl)amino}furan-2(5H)-on (bekannt aus WO 2007/115643), 4-{[(5,6-Dichlorpyrid- 3-yl)methyl](2-fluorethyl)amino}furan-2(5H)-on (bekannt aus WO 2007/115646), 4-{[(6-Chlor-5- fluoφyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on (bekannt aus WO 2007/115643), 4- {[(6-Chloφyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on (bekannt aus EP-A-O 539 588), 4-{[(6-Chloφyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on (bekannt aus EP-A-O 539 588), [(6- Chloφyridin-3-yl)methyl](methyl)oxido-λ4-sulfanylidencyanamid (bekannt aus WO 2007/149134), [l-(6-Chloφyridin-3-yl)ethyl](methyl)oxido-λ4-sulfanylidencyanamid (bekannt aus WO 2007/149134) und seine Diastereomere (A) und (B)4 - {[(6-bromopyrid-3-yl) methyl] (2-fluoroethyl) amino} furan-2 (5H) -one (known from WO 2007/115644), 4 - {[(6-fluoropyrid-3-ol) yl) methyl] (2,2-difluoroethyl) amino} furan-2 (5H) -one (known from WO 2007/115644), 4 - {[(2-chloro-1,3-thiazol-5-yl) methyl ] (2-fluoroethyl) amino} furan-2 (5H) -one (known from WO 2007/115644), 4 - {[(6-chloropyrid-3-yl) methyl] (2-fluoroethyl) amino} furan-2 (5H) -one (known from WO 2007/115644), 4 - {[(6-chloropyrid-3-yl) methyl] (2,2-difluoroethyl) amino} furan-2 (5H) -one (known from WO 2007/115644), 4 - {[(6-chloro-5-fluoropyrid-3-yl) methyl] (methyl) amino} furan-2 (5H) -one (known from WO 2007/115643), 4 - {[ (5,6-dichloropyrid-3-yl) methyl] (2-fluoroethyl) amino} furan-2 (5H) -one (known from WO 2007/115646), 4 - {[(6-chloro-5-fluoropyridone) 3-yl) methyl] (cyclopropyl) amino} furan-2 (5H) -one (known from WO 2007/115643), 4- {[(6-chloropyrid-3-yl) methyl] (cyclopropyl) amino} furan 2 (5H) -one (known from EP-A-0 539 588), 4 - {[(6-chloropyrid-3-yl) methyl] (methyl) amino} furan-2 (5H) -one (known from EP-AO 539 588), [(6-chloropyridin-3-yl) me ethyl] (methyl) oxido-λ 4 -sulfanylidenecyanoanamide (known from WO 2007/149134), [1- (6-chloropyridin-3-yl) ethyl] (methyl) oxido- 4- sulfanylidenecyanoanamide (known from WO 2007/149134 ) and its diastereomers (A) and (B)
(A) (B)(A) (B)
(ebenfalls bekannt aus WO 2007/149134), [(6-Trifluormethylpyridin-3-yl)methyl](methyl)oxido- λ4-sulfanylidencyanamid (bekannt aus WO 2007/095229), Sulfoxaflor(also known from WO 2007/149134), [(6-trifluoromethylpyridin-3-yl) methyl] (methyl) oxido-λ 4 -sulfanylidenecyanoanamide (known from WO 2007/095229), sulfoxaflor
(ebenfalls bekannt aus WO 2007/149134), l l-(4-Chlor-2,6-dimethylphenyl)-12-hydroxy-l,4- dioxa-9-azadispiro[4.2.4.2]tetradec-l l-en-10-on (bekannt aus WO 2006/089633), 3-(4'-Fluor-2,4- dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-l -azaspiro[4.5]dec-3-en-2-on (bekannt aus(also known from WO 2007/149134), 1- (4-chloro-2,6-dimethylphenyl) -12-hydroxy-1,4-dioxa-9-azadispiro [4.2.4.2] tetradec-1-ene 10-on (known from WO 2006/089633), 3- (4'-fluoro-2,4-dimethylbiphenyl-3-yl) -4-hydroxy-8-oxa-1-azaspiro [4.5] dec-3-ene -2-on (known from
WO 2008/067911) und l-{2,4-Dimethyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-3-WO 2008/067911) and 1- {2,4-dimethyl-5 - [(2,2,2-trifluoroethyl) sulfinyl] phenyl} -3-
(trifluoromethyl)-lH-l,2,4-triazol (bekannt aus WO 1999/55668). Auch eine Mischimg mit anderen bekannten Wirkstoffen, wie Herbiziden, Düngemitteln, Wachstumsregulatoren, Safenern, Semiochemicals, oder auch mit Mitteln zur Verbesserung der Pflanzeneigenschaften ist möglich.(trifluoromethyl) -1H-l, 2,4-triazole (known from WO 1999/55668). It is also possible to mix with other known active compounds, such as herbicides, fertilizers, growth regulators, safeners, semiochemicals, or else with agents for improving the plant properties.
Die erfindungsgemäßen Wirkstoffe können ferner beim Einsatz als Insektizide in ihren handels- üblichen Formulierungen sowie in den aus diesen Formulierungen bereiteten Anwendungsformen in Mischung mit Synergisten vorliegen. Synergisten sind Verbindungen, durch die die Wirkung der Wirkstoffe gesteigert wird, ohne daß der zugesetzte Synergist selbst aktiv wirksam sein muß.The active compounds according to the invention can furthermore be present when used as insecticides in their commercial formulations as well as in the formulations prepared from these formulations in admixture with synergists. Synergists are compounds which increase the effect of the active ingredients without the added synergist itself having to be active.
Die erfindungsgemäßen Wirkstoffe können ferner beim Einsatz als Insektizide in ihren handelsüblichen Formulierungen sowie in den aus diesen Formulierungen bereiteten Anwendungsformen in Mischungen mit Hemmstoffen vorliegen, die einen Abbau des Wirkstoffes nach Anwendung in der Umgebung der Pflanze, auf der Oberfläche von Pflanzenteilen oder in pflanzlichen Geweben vermindern.The active compounds according to the invention may furthermore, when used as insecticides in their commercial formulations and in the forms of use prepared from these formulations, be present in mixtures with inhibitors which reduce degradation of the active ingredient after application in the environment of the plant, on the surface of plant parts or in plant tissues ,
Der Wirkstoffgehalt der aus den handelsüblichen Formulierungen bereiteten Anwendungsformen kann in weiten Bereichen variieren. Die Wirkstoffkonzentration der Anwendungsformen kann von 0,00000001 bis zu 95 Gew.-% Wirkstoff, vorzugsweise zwischen 0,00001 und 1 Gew.-% liegen.The active substance content of the application forms prepared from the commercial formulations can vary within wide ranges. The active ingredient concentration of the use forms may be from 0.00000001 up to 95% by weight of active compound, preferably between 0.00001 and 1% by weight.
Die Anwendung geschieht in einer den Anwendungsformen angepaßten üblichen Weise.The application is done in a custom forms adapted to the application.
Erfindungsgemäß können alle Pflanzen und Pflanzenteile behandelt werden. Unter Pflanzen werden hierbei alle Pflanzen und Pflanzenpopulationen verstanden, wie erwünschte und unerwünschte Wildpflanzen oder Kulturpflanzen (einschließlich natürlich vorkommender Kulturpflanzen). KuI- turpfianzen können Pflanzen sein, die durch konventionelle Züchtungs- und Optimierungsmethoden oder durch biotechnologische und gentechnologische Methoden oder Kombinationen dieser Methoden erhalten werden können, einschließlich der transgenen Pflanzen und einschließlich der durch Sortenschutzrechte schützbaren oder nicht schützbaren Pflanzensorten. Unter Pflanzenteilen sollen alle oberirdischen und unterirdischen Teile und Organe der Pflanzen, wie Sproß, Blatt, Blüte und Wurzel verstanden werden, wobei beispielhaft Blätter, Nadeln, Stengel, Stämme, Blüten, Fruchtkörper, Früchte und Saatgut sowie Wurzeln, Knollen und Rhizome aufgeführt werden. Zu den Pflanzenteilen gehört auch Erntegut sowie vegetatives und generatives Vermehrungsmaterial, beispielsweise Stecklinge, Knollen, Rhizome, Ableger und Saatgut.According to the invention, all plants and parts of plants can be treated. In this context, plants are understood as meaning 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 plant varieties that are protectable or unprotectable by plant variety rights. Plant parts are to be understood as meaning all aboveground and underground parts and organs of the plants, such as shoot, leaf, flower and root, by way of example leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds and roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.
Die erfϊndungsgemäße Behandlung der Pflanzen und Pflanzenteile mit den Wirkstoffen erfolgt di- rekt oder durch Einwirkung auf deren Umgebung, Lebensraum oder Lagerraum nach den üblichenThe erfϊndungsgemäße treatment of plants and parts of plants with the active ingredients takes place directly or by acting on their environment, habitat or storage space according to the usual
Behandlungsmethoden, z.B. durch Tauchen, Sprühen, Verdampfen, Vernebeln, Streuen, Auf- streichen, Injizieren und bei Vermehrungsmaterial, insbesondere bei Saatgut, weiterhin durch ein- oder mehrschichtiges Umhüllen.Treatment methods, eg by dipping, spraying, evaporating, misting, spreading, spreading painting, injecting and propagating material, in particular seed, by single or multi-layer coating.
Wie bereits oben erwähnt, können erfindungsgemäß alle Pflanzen und deren Teile behandelt werden. In einer bevorzugten Ausfuhrungsform werden wild vorkommende oder durch konventionelle biologische Zuchtmethoden, wie Kreuzung oder Protoplastenfusion erhaltenen Pflanzenarten und Pflanzensorten sowie deren Teile behandelt. In einer weiteren bevorzugten Ausführungsform werden transgene Pflanzen und Pflanzensorten, die durch gentechnologische Methoden gegebenenfalls in Kombination mit konventionellen Methoden erhalten wurden (Genetically Modified Organisms) und deren Teile behandelt. Die Begriffe "Teile" bzw. "Teile von Pflanzen" oder "Pflanzenteile" wurden oben erläutert.As already mentioned above, according to the invention all plants and their parts can be treated. In a preferred embodiment, wild species or plant species obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and plant varieties and their parts are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The terms "parts" or "parts of plants" or "plant parts" have been explained above.
Besonders bevorzugt werden erfindungsgemäß Pflanzen der jeweils handelsüblichen oder in Gebrauch befindlichen Pflanzensorten behandelt. Unter Pflanzensorten versteht man Pflanzen mit neuen Eigenschaften ("Traits"), die sowohl durch konventionelle Züchtung, durch Mutagenese oder durch rekombinante DNA-Techniken gezüchtet worden sind. Dies können Sorten, Bio- und Geno- typen sein.It is particularly preferred according to the invention to treat plants of the respective commercially available or in use plant cultivars. Plant varieties are understood as meaning plants having new traits which have been bred by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, biotypes and genotypes.
Je nach Pflanzenarten bzw. Pflanzensorten, deren Standort und Wachstumsbedingungen (Böden, Klima, Vegetationsperiode, Ernährung) können durch die erfindungsgemäße Behandlung auch ü- beradditive ("synergistische") Effekte auftreten. So sind beispielsweise erniedrigte Aufwandmengen und/oder Erweiterungen des Wirkungsspektrums und/oder eine Verstärkung der Wirkung der erfindungsgemäß verwendbaren Stoffe und Mittel, besseres Pflanzenwachstum, erhöhte Toleranz gegenüber hohen oder niedrigen Temperaturen, erhöhte Toleranz gegen Trockenheit oder gegen Wasser- bzw. Bodensalzgehalt, erhöhte Blühleistung, erleichterte Ernte, Beschleunigung der Reife, höhere Ernteerträge, höhere Qualität und/oder höherer Ernährungswert der Ernteprodukte, höhere Lagerfähigkeit und/oder Bearbeitbarkeit der Ernteprodukte möglich, die über die eigentlich zu er- wartenden Effekte hinausgehen.Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive ("synergistic") effects. Thus, for example, reduced application rates and / or extensions of the spectrum of action and / or an increase in the effect of the substances and agents usable in 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 power , facilitated harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or machinability of the harvested products, which go beyond the actual expected effects.
Zu den bevorzugten erfindungsgemäß zu behandelnden transgenen (gentechnologisch erhaltenen) Pflanzen bzw. Pflanzensorten gehören alle Pflanzen, die durch die gentechnologische Modifikation genetisches Material erhielten, welches diesen Pflanzen besondere vorteilhafte wertvolle Eigenschaften ("Traits") verleiht. Beispiele für solche Eigenschaften sind besseres Pflanzenwachstum, erhöhte Toleranz gegenüber hohen oder niedrigen Temperaturen, erhöhte Toleranz gegen Trockenheit oder gegen Wasser- bzw. Bodensalzgehalt, erhöhte Blühleistung, erleichterte Ernte, Beschleunigung der Reife, höhere Ernteerträge, höhere Qualität und/oder höherer Ernährungswert der Ernteprodukte, höhere Lagerfähigkeit und/oder Bearbeitbarkeit der Ernteprodukte. Weitere und besonders hervorgehobene Beispiele für solche Eigenschaften sind eine erhöhte Abwehr der Pflan- zen gegen tierische und mikrobielle Schädlinge, wie gegenüber Insekten, Milben, pflanzenpatho- genen Pilzen, Bakterien und/oder Viren sowie eine erhöhte Toleranz der Pflanzen gegen bestimmte herbizide Wirkstoffe. Als Beispiele transgener Pflanzen werden die wichtigen Kulturpflanzen, wie Getreide (Weizen, Reis), Mais, Soja, Kartoffel, Zuckerrüben, Tomaten, Erbsen und andere Gemü- sesorten, Baumwolle, Tabak, Raps, sowie Obstpflanzen (mit den Früchten Äpfel, Birnen, Zitrusfrüchten und Weintrauben) erwähnt, wobei Mais, Soja, Kartoffel, Baumwolle, Tabak und Raps besonders hervorgehoben werden. Als Eigenschaften ("Traits") werden besonders hervorgehoben die erhöhte Abwehr der Pflanzen gegen Insekten, Spinnentiere, Nematoden und Schnecken durch in den Pflanzen entstehende Toxine, insbesondere solche, die durch das genetische Material aus Ba- cillus Thuringiensis (z.B. durch die Gene CryΙA(a), CryIA(b), CryΙA(c), CryKA, CrylllA, Cryl- IIB2, Cry9c Cry2Ab, Cry3Bb und CryEF sowie deren Kombinationen) in den Pflanzen erzeugt werden (im folgenden "Bt Pflanzen"). Als Eigenschaften ("Traits") werden auch besonders hervorgehoben die erhöhte Abwehr von Pflanzen gegen Pilze, Bakterien und Viren durch Systemische Akquirierte Resistenz (SAR), Systemin, Phytoalexine, Elicitoren sowie Resistenzgene und ent- sprechend exprimierte Proteine und Toxine. Als Eigenschaften ("Traits") werden weiterhin besonders hervorgehoben die erhöhte Toleranz der Pflanzen gegenüber bestimmten herbiziden Wirkstoffen, beispielsweise Imidazolinonen, Sulfonylharnstoffen, Glyphosate oder Phosphinotricin (z.B. "PAT"-Gen). Die jeweils die gewünschten Eigenschaften ("Traits") verleihenden Gene können auch in Kombinationen miteinander in den transgenen Pflanzen vorkommen. Als Beispiele für "Bt Pflanzen" seien Maissorten, Baumwollsorten, Sojasorten und Kartoffelsorten genannt, die unter den Handelsbezeichnungen YIELD GARD® (z.B. Mais, Baumwolle, Soja), KnockOut® (z.B. Mais), StarLink® (z.B. Mais), Bollgard® (Baumwolle), Nucotn® (Baumwolle) und NewLeaf® (Kartoffel) vertrieben werden. Als Beispiele für Herbizid-tolerante Pflanzen seien Maissorten, Baumwollsorten und Sojasorten genannt, die unter den Handelsbezeichnungen Roundup Ready® (Toleranz gegen Glyphosate z.B. Mais, Baumwolle, Soja), Liberty Link® (Toleranz gegen Phosphinotricin, z.B. Raps), IMI® (Toleranz gegen Imidazolinone) und STS® (Toleranz gegen Sulfonylharnstoffe z.B. Mais) vertrieben werden. Als Herbizid- resistente (konventionell auf Herbizid-Toleranz gezüchtete) Pflanzen seien auch die unter der Bezeichnung Clearfield® vertriebenen Sorten (z.B. Mais) erwähnt. Selbstverständlich gelten diese Aussagen auch für in der Zukunft entwickelte bzw. zukünftig auf den Markt kommende Pflanzensorten mit diesen oder zukünftig entwickelten genetischen Eigenschaften ("Traits").The preferred plants or plant varieties to be treated according to the invention to be treated include all plants which, as a result of the genetic engineering modification, obtained genetic material which gives these plants particularly advantageous valuable properties ("traits"). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to bottoms salt, increased flowering, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products , higher shelf life and / or workability of the harvested products. Further and particularly emphasized examples of such properties are an increased defense of the plant against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as increased tolerance of the plants to certain herbicidal active substances. Examples of transgenic plants are the important crops, such as cereals (wheat, rice), maize, soya, potatoes, sugar beets, tomatoes, peas and other vegetables, cotton, tobacco, rapeseed, and fruit plants (with the fruits apples, pears, Citrus fruits and grapes), with special emphasis on maize, soya, potato, cotton, tobacco and oilseed rape. Traits which are particularly emphasized are the increased defense of the plants against insects, arachnids, nematodes and snails by toxins which are formed in the plants, in particular those which are produced by the genetic material from Bacillus thuringiensis (for example by the genes CryΙA (cf. a), CryIA (b), CryΙA (c), CryKA, CrylllA, CrylIIB2, Cry9c Cry2Ab, Cry3Bb and CryEF and combinations thereof) are produced in the plants (hereinafter "Bt plants"). Traits also highlight the increased resistance of plants to fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (eg "PAT" gene). The genes which confer the desired properties ("traits") can also occur in combinations with one another in the transgenic plants. Examples of "Bt plants" are maize varieties, cotton varieties, soybean varieties and potato varieties which are sold under the trade names YIELD GARD® (eg corn, cotton, soya), KnockOut® (eg maize), StarLink® (eg maize), Bollgard® ( Cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties, which are sold under the trade names Roundup Ready® (tolerance to glyphosate eg corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, eg rapeseed), IMI® (tolerance against imidazolinone) and STS® (tolerance to sulfonylureas eg corn). As herbicide-resistant (grown on conventional herbicide tolerance) plants are also sold under the name Clearfield® varieties (eg corn) mentioned. Of course, these statements also apply to future or future marketed plant varieties with these or future developed genetic traits.
Die aufgeführten Pflanzen können besonders vorteilhaft erfindungsgemäß mit den Verbindungen der allgemeinen Formel I bzw. den erfindungsgemäßen Wirkstoffmischungen behandelt werden. Die bei den Wirkstoffen bzw. Mischungen oben angegebenen Vorzugsbereiche gelten auch für die Behandlung dieser Pflanzen. Besonders hervorgehoben sei die Pflanzenbehandlung mit den im vorliegenden Text speziell aufgeführten Verbindungen bzw. Mischungen.The listed plants can be treated particularly advantageously according to the invention with the compounds of the general formula I or the active substance mixtures according to the invention. The preferred ranges given above for the active compounds or mixtures also apply to the Treatment of these plants. Particularly emphasized is the plant treatment with the compounds or mixtures specifically mentioned in the present text.
Darüber hinaus können die erfindungsgemäßen Verbindungen zur Bekämpfung einer Vielzahl verschiedener Schädlinge einschließlich beispielsweise schädlicher saugender Insekten, beißender In- sekten und anderen an Pflanzen parasitierenden Schädlingen, Vorratsschädlingen, Schädlingen, die industrielle Materialien zerstören und Hygieneschädlingen einschließlich Parasiten im Bereich Tiergesundheit verwendet und zu ihrer Bekämpfung wie zum Beispiel ihrer Auslöschung und Ausmerzung eingesetzt werden. Die vorliegende Erfindung schließt somit auch ein Verfahren zur Bekämpfung von Schädlingen ein.In addition, the compounds of the present invention can be used to control a variety of pests including, for example, noxious sucking insects, biting insects and other plant parasitic pests, storage pests, pests that destroy industrial materials and use and control pests including parasites in the animal health field for example their extinction and eradication. The present invention thus also includes a method of controlling pests.
Im Bereich Tiergesundheit, d.h. auf dem veterinärmedizinischen Gebiet, wirken die Wirkstoffe gemäß der vorliegenden Erfindung gegen tierische Parasiten, insbesondere Ektoparasiten oder En- doparasiten. Der Begriff Endoparasiten schließt insbesondere Helminthen wie Cestoden, Nematoden oder Trematoden, und Protozoen wie Kozzidien ein. Ektoparasiten sind typischerweise und vorzugsweise Arthropoden, insbesondere Insekten wie Fliegen (stechend und leckend), parasitische Fliegenlarven, Läuse, Haarlinge, Federlinge, Flöhe und dergleichen; oder Akariden wie Zecken, zum Beispiel Schildzecken oder Lederzecken, oder Milben wie Räudemilben, Laufmilben, Federmilben und dergleichen.In the area of animal health, i. In the veterinary field, the active substances according to the present invention act against animal parasites, in particular ectoparasites or endoparasites. The term endoparasites includes in particular helminths such as cestodes, nematodes or trematodes, and protozoa such as kozzidia. Ectoparasites are typically and preferably arthropods, especially insects such as flies (stinging and licking), parasitic fly larvae, lice, hair-pieces, feathers, fleas and the like; or acarids such as ticks, for example ticks or leather ticks, or mites such as mange mites, mites, feather mites and the like.
Zu diesen Parasiten gehören:These parasites include:
Aus der Ordnung der Anoplurida z.B. Haematopinus spp., Linognathus spp., Pediculus spp., Phti- rus spp., Solenopotes spp.; spezielle Beispiele sind: Linognathus setosus, Linognathus vituli, Linognathus ovillus, Linognathus oviformis, Linognathus pedalis, Linognathus stenopsis, Haematopinus asini macrocephalus, Haematopinus eurysternus, Haematopinus suis, Pediculus humanus capitis, Pediculus humanus corporis, Phylloera vastatrix, Phthirus pubis, Solenopotes capillatus;From the order of the Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phytus spp., 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 humanus capitis, Pediculus humanus corporis, Phylloera vastatrix, Phthirus pubis, Solenopotes capillatus;
Aus der Ordnung der Mallophagida und den Unterordnungen Amblycerina und Ischnocerina z.B. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.; spezielle Beispiele sind: Bovicola bovis, Bovicola ovis, Bovicola limbata, Damalina bovis, Trichodectes canis, Felicola subrostratus, Bovicola caprae, Lepikentron ovis, Werneckiella equi;From the order of Mallophagida and submissions Amblycerina and Ischnocerina, for example. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp .; specific examples are: Bovicola bovis, Bovicola ovis, Bovicola limbata, Damalina bovis, Trichodectes canis, Felicola subrostratus, Bovicola caprae, Lepikentron ovis, Werneckiella equi;
Aus der Ordnung der Diptera und den Unterordnungen Nematocerina und Brachycerina z.B. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Odagmia spp., Wilhelmia spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gaste- rophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp., Rhinoestrus spp., Tipula spp.; spezielle Beispiele sind: Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles gam- biae, Anopheles maculipennis, Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefas- ciatus, Culex pipiens, Culex tarsalis, Fannia canicularis, Sarcophaga carnaria, Stomoxys calcitrans, Tipula paludosa, Lucilia cuprina, Lucilia sericata, Simulium reptans, Phlebotomus papatasi, Phlebotomus longipalpis, Odagmia omata, Wilhelmia equina, Boophthora erythrocephala, Tabanus bromius, Tabanus spodopterus, Tabanus atratus, Tabanus sudeticus, Hybomitra ciurea, Chrysops caecutiens, Chrysops relictus, Haematopota pluvialis, Haematopota italica, Musca autumnalis, Musca domestica, Haematobia irritans irritans, Haematobia irritans exigua, Haematobia Stimulans, Hydrotaea irritans, Hydrotaea albipuncta, Chrysomya chloropyga, Chrysomya bezziana, Oestrus ovis, Hypoderma bovis, Hypoderma lineatum, Przhevalskiana silenus, Dermatobia hominis, Melophagus ovinus, Lipoptena capreoli, Lipoptena cervi, Hippobosca variegata, Hippobosca equina, Gasterophilus intestinalis, Gasterophilus haemorroidalis, Gasterophilus inermis, Gasterophilus na- salis, Gasterophilus nigricornis, Gasterophilus pecorum, Braula coeca;From the order of Diptera and the suborders Nematocerina and Brachycerina eg Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Odagmia spp , Wilhelmia spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp. rophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp., Rhinoestrus spp., Tipula spp .; specific examples are: Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles gambiae, Anopheles maculipennis, Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Fannia canicularis, Sarcophaga carnaria, Stomoxys calcitrans, Tipula paludosa, Lucilia cuprina, Lucilia sericata, Simulium reptans, Phlebotomus papatasi, Phlebotomus longipalpis, Odagmia omata, Wilhelmia equina, Boophthora erythrocephala, Tabanus bromius, Tabanus spodopterus, Tabanus atratus, Tabanus sudeticus, Hybomitra ciurea, Chrysops caecutiens, Chrysops relictus, Haematopota pluvialis, Haematopota italica Musca autumnalis, Musca domestica, Haematobia irritans irritans, Haematobia irritans exigua, Haematobia stimulant, Hydrotaea irritans, Hydrotaea albipuncta, Chrysomya chloropyga, Chrysomya bezziana, Oestrus ovis, Hypoderma bovis, Hypoderma lineatum, Przhevalskiana silenus, Dermatobia hominis, Melophagus ovinus, Lipoptena capreoli , Lipoptena cervi, Hip pobosca variegata, Hippobosca equina, Gasterophilus intestinalis, Gasterophilus haemorroidalis, Gasterophilus inermis, Gasterophilus nasalis, Gasterophilus nigricornis, Gasterophilus pecorum, Braula coeca;
Aus der Ordnung der Siphonapterida z.B. Pulex spp., Ctenocephalides spp., Tunga spp., Xenopsyl- Ia spp., Ceratophyllus spp.; spezielle Beispiele sind: Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis;From the order of siphonapterida e.g. Pulex spp., Ctenocephalides spp., Tunga spp., Xenopsyl Ia spp., Ceratophyllus spp .; specific examples are: Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis;
Aus der Ordnung der Heteropterida z.B. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.From the order of the heteropterid e.g. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
Aus der Ordnung der Blattarida z.B. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp. (z.B. Suppella longipalpa);From the order of Blattarida e.g. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp. (e.g., suppella longipalpa);
Aus der Unterklasse der Acari (Acarina) und den Ordnungen der Meta- und Mesostigmata z.B. Ar- gas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Rhipicephalus (Boophi- lus) spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Dermanyssus spp., Rhipicephalus spp. (der ursprünglichen Gattung der Mehrwirtszecken), Omithonyssus spp., Pneumonyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp., Acarapis spp.; spezielle Beispiele sind: Argas persicus, Argas reflexus, Ornithodorus moubata, Otobius megnini, Rhipi- cephalus (Boophilus) microplus, Rhipicephalus (Boophilus) decoloratus, Rhipicephalus (Boophi- lus) annulatus, Rhipicephalus (Boophilus) calceratus, Hyalomma anatolicum, Hyalomma aegypti- cum, Hyalomma marginatum, Hyalomma transiens, Rhipicephalus evertsi, Ixodes ricinus, Ixodes hexagonus, Ixodes canisuga, Ixodes pilosus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyc- lus, Haemaphysalis concinna, Haemaphysalis punctata, Haemaphysalis cinnabarina, Haemaphysa- lis otophila, Haemaphysalis leachi, Haemaphysalis longicorni, Dermacentor marginatus, Derma- centor reticulatus, Dermacentor pictus, Dermacentor albipictus, Dermacentor andersoni, Dermacentor variabilis, Hyalomma mauritanicum, Rhipicephalus sanguineus, Rhipicephalus bursa, Rhipi- cephalus appendiculatus, Rhipicephalus capensis, Rhipicephalus turanicus, Rhipicephalus zambe- ziensis, Amblyomma americanum, Amblyomma variegatum, Amblyomma maculatum, Ambly- omma hebraeum, Amblyomma cajennense, Dermanyssus gallinae, Ornithonyssus bursa, Ornitho- nyssus sylviarum, Varroa jacobsoni;From the subclass of the Acari (Acarina) and the orders of the Meta and Mesostigmata eg Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Rhipicephalus (Boophillus spp.), Dermacentor spp , Haemophysalis spp., Hyalomma spp., Dermanyssus spp., Rhipicephalus spp. (the original genus of the multiple ticks), Omithonyssus 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 (Boophillus annulatus), Rhipicephalus (Boophilus) calceratus, Hyalomma anatolicum, Hyalomma aegypti cumulus, Hyalomma marginatum, Hyalomma transiens, Rhipicephalus evertsi, Ixodes ricinus, Ixodes hexagonus, Ixodes canisuga, Ixodes pilosus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Haemaphysalis concinna, Haemaphysalis punctata, Haemaphysalis cinnabarina, Haemaphysa lis otophila, Haemaphysalis leachi, Haemaphysalis longicorni, Dermacentor marginatus, Dermatentor reticulatus, Dermacentor pictus, Dermacentor albipictus, Dermacentor andersoni, Dermacentor variabilis, Hyalomma mauritanicum, Rhipicephalus sanguineus, Rhipicephalus bursa, Rhipicephalus appendiculatus, Rhipicephalus capensis, Rhipicephalus turanicus, Rhipicephalus zambeziisis, Amblyomma americanum, Amblyomma variegatum, Amblyomma maculatum, Amblyomma hebraeum, Amblyomma cajennense, Dermanyssus gallinae, Ornithonyssus bursa, Ornithonysus sylviarum, Varroa jacobsoni;
Aus der Ordnung der Actinedida (Prostigmata) und Acaridida (Astigmata) z.B. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pteroli- chus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemi- docoptes spp., Cytodites spp., Laminosioptes spp.; spezielle Beispiele sind: Cheyletiella yasguri, Cheyletiella blakei, Demodex canis, Demodex bovis, Demodex ovis, Demodex caprae, Demodex equi, Demodex caballi, Demodex suis, Neotrombicula autumnalis, Neotrombicula desaleri, Neo- schöngastia xerothermobia, Trombicula akamushi, Otodectes cynotis, Notoedres cati, Sarcoptis canis, Sarcoptes bovis, Sarcoptes ovis, Sarcoptes rupicaprae (=S. caprae), Sarcoptes equi, Sarcoptes suis, Psoroptes ovis, Psoroptes cuniculi, Psoroptes equi, Chorioptes bovis, Psoergates ovis, Pneu- monyssoidic mange, Pneumonyssoides caninum, Acarapis woodi.From the order of Actinedida (Prostigmata) and Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pteroli- spp. Chus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemi- docoptes spp., Cytodites spp., Laminosioptes spp .; specific examples are: Cheyletiella yasguri, Cheyletiella blakei, Demodex canis, Demodex bovis, Demodex ovis, Demodex caprae, Demodex equi, Demodex caballi, Demodex suis, Neotrombicula autumnalis, Neotrombicula desaleri, Neo-nicogastia xerothermobia, Trombicula akamushi, Otodectes cynotis, Notoedres cati Sarcoptis canis, Sarcoptes bovis, Sarcoptes ovis, Sarcoptes rupicaprae (= S. caprae), Sarcoptes equi, Sarcoptes suis, Psoroptes ovis, Psoroptes cuniculi, Psoroptes equi, Chorioptes bovis, Psoergates ovis, Pneu- monyssoidic mange, Pneumonyssoides caninum, Acarapis woodi ,
Die erfindungsgemäßen Wirkstoffe eignen sich auch zur Bekämpfung von Arthropoden, HeI- minthen und Protozoen, die Tiere befallen. Zu den Tieren zählen landwirtschaftliche Nutztiere wie z.B. Rinder, Schafe, Ziegen, Pferde, Schweine, Esel, Kamele, Büffel, Kaninchen, Hühner, Puten, Enten, Gänse, Zuchtfische, Honigbienen. Zu den Tieren zählen außerdem Haustiere - die auch als Heimtiere bezeichnet werden - wie z.B. Hunde, Katzen, Stubenvögel, Aquarienfische sowie sogenannte Versuchstiere wie z.B. Hamster, Meerschweinchen, Ratten und Mäuse.The active compounds according to the invention are also suitable for controlling arthropods, helminths and protozoa which infest animals. The animals include farm animals such as e.g. Cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, farmed fish, honey bees. The animals also include domestic animals - also referred to as pets - such as pets. Dogs, cats, caged birds, aquarium fish and so-called experimental animals such. Hamsters, guinea pigs, rats and mice.
Durch die Bekämpfung dieser Arthropoden, Helminthen und/oder Protozoen sollen Todesfalle vermindert und die Leistung (bei Fleisch, Milch, Wolle, Häuten, Eiern, Honig usw.) und die Gesundheit des Wirtstieres verbessert werden, so dass durch den Einsatz der erfindungsgemäßen Wirkstoffe eine wirtschaftlichere und einfachere Tierhaltung möglich ist.By controlling these arthropods, helminths and / or protozoa deaths are to be reduced and the performance (in meat, milk, wool, hides, eggs, honey, etc.) and the health of the host animal to be improved, so that by using the active compounds of the invention more economical and easier animal husbandry is possible.
So ist es beispielsweise wünschenswert, die Aufnahme von Blut des Wirts durch die Parasiten (falls zutreffend) zu verhindern oder zu unterbrechen. Eine Bekämpfung der Parasiten kann außerdem dazu beitragen, die Übertragung infektiöser Substanzen zu verhindern.For example, it is desirable to prevent or interrupt the ingestion of the host's blood by the parasites (if applicable). Control of the parasites can also help to prevent the transmission of infectious substances.
Der Begriff "Bekämpfung", so wie er hier bezogen auf den Bereich Tiergesundheit verwendet wird, bedeutet, dass die Wirkstoffe wirken, indem sie das Vorkommen des betreffenden Parasiten in ei- nem mit solchen Parasiten befallenen Tier auf unschädliche Niveaus reduzieren. Genauer gesagt bedeutet "Bekämpfung", wie hier verwendet, dass der Wirkstoff den betreffenden Parasiten tötet, sein Wachstum hemmt oder seine Proliferation inhibiert.The term "control", as used herein in relation to animal health, means that the active substances act by controlling the occurrence of the parasite reduce the animal infected with such parasites to harmless levels. More specifically, as used herein, "control" means that the agent kills the subject parasite, inhibits its growth, or inhibits its proliferation.
Im allgemeinen können die erfϊndungsgemäßen Wirkstoffe, wenn sie für die Behandlung von Tie- ren eingesetzt werden, direkt angewendet werden. Vorzugsweise werden sie als pharmazeutische Zusammensetzungen angewendet, die im Stand der Technik bekannte pharmazeutisch unbedenkliche Exzipienten und/oder Hilfsstoffe enthalten können.In general, the active compounds according to the invention, when used for the treatment of animals, can be used directly. Preferably, they are used as pharmaceutical compositions which may contain pharmaceutically acceptable excipients and / or adjuvants known in the art.
Die Anwendung (= Verabreichung) der Wirkstoffe im Bereich Tiergesundheit und in der Tierhaltung erfolgt in bekannter Weise durch enterale Verabreichung in Form von beispielsweise Tab- letten, Kapseln, Tränken, Drenchen, Granulaten, Pasten, BoIi, des feed-through- Verfahrens, von Zäpfchen, durch parenterale Verabreichung, wie zum Beispiel durch Injektionen (intramuskulär, subkutan, intravenös, intraperitoneal u.a.), Implantate, durch nasale Applikation, durch dermale Applikation in Form beispielsweise des Tauchens oder Badens (Dippen), Sprühens (Spray), Aufgießens (Pour-on und Spot-on), des Waschens, des Einpuderns sowie mit Hilfe von wirkstoffhalti- gen Formkörpern, wie Halsbändern, Ohrmarken, Schwanzmarken, Gliedmaßenbändern, Halftern, Markierungsvorrichtungen usw. Die Wirkstoffe können als Shampoo oder als geeignete, in Aerosolen oder drucklosen Sprays, z.B. Pumpsprays und Zerstäubersprays, anwendbare, Formulierungen formuliert werden.The application (= administration) of the active ingredients in the field of animal health and animal husbandry is carried out in a known manner by enteral administration in the form of, for example, tablets, capsules, infusions, drenches, granules, pastes, BoIi, the feed-through method Suppositories, by parenteral administration, for example by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, by nasal application, by dermal application in the form of, for example, dipping or bathing (dipping), spraying, pouring (Pour -one and spot-on), washing, powdering and with the aid of active substance-containing shaped bodies, such as collars, ear tags, tail marks, limb bands, holsters, marking devices, etc. The active ingredients may be shampoo or suitable, in aerosols or pressureless sprays , eg Pump sprays and atomizer sprays, applicable, formulated formulations.
Bei der Anwendung für Nutztiere, Geflügel, Haustiere etc. kann man die erfϊndungsgemäßen Wirk- Stoffe als Formulierungen (beispielsweise Pulver, Spritzpulver [wettable powders, "WP"], Emulsionen, Emulsionskonzentrate [emulsifiable concentrates ,"EC"], fließfähige Mittel, homogene Lösungen und Suspensionskonzentrate [suspension concentrates, "SC"]), die die Wirkstoffe in einer Menge von 1 bis 80 Gew.-% enthalten, direkt oder nach Verdünnung (z.B. 100- bis 10 OOOfacher Verdünnung) anwenden oder sie als chemisches Bad verwenden.When used on livestock, poultry, pets, etc., the active compounds according to the invention can be used as formulations (for example powders, wettable powders, WPs), emulsions, emulsifiable concentrates (EC), flowable agents, homogeneous Solutions and suspension concentrates [suspension concentrates, "SC"]) containing the active ingredients in an amount of 1 to 80 wt .-%, directly or after dilution (eg 100- to 10,000facher dilution) apply or use them as a chemical bath.
Beim Einsatz im Bereich Tiergesundheit können die erfindungsgemäßen Wirkstoffe in Kombination mit geeigneten Synergisten oder anderen Wirkstoffen wie beispielsweise Akariziden, Insektiziden, Anthelmintika, Mittel gegen Protozoen, verwendet werden.When used in the animal health field, the active compounds according to the invention can be used in combination with suitable synergists or other active substances such as, for example, acaricides, insecticides, anthelmintics, antiprotozoal agents.
Außerdem wurde gefunden, daß die erfindungsgemäßen Verbindungen eine hohe insektizide Wirkung gegen Insekten zeigen, die technische Materialien zerstören.In addition, it has been found that the compounds according to the invention show a high insecticidal activity against insects which destroy industrial materials.
Beispielhaft und vorzugsweise - ohne jedoch zu limitieren - seien die folgenden Insekten genannt:By way of example and preferably without limiting however, the following insects are mentioned:
Käfer wie Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillo- sum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brun- neus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus;Beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillo- sum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brun- neus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus;
Hautflügler wie Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur;Hymenoptera such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur;
Termiten wie Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zooter- mopsis nevadensis, Coptotermes formosanus;Termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zooter- mopsis nevadensis, Coptotermes formosanus;
Borstenschwänze wie Lepisma saccharina.Bristle tails like Lepisma saccharina.
Unter technischen Materialien sind im vorliegenden Zusammenhang nicht-lebende Materialien zu verstehen, wie vorzugsweise Kunststoffe, Klebstoffe, Leime, Papiere und Kartone, Leder, Holz, Holzverarbeitungsprodukte und Anstrichmittel.Technical materials in the present context are non-living materials, such as preferably plastics, adhesives, glues, papers and cardboard, leather, wood, wood processing products and paints.
Die anwendungsfertigen Mittel können gegebenenfalls noch weitere Insektizide und gegebenenfalls noch ein oder mehrere Fungizide enthalten.The ready-to-use agents may optionally contain further insecticides and optionally one or more fungicides.
Hinsichtlich möglicher zusätzlicher Zumischpartner sei auf die oben genannten Insektizide und Fungizide verwiesen.With regard to possible additional admixing partners, reference is made to the above-mentioned insecticides and fungicides.
Zugleich können die erfindungsgemäßen Verbindungen zum Schutz vor Bewuchs von Gegenständen, insbesondere von Schiffskörpern, Sieben, Netzen, Bauwerken, Kaianlagen und Signalanlagen, welche mit See- oder Brackwasser in Verbindung kommen, eingesetzt werden.At the same time, the compounds according to the invention can be used to protect against fouling of objects, in particular hulls, sieves, nets, structures, quay systems and signal systems, which come into contact with seawater or brackish water.
Weiter können die erfindungsgemäßen Verbindungen allein oder in Kombinationen mit anderen Wirkstoffen als Antifouling-Mittel eingesetzt werden.Furthermore, the compounds according to the invention can be used alone or in combinations with other active substances as antifouling agents.
Die Wirkstoffe eignen sich auch zur Bekämpfung von tierischen Schädlingen im Haushalts-, Hygiene- und Vorratsschutz, insbesondere von Insekten, Spinnentieren und Milben, die in geschlossenen Räumen, wie beispielsweise Wohnungen, Fabrikhallen, Büros, Fahrzeugkabinen u.a. vorkommen. Sie können zur Bekämpfung dieser Schädlinge allein oder in Kombination mit anderen Wirk- und Hilfsstoffen in Haushaltsinsektizid-Produkten verwendet werden. Sie sind gegen sensible und resistente Arten sowie gegen alle Entwicklungsstadien wirksam. Zu diesen Schädlingen gehören:The active compounds are also suitable for controlling animal pests in household, hygiene and storage protection, in particular of insects, arachnids and mites, which are used in closed rooms, such as apartments, factory buildings, offices, vehicle cabins u.a. occurrence. They can be used to control these pests, alone or in combination with other active ingredients and adjuvants in household insecticide products. They are effective against sensitive and resistant species and against all stages of development. These pests include:
Aus der Ordnung der Scorpionidea z.B. Buthus occitanus. Aus der Ordnung der Acarina z.B. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gal- linae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alf- reddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides fori- nae.From the order of Scorpionidea eg Buthus occitanus. From the order of Acarina, for example, Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus galinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.
Aus der Ordnung der Araneae z.B. Aviculariidae, Araneidae.From the order of the Araneae e.g. Aviculariidae, Araneidae.
Aus der Ordnung der Opiliones z.B. Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opi- liones phalangium.From the order of Opiliones e.g. Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opionouses phalangium.
Aus der Ordnung der Isopoda z.B. Oniscus asellus, Porcellio scaber.From the order of isopods e.g. Oniscus asellus, Porcellio scaber.
Aus der Ordnung der Diplopoda z.B. Blaniulus guttulatus, Polydesmus spp..From the order of diplopoda e.g. Blaniulus guttulatus, Polydesmus spp ..
Aus der Ordnung der Chilopoda z.B. Geophilus spp..From the order of Chilopoda e.g. Geophilus spp ..
Aus der Ordnung der Zygentoma z.B. Ctenolepisma spp., Lepisma saccharina, Lepismodes inquili- nus.From the order of Zygentoma e.g. Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.
Aus der Ordnung der Blattaria z.B. Blatta orientalies, Blattella germanica, Blattella asahinai, Leu- cophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.From the order of the Blattaria e.g. Blatta orientalies, Blattella germanica, Blattella asahinai, Leucaphaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.
Aus der Ordnung der Saltatoria z.B. Acheta domesticus.From the order of Saltatoria e.g. Acheta domesticus.
Aus der Ordnung der Dermaptera z.B. Forficula auricularia.From the order of the Dermaptera e.g. Forficula auricularia.
Aus der Ordnung der Isoptera z.B. Kalotermes spp., Reticulitermes spp.From the order of Isoptera e.g. Kalotermes spp., Reticulitermes spp.
Aus der Ordnung der Psocoptera z.B. Lepinatus spp., Liposcelis spp.From the order of Psocoptera e.g. Lepinatus spp., Liposcelis spp.
Aus der Ordnung der Coleoptera z.B. Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.From the order of Coleoptera e.g. Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.
Aus der Ordnung der Diptera z.B. Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, A- nopheles 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. Aus der Ordnung der Lepidoptera z.B. Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.From the order of the Diptera eg 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. From the order of Lepidoptera eg Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
Aus der Ordnung der Siphonaptera z.B. Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.From the order of siphonaptera e.g. Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
Aus der Ordnung der Hymenoptera z.B. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.From the order of Hymenoptera e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
Aus der Ordnung der Anoplura z.B. Pediculus humanus capitis, Pediculus humanus corporis, Pemphigus spp., Phylloera vastatrix, Phthirus pubis.From the order of the Anoplura e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pemphigus spp., Phylloera vastatrix, Phthirus pubis.
Aus der Ordnung der Heteroptera z.B. Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.From the order of Heteroptera, e.g. Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.
Die Anwendung im Bereich der Haushaltsinsektizide erfolgt allein oder in Kombination mit anderen geeigneten Wirkstoffen wie Phosphorsäureestern, Carbamaten, Pyrethroiden, Neo-nicotinoiden, Wachstumsregulatoren oder Wirkstoffen aus anderen bekannten Insektizidklassen.The application in the field of household insecticides is carried out alone or in combination with other suitable active ingredients such as phosphoric acid esters, carbamates, pyrethroids, neo-nicotinoids, growth regulators or agents from other known insecticide classes.
Die Anwendung erfolgt in Aerosolen, drucklosen Sprühmitteln, z.B. Pump- und Zerstäubersprays, Nebelautomaten, Foggern, Schäumen, Gelen, Verdampferprodukten mit Verdampferplättchen aus Cellulose oder Kunststoff, Flüssigverdampfern, Gel- und Membranverdampfern, propellergetriebenen Verdampfern, energielosen bzw. passiven Verdampfungssystemen, Mottenpapieren, Motten- säckchen und Mottengelen, als Granulate oder Stäube, in Streuködem oder Köderstationen.Application is in aerosols, non-pressurized sprays, e.g. Pump and atomizer sprays, misting machines, foggers, foams, gels, evaporator products with cellulose or plastic evaporator plates, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-less or passive evaporation systems, moth papers, moth cakes and moth gels, as granules or dusts, in scattered edema or bait stations.
Synthesebeispielesynthesis Examples
1. 4-[3-Chlor-5-(trifluormethyl)phenyl]-3-(methylsulfanyl)-l-(pyrimidin-2-yl)-lH-pyrazol-5- amin (Verbindung Beispiel 1-045 aus Tabelle 1)1. 4- [3-Chloro-5- (trifluoromethyl) phenyl] -3- (methylsulfanyl) -1- (pyrimidin-2-yl) -1H-pyrazole-5-amine (Compound Example 1-045 from Table 1)
1.1 Stufe 1 (Zwischenprodukt 6-034 aus Tabelle 6):1.1 Step 1 (Intermediate 6-034 of Table 6):
2,28 g (57 mmol) Natriumhydrid (60%ig in Mineralöl) werden in 10 mL trockenem Toluol unter Argon vorgelegt. Bei Raumtemperatur wird ein Gemisch aus 5 g (22,7 mmol) 3- Chlor-5-trifluormethyl-benzylnitril und 2,6 g (34,2 mmol) Schwefelkohlenstoff in 10 mL2.28 g (57 mmol) of sodium hydride (60% in mineral oil) are placed in 10 mL of dry toluene under argon. At room temperature, a mixture of 5 g (22.7 mmol) of 3-chloro-5-trifluoromethyl-benzylnitrile and 2.6 g (34.2 mmol) of carbon disulfide in 10 mL
DMF langsam zugetropft. Anschließend erfolgt bei Eiskühlung die tropfenweise Zugabe von 8,08 g (57 mmol) Methyliodid. Es wird 12 h bei Raumtemperatur nachgerührt, anschließend 2 h auf 120 0C erhitzt. Nach Abkühlen wird das Reaktionsgemisch vorsichtig mit Wasser versetzt und mehrfach mit Dichlormethan extrahiert. Die vereinigten organi- sehen Phasen werden über Magnesiumsulfat getrocknet, filtriert und im Vakuum einge- engt. Nach Chromatographie an Kieselgel wurden 6,7 g (Ausbeute 84,5 % d. Th.) 2-[3- Chlor-5-(trifluormethyl)phenyl]-3,3-bis(methylsulfanyl)prop-2-enenitril erhalten.DMF slowly added dropwise. Subsequently, with ice cooling, the dropwise addition of 8.08 g (57 mmol) of methyl iodide. The mixture is stirred for 12 h at room temperature, then for 2 hours at 120 0 C heated. After cooling, the reaction mixture is carefully mixed with water and extracted several times with dichloromethane. The combined organic phases are dried over magnesium sulfate, filtered and concentrated in vacuo. concentrated. After chromatography on silica gel, 6.7 g (yield 84.5% of theory) of 2- [3-chloro-5- (trifluoromethyl) phenyl] -3,3-bis (methylsulfanyl) prop-2-enenitrile were obtained.
1H-NMR (400 MHz, d6-DMSO), δ 7.87-7.86 (s+s, 2H), 7.79 (s, IH), 2.65 (s, 3H), 2.38 (s, 3H,). 1 H NMR (400 MHz, d 6 -DMSO), δ 7.87-7.86 (s + s, 2H), 7.79 (s, IH), 2.65 (s, 3H), 2.38 (s, 3H,).
IgP (HCOOH) = 4,40IgP (HCOOH) = 4.40
1.2 Stufe 2 (Zwischenprodukt 5-034 aus Tabelle 5):1.2 Step 2 (Intermediate 5-034 of Table 5):
6,7 g (19,2 mmol) 2-[3-Chlor-5-(trifluoπnethyl)phenyl]-3,3-bis(methylsulfanyl)prop-2- enenitril und 1,93 g (38,5 mmol) Hydrazinhydrat werden in 50 mL Ethanol 12 h unter Rückfluss erhitzt. Das Reaktionsgemisch wird im Vakuum eingeengt, der Rückstand in Wasser aufgenommen und mehrfach mit Dichlormethan extrahiert. Die vereinigten organischen Phasen werden über Magnesiumsulfat getrocknet, filtriert und im Vakuum eingeengt. Es wurden 5,8 g (98 % d. Th.) der Verbindung 4-[3-Chlor-5-(trifluormethyl)phenyl]- 3-(methylsulfanyl)-lH-pyrazol-5-amm erhalten, die ohne weitere Reinigung in Stufe 3 weiter umgesetzt werden kann.6.7 g (19.2 mmol) of 2- [3-chloro-5- (trifluoromethyl) phenyl] -3,3-bis (methylsulfanyl) prop-2-enenitrile and 1.93 g (38.5 mmol) of hydrazine hydrate are refluxed in 50 mL ethanol for 12 h. The reaction mixture is concentrated in vacuo, the residue taken up in water and extracted several times with dichloromethane. The combined organic phases are dried over magnesium sulfate, filtered and concentrated in vacuo. There were obtained 5.8 g (98% of theory) of the compound 4- [3-chloro-5- (trifluoromethyl) phenyl] -3- (methylsulfanyl) -1H-pyrazole-5-amm, which without further purification can be further implemented in stage 3.
1H-NMR (400 MHz, d6-DMSO), δ (NH und NH2 nicht detektiert) 7.72 (s, IH), 7.70 (s,1H NMR (400 MHz, d 6 -DMSO), δ (NH and NH 2 not detected) 7.72 (s, IH), 7.70 (s,
IH), 7.54 (s, IH), 2.38 (s, 3H).IH), 7.54 (s, IH), 2.38 (s, 3H).
IgP (HCOOH) = 2,77IgP (HCOOH) = 2.77
1.3 Stufe 3 (Verbindung Beispiel 1-045 aus Tabelle 1)1.3 Step 3 (Compound Example 1-045 of Table 1)
5 g (16,25 mmol) 4-[3-Chlor-5-(trifluormethyl)phenyl]-3-(methylsulfanyl)-lH-pyrazol-5- amin werden in 10 mL DMF gelöst und mit 0,65 g Natriumhydrid (60 %ig in Mineralöl) versetzt. Nach Beendigung der Gasentwicklung werden 2,09 g (17,9 mmol) 2- Chlorpyrimidin zugegeben und das Reaktionsgemisch 12 h bei 100 0C gerührt. Nach Abkühlen auf Raumtemperatur wird mit 30 mL 1 N Salzsäure und Wasser verdünnt. Der resultierende Niederschlag wird abgesaugt und mit n-Pentan nachgewaschen. Es wurden 5,4 g (63,8 % d. Th.) 4-[3-Chlor-5-(trifluormethyl)phenyl]-3-(methylsulfanyl)-l-(pyrimidin-2- yl)-lH-pyrazol-5-amin erhalten.5 g (16.25 mmol) of 4- [3-chloro-5- (trifluoromethyl) phenyl] -3- (methylsulfanyl) -1H-pyrazole-5-amine are dissolved in 10 ml of DMF and treated with 0.65 g of sodium hydride ( 60% in mineral oil). After the evolution of gas has ended, 2.09 g (17.9 mmol) of 2-chloropyrimidine are added and the reaction mixture is stirred at 100 ° C. for 12 hours. After cooling to room temperature, it is diluted with 30 ml of 1 N hydrochloric acid and water. The resulting precipitate is filtered off with suction and washed with n-pentane. There was added 5.4 g (63.8% of theory) of 4- [3-chloro-5- (trifluoromethyl) phenyl] -3- (methylsulfanyl) -1- (pyrimidin-2-yl) -1H-pyrazole -5-amine received.
1H-NMR (400 MHz, d6-DMSO), δ 8.88 (d, 2H), 7.73 (s, IH), 7.68 (s, IH), 7.65 (s, IH), 7.38 (t, IH), 7.07 (breites s, 2H, NH2), 2.53 (s, 3H). 1 H-NMR (400 MHz, d 6 -DMSO), δ 8.88 (d, 2H), 7.73 (s, IH), 7.68 (s, IH), 7.65 (s, IH), 7.38 (t, IH), 7.07 (broad s, 2H, NH 2 ), 2.53 (s, 3H).
IgP (HCOOH) = 3,51 2. 4-[3 -Chlor-5 -(trifluormethyl)phenyl]-3-(methylsulfinyl)- 1 -(pyrimidin-2-yl)- 1 H-pyrazol-5 - amin (Beispiel 2-045 aus Tabelle 2):IgP (HCOOH) = 3.51 2. 4- [3-Chloro-5 - (trifluoromethyl) phenyl] -3- (methylsulfinyl) -1- (pyrimidin-2-yl) -1 H -pyrazole-5-amine (Example 2-045 from Table 2) :
2,3 g (4,4 mmol) 4-[3-Chlor-5-(trifluormethyl)phenyl]-3-(methylsulfanyl)-l-(pyrimidin-2- yl)-lH-pyrazol-5-amin werden in 10 mL Dichlormethan gelöst und bei Raumtemperatur mit 0,99 g (4,4 mmol) meta-Chlorperbenzoesäure (77%ig) versetzt. Es wird 12 h bei2.3 g (4.4 mmol) of 4- [3-chloro-5- (trifluoromethyl) phenyl] -3- (methylsulfanyl) -1- (pyrimidin-2-yl) -1H-pyrazole-5-amine are dissolved in Dissolved 10 mL of dichloromethane and treated at room temperature with 0.99 g (4.4 mmol) of meta-chloroperbenzoic acid (77%). It will be 12 h
Raumtemperatur gerührt, dann wird das Reaktionsgemisch mit ges. wässriger Natrium- hydrogencarbonat-Lösung verrührt. Nach Phasentrennung und Nachextraktion mit Dichlormethan werden die vereinigten organischen Phasen über Magnesiumsulfat getrocknet, filtriert und im Vakuum eingeengt. Nach Chromatographie an Kieselgel (Lösungsmittel: Dichlormethan / Methanol = 30: 1) wurden 0,92 g (48,4 % d. Th.) 4-[3-Chlor-5-Room temperature stirred, then the reaction mixture is washed with sat. stirred aqueous sodium bicarbonate solution. After phase separation and subsequent extraction with dichloromethane, the combined organic phases are dried over magnesium sulfate, filtered and concentrated in vacuo. After chromatography on silica gel (solvent: dichloromethane / methanol = 30: 1), 0.92 g (48.4% of theory) of 4- [3-chloro-5-
(trifluormethyl)phenyl]-3 -(methylsulfinyl)- 1 -(pyrimidin-2-yl)- 1 H-pyrazol-5 -amin als farbloser Feststoff erhalten.(trifluoromethyl) phenyl] -3- (methylsulfinyl) -1- (pyrimidin-2-yl) -1 H -pyrazole-5-amine as a colorless solid.
1H-NMR (400 MHz, d6-DMSO), δ 8.94 (d, 2H), 7.89 (s, 2H), 7.72 (s, IH), 7.52 (t, IH), 7.12 (breites s, 2H, NH2), 2.90 (s, 3H). 1 H NMR (400 MHz, d 6 -DMSO), δ 8.94 (d, 2H), 7.89 (s, 2H), 7.72 (s, IH), 7.52 (t, IH), 7.12 (broad s, 2H, NH 2 ), 2.90 (s, 3H).
IgP (HCOOH) = 2,21IgP (HCOOH) = 2.21
3. 4-[3-Chlor-5-(trifluormethyl)phenyl]-3-(methylsulfonyl)-l-(pyrimidin-2-yl)-lH-pyrazol-5- amin (Beispiel 3-045 aus Tabelle 3):3. 4- [3-Chloro-5- (trifluoromethyl) phenyl] -3- (methylsulfonyl) -1- (pyrimidin-2-yl) -1H-pyrazole-5-amine (Example 3-045 from Table 3):
0,36 g (0,88 mmol) 4-[3-Chlor-5-(trifluormethyl)phenyl]-3-(methylsulfanyl)-l -(pyrimidin- 2-yl)- 1 H-pyrazol-5 -amin werden in 5 mL Dichlormethan gelöst und bei Raumtemperatur mit 0,39 g (1,75 mmol) meta-Chlorperbenzoesäure (77%ig) versetzt. Es wird 12 h bei0.36 g (0.88 mmol) of 4- [3-chloro-5- (trifluoromethyl) phenyl] -3- (methylsulfanyl) -1- (pyrimidin-2-yl) -1 H -pyrazole-5-amine dissolved in 5 mL dichloromethane and at room temperature with 0.39 g (1.75 mmol) of meta-chloroperbenzoic acid (77%) was added. It will be 12 h
Raumtemperatur gerührt, dann wird das Reaktionsgemisch mit ges. wässriger Natrium- hydrogencarbonat-Lösung verrührt. Nach Phasentrennung und Nachextraktion mit Dichlormethan werden die vereinigten organischen Phasen über Magnesiumsulfat getrocknet, filtriert und im Vakuum eingeengt. Nach Chromatographie an Kieselgel (Lösungsmittel: Dichlormethan / Methanol = 30:1) wurden 0,08 g (20,7 % d. Th.) 4-[3-Chlor-5-Room temperature stirred, then the reaction mixture is washed with sat. stirred aqueous sodium bicarbonate solution. After phase separation and subsequent extraction with dichloromethane, the combined organic phases are dried over magnesium sulfate, filtered and concentrated in vacuo. After chromatography on silica gel (solvent: dichloromethane / methanol = 30: 1), 0.08 g (20.7% of theory) of 4- [3-chloro-5-
(trifluormethyl)phenyl]-3-(methylsulfonyl)-l-(pyrimidin-2-yl)-lH-pyrazol-5-amin als farbloser Feststoff erhalten.(trifluoromethyl) phenyl] -3- (methylsulfonyl) -1- (pyrimidin-2-yl) -1H-pyrazole-5-amine as a colorless solid.
1H-NMR (400 MHz, d6-DMSO), δ 8.96 (d, 2H), 7.79 (s, IH), 7.77 (s, IH), 7.74 (s, IH), 7.55 (t, IH), 7.09 (breites s, 2H, NH2), 3.27 (s, 3H). 1 H NMR (400 MHz, d 6 -DMSO), δ 8.96 (d, 2H), 7.79 (s, IH), 7.77 (s, IH), 7.74 (s, IH), 7.55 (t, IH), 7.09 (broad s, 2H, NH 2 ), 3.27 (s, 3H).
IgP (HCOOH) = 2,53 4. N'-{4-[3-Chlor-5-(trifluormethyl)phenyl]-3-(ethylsulfanyl)-l-(pyrimidin-2-yl)-lH-pyrazol-IgP (HCOOH) = 2.53 4. N '- {4- [3-Chloro-5- (trifluoromethyl) phenyl] -3- (ethylsulfanyl) -1- (pyrimidin-2-yl) -1H-pyrazole
5-yl}-N,N-dimethylimidoformamid (Beispiel 4-004 aus Tabelle 4)5-yl} -N, N-dimethylimidoformamide (Example 4-004 from Table 4)
0,3 g (0,75 mmol) 4-[3-Chlor-5-(trifluormethyl)phenyl]-3-(ethylsulfanyl)-l-(pyrimidin-2- yl)-lH-pyrazol-5-amin werden in 5 mL Toluol mit 0,11 g (0,9 mmol; 0,12 mL) Dimethylformamid-dimethylacetal (DMF-DMA) verset.it und bei Rückfluß 12 h gerrührt.0.3 g (0.75 mmol) of 4- [3-chloro-5- (trifluoromethyl) phenyl] -3- (ethylsulfanyl) -1- (pyrimidin-2-yl) -1H-pyrazole-5-amine are dissolved in 5 mL of toluene with 0.11 g (0.9 mmol, 0.12 mL) of dimethylformamide dimethyl acetal (DMF-DMA) verset.it and stirred at reflux for 12 h.
Die Lösungsmittel werden im Vakuum abdestilliert, der verbleibende farblose Feststoff N'- {4-[3 -Chlor-5 -(trifluormethyl)phenyl] -3 -(ethylsulfanyl)- 1 -(pyrimidin-2-yl)- lH-pyrazol-5- yl}-N,N-dimethylimidoformamid wurde mit 0,31 g (91,4 % d. Th.) erhalten.The solvents are distilled off in vacuo, the remaining colorless solid N'- {4- [3-chloro-5 - (trifluoromethyl) phenyl] -3 - (ethylsulfanyl) -1 - (pyrimidin-2-yl) - lH-pyrazole 5-yl} -N, N-dimethylimidoformamide was obtained with 0.31 g (91.4% of theory).
1H-NMR (400 MHz, d6-DMSO), δ 8.86 (d, 2H), 7.91 (m, 2H), 7.60 (s, IH), 7.47 (t, IH), 3.08 (q, 2H), 2.88 (s, 3H), 1.31 (t, 3H). 1 H-NMR (400 MHz, d 6 -DMSO), δ 8.86 (d, 2H), 7.91 (m, 2H), 7.60 (s, IH), 7.47 (t, IH), 3.08 (q, 2H), 2.88 (s, 3H), 1.31 (t, 3H).
IgP (HCOOH) = 3,48 IgP (HCOOH) = 3.48
Tabelle 1Table 1
Figure imgf000061_0001
Figure imgf000061_0001
R1 = R2 = H n = 0 oder 1R 1 = R 2 = H n = 0 or 1
Figure imgf000061_0002
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Tabelle 2
Figure imgf000069_0001
n = 0 oder 1
Figure imgf000069_0002
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0002
Figure imgf000061_0002
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Table 2
Figure imgf000069_0001
n = 0 or 1
Figure imgf000069_0002
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0002
Tabelle 3
Figure imgf000076_0001
n = O oder 1
Figure imgf000076_0003
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0002
Table 3
Figure imgf000076_0001
n = 0 or 1
Figure imgf000076_0003
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0002
Tabelle 4
Figure imgf000084_0001
Figure imgf000084_0003
Figure imgf000085_0001
Figure imgf000086_0002
Table 4
Figure imgf000084_0001
Figure imgf000084_0003
Figure imgf000085_0001
Figure imgf000086_0002
Tabelle 5 - Zwischenprodukte.
Figure imgf000086_0001
Figure imgf000086_0003
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0002
Table 5 - Intermediates.
Figure imgf000086_0001
Figure imgf000086_0003
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0002
Tabelle 6 - Zwischenprodukte
Figure imgf000092_0001
Figure imgf000092_0003
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0002
Table 6 - Intermediates
Figure imgf000092_0001
Figure imgf000092_0003
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0002
Tabelle 7 - ZwischenprodukteTable 7 - Intermediates
Figure imgf000097_0001
Figure imgf000098_0002
Figure imgf000097_0001
Figure imgf000098_0002
Tabelle 8
Figure imgf000098_0001
R1 = R2 = H n = 0 oder 1Table 8
Figure imgf000098_0001
R 1 = R 2 = H n = 0 or 1
Figure imgf000098_0003
Tabelle 9 - Zwischenprodukte
Figure imgf000099_0002
Figure imgf000098_0003
Table 9 - Intermediates
Figure imgf000099_0002
BIOLOGISCHE DATENBIOLOGICAL DATA
Beispiel Nr. 1Example No. 1
Phaedon-Test (Spritzbehandlung)Phaedon test (spray treatment)
Lösungsmittel: 78,0 Gewichtsteile Aceton 1,5 Gewichtsteile DimethylformamidSolvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide
Emulgator: 0,5 Gewichtsteile AlkylarylpolyglykoletherEmulsifier: 0.5 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit emulgatorhaltigem Wasser auf die gewünschte Konzentration.To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
Chinakohlblattscheiben (Brassica pekinensis) werden mit einer Wirkstoffzubereitung der gewünschten Konzentration gespritzt und nach dem Abtrocknen mit Larven des Meerrettichblattkäfers (Phaedon cochleariae) besetzt.Chinese cabbage leaf discs (Brassica pekinensis) are sprayed with a preparation of active compound of the desired concentration and, after drying, are populated with larvae of the horseradish leaf beetle (Phaedon cochleariae).
Nach 7 Tagen wird die Wirkung in % bestimmt. Dabei bedeutet 100 %, dass alle Käferlarven abgetötet wurden; 0 % bedeutet, dass keine Käferlarven abgetötet wurden.After 7 days, the effect is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.
Bei diesem Test zeigen z. B. die folgenden Verbindungen der Herstellungsbeispiele eine Wirkung von > 80 % bei einer Aufwandmenge von 500 g/ha:In this test, z. B. the following compounds of the preparation examples an effect of> 80% at a rate of 500 g / ha:
Bsp. Nr.: 1-009, 1-013, 1-017, 1-021, 1-025, 1-029, 1-033, 1-036, 1-037, 1-038, 1-039, 1-041, 1- 045, 1-046, 1-047, 1-048, 1-049, 1-050, 1-053, 1-057, 1-058, 1-060, 1-061, 1-062, 1-064, 1-065, 1- 082, 1-083, 1-089, 1-091, 1-092, 1-093, 1-094, 1-095, 1-097, 1-098, 1-099, 1-100, 2-013, 2-017, 2- 021, 2-025, 2-029, 2-033, 2-037, 2-039, 2-040, 2-041, 2-045, 2-046, 2-047, 2-048, 2-049, 2-050, 2- 053, 2-058, 2-060, 2-061, 2-062, 2-064, 2-065, 2-082, 2-083, 2-089, 2-092, 2-094, 2-096, 2-097, 2- 099, 3-009, 3-013, 3-017, 3-021, 3-025, 3-029, 3-033, 3-036, 3-037, 3-039, 3-040, 3-045, 3-046, 3- 048, 3-049, 3-050, 3-053, 3-057, 3-058, 3-060, 3-061, 3-062, 3-064, 3-065, 3-083, 3-084, 3-089, 3- 091, 3-093, 3-095, 3-099, 4-010, 4-012, 7-001Ex. Nos. 1-009, 1-013, 1-017, 1-021, 1-025, 1-029, 1-033, 1-036, 1-037, 1-038, 1-039, 1 -041, 1-045, 1-046, 1-047, 1-048, 1-049, 1-050, 1-053, 1-057, 1-058, 1-060, 1-061, 1-062 , 1-064, 1-065, 1-082, 1-083, 1-089, 1-091, 1-092, 1-093, 1-094, 1-095, 1-097, 1-098, 1 -099, 1-100, 2-013, 2-017, 2-021, 2-025, 2-029, 2-033, 2-037, 2-039, 2-040, 2-041, 2-045 , 2-046, 2-047, 2-048, 2-049, 2-050, 2-053, 2-058, 2-060, 2-061, 2-062, 2-064, 2-065, 2 -082, 2-083, 2-089, 2-092, 2-094, 2-096, 2-097, 2-099, 3-009, 3-013, 3-017, 3-021, 3-025 , 3-029, 3-033, 3-036, 3-037, 3-039, 3-040, 3-045, 3-046, 3-048, 3-049, 3-050, 3-053, 3 -057, 3-058, 3-060, 3-061, 3-062, 3-064, 3-065, 3-083, 3-084, 3-089, 3- 091, 3-093, 3-095 , 3-099, 4-010, 4-012, 7-001
Beispiel Nr. 2Example No. 2
Spodoptera frugiperda-Test (Spritzbehandlung)Spodoptera frugiperda test (spray treatment)
Lösungsmittel: 78,0 Gewichtsteile AcetonSolvent: 78.0 parts by weight of acetone
1,5 Gewichtsteile Dimethylformamid Emulgator: 0,5 Gewichtsteile Alkylarylpolyglykolether1.5 parts by weight of dimethylformamide Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit emulgatorhaltigem Wasser auf die gewünschte Konzentration.To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
Maisblattscheiben (Zea mays) werden mit einer Wirkstoffzubereitung der gewünschten Konzentration gespritzt und nach dem Abtrocknen mit Raupen des Heerwurms (Spodoptera frugiperdά) besetzt.Maize leaf discs (Zea mays) are sprayed with an active compound preparation of the desired concentration and, after drying, are infested with caterpillars of the armyworm (Spodoptera frugiperd®).
Nach 7 Tagen wird die Wirkung in % bestimmt. Dabei bedeutet 100 %, dass alle Raupen abgetötet wurden; 0 % bedeutet, dass keine Raupe abgetötet wurde.After 7 days, the effect is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillar has been killed.
Bei diesem Test zeigen z. B. die folgenden Verbindungen der Herstellungsbeispiele eine Wirkung von > 80 % bei einer Aufwandmenge von 500 g/ha:In this test, z. B. the following compounds of the preparation examples an effect of> 80% at a rate of 500 g / ha:
Bsp. Nr.: 1-038, 1-039, 1-045, 1-046, 1-049, 1-050, 1-058, 1-061, 1-062, 1-064, 1-065, 1-082, 1- 083, 1-091, 1-092, 1-094, 1-095, 1-097, 1-099, 1-100, 2-025, 2-032, 2-033, 2-036, 2-039, 2-045, 2- 046, 2-049, 2-050, 2-058, 2-060, 2-061, 2-062, 2-064, 2-065, 2-083, 2-092, 2-093, 2-094, 2-097, 2- 099, 3-025, 3-029, 3-033, 3-036, 3-037, 3-039, 3-041, 3-045, 3-046, 3-048, 3-049, 3-050, 3-058, 3- 060, 3-061, 3-062, 3-064, 3-065, 3-083, 3-095, 3-099, 4-012Ex. Nos. 1-038, 1-039, 1-045, 1-046, 1-049, 1-050, 1-058, 1-061, 1-062, 1-064, 1-065, 1 -082, 1-083, 1-091, 1-092, 1-094, 1-095, 1-097, 1-099, 1-100, 2-025, 2-032, 2-033, 2-036 , 2-039, 2-045, 2-046, 2-049, 2-050, 2-058, 2-060, 2-061, 2-062, 2-064, 2-065, 2-083, 2 -092, 2-093, 2-094, 2-097, 2-099, 3-025, 3-029, 3-033, 3-036, 3-037, 3-039, 3-041, 3-045 , 3-046, 3-048, 3-049, 3-050, 3-058, 3-060, 3-061, 3-062, 3-064, 3-065, 3-083, 3-095, 3 -099, 4-012
Bei diesem Test zeigen z. B. die folgenden Verbindungen der Herstellungsbeispiele eine Wirkung von > 80 % bei einer Aufwandmenge von 100 g/ha:In this test, z. B. the following compounds of the preparation examples an effect of> 80% at a rate of 100 g / ha:
Bsp. Nr.: 1-047, 1-049, 2-047, 3-057Ex. No. 1-047, 1-049, 2-047, 3-057
Beispiel Nr. 3Example No. 3
Tetranychus-Test, OP-resistent (TETRUR Spritzbehandlung)Tetranychus test, surgical-resistant (TETRUR spray treatment)
Lösungsmittel: 78,0 Gewichtsteile Aceton 1,5 Gewichtsteile DimethylformamidSolvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide
Emulgator: 0,5 Gewichtsteile Alkylarylpolyglykolether Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit emulgatorhaltigem Wasser auf die gewünschte Konzentration.Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
Bohnenblattscheiben (Phaseolus vulgaris), die von allen Stadien der Gemeinen Spinnmilbe (Tetra- nychus urticae) befallen sind, werden mit einer Wirkstoffzubereitung der gewünschten Konzentration gespritzt.Bean leaf discs (Phaseolus vulgaris) infected by all stages of the common spider mite (Tetranychus urticae) are sprayed with an active compound preparation of the desired concentration.
Nach 6 Tagen wird die Wirkung in % bestimmt. Dabei bedeutet 100 %, dass alle Spinnmilben abgetötet wurden; 0 % bedeutet, dass keine Spinnmilben abgetötet wurden.After 6 days, the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
Bei diesem Test zeigen z. B. die folgenden Verbindungen der Herstellungsbeispiele eine Wirkung von > 80 % bei einer Aufwandmenge von 500 g/ha:In this test, z. B. the following compounds of the preparation examples an effect of> 80% at a rate of 500 g / ha:
Bsp. Nr.: 1-053, 1-082, 1-083, 1-093, 1-097, 2-039, 2-046, 2-053, 2-094, 2-097, 2-099, 3-029, 3- 033, 3-037, 3-046, 3-093, 6-010, 6-045Ex. Nos. 1-053, 1-082, 1-083, 1-093, 1-097, 2-039, 2-046, 2-053, 2-094, 2-097, 2-099, 3 -029, 3-033, 3-037, 3-046, 3-093, 6-010, 6-045
Beispiel Nr. 4Example No. 4
Myzus-Test (MYZUPE Spritzbehandlung)Myzus test (MYZUPE spray treatment)
Lösungsmittel: 78,0 Gewichtsteile AcetonSolvent: 78.0 parts by weight of acetone
1,5 Gewichtsteile Dimethylformamid1.5 parts by weight of dimethylformamide
Emulgator: 0,5 Gewichtsteile AlkylarylpolyglykoletherEmulsifier: 0.5 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirk- stoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit emulgatorhaltigem Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
Chinakohlblattscheiben (Brassica pekinensis), die von allen Stadien der Grünen Pfϊrsichblattlaus (Myzus persicae) befallen sind, werden mit einer Wirkstoffzubereitung der gewünschten Konzentration gespritzt.Chinese cabbage leaf discs (Brassica pekinensis), which are infested by all stages of the green pepper aphid (Myzus persicae), are sprayed with an active compound preparation of the desired concentration.
Nach 6 Tagen wird die Wirkung in % bestimmt. Dabei bedeutet 100 %, dass alle Blattläuse abgetötet wurden; 0 % bedeutet, dass keine Blattläuse abgetötet wurden.After 6 days, the effect is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
Bei diesem Test zeigen z. B. die folgenden Verbindungen der Herstellungsbeispiele eine Wirkung von > 80 % bei einer Aufwandmenge von 500 g/ha: Bsp. Nr.: 1-046, 1-061, 1-082, 2-013, 2-041, 2-045, 2-046, 2-058, 2-083, 2-094, 2-097, 3-033, 3- 045, 3-046In this test, z. B. the following compounds of the preparation examples an effect of> 80% at a rate of 500 g / ha: Ex. No. 1-046, 1-061, 1-082, 2-013, 2-041, 2-045, 2-046, 2-058, 2-083, 2-094, 2-097, 3 -033, 3-045, 3-046
Beispiel Nr. 5Example No. 5
Meloidogyne-Test (MELGEV Spritzbehandlung)Meloidogyne test (MELGEV spray treatment)
Lösungsmittel: 80 Gewichtsteile AcetonSolvent: 80 parts by weight of acetone
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with water to the desired concentration.
Gefäße werden mit Sand, Wirkstofflösung, Meloidogyne j/icogM/ta-Ei-Larven-Suspension und Salatsamen gefüllt. Die Salatsamen keimen und die Pflänzchen entwickeln sich. An den Wurzeln entwickeln sich die Gallen.Vessels are filled with sand, drug solution, Meloidogyne j / icogM / ta-egg larvae suspension and lettuce seeds. The lettuce seeds germinate and the plantlets develop. The galls develop at the roots.
Nach 14 Tagen wird die nematizide Wirkung an Hand der Gallenbildung in % bestimmt. Dabei bedeutet 100 %, dass keine Gallen gefunden wurden; 0 % bedeutet, dass die Zahl der Gallen an den behandelten Pflanzen der der unbehandelten Kontrolle entspricht.After 14 days, the nematicidal activity is determined by means of bile formation in%. 100% means that no bile was found; 0% means that the number of bile on the treated plants corresponds to that of the untreated control.
Bei diesem Test zeigen z. B. die folgenden Verbindungen der Herstellungsbeispiele eine Wirkung von > 80 % bei einer Aufwandmenge von 20 ppm:In this test, z. B. the following compounds of the preparation examples an effect of> 80% at a rate of 20 ppm:
Bsp. Nr. 3-029, 3-033Ex. No. 3-029, 3-033
Beispiel Nr. 6Example No. 6
Boophilus microplus -Test (BOOPMI Injektion)Boophilus microplus test (BOOPMI injection)
Lösungsmittel: DimethylsulfoxidSolvent: dimethyl sulfoxide
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration. Die Wirkstofflösung wird in das Abdomen (Boophilus microplus) injiziert, die Tiere werden in Schalen überfuhrt und in einem klimatisierten Raum aufbewahrt. Die Wirkungskontrolle erfolgt auf Ablage fertiler Eier.To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with water to the desired concentration. The drug solution is injected into the abdomen (Boophilus microplus), the animals are transferred into trays and stored in an air-conditioned room. The effect control takes place on storage of fertile eggs.
Nach 7 Tagen wird die Wirkung in % bestimmt. Dabei bedeutet 100%, dass keine Zecke fertile Eier gelegt hat.After 7 days, the effect is determined in%. 100% means that no ticks have laid fertile eggs.
Bei diesem Test zeigen z. B. die folgenden Verbindungen der Herstellungsbeispiele eine Wirkung von > 80 % bei einer Aufwandmenge von 20 μg/Tier:In this test, z. B. the following compounds of the preparation examples an effect of> 80% at a rate of 20 ug / animal:
Bsp. Nr.: 1-021, 1-025, 1-029, 1-033, 1-046, 1-061, 1-062, 1-064, 1-065, 2-025, 2-029, 2-062, 3- 025, 3-046, 3-061, 3-062, 3-065, 4-010, 4-012Ex. No. 1-021, 1-025, 1-029, 1-033, 1-046, 1-061, 1-062, 1-064, 1-065, 2-025, 2-029, 2 -062, 3-025, 3-046, 3-061, 3-062, 3-065, 4-010, 4-012
Beispiel Nr. 7Example No. 7
Ctenocephalides felis; oral (CTECFE)Ctenocephalides felis; oral (CTECFE)
Lösungsmittel: 1 Gewichtsteil DimethylsulfoxidSolvent: 1 part by weight of dimethyl sulfoxide
Zwecks Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 2 Gewichtsteile Wirkstoff mit der angegebenen Menge Lösungsmittel. Ein Teil des Konzentrats wird mit citirier- tem Rinderblut verdünnt und die gewünschte Konzentration hergestellt.For the preparation of a suitable preparation of active compound, 2 parts by weight of active compound are mixed with the stated amount of solvent. Part of the concentrate is diluted with citrated bovine blood and the desired concentration is produced.
20 nüchterne adulte Flöhe {Ctenocephalides felis) werden in eine Kammer eingesetzt, die oben und unten mit Gaze verschlossen ist. Auf die Kammer wird ein Metalizylinder gestellt, dessen Unterseite mit Parafilm verschlossen ist. Der Zylinder enthält die Blut- Wirkstoffzubereitung, die von den Flöhen durch die Parafilmmembran aufgenommen werden kann.20 fasting adult fleas (Ctenocephalides felis) are placed in a chamber sealed with gauze at the top and bottom. A metal cylinder is placed on the chamber, the underside of which is sealed with parafilm. The cylinder contains the blood-drug preparation that can be absorbed by the fleas through the parafilm membrane.
Nach 2 Tagen wird die Abtötung in % bestimmt. Dabei bedeutet 100 %, dass alle Flöhe abgetötet wurden; 0 % bedeutet, dass kein Floh abgetötet wurde.After 2 days the kill is determined in%. 100% means that all fleas have been killed; 0% means that no flea has been killed.
Bei diesem Test zeigen z. B. die folgenden Verbindungen der Herstellungsbeispiele eine Wirkung von > 80 % bei einer Aufwandmenge von 100 ppm:In this test, z. B. the following compounds of the preparation examples an effect of> 80% at a rate of 100 ppm:
Bsp. Nr.: 1-046, 1-061, 1-062, 1-064, 1-065, 2-045, 2-046, 2-060, 2-061, 2-062, 2-064, 2-065, 3- 041, 3-045, 3-046, 3-060, 3-061, 3-062, 3-065, 4-010, 4-012 Beispiel Nr. 8Ex. No. 1-046, 1-061, 1-062, 1-064, 1-065, 2-045, 2-046, 2-060, 2-061, 2-062, 2-064, 2 -065, 3-041, 3-045, 3-046, 3-060, 3-061, 3-062, 3-065, 4-010, 4-012 Example No. 8
Lucilia cuprina-Test (LUCICU)Lucilia cuprina test (LUCICU)
Lösungsmittel: DimethylsulfoxidSolvent: dimethyl sulfoxide
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirk- stoff mit der angegebenen Menge Lösungsmittel und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with water to the desired concentration.
Gefäße, die Pferdefleisch enthalten, das mit der Wirkstoffzubereitung der gewünschten Konzentration behandelt wurde, werden mit Lucilia cuprina Larven besetzt.Vessels containing horsemeat treated with the preparation of active compound of the desired concentration are infested with Lucilia cuprina larvae.
Nach 2 Tagen wird die Abtötung in % bestimmt. Dabei bedeutet 100 %, dass alle Larven abgetötet wurden; 0 % bedeutet, dass keine Larven abgetötet wurden.After 2 days the kill is determined in%. 100% means that all larvae have been killed; 0% means that no larvae have been killed.
Bei diesem Test zeigen z. B. die folgenden Verbindungen der Herstellungsbeispiele eine Wirkung von > 80 % bei einer Aufwandmenge von 100 ppm:In this test, z. B. the following compounds of the preparation examples an effect of> 80% at a rate of 100 ppm:
Bsp. Nr.: 1-021, 1-025, 1-029, 1-033, 1-037, 1-041, 1-045, 1-046, 1-060, 1-061, 1-062, 1-064, 1- 065, 2-013, 2-017, 2-021, 2-025, 2-029, 2-033, 2-045, 2-046, 2-060, 2-061, 2-062, 2-064, 2-065, 3- 017, 3-025, 3-029, 3-036, 3-041, 3-045, 3-046, 3-060, 3-061, 3-062, 3-065, 4-010, 4-012Ex. No. 1-021, 1-025, 1-029, 1-033, 1-037, 1-041, 1-045, 1-046, 1-060, 1-061, 1-062, 1 -064, 1-065, 2-013, 2-017, 2-021, 2-025, 2-029, 2-033, 2-045, 2-046, 2-060, 2-061, 2-062 , 2-064, 2-065, 3-017, 3-025, 3-029, 3-036, 3-041, 3-045, 3-046, 3-060, 3-061, 3-062, 3 -065, 4-010, 4-012
Beispiel Nr. 9Example No. 9
Musca domestica-Test (MUSCDO)Musca domestica test (MUSCDO)
Lösungsmittel: DimethylsulfoxidSolvent: dimethyl sulfoxide
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the concentrate is diluted with water to the desired concentration.
Gefäße, die einen Schwamm enthalten, der mit der Wirkstoffzubereitung der gewünschten Konzentration behandelt wurde, werden mit Musca domestica Adulten besetzt.Vessels containing a sponge treated with the preparation of active compound of the desired concentration are mated with Musca domestica adults.
Nach 2Tagen wird die Abtötung in % bestimmt. Dabei bedeutet 100 %, dass alle Fliegen abgetötet wurden; 0 % bedeutet, dass keine Fliegen abgetötet wurden. Bei diesem Test zeigen z. B. die folgenden Verbindungen der Herstellungsbeispiele eine Wirkung von > 80 % bei einer Aufwandmenge von 100 ppm:After 2 days the kill is determined in%. 100% means that all flies have been killed; 0% means that no flies have been killed. In this test, z. B. the following compounds of the preparation examples an effect of> 80% at a rate of 100 ppm:
Bsp. Nr.: 1-025, 1-029, 1-046, 1-062, 2-025, 2-046, 2-060, 2-061, 2-062, 2-065, 3-041, 3-045, 3- 046, 3-061, 3-062Ex. No. 1-025, 1-029, 1-046, 1-062, 2-025, 2-046, 2-060, 2-061, 2-062, 2-065, 3-041, 3 -045, 3-046, 3-061, 3-062
Bei diesem Test zeigen z. B. die folgenden Verbindungen der Herstellungsbeispiele eine Wirkung von >80 % bei einer Aufwandmenge von 20 ppm :In this test, z. B. the following compounds of the preparation examples an effect of> 80% at a rate of 20 ppm:
Bsp Nr : 2-029 Example number: 2-029

Claims

Patentansprüche: claims:
1. Schwefel -derivatisierte 1-Azinylpyτazole der allgemeinen Formel (I)1. Sulfur-derivatized 1-azinylpyrazoles of the general formula (I)
Figure imgf000107_0001
Figure imgf000107_0001
in welcherin which
A1 und A2, jeweils unabhängig voneinander, für Stickstoff oder C-R3 stehen;A 1 and A 2 , each independently, are nitrogen or CR 3 ;
B für Alkyl, Cycloalkyl, Cycloalkenyl, Cycloalkylalkyl, Haloalkyl, Alkoxyalkyl, Cyanoalkyl,B is alkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, haloalkyl, alkoxyalkyl, cyanoalkyl,
Alkylthioalkyl, Alkylsulfinylalkyl, Alkylsulfonylalkyl, Aminoalkyl, Monoalkylaminoalkyl, Dialkylaminoalkyl, Alkylcarbonylalkyl, Alkoxycarbonylalkyl, Monoalkylaminocarbony- lalkyl, Diaminoalkylcarbonylalkyl, Alkenyl und Alkinyl, welche jeweils gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein können durch Halogen, Alkyl, Haloalkyl, Alkoxy, Trialkylsilyl, Nitro oder Cyano; Phenalkyl, welches am Aromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano; Heterocyclylalkyl, welches am He- terocyclus gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH / =0, -SH / =S, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl,Alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, aminoalkyl, monoalkylaminoalkyl, dialkylaminoalkyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, monoalkylaminocarbony- lalkyl, diaminoalkylcarbonylalkyl, alkenyl and alkynyl, which may each be optionally mono- or polysubstituted by or differently substituted by halogen, alkyl, haloalkyl, alkoxy, trialkylsilyl, nitro or cyano; Phenalkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the aromatic group by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; Heterocyclylalkyl which may optionally be mono- or polysubstituted by identical or different substituents on the heterocycle by -OH / = O, -SH / SS, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl,
Alkylsulfϊnyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; Heteroa- rylalkyl, welches am Heteraromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH, -SH, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfϊnyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; Phenyl, welches gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH, -SH, -NH2 Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfϊnyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; Heteroaryl, welches gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH, -SH, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; oder He- terocyclyl, welches gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH / =0, -SH / =S, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; steht;Alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; Heteroarylalkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the heteroaromatic radical by -OH, -SH, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; Phenyl, which may optionally be mono- or polysubstituted by identical or different substituents, by -OH, -SH, -NH 2 halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; Heteroaryl, which may optionally be mono- or polysubstituted by identical or different substituents by -OH, -SH, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; or heterocyclyl, which may optionally be mono- or polysubstituted by identical or different substituents by -OH / = O, -SH / SS, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino , Nitro or cyano; stands;
R1 und R2, jeweils unabhängig voneinander, für Wasserstoff, Alkyl, Haloalkyl, Cyanoalkyl, Alko- xyalkyl, Alkylcarbonyl, Haloalkylcarbonyl, Cycloalkyl, Cycloalkylalkyl, Alkylsulfonyl, Alkenyl, Alkinyl, Alkoxycarbonyl, Alkenyloxycarbonyl, Alkinyloxycarbonyl, Alkoxycar- bonylalkyl; Phenalkyl, welches am Aromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano; Heterocyclylalkyl, welches am Heterocyclus gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano; Heteroarylalkyl, welches am Heteraromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl,R 1 and R 2 are each independently hydrogen, alkyl, haloalkyl, cyanoalkyl, alkoxyalkyl, alkylcarbonyl, haloalkylcarbonyl, cycloalkyl, cycloalkylalkyl, alkylsulfonyl, alkenyl, alkynyl, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, alkoxycarbonylalkyl; Phenalkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the aromatic group by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; Heterocyclylalkyl which may optionally be mono- or polysubstituted by identical or different substituents on the heterocycle by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; Heteroarylalkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the heteroaromatic radical by halogen, alkyl,
Haloalkyl, Alkoxy, Nitro oder Cyano; oder Phenylcarbonyl, welches am Aromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano;Haloalkyl, alkoxy, nitro or cyano; or phenylcarbonyl which optionally substituted one or more times identically or differently on the aromatic by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano;
stehen; oderstand; or
R1 und R2 gemeinsam für =CH-NR4R5 R 1 and R 2 together for = CH-NR 4 R 5
stehen;stand;
R3 für Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfinyl, Alkylsulfonyl, HaIo- alkoxy, Haloalkylsulfanyl, Haloalkylsulfinyl, Haloalkylsulfonyl, Alkylcarbonyl, Formyl, - CR6=NO-R6, Alkoxycarbonyl, Hydroxy, -SH, Nitro, Cyano, NH2, Monoalkylamino oder DialkylaminoR 3 is halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, haloalkoxy, haloalkylsulfanyl, haloalkylsulfinyl, haloalkylsulfonyl, alkylcarbonyl, formyl, --CR 6 = NO-R 6 , alkoxycarbonyl, hydroxy, -SH, nitro, cyano , NH 2 , monoalkylamino or dialkylamino
steht;stands;
R4 und R5 jeweils unabhängig voneinander für Alkyl oder gemeinsam für verbrückendes AlkylidenR 4 and R 5 are each independently alkyl or together bridging alkylidene
stehen;stand;
R6 für Wasserstoff oder für AlkylR 6 is hydrogen or alkyl
steht;stands;
X für Phenyl, 2-Pyridyl oder 3-Pyridyl steht, jeweils substituiert durch einen oder mehrere gleiche oder verschiedene Substituenten ausgewählt aus der Gruppe, bestehend aus Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alkoxyalkoxy, Cycloalkyl, Alkenoxy, Alki- noxy, Cycloalkylalkoxy, Haloalkoxy, Haloalkoxyalkyl, Alkylsulfanyl, Haloalkylsulfanyl, Alkylsulfinyl, Haloalkylsulfinyl, Alkylsulfonyl, Haloalkylsulfonyl, Cyano, Alkylcarbonyl, Alkoxycarbonyl, Alkoxycarbonylalkyl, Carboxyl, Carboxamid, Dialkylcarboxamid, Trial- kylsilyl, Nitro, Amino, Alkylamino, Dialkylamino, Alkylsulfonylamino, Dialkylsulfony- lamino, -CR6=NO-R6, -CR6=NO-Haloalkyl, oder Formyl steht, wobei vicinale Alkyl-, Ha- loalkyl, Alkoxy- und/oder Haloalkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann;X is phenyl, 2-pyridyl or 3-pyridyl, each substituted by one or more identical or different substituents selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkenoxy, alkynyloxy, Cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, haloalkylsulfanyl, Alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, nitro, amino, alkylamino, dialkylamino, alkylsulfonylamino, dialkylsulfonylamino, -CR 6 = NO-R 6 , - CR 6 = NO-haloalkyl, or formyl, where vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached, may form a five- to six-membered cyclic system containing from 0 to Contains 2 oxygen atoms, and its alkyl moiety may optionally be substituted with one or more fluorine atoms;
Y für -S-, -S(O)-, -SO2-, oder eine der folgenden GruppierungenY is -S-, -S (O) -, -SO 2 -, or one of the following groupings
Figure imgf000109_0001
Figure imgf000109_0001
steht;stands;
n für 0 bis 3n for 0 to 3
steht;stands;
und die Verbindungen der allgemeinen Formel (I) - insofern chemisch möglich - deren N-Oxide, Salze, Tautomere, Diastereomere und optische Isomere umfassen.and the compounds of the general formula (I) - insofar chemically possible - whose N-oxides, salts, tautomers, diastereomers and optical isomers.
2. Schwefel -derivatisierte 1-Azinylpyrazole nach Anspruch 1, dadurch gekennzeichnet, dass in der allgemeinen Formel (I) gemeinsam A1 für Stickstoff und A2 für CH oder C-R3 stehen.2. sulfur-derivatized 1-Azinylpyrazole according to claim 1, characterized in that in the general formula (I) together A 1 is nitrogen and A 2 is CH or CR 3 .
3. Schwefel -derivatisierte 1-Azinylpyrazole nach Anspruch 1, dadurch gekennzeichnet, dass in der allgemeinen Formel (I) gemeinsam A1 für CH oder C-R3 und A2 für CH oder C-R3 stehen, wobei bei mehr als einem Rest R3 die Reste R3 gleich oder verschieden sein können. 3. sulfur-derivatized 1-Azinylpyrazole according to claim 1, characterized in that in the general formula (I) together A 1 is CH or CR 3 and A 2 is CH or CR 3 , wherein when more than one radical R 3 is the Radicals R 3 may be the same or different.
4. Schwefel-derivatisierte 1 -Azinylpyrazole nach Anspruch 1, dadurch gekennzeichnet, dass in der allgemeinen Formel (I) gemeinsam A1 für CH oder C-R3 und A2 für Stickstoff stehen.4. sulfur-derivatized 1-azinylpyrazoles according to claim 1, characterized in that in the general formula (I) together A 1 is CH or CR 3 and A 2 is nitrogen.
5. Schwefel-derivatisierte 1 -Azinylpyrazole nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass in der allgemeinen Formel (I) der Rest B für Alkyl, Cycloalkyl, Cyclo- alkylalkyl, Haloalkyl, Alkoxyalkyl, Cyanoalkyl, Alkylthioalkyl, Alkylsulfinylalkyl, Alkyl- sulfonylalkyl, Aminoalkyl, Alkylcarbonylalkyl, Alkoxycarbonylalkyl, Alkenyl und Alki- nyl, welche jeweils gegebenenfalls einfach oder mehrfach gleich oder verschieden substitu- iert sein können durch Halogen, Alkyl, Haloalkyl, Alkoxy, Trialkylsilyl, Nitro oder Cyano;5. Sulfur-derivatized 1-azinylpyrazoles according to any one of claims 1 to 4, characterized in that in the general formula (I) the radical B is alkyl, cycloalkyl, cycloalkylalkyl, haloalkyl, alkoxyalkyl, cyanoalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkyl - sulfonylalkyl, aminoalkyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkenyl and alkynyl, which may each optionally be monosubstituted or polysubstituted by identical or different substituents by halogen, alkyl, haloalkyl, alkoxy, trialkylsilyl, nitro or cyano;
Phenalkyl, welches am Aromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch Halogen, Alkyl, Haloalkyl, Alkoxy, Nitro oder Cyano; Heterocyclylalkyl, welches am Heterocyclus gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH / =0, -SH / =S, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfϊnyl, Alkylsulfonyl, Monoalkylamino,Phenalkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the aromatic group by halogen, alkyl, haloalkyl, alkoxy, nitro or cyano; Heterocyclylalkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the heterocycle by -OH / = O, -SH / SS, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino,
Dialkylamino, Nitro oder Cyano; Heteroarylalkyl, welches am Heteraromaten gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH, -SH, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfϊnyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; Phenyl, welches gegebenenfalls ein- fach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH, -SH, -NH2,Dialkylamino, nitro or cyano; Heteroarylalkyl which may optionally be monosubstituted or polysubstituted by identical or different substituents on the heteroaromatic radical by means of -OH, -SH, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; Phenyl, which may optionally be substituted once or more than once or differently by -OH, -SH, -NH 2 ,
Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfϊnyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; Heteroaryl, welches gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH, -SH, -NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfϊnyl, Alkylsulfonyl, Monoalkyla- mino, Dialkylamino, Nitro oder Cyano; oder Heterocyclyl, welches gegebenenfalls einfach oder mehrfach gleich oder verschieden substituiert sein kann durch -OH / =0, -SH / =S, - NH2, Halogen, Alkyl, Haloalkyl, Alkoxy, Alkylsulfanyl, Alkylsulfϊnyl, Alkylsulfonyl, Monoalkylamino, Dialkylamino, Nitro oder Cyano; steht.Halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; Heteroaryl, which may optionally be mono- or polysubstituted by identical or different substituents by -OH, -SH, -NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, Alkylsulfϊnyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; or heterocyclyl which may optionally be monosubstituted or polysubstituted by identical or different substituents by -OH / = O, -SH / SS, - NH 2 , halogen, alkyl, haloalkyl, alkoxy, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, monoalkylamino, dialkylamino, nitro or cyano; stands.
6. Schwefel-derivatisierte 1 -Azinylpyrazole nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass in der allgemeinen Formel (I) der Substituent X für substituiertes Phenyl steht und als Substituenten Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alkoxy- alkoxy, Cycloalkyl, Alkenoxy, Alkinoxy, Cycloalkylalkoxy, Haloalkoxy, Haloalkoxyalkyl, Alkylsulfanyl, Haloalkylsulfanyl, Alkylsulfinyl, Haloalkylsulfinyl, Alkylsulfonyl, Haloal- kylsulfonyl, Cyano, Alkylcarbonyl, Alkoxycarbonyl, Alkoxycarbonylalkyl, Carboxyl, Car- boxamid, Dialkylcarboxamid, Trialkylsilyl, Nitro, Amino, Alkylamino, Dialkylamino, Al- kylsulfonylamino, Dialkylsulfonylamino, -CR6=NO-R6, -CR6=NO-Haloalkyl, oder Formyl verwendet werden, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder Haloalkoxygrup- pen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechs- gliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann.6. sulfur-derivatized 1-azinylpyrazoles according to any one of claims 1 to 5, characterized in that in the general formula (I), the substituent X is substituted phenyl and as substituents halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxy alkoxy , Cycloalkyl, alkenoxy, alkynoxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, haloalkylsulfanyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkyl kylsulfonyl, cyano, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, nitro, amino, alkylamino, dialkylamino, alkylsulfonylamino, dialkylsulfonylamino, -CR 6 = NO-R 6 , -CR 6 = NO-haloalkyl , or formyl, where vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms , and its alkyl moiety may be optionally substituted with one or more fluorine atoms.
7. Schwefel-derivatisierte 1-Azinylpyrazole nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass in der allgemeinen Formel (I) die Substituenten R1 und R2 für Wasserstoff stehen.7. sulfur-derivatized 1-Azinylpyrazole according to any one of claims 1 to 6, characterized in that in the general formula (I), the substituents R 1 and R 2 are hydrogen.
8. Verfahren zur Herstellung von Verbindungen der allgemeinen Formel (I) gemäß einem der Asprüche 1 bis 7, gekennzeichnet durch mindestens einen der folgenden Reaktionsschritte8. A process for the preparation of compounds of the general formula (I) according to one of the Asprüche 1 to 7, characterized by at least one of the following reaction steps
(a) bis (h):(a) to (h):
(a) Umsetzung zur Verbindung der allgemeinen Formel (I) mit R1 und R2 gleich Wasserstoff(a) Reaction to the compound of general formula (I) with R 1 and R 2 is hydrogen
Figure imgf000111_0001
Figure imgf000111_0001
wobei die Reste R1 und R2 gleich Wasserstoff sind, R3, X, Y, B und n die Bedeutung gemäß einem der Ansprüche 1 bis 7 aufweisen;wherein the radicals R 1 and R 2 are hydrogen, R 3 , X, Y, B and n have the meaning according to one of claims 1 to 7;
(b) Umsetzung zur Herstellung der Verbindungen der allgemeinen Formel (I-B) mit Y = - S(O)- (Verbindung der allgemeinen Formel (1-B)) durch:(b) Reaction for the preparation of the compounds of general formula (I-B) with Y = -S (O) - (compound of general formula (1-B)) by:
Figure imgf000111_0002
wobei die Reste R1, R2, R3, X, B und n die Bedeutung gemäß einem der Ansprüche 1 bis 7 aufweisen;
Figure imgf000111_0002
wherein the radicals R 1 , R 2 , R 3 , X, B and n have the meaning according to one of claims 1 to 7;
(c) Umsetzung zur Herstellung der Verbindungen der allgemeinen Formel (I-C) mit Y = - S(O)2- (Verbindung der allgemeinen Formel I-C) durch folgende Umsetzung:(c) Reaction for the preparation of the compounds of general formula (IC) with Y = -S (O) 2 - (compound of general formula IC) by the following reaction:
tA2
Figure imgf000112_0001
tA 2
Figure imgf000112_0001
2 Oxidations- Äquivalente2 oxidation equivalents
wobei die Reste R1, R2, R3, X, B und n die Bedeutung gemäß einem der Ansprüche 1 bis 7 aufweisen;wherein the radicals R 1 , R 2 , R 3 , X, B and n have the meaning according to one of claims 1 to 7;
(d) Umsetzung zur Herstellung der Verbindungen der allgemeinen Formel (I) mit Y = - S(O)(=N-CN)-:(d) Reaction for the preparation of the compounds of general formula (I) with Y = -S (O) (= N-CN) -:
Figure imgf000112_0002
Figure imgf000112_0002
wobei A1, A2, B, X, R3, R6 und n die Bedeutung gemäß einem der Ansprüche 1 bis 7 aufweisen;wherein A 1 , A 2 , B, X, R 3 , R 6 and n have the meaning of any one of claims 1 to 7;
(e) Umsetzung zur Herstellung der Verbindung der allgemeinen Formel (I) mit Y = -S(=N- CN)- (Verbindung der allgemeinen Formel I-D) bzw. -S(O)(=N-CN)- (Verbindung der allgemeinen Formel I-E):(e) Reaction for the preparation of the compound of general formula (I) with Y = -S (= N-CN) - (compound of general formula ID) or -S (O) (= N-CN) - (compound of general formula IE):
Figure imgf000112_0003
Figure imgf000112_0003
wobei A1, A2, B, X, R3, R6 und n die Bedeutung gemäß einem der Ansprüche 1 bis 7 aufweisen; (f) Umsetzung zur Verbindung der allgemeinen Formel (I-G; R1 ungleich Wasserstoff) und (I- H; R1 und R2 ungleich Wasserstoff):wherein A 1, A 2, B, X, R 3, R 6 and n are as defined according to any one of claims 1 to 7 comprising; (f) Reaction to the compound of general formula (IG; R 1 other than hydrogen) and (I-H; R 1 and R 2 other than hydrogen):
(XII)
Figure imgf000113_0001
(XII)
Figure imgf000113_0001
wobei A , A , B, X, R , R und n die Bedeutung gemäß einem der Ansprüche 1 bis 7 aufweisen;wherein A, A, B, X, R, R and n are as defined in any one of claims 1 to 7;
(g) Umsetzung zur Verbindung der allgemeinen Formel (I- J) mit R1 und R2 gemeinsam gleich =C-N(R4)(R5) (g) Reaction to the compound of general formula (I-J) with R 1 and R 2 together = CN (R 4 ) (R 5 )
Figure imgf000114_0001
Figure imgf000114_0001
wobei A , A , B, X, R , R und n die Bedeutung gemäß einem der Ansprüche 1 bis 7 aufweisen;wherein A, A, B, X, R, R and n are as defined in any one of claims 1 to 7;
(h) Umsetzung der Verbindung der allgemeinen Formel (XX) zu einer Verbindung der allgemeinen Formel (I-A) unter Palladium-Katalyse sowie unter Verwendung einer Boronsäure oder eines Boronsäuresters(h) reacting the compound of the general formula (XX) to give a compound of the general formula (I-A) under palladium catalysis and using a boronic acid or a boronic acid ester
Figure imgf000114_0002
Figure imgf000114_0002
9. Verbindungen der allgemeinen Formel (IV)9. Compounds of the general formula (IV)
Figure imgf000114_0003
(IV)
Figure imgf000114_0003
(IV)
mit X gleich
Figure imgf000115_0001
equal to X
Figure imgf000115_0001
wobei G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt werden aus der Gruppe, bestehend aus Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alkoxyalkoxy, Cycloalkyl, Al- kenoxy, Alkinoxy, Cycloalkylalkoxy, Haloalkoxy, Haloalkoxyalkyl, Alkylsulfanyl, HaIo- alkylsulfanyl, Alkylsulfinyl, Haloalkylsulfϊnyl, Alkylsulfonyl, Haloalkylsulfonyl, Cyano,wherein G 1 , G 2 and G 3 , each independently of one another, are selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkeneoxy, alkynoxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, Haloalkylsulfanyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano,
Alkylcarbonyl, Alkoxycarbonyl, Alkoxycarbonylalkyl, Carboxyl, Carboxamid, Dialkylcar- boxamid, Trialkylsilyl, Nitro, Amino, Alkylamino, Dialkylamino, Alkylsulfonylamino, Di- alkylsulfonylamino, -CR6=NO-R6, -CR6=NO-Haloalkyl, oder Formyl steht, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder Haloalkoxygruppen zusammen mit den Kohlenstoff- atomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann; und B die Definition gemäß einem der Ansprüche 1 bis 7 aufweist.Alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, nitro, amino, alkylamino, dialkylamino, alkylsulfonylamino, di-alkylsulfonylamino, -CR 6 = NO-R 6 , -CR 6 = NO-haloalkyl, or formyl in which vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached can form a five- to six-membered cyclic system which contains 0 to 2 oxygen atoms, and whose alkyl moiety optionally has one or a plurality of fluorine atoms may be substituted; and B has the definition of any one of claims 1 to 7.
10. Verbindungen der allgemeinen Formel (FV) nach Anspruch 9, in welcher ein Rest B einem Methylrest entspricht (FV-A) und der andere Rest B die Definition gemäß Ansprüche 1 und 5 aufweist.10. Compounds of the general formula (IV) according to claim 9, in which one radical B corresponds to a methyl radical (FV-A) and the other radical B has the definition according to claims 1 and 5.
Figure imgf000115_0002
'3
Figure imgf000115_0002
'3
11. Verbindungen der allgemeinen Formel (V)11. Compounds of the general formula (V)
Figure imgf000115_0003
Figure imgf000115_0003
mit X gleich
Figure imgf000116_0001
equal to X
Figure imgf000116_0001
wobei G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt werden aus der Gruppe, bestehend aus Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alkoxyalkoxy, Cycloalkyl, Al- kenoxy, Alkinoxy, Cycloalkylalkoxy, Haloalkoxy, Haloalkoxyalkyl, Alkylsulfanyl, HaIo- alkylsulfanyl, Alkylsulfinyl, Haloalkylsulfinyl, Alkylsulfonyl, Haloalkylsulfonyl, Cyano, Alkylcarbonyl, Alkoxycarbonyl, Alkoxycarbonylalkyl, Carboxyl, Carboxamid, Dialkylcar- boxamid, Trialkylsilyl, Nitro, Amino, Alkylamino, Dialkylamino, Alkylsulfonylamino, Di- alkylsulfonylamino, -CR6=NO-R6, -CR6=NO-Haloalkyl, oder Formyl steht, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder Haloalkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann; und B die Definition gemäß einem der Ansprüche 1 bis 7 aufweist.wherein G 1 , G 2 and G 3 , each independently of one another, are selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkeneoxy, alkynoxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, Haloalkylsulfanyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, nitro, amino, alkylamino, dialkylamino, alkylsulfonylamino, dialkylsulfonylamino, -CR 6 = NO- R 6 , -CR 6 = NO-haloalkyl, or formyl, wherein vicinal alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached, can form a five- to six-membered cyclic system, the 0 to 2 oxygen atoms, and its alkyl moiety may be optionally substituted with one or more fluorine atoms; and B has the definition of any one of claims 1 to 7.
12. Verbindungen der allgemeinen Formel (XXm)12. Compounds of the general formula (XXm)
Figure imgf000116_0002
Figure imgf000116_0002
mit X gleichequal to X
Figure imgf000116_0003
Figure imgf000116_0003
wobei G1, G2 und G3, jeweils unabhängig voneinander, ausgewählt werden aus der Gruppe, bestehend aus Halogen, Alkyl, Haloalkyl, Alkoxy, Alkoxyalkyl, Alkoxyalkoxy, Cycloalkyl, Al- kenoxy, Alkinoxy, Cycloalkylalkoxy, Haloalkoxy, Haloalkoxyalkyl, Alkylsulfanyl, HaIo- alkylsulfanyl, Alkylsulfinyl, Haloalkylsulfinyl, Alkylsulfonyl, Haloalkylsulfonyl, Cyano, Alkylcarbonyl, Alkoxycarbonyl, Alkoxycarbonylalkyl, Carboxyl, Carboxamid, Dialkylcar- boxamid, Trialkylsilyl, Nitro, Amino, Alkylamino, Dialkylamino, Alkylsulfonylamino, Di- alkylsulfonylamino, -CR6=NO-R6, -CR6=NO-Haloalkyl, oder Formyl steht, wobei vicinale Alkyl-, Haloalkyl, Alkoxy- und/oder Haloalkoxygruppen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, ein fünf- bis sechsgliedriges cyclisches System bilden können, das 0 bis 2 Sauerstoffatome enthält, und dessen Alkylanteil gegebenenfalls mit einem oder mehreren Fluoratomen substituiert sein kann.wherein G 1 , G 2 and G 3 , each independently of one another, are selected from the group consisting of halogen, alkyl, haloalkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, alkeneoxy, alkynoxy, cycloalkylalkoxy, haloalkoxy, haloalkoxyalkyl, alkylsulfanyl, Haloalkylsulfanyl, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, cyano, alkylcarbonyl, alkoxycarbonyl, alkoxycarbonylalkyl, carboxyl, carboxamide, dialkylcarboxamide, trialkylsilyl, nitro, amino, alkylamino, dialkylamino, alkylsulfonylamino, dialkylsulfonylamino, -CR 6 = NO- R 6 , -CR 6 = NO-haloalkyl, or formyl, where vicinal Alkyl, haloalkyl, alkoxy and / or haloalkoxy groups together with the carbon atoms to which they are attached, can form a five- to six-membered cyclic system containing 0 to 2 oxygen atoms, and its alkyl moiety optionally substituted with one or more fluorine atoms can.
13. Mittel, enthaltend mindestens eine Verbindung der allgemeinen Formel (I) gemäß einem der Ansprüche 1 bis 7.13. A composition containing at least one compound of the general formula (I) according to one of claims 1 to 7.
14. Verwendung von Verbindungen der Formel (I) gemäß einem der Ansprüche 1 bis 7 oder des Mittels gemäß Anspruch 13 zur Bekämpfung tierischer Schädlinge.14. Use of compounds of formula (I) according to any one of claims 1 to 7 or the composition according to claim 13 for controlling animal pests.
15. Verfahren zur Bekämpfung tierischer Schädlinge, dadurch gekennzeichnet, dass man Verbindungen der Formel (I) gemäß einem der Ansprüche 1 bis 7 oder Mittel gemäß Anspruch 13 auf tierische Schädlinge und/oder deren Lebensraum und/oder Saatgut einwirken lässt.15. A method for controlling animal pests, which comprises allowing compounds of the formula (I) according to one of claims 1 to 7 or agents according to claim 13 to act on animal pests and / or their habitat and / or seed.
16. Verfahren zur Herstellung von Mitteln gemäß Anspruch 13, dadurch gekennzeichnet, dass man Verbindungen der Formel (I) gemäß einem der Ansprüche 1 bis 7 mit Streckmitteln und/oder oberflächenaktiven Stoffen vermischt. 16. A process for the preparation of agents according to claim 13, characterized in that one mixes compounds of formula (I) according to any one of claims 1 to 7 with extenders and / or surface-active substances.
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